JPS617394A - Composition for metal processing - Google Patents

Abstract

PURPOSE:A composition for metal processing that contains, as active ingredient, a water-soluble cation which is prepared by neutralizing a condensation product between a specific aliphatic dicarboxylic acid and a specific polyamine, with an oxyacid of phosphorus, thus having lubricating and cleaning actions. CONSTITUTION:The objective composition contains, as an active ingredient, a water-soluble cation which is obtained by neutralizing a condensation product with an average molecular weight of 500-1,000, obtained from (A) 1mol of an aliphatic dicarboxylic acid of 6-22 carbon atoms and (B) 1-1.5mol of a polyamine selected from (i) compounds of formula ( I ) (R1-R4 are H, 1-3C alkyl; R5 is 1-4C alkylene), (iii) compounds of formula (III) (n is 3-5) and (iv) hydroxyl-containing basic nitrogen compounds such as ethylaminoethanolamine, 1,3- diamino-2-propanol, with (C) at least one of oxyacids of phosphorus selected from phosphoric, phosphorous and pyrophosphoric and other phosphorus acids.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to metalworking compositions (with lubricating and cleaning properties). More specifically, the present invention relates to a metal processing composition containing a water-soluble cationic compound whose counter-anion is a phosphorus oxygen acid.

BACKGROUND ART Conventionally, lubricants used in metal machining, such as rolling, drawing, cutting, and grinding, use animal and vegetable oils, mineral oils, etc. as a base oil, and fatty acids, alcohols, etc. as oily agents. The composition contains organic phosphorus compounds, organic chlorine compounds, etc. as extreme pressure additives, and an emulsifier as necessary. It is designed to exhibit its lubricating effect. Among the above basic compositions, the one that greatly influences the lubricating performance is the oily agent, and conventionally, fatty acids having about 8 to 20 carbon atoms, their dimer acids, and their salts have been used as the oily agent. . Fatty acids have traditionally been widely used during metal processing because they react with the respective metals on the two surfaces of tools and workpieces, firmly adsorbing and arranging them on the metal surface, and exhibiting good lubricity.
As a matter of course, it also reacts with abrasion metal powder generated during machining, and as a result, metal and soap become raw and easily disappear from the lubricating fluid. As a result, there is a problem in that the lubrication performance changes over time, which impedes work stability. Moreover, the stability of the produced metal soap #'i lubricating liquid is impaired, and the liquid often becomes unusable. Furthermore, since it partially deteriorates due to the heat and shearing force generated during metal processing, it accelerates the deterioration of the floating oil content, significantly contaminating processed products and processing machines, and requiring a large amount of expense to clean them. In order to avoid the various problems caused by the use of fatty acid-based oil-based agents, the current situation is to frequently replace the lubricating fluid. Current demand - The development of new lubricants has been strongly desired.

OBJECTS OF THE INVENTION As mentioned above, fatty acids, which are oily agents often used in conventional oils, combine with iron ions 17 to form iron soaps, causing various adverse effects. The main reason for this is that the coolant system is a multi-component emulsion system, and the breaking of the emulsion by the generated iron soap causes changes in lubrication performance and workability over time. The present invention was achieved by searching for and studying materials with excellent lubricating properties that can be used as main components to form metal working oils, while avoiding the fact that metal working oils are a metal working oil.

The water-soluble cationic compound used in this invention is rapidly lost due to the presence of iron, but this appears as a decrease in the concentration in the liquid, and is easily restored by replenishing the lost amount. Therefore, stable work is possible.

Structure of the Invention The metal working composition of the present invention comprises 1 mol of aliphatic dicarboxylic acid having 6 to 22 carbon atoms and polyamino 1' having the general formula of 6) to (dl) having an average molecular weight of 500 or more. A condensate of less than 1000,
1 of the phosphorus oxygen acids shown in (1) to 3) below
This is a metal processing composition characterized in that the active ingredient is a water-soluble cationic compound obtained by neutralization with one or more species.

In the formula, 1.1 to R14 are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H.

R11 is an alkylene group having 1 to 4 carbon atoms.

