JPS6296595A - Metal rolling oil - Google Patents

Abstract

PURPOSE:To obtain a metal rolling oil having an excellent rolling performance, by reacting a particular amide compd. with an isocyanate compd. CONSTITUTION:At least one compd. selected from a 12C or higher aliphatic carboxylic acid (e.g., lauric acid), a 12C or higher polycarboxylic acid (e.g., japanic acid), a 4C or higher polycarboxylate having an 11C or higher alkyl group and carboxyl group is reacted with a polyamine (e.g., ethylenediamine) in an inert gas at 140-260 deg.C for 2-25hr to obtain an amide compd. (A) having at least one remaining amine group. 1mol of the component A is reacted with 0.2-2mol of an isocyanate compd. (B) having in its molecule at least two isocyanate groups capable of reacting with the remaining amine group in the component A (e.g., methylene diisocyanate) at 60-150 deg.C for 2-6hr.

Description

[Detailed description of the invention] The present invention relates to metal rolling oil.

Conventionally, palm oil has been used as rolling oil for steel sheets for a long time, but instead, animal and vegetable oils such as beef tallow, pork fat, Nagasu whale hardened oil, mineral oils, or quasi-combined oils thereof are used as bases, and additives are added to them. , oiliness 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 beef tallow-based rolling oils are no longer able to satisfy these conditions, but rolling oils that can 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 superior rolling performance to conventional rolling oils based on palm oil or beef tallow, and which 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.

An amide compound with at least one remaining amine group obtained by reacting at least one selected from the group of (A) and (B) with a polyamine, which is capable of reacting with the remaining amine group. At least 2 isocyanate groups in the molecule
This is a metal rolling oil characterized by using a compound obtained by reaction with an isocyanate compound having .

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, valmitic 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 polycarboxylic acid ester having 4 or more carbon atoms and having at least 1 alkyl group having 11 or more carbon atoms and at least 1 carboxyl group in each molecule used in (B) is a polycarboxylic acid ester having 4 or more carbon atoms and a hydroxyl group having 4 or more carbon atoms. It is obtained by forming an ester with a compound, but as a hydroxyl compound,
An ester of an aliphatic 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, with at least one hydroxyl group remaining in the molecule, or Examples include alkylene oxide adducts of these.As aliphatic alcohols having 12 or more carbon atoms, lauryl alcohol,
Examples include myristyl alcohol, valmityl alcohol, oleyl alcohol, stearyl alcohol, and synthetic alcohols synthesized from olefins. 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, pentaerythritol distearate, pentaerythritol trioleate, pentaerythritol tetralaurate, etc. These include, but are not limited to. 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, and their acid anhydrides, trimellitic acid, Further examples include so-called dimer acids, trimer acids, etc. 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.

4 carbon atoms having at least one alkyl group and carboxyl group each having 11 or more carbon atoms in one molecule used for (B)
The above polycarboxylic acid ester can be obtained by an esterification reaction using a polycarboxylic acid and a hydroxyl compound by a conventional method, but at least one carboxyl ester is always present in one molecule of the polycarboxylic acid ester obtained at the end of the reaction. group, and must always have at least one ester group and at least one alkyl group having 11 or more carbon atoms.

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.

These esters are obtained by a dehydration esterification reaction between a carboxyl group and a hydroxyl group, and also by a transesterification reaction with a lower alcohol ester of a carboxyl group.

An example of an ester production reaction between a polycarboxylic acid and a hydroxyl compound, and a polyhydric alcohol and a fatty acid having 12 or more carbon atoms is as follows: 1 mole of a hydroxyl compound or polyhydric alcohol and 0.5 to 0.5 to
An esterification reaction is carried out at 160 to 260°C for 2 to 15 hours 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 flow. The desired ester is obtained. 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 selected from the groups (A) and (B) is reacted with a polyamine to obtain an amide compound having at least one amine group remaining in the molecule, and the polyamine used here Examples include, but are not limited to, ethylene diamine, propylene diamine, hexaethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine.

The above amide compound contains polyamine, (A), (B)
It is obtained by performing an amide reaction with at least one selected from among the above. To give an example of the reaction conditions, the number of moles of carboxyl compound is determined and used in the reaction so that at least one amine group remains in the molecule per mole of polyamine.

For example, to 1 mole of ethylenediamine, a carboxyl compound is added in an amount of 1 mole or less for lauric acid or 0.5 mole or less for dimer acid, and the mixture is heated for 2 to 25 minutes at a temperature of 140 to 260°C under a nitrogen gas flow. Obtain the desired amide by time reaction. The number of amine groups remaining in the amide molecule is calculated from the amine value. The reaction of the amide compound with at least one remaining amine group obtained as described above with the isocyanate compound is carried out as follows.

