JPS6339987A - Metal rolling oil - Google Patents

Abstract

PURPOSE:To obtain a rolling oil exhibiting a rolling performance superior to that of a conventional rolling oil comprising a palm oil or the like, by preparing a compd. by addition of an alkylene oxide to an amide compd. obtd. by a reaction of an aliphatic carboxylic acid with a polyamine to prepare an amide compd. and reacting the compd. with a polyepoxy compd. CONSTITUTION:At least one compd. selected from among the following compds. (A) and (B) is reacted with a polyamine to prepare an amide compd. having at least one residual active hydrogen atom in a molecule. An alkylene oxide is added to the amide compd. The compd. thus obtd. is reacted with a polyepoxy compd. having at least two epoxy groups to prepare a compd. to be incorporated into a rolling oil. Compd. (A): 12C or higher aliphatic carboxylic acid or polycarboxylic acid. Compd. (B): a partial ester of 4C or higher polycarboxylic acid having at least one 11C or higher alkyl grup in a molecule and at least one residual carboxyl group of the polycarboxylic acid.

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 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) having at least one alkyl group having 11 or more carbon atoms in one molecule, and at least one carboxyl group of polycarboxylic acid. At least one active polyamine in one molecule obtained by reacting a polyamine with at least one member selected from the group (A) and (B) of the remaining partial ester of a polycarboxylic acid having 4 or more carbon atoms. In the amide compound that allows hydrogen to remain,
Furthermore, the compound obtained by adding alkylene oxide (
This metal rolling oil is characterized by using a compound obtained by reacting C compound (hereinafter abbreviated as compound C) and a polyvalent epoxy compound having a small number of epoxy groups (both have two epoxy groups). It is also possible to mix and use additives, surfactants, 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, which has a small number of alkyl groups having 11 or more carbon atoms and carboxyl groups in one molecule (both 1 in each molecule) used in (B), is a polycarboxylic acid having 4 or more carbon atoms. It is obtained by producing an ester from an acid and a hydroxyl compound, and the hydroxyl compound includes 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 include esters with at least one hydroxyl group remaining in the molecule, and alkylene oxide adducts of these.As aliphatic alcohols having 12 or more carbon atoms,
Examples of polyhydric alcohol esters having at least one hydroxyl group remaining in each molecule include lauryl alcohol, myristyl alcohol, palmityl alcohol, oleyl alcohol, stearyl alcohol, and synthetic alcohols synthesized from olefins. Ethylene glycol quinola lylate, propylene glycol monopalmitate, polyethylene glycol monooleate, glycerin monostearate, glycerin silarylate, trimethylolpropane monopalmitate, trimethylolpropane distearate, sorbitol monolaurate, sorbitol diole ate, sorbitol tristearate, pentaerythritol monopalmitate, pentaerythritol distearate,
Examples include, but are not limited to, pentaerythritol trioleate, pentaerythritol tetralaurate, etc. Polycarboxylic acids having 4 or more carbon atoms include succinic acid, adipic acid, azelaic acid,
Obtained by polymerizing dibasic carboxylic acids such as sebacic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, and unsaturated fatty acids such as oleic acid and linoleic acid.
Examples include so-called dimer acids and trimer acids.

In addition, alkylene oxides include 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, one molecule of the polycarboxylic acid ester obtained always contains a small number of carboxyl groups (one carboxyl group remaining, and one ester group and at least one carbon number). Must possess 11 or more alkyl groups.

An ester of a polyhydric alcohol in which at least one hydroxyl group remains in the molecule that is a 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, as well as a polyhydric alcohol and a fatty acid having 12 or more carbon atoms, is 1 mole of a hydroxyl compound or polyhydric alcohol, and 0.5 to 0.5 to 1 mol of a polycarboxylic acid or fatty acid.
5 moles in a nitrogen gas stream at 160 to 2 eO<0>C 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 for ~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, a polyamine is reacted with a polyamine selected from the groups (A) and (B) to obtain an amide compound with a small number (one amine group remaining in the molecule). Examples of the polyamines used 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 carrying out an amide reaction with at least one selected from the following. To give an example of the reaction conditions, the number of moles of carboxyl compound is determined and used in the reaction so that the number of amine groups in the molecule is as small as possible (at least one remains) per mole of polyamine.

For example, to 1 mole of ethylenediamine, add a carboxyl compound in an amount of 1 mole or less for lauric acid or 0.5 mole or less for dimer acid, and add 1 mole or less of carboxyl compound to 1 mole of ethylenediamine.
The desired amide is obtained by reacting at a temperature of 40 to 260°C for 2 to 25 hours. The number of amine groups remaining in the amide molecule is calculated from the amine value.

