JPS6138758B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel metal plastic working oil composition for cold rolling (hereinafter referred to as metal plastic working oil composition). Therefore, the object of the present invention is to achieve a melting point of 20
A lubricating oil component containing oil or wax at ~100°C is in a stable suspension/dispersion state at temperatures below the melting point, and is unstable at temperatures above the melting point when being supplied to the processing section during plastic working. It is an object of the present invention to provide a metal plastic working oil composition which is in a turbidly dispersed state and adheres well to the working part, and which can be used in circulation. Conventionally, commonly used cold rolling oils for steel sheets include animal and vegetable oil-based rolling oils such as palm oil and tallow-based rolling oil, as well as mineral oil-based rolling oils.
The former uses triglyceride as the base oil, while the latter uses petroleum-based hydrocarbon as the base oil.The oiliness improver, extreme pressure agent, antioxidant, etc. are added to this as a base oil, and an emulsifier is added to it, usually at a concentration of 1 to 20%. It is used as an O/W type emulsion. Much research has been carried out on metal working oil compositions, for example compositions consisting of liquid lubricants, fatty acids or their glycerides and waxes such as slacks waxes have been used as protective coatings for metal surfaces during storage and during cold processing. Acts as a lubricant during rolling operations,
Moreover, it is a preferable composition that effectively suspends dirt, etc. in the emulsion produced (Special Publication No. 48-
42927); or paraffin wax and α
-Lubricating oil compositions containing olefin oxidation products have good lubricity and generate less oil stain (Japanese Patent Publication No. 7174/1983, Japanese Patent Application Laid-Open No. 49/1989)
67906, 49-82707) have been reported. However, these are not necessarily satisfactory. Rolling oil intervenes in the lubrication of the contact arc between the roll and the steel plate, and plays the role of preventing direct contact between them under high load conditions. In cold rolling, rolling speeds are becoming more sophisticated in order to increase productivity. Therefore, in recent years, research has been actively conducted to improve rolling oils that meet the requirements for rolling performed at such high loads and high speeds. Therefore, in improving rolling oil, the selection of base oil, oiliness improver, extreme pressure agent, etc., which are the components of the rolling oil composition, are important factors. The properties of the system are very important. In other words, in the case of lubrication in rolling, the lubricated material is supplied in a dispersed state in water, so even if the lubricating oil components have the same composition, the difference in stability of the dispersed particles causes the difference between the roll and the steel plate. Since the amount of oil adhering to the surface (plate-out amount) differs, the amount of rolling oil taken into the arc of contact between the roll and the steel plate differs, and as a result, the rolling lubrication characteristics also differ. Normally, when a large amount of oil is taken into the arc of contact between the roll and the steel plate, it facilitates lubrication of the surface where the area of the steel plate is expanded due to plastic deformation.
The mutual contact area is also reduced, resulting in improved rolling lubrication conditions. Therefore, when using rolling oil dispersed in water, it is desirable to make the system as unstable as possible to increase the amount of plateout. When used as a dispersion, it is desirable that the dispersion be stable and easy to handle. Generally, an emulsifier is used, the amount added,
The stability (ESI) of the rolling oil emulsion is adjusted by adjusting the HLB balance (usually HLB8 to 14), but with this dispersion method, the plateout amount and
This shows a tendency contrary to the increase in ESI. In other words, if the stability of the emulsion is increased, the amount of plate-out to the steel plate will be reduced, resulting in insufficient lubricity, and if the amount of plate-out is not increased, the emulsion will become unstable, causing various problems during cyclic use. cause trouble. As such, it is extremely difficult to provide both properties at the same time, and a metal plastic working oil composition that has both properties has not yet been provided. Therefore, the present inventor conducted intensive research to develop a metal plastic working oil composition that satisfies such conditions. As a result, the inventors of the present invention have conducted intensive research to develop a metal plastic working oil composition that meets these conditions. By using an agent, it is stably suspended and dispersed in water in a solid state below the melting point, and becomes unstable when being supplied to the processing section, that is, above the melting point,