0.2 to 1 mole of amide compound to isocyanate compound
Add 2 mol and react at 60-150°C for 2-6 hours.

At least 2 isocyanate groups used in the present invention are contained in the molecule.
Examples of the isocyanate compounds include methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, nitrodiphenyl diisocyanate, nitrodiphenylmethane diisocyanate, diphenylmethane sulfone diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate, fluorene diisocyanate, chrysene diisocyanate, and methane diisocyanate. xyphenylene diisocyanate, Examples include biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, triphenylmethane triisocyanate, and the like.

If amine remains in the reaction product obtained in the above manner, generally known treatments such as neutralization, quaternization, amphotericization, etc. may be carried out as necessary for the corresponding amine value.
It can be used after carrying out using a processing agent suitable for each treatment.

These reaction products have extremely high rolling performance when used directly as rolling oil, but if necessary, they may be mixed with other lubricating oils, animal or vegetable oils, mineral oils, or added with extreme pressure additives, antioxidants, and interfaces. It can also be used by adding an activator or the like.

The present invention will be described in detail below using Examples.

Synthesis Example 1 After reacting 400 parts of lauric acid and 103 parts of diethylene triamine at 140 to 160°C under a nitrogen gas stream for 2 hours, the reaction was further carried out at 180 to 200°C for 4 hours to produce an amide with an acid value of 0.6 and an amine value of 114. Obtained. 4.4 to this amide
”-110 parts of diphenylmethane diisocyanate to 10
The mixture was added dropwise at 0 to 110°C, and after completion of the dropwise addition, the mixture was reacted at 110 to 120°C for 2 hours to obtain a compound having an acid value of 0.4 and an amine value of 20.

Synthesis Example 2 792 parts of adipic acid monooleyl ester and 103 parts of diethylenetriamine were mixed at 220 to 240 parts under a nitrogen gas stream.
The reaction was carried out at ℃ for 16 hours to obtain an amide having an acid value of 3.0 and an amine value of 50. Next, 66 parts of tolylene diisocyanate was added and reacted at 60 to 80°C for 4 hours to obtain a compound with an acid value of 1.8 and an amine value of 8.0.

Synthesis Example 3 516 parts of valmitic acid, 382 parts of succinic acid monooleyl ester, and 189 parts of tetraethylenepentamine were reacted at 200 to 220°C for 12 hours under a nitrogen gas stream to obtain an amide with an acid value of 18 and an amine value of 85. .

Then 4.4'-diphenylmethane diisocyanate 2
00 parts was added dropwise at 100 to 110°C, and after the completion of dropping 110 parts
The reaction was carried out at ~120°C for 2 hours to obtain a compound having an acid value of 8 and an amine value of 10.

Synthesis Example 4 568 parts of stearic acid, 146 parts of triethylenetetramine
A portion was reacted at 200 to 220° C. for 6 hours under a nitrogen gas stream to obtain an amide with an acid value of 5.6 and an amine value of 143. Add 84 parts of hexamethylene diisocyanate to this amide.
Drop at 00~110℃, 110~120℃ after dropping
The mixture was reacted for 3 hours to obtain a compound having an acid value of 4.1 and an amine value of 22.

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, and the results were used as comparative examples. The results are shown in Table 2 along with the measurement results of the system 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.

In addition, as a comparative example, tallow-based rolling oil shown in Table 1 was used.

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 Sota-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 150mm x medium 140mm backup Roll diameter 250mm x Width 140mm Roll material Chrome steel Roll peripheral speed 30m/min Rolling material: 5pc-c Thickness 0.6mm x Width 50mm x Length 150mm Measuring method of rolling performance 50mm spacing on the steel plate before rolling (1,) Two lines were drawn, the lines were rolled, the distance (12) after rolling was measured, and the rolling reduction was determined using the following formula.

Further, the rolling load (ton) at that time was measured using a load cell.

[Brief explanation of drawings]

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 example. Patent applicant: Miyoshi Oil Co., Ltd.

Claims (1)

[Claims] (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. An amide compound with at least one remaining amine group obtained by reacting at least one selected from the group of (A) and (B) with a polyamine, which is capable of reacting with the remaining amine group. At least 2 isocyanate groups in the molecule
A metal rolling oil characterized in that it uses a compound obtained by a reaction with an isocyanate compound.