Next, alkylene oxide is added to this amide compound to obtain compound C. The addition reaction of alkylene oxide to this amide 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 epoxy compound having at least two epoxy groups to obtain a compound used in the metal 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 to 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 glycol diglycidyl ether. Examples include glycidyl ether and triglycidyl ether of glycerin added with alkylene oxide.

If amines remain in the resulting reaction product, generally known treatments such as neutralization, quaternization, and amphotericization may be performed as necessary using processing agents suitable for each treatment. After doing so, you can use it.

By performing these treatments, it is possible to appropriately adjust the hydrophilicity of the reaction product according to the usage conditions, and also to adjust the polarity of the reaction product and control its adsorption to metal surfaces. .

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.

Synthesis Example 1 282 parts of oleic acid, 282 parts of dimer acid, and 146 parts of triethylenetetramine were mixed under a nitrogen gas stream at 200 to 240 parts.
After reacting at ℃ for 6 hours, 1000 parts of ethylene oxide was added to obtain a compound with an acid value of 3.1 and a hydroxyl value of 70.Next, polyethylene glycol diglycidyl ether (M
Add 1540 parts of W-1540) and heat to 100-120°C
The mixture was reacted for 4 hours to obtain a compound having an acid value of 1.2 and a hydroxyl value of 31.5.

Synthesis Example 2 After reacting 568 parts of stearic acid and 103 parts of diethylene triamine at 230 to 240°C under a nitrogen gas stream for 6 hours, addition reaction of 220 parts of ethylene oxide was carried out at 170 to 180°C, and then 174 parts of propylene oxide was added to 170 parts of diethylene triamine.
An addition reaction takes place at ~190°C, resulting in an acid value of 1.2 and a hydroxyl value of 7.
Next, 146 parts of adipic acid diglycidyl ester was added to this and reacted at 0 to 110°C for 6 hours to obtain a compound with an acid value of 0.5 and a hydroxyl value of 25.0.

Synthesis Example 3 1158 parts of sebacic acid monolauryl ester and 189 parts of tetraethylenepentamine were mixed under a nitrogen gas stream at 180-2.
After reacting at 40°C for 20 hours, propylene oxide 10
00 parts was subjected to an addition reaction at 170 to 190°C to obtain an acid value of 8.0.
, a compound with a hydroxyl value of 46.5 was obtained.Next, 207 parts of diglycidyl succinate was added to this to give a compound with a hydroxyl value of 46.5.
Reacted at 0°C for 10 hours, acid value 4.5, hydroxyl value 42.0
The compound was obtained.

Synthesis Example 4 After reacting 516 parts of palmitic acid, 382 parts of succinic acid monooleyl ester, and 189 parts of tetraethylene pentamine at 230 to 240°C under a nitrogen gas stream for 16 hours, 880 parts of ethylene oxide was added to give an acid value of 12. A compound with a hydroxyl value of 85.3 was obtained.Next, 174 parts of ethylene glycol diglycidyl ether was added to this, and 1
The reaction was carried out at 10 to 120°C for 4 hours to obtain a compound having an acid value of 12.3 and a hydroxyl value of 36.0.

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 a comparative example for tallow-based rolling. The results are shown in Table 2 along with the oil measurement results.

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.
For comparative examples, tests were conducted by supplying emulsions at a concentration of 5%. The amount of oil adhering to the rolled material was set to 1 g/cd in all of 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 Soda pendulum type oil tester NII type load-bearing capacity test method Shell type high-speed four-ball friction tester Rolling test method Rolling machine: Four-roll rolling machine Work roll diameter 150mm X width 140++ue backup roll Diameter 250mm x Width 140m5 + Roll material Chrome steel roll circumferential speed 30m/win Rolling material: 5pc-c Thickness 0.6am x Width 50m5 x Length 150mm Measuring method of rolling performance Steel plate before rolling was placed at intervals of 5 strokes (j! The two lines in 1) were drawn, rolled, and the distance after rolling (j! z) 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 the drawing]

Figure 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. Show the harpoon.

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, obtained by reacting a polyamine with at least one member selected from the group (A) and (¥B¥)¥ of A compound obtained by further adding an alkylene oxide to an amide compound with at least one active hydrogen remaining in one molecule, and a polyepoxy compound having at least two epoxy groups are reacted. Compounds obtained by
Metal rolling oil characterized by using ¥.