R Tsu The compound shown in

R1 in the formula. - R14 and R7 are H or an alkyl group having 1 to 3 carbon atoms, of which at least one
One is H.

R1 and 8.6 are alkylene formulas having 1 to 4 carbon atoms, and each is an integer of 3 to 5.

(d) A basic nitrogen compound having a hydroxyl group shown below.

Ethylamineethanolamine, 1,2-bis(hydroxyethylamino)ethane, 1.

3-diamino-2-propatol, 2-hy)'oxyethylaminopropylamine, N,N'-bis(hydroxyethyl)diethylenetriamine, 2-hydroxypropyl-trimethylenetetramine, N-2-oxypropyl-triethylene Tetramine (11) Phosphoric acid, phosphorous acid, hypophosphorous acid, superphosphoric acid (2) selected from pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, pyrrhous acid, polymetaphosphorous acid, disuperphosphoric acid Condensate of phosphorus oxyacid.

(3) Compounds represented by the following formulas (1) to (11D).

(1) N(-0Hz -P -0H)sOH (aliphatic dicarboxylic acid) The aliphatic dicarboxylic acid that is at risk for developing the metal processing composition of the present invention is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms. You can use one. These dical I phosphoric acids may be saturated or unsaturated acids, and may have a linear or branched structure.

These aliphatic dicarboxylic acids may be used alone for condensation with amines, but several types of aliphatic dicarboxylic acids may be used in combination for condensation with amines.

Specific examples of these acids are shown below.

Adipic acid, azelaic acid, henanosinic acid, 1.

In addition to 10-7'candicardinic acid, 1,14-nato-2decanedicarboxylic acid, 1,18-octadecanedicalonic acid, and the like, dicarboxylic acids represented by the following formulas may be mentioned.

HOOO-OH(OHs)s 0OOH4H9 2-zotyloctanioic acid HOOO(OH1)gOH(OHs)to 0OOHO
．． H.

7-nityl octadecanedioic acid HOOO(OHs)s 0H=OH(OHz)
s0OOH8,13dimethyl-8,2-eicosadienioic acid (polyamine) Specific examples of polyamines of general formulas (a) to (c3) to be condensed with aliphatic dicarboxylic acids to produce the metal processing composition of the present invention are as follows: If you show it, you can move on to the next step.

Ethylenediamine, r-(methylamino)propylamine, diaminopropane, tetramethylenediamine, N-methylaminogundiamine.

N, N'-dimethyl-propanediamine, N-ethyl-propane diamino, N, N'--, ? Ethylpronogundiamine, diethylenetriamine, methyliminobisprobylamine, 1,3,6-dolyaminomethylhexane, N-aminoethyl-N-methyl-1,3-diaminopronozone, iminobiszolobylamine, triethylenetetramine , Tetraethylenepentahan, Pentaethylenehexamine.

(Condensation reaction) In the condensation reaction between the aliphatic dicarboxylic acid and amines, the product exhibits useful lubricity and water solubility in the following cases:
It ranges from 1:1 to 1:1.5.

The molecular weight of the condensate has an appropriate range in terms of water solubility, lubricity when used in metal processing, and secondary performance. That is,
To easily impart water solubility industrially, the average molecular weight is 1.
It is preferable that it is less than 000, and if it exceeds it, it will be extremely difficult to provide water solubility, and even if it is possible, the water-soluble cationic compound will not be able to be used in processed products, processing machines, etc. during drying. A film is formed, which deteriorates the appearance of the product and the accuracy of machine operation. Regarding lubricity, when the average molecular weight is less than 500, no remarkable results are observed, and when it is 500 or more, the expected performance is obtained. Therefore, it is desirable that the average molecular weight of the condensate is in the range of 500 or more and less than 1,000.