The present invention has been completed by successfully obtaining a metal plastic working oil composition that satisfies both of the above characteristics. That is, the present invention provides a lubricating oil component containing 10 to 100% by weight of one or more mixtures selected from the group consisting of fats and waxes having a melting point of 20 to 100°C, and a lubricating oil component containing 0.5 to 20% by weight of a mixture of one or more types selected from the group consisting of fats and waxes having a melting point of 20 to 100°C. Olefin-maleic acid copolymer salts, acrylic acid or methacrylic acid-maleic acid copolymer salts, homopolymer salts of acrylic acid or methacrylic acid, or copolymer salts thereof, with a molecular weight of 250 to 25,000 in weight%; and an aromatic compound sulfonic acid-formalin condensate salt.The present invention provides a metal plastic working oil composition for cold rolling containing as an essential component one or more anionic water-soluble dispersants selected from the group consisting of aromatic compound sulfonic acid-formalin condensate salt. It is something. Melting point used in metal plastic working oil composition of the present invention
Examples of fats or waxes with a temperature of 20 to 100°C include normal animal and vegetable oils with a melting point of 20°C or higher, such as palm oil, beef tallow, lard, mutton fat, etc.; natural waxes, such as beeswax, carnauba wax, montan wax, micro Crystalline wax etc.; Synthetic wax such as polyethylene wax, ketone wax, ester wax etc. These oils and waxes can be used alone or in combination of two or more, and it is preferable that the amount of these oils and waxes is 10 to 100% by weight in the lubricating oil component. As other components of the lubricating oil component, mineral oils such as spindle oil, machine oil, turbine oil, cylinder oil, etc. or other known lubricating oils are used, and these are used in an amount of 90% by weight or less of the lubricating oil components. However, it is preferable to use a large amount of the above-mentioned oil or fat or wax. Further, examples of anionic water-soluble dispersants include the following. (1) Anionic polymeric dispersant with a molecular weight of 250 to 25,000 (a) Olefin-maleic acid copolymer salt For example, an alkali metal, ammonium or amine copolymer of maleic acid and an olefin having 2 to 20 carbon atoms Salt with an average molecular weight of 250~
20000 things. (b) Acrylic acid or methacrylic acid-maleic acid copolymer salt, for example, an alkali metal, ammonium or amine salt of the copolymer with an average molecular weight of 500.
~25000 stuff. (c) Homopolymer salts of acrylic acid or methacrylic acid or copolymer salts thereof For example, alkali metal, ammonium or amine salts of the polymer or copolymer salts having an average molecular weight of 500 to 25,000. (d) Sulfonic acid-formalin condensation salt of an aromatic compound, for example, one or two of naphthalenesulfonic acid, creosotesulfonic acid, cresolsulfonic acid, alkylnaphthalenesulfonic acid having an alkyl group having 1 to 4 carbon atoms, or ligninsulfonic acid. Alkali metal, ammonium or amine salts of condensates (degree of condensation 2 to 50) of the above and formalin. Among the above anionic polymer dispersants, (a) to (c)
Particularly preferred are those having a molecular weight of 2,000 to 10,000. These water-soluble dispersants can be used alone or in combination of two or more, and are preferably used in an amount of 0.5 to 20% by weight based on the lubricating oil component. In addition to the above-mentioned components, various known additives, such as rust preventive agents, oiliness improvers, extreme pressure agents, etc., may be added to the metal plastic working oil composition powder of the present invention, if necessary. The metal plastic working oil composition of the present invention can be prepared by simply mixing the above-mentioned lubricating oil component and a water-soluble dispersant, or prepared as a concentrated solution with a water content of up to 80%, and diluted with water before use. and use it. When the metal plastic working oil composition of the present invention is suspended in water at a temperature below the melting point of the oil or wax contained in the lubricating oil component, the metal plastic working oil composition dissolves in water as solid particles due to the action of the water-soluble dispersant. Disperses to form a stable dispersion. On the other hand, when the temperature exceeds the melting point, liquid particles are dispersed in water, so-called O/W.
It becomes a type dispersion liquid. Therefore, in the present invention, a dispersion system in which solid particles are dispersed in water is stably maintained, but is not very effective for stabilizing an O/W type dispersion liