JPS6339988A - 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 alkylene oxide to an aminde compd. obtd. by a reaction of an aliphatic carboxylic acid with a polyamine to prepare an amide compd. and reacting the compd. with a polyisocyante 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 polyisocyanate compd. having at least two isocyanate 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 leastone 11C or higher alkyl group 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 superior rolling performance to conventional palm oil or beef tallow-based rolling oils and is satisfactory for 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 a carbon number of 11 or more in one molecule, and at least one carboxyl group of the polycarboxylic acid remaining. At least one active hydrogen per molecule obtained by reacting a polyamine with at least one member selected from the group (A) and (B) of a partial ester of a polycarboxylic acid having 4 or more carbon atoms, In the amide compound that causes the remaining
Compounds obtained by further 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 isocyanate compound having at least two isocyanate 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, palmic acid, cic acid, stearic acid, arachidic acid, and behenic acid, oleic acid, and linoleic acid. , unsaturated fatty acids such as linuric acid, ricinoleic acid, and arachidonic acid, neoacids, 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. As aliphatic alcohols having 12 or more carbon atoms,
Examples 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, trimethylolpropane monopalmitate, trimethylolpropane distearate, sorbitol monolaurate, sorbitol dioleate, sorbitol tristearate, pentaerythritol monopalmitate, vegetable erythritol distearate, pendaerythritol trioleate, Examples of polycarboxylic acids having 4 or more carbon atoms include, but are not limited to, pentaerythritol tetralaurate, succinic acid, adipic acid, azelaic acid, zebacic acid, maleic acid, fumaric acid, Examples include dibasic carboxylic acids such as itaconic acid, trimellitic acid, and so-called dimer acids and trimer acids obtained by polymerizing unsaturated fatty acids such as oleic acid and linoleic acid.

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, 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 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 at 160 to 260°C 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 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, at least one selected from the groups (A) and (B) is reacted with a polyamine to obtain an amide compound in which at least one amine group remains in the molecule. Examples include, but are not limited to, ethylenediamine, propylenediamine, hexaethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

The above amide compound has polyamine and (A >, (B
) 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 at least one amine group remains in the molecule 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 oxytone 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 at least two 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, nitrodiphenylmethane diisocyanate, diphenylmethane sulfone diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate, Examples include fluorene diisocyanate, chrysene diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, and triphenylmethane triisocyanate.

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.

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

Synthesis Example 1 After reacting 400 parts of lauric acid and 103 parts of diethylenetriamine at 140 to 160°C under a nitrogen gas stream for 2 hours, and further reacting at 180 to 200°C for 4 hours, 440 parts of ethylene oxide was added at 160 to 180°C. , acid value 2.
6. A compound with a hydroxyl value of 72 was obtained. Then, 112.5 parts of 4.4"-diphenylmethane diisocyanate was added to 100
Dropped at ~110℃, and after dropping at 110~120℃
The reaction was carried out for a period of time to obtain a compound having an acid value of 0.9 and a hydroxyl value of 6.0.

Synthesis Example 2 After reacting 568 parts of stearic acid and 103 parts of diethylenetriamine at 220 to 240°C under a nitrogen gas stream for 8 hours, addition reaction of 220 parts of ethylene oxide was carried out at 160 to 180°C, and then 174 parts of propylene oxide was reacted at 170 to 240°C.
Addition reaction at 190°C resulted in an acid value of 1.2 and a hydroxyl value of 79.
Next, 105 parts of naphthalene diisocyanate was added dropwise to this compound at 110 to 120°C, and after the completion of the dropwise addition, 120 parts of naphthalene diisocyanate was obtained. The reaction was carried out at 30° C. for 4 hours to obtain a compound having an acid value of 2.4 and a hydroxyl value of 10.5.

Synthesis example 3 Valmitic acid 516, succinic acid monooleyl ester 3
After reacting 82 parts of ethylene pentamine and 189 parts of tetraethylene pentamine at 165 to 220°C under a nitrogen gas stream for 12 hours, 2000 parts of ethylene oxide was added at 160 to 180°C to obtain an acid value of 0.8 and a hydroxyl value of 37.0. Compound obtained 0
Next, 212 parts of 4.4°-diphenylmethane diisocyanate was added dropwise at 100 to 110°C, and after the dropwise addition was completed, the reaction was carried out at 110 to 120°C for 2 hours to give an acid value of 0.5 J.
A compound with a hydroxyl value of 4.8 was obtained.

Example 4 792 parts of adipic acid monooleyl ester and 103 parts of diethylenetriamine were heated at 220 to 240°C under a nitrogen gas stream.
After reacting for 16 hours, 220 parts of ethylene oxide was added to 160 parts of
Addition reaction takes place at ~180°C, resulting in an acid value of 6.2 and a hydroxyl value of 50.
Compound 5 was obtained. Then tolylene diisocyanate 7
Add 8 parts of
, a compound with a hydroxyl value of 5.5 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, 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 attached to the rolled material was set to Ig/nf 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 Soda pendulum type oil tester NII 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 + n + X width 140 m + w Backup roll Diameter 250mm
Measuring method of m rolling performance Two lines with a spacing (II) of 50+wo+ were drawn on the steel plate before rolling, and the spacing (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 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 positive side of the comparison line in the figure indicates the example magnet.

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