(Counteranion) Next, counteranions for neutralizing the condensate to obtain a water-soluble cationic compound include organic acid ions such as acetate ion, oxalate ion, and citrate ion, and furthermore, Inorganic acid ions such as , nitric acid ion, sulfate ion, phosphorous oxyacid ion, and boric acid ion can be mentioned, but phosphorus oxyacid ion is preferable in order to provide useful lubricity and rust prevention. Anions are unsuitable because they have drawbacks in either lubricity or rust prevention. The amount of phosphorus oxyacid is 50 to 120%, preferably 75% of the amount of phosphorus oxyacid necessary to neutralize the total amine value of the condensate.
~100%.

(Water-soluble cationic compound) Water-soluble cationic compound is
A predetermined amount of the aliphatic dicarboxylic acid and amines were placed in an iron reaction vessel equipped with a stirrer and a counterflow cooling tube via a dehydration tube, and the mixture was heated under reflux of Kijiroru in a nitrogen atmosphere at 160 to 170°C for 4 to 5 hours. It can be easily obtained by carrying out a dehydration reaction, calculating this from the total amine value of the product, adding it to water containing a predetermined amount of counter anion, and dissolving it by heating appropriately while stirring.

(Optional Components) Although the metal processing composition of the present invention is used as a sole aqueous solution, an ethanolamine neutralized product of molybdic acid or sodium nitrite may be added to further improve the rust prevention properties. . These compounds can be mixed in a proportion of 0.5 to 10% by weight of the compound of the invention.

Further, in the present invention, other anticorrosive agents such as benzoazole may be added for the purpose of preventing corrosion of copper and copper alloys. The appropriate proportion of the anticorrosive agent added is 0.1 to 2% by weight of the compound of the present invention.

(How to use) When using the metal processing composition of the present invention, prepare an aqueous solution of the water-soluble cationic compound of the present invention with a concentration of 0.05 to 5%, and adjust the temperature of the aqueous solution to room temperature to 6.5%. It is held at ゛Oc and fed under pressure by the pump, and the target location (
In other words, the dust and abrasion powder that is injected into the plate and roll in cold rolling, the roll in hot roll rolling, and the plate and roll in differential rolling and collected and mixed into 7tffl. be removed and reused.

(Examples) Examples are shown below to make it easier to understand the present invention, but the following examples do not limit the present invention in any way.

First, water-soluble cationic compounds of the present invention are illustrated in Table 1.

Example 1 (Example of rolling lubrication) Rolling conditions Rolling roll: Forged steel expanded roll, diameter 60X Rolling speed: 30 m7'h Plate material: 8PO0,0,8X 80bm Coolant temperature 50℃±3℃ (rolling oil) =50% Rolling results (Note) The composition number is the same as the number in Table 1.

Example 2 (detergent rolling) After using normal oil, final #5 in case of tandem mill
Spray detergent on the stand in the same way as applying rolling oil and roll.

This is an operation to remove hazardous oil and iron powder adhering to the front stand salt, and its effectiveness is expressed as a cleaning rate relative to the total adhesion t (oil, iron powder).

Test conditions Test steel plate Steel plate rolled with mineral oil/ester paste commercial rolling oil (5PO0, 0.47'X100bX200"X,
140℃) Total amount of deposits 0.234 f/rI! Roll 60! ! Dull roll speed 5 m/- Rolling reduction 6.5% Detergent 0°05%, SOC result (Note) The composition number is the same as the number in Table 1.

Example 3 (Hot Roll Lubrication) This example shows roll wear and coefficient of friction (μ) for hot rolling.

Test method A heating element cleaned with clean bent naphtha is fixed between copper electrodes whose end faces have been polished with a file, and a thermocouple is set in a small hole on the side of the heating element through an unglazed protective tube.

Raise the heating element along with the electrodes about 10 minutes directly above the rotating body attached to the rotating shaft.

Start the motor and adjust it to the specified rotation speed.

Record the zero point of rotational torque. Gradually increase the power input for heating using a slider and maintain the specified temperature.

Remove visible iron oxide (scale), lower the heating element together with the electrode, and apply #1'% approximately in the thickness direction of the rotating element:
Contact with no load. At this time, confirm that the zero point of torque does not change. Next, add oil and gently place a weight of a predetermined weight directly above the contact area.

From this point on, we begin measuring the friction time.

With careful manipulation, the temperature of the heating element during the experiment can be adjusted to ±10°C. However, if local welding or seizure occurs, a temporary temperature increase of approximately 50°C will be observed.
In this case, the temperature rise is accompanied by abnormal vibrations of the heating element, so it can be easily determined whether the temperature rise is due to poor input adjustment or frictional heat. In the case of temporary localized seizure, if the abnormal part on the surface of the seizure falls off, the temperature will return to the original predetermined temperature, but if it develops into full-scale seizure, the temperature will continue to rise to 100℃.
This results in abnormal temperature rise. At that time, the abnormality is also detected in the torque.

After the friction is finished, the rotating body is washed with solvent naphtha, and the wear profile of four locations located at 906 points relative to each other is determined using a Kosaka type stylus roughness meter, and the average area is multiplied by the circumferential length of the rotating body. Wear t(y'') was calculated.

The friction coefficient was calculated by a conventional method from the torque measured during the friction test.

result (Note) The composition number is the same as the number in Table 1.

Although the reason for this is not clear, the composition of the present invention has lubricity due to adsorption to the iron surface due to its cationic nature, and characteristics caused by the dispersion of iron powder in the liquid. It is thought that effects such as roll lubrication and ditargent will be exhibited. Therefore, in rolling, by using a lubricating fluid with a concentration of 0.0% and 1% O, which was not available in the past, rolling can be performed with a rolling load approximately 20% lower than that of a commonly used rolling lubricating fluid.

In addition, the amount of wear on the hot rolls has been significantly reduced by υ compared to conventional lubrication methods using mineral oil and beef tallow;
Because it is a dilute liquid of only 1.5%, it does not impede cooling of the rolls and exhibits an extremely advantageous lubrication effect.

By supplying only 0.05% aqueous solution in the final stand of cold rolling (in the case of tandem mills) or the final pass (in the case of Reno-Sumi mills),
Iron powder generated by previous rolling can be washed and removed.

Thereby, the plate surface quality can be improved in mill-clean material rolling production.

Applicant: Nippon Kokan Co., Ltd. (t’l or 1 person)

Claims (1)

[Claims] Obtained by reacting 1 mol of aliphatic dicarboxylic acid having 6 to 22 carbon atoms with 1 mol to 1.5 mol of a polyamine having the following general formulas (a) to (d): A condensate with an average molecular weight of 500 or more and less than 1000 is prepared by
) to (3) 1 or 2 of the phosphorus oxyacids shown in
1. A composition for metal processing, characterized in that the active ingredient is a water-soluble cationic compound obtained by neutralization with at least one species. (a) Compounds represented by the general formula ▲Mathematical formulas, chemical formulas, tables, etc. available▼. R_1 to R_4 in the formula are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H. R_5 is an alkylene group having 1 to 4 carbon atoms. (b) Compounds represented by the general formula ▲Mathematical formulas, chemical formulas, tables, etc.▼. In the formula, R_1 to R_4 and R_7 are H or an alkyl group having 1 to 3 carbon atoms, and at least one of them is H. R_5 and R_6 are alkylene groups having 1 to 4 carbon atoms. (c) A compound represented by the general formula H_2N-(C_3H_4NH)-n. n in the formula is an integer of 3 to 5. (d) A basic nitrogen compound having a hydroxyl group shown below. Ethylaminoethanolamine, 1,2-bis(hydroxyethylamino)ethane, 1,3-diamino-2-propanol, 2-hydroxyethelaminopropylamine, N,N'-bis(hydroxyether)
Diethylenetriamine, 2-hydroxypropyl-trimethylenetetramine, N-2oxypropyl-triethylenetetramine (1) Phosphoric acid, phosphorous acid, hypophosphorous acid, perphosphoric acid (2) Pyrophosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid , a condensate of phosphorous oxyacids selected from pyrophosphorous acid, polymetathosphous acid, disuperphosphorous acid. (3) Compounds represented by the following formulas (i) to (iii). (i)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (ii)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (iii)▲There are mathematical formulas, chemical formulas, tables, etc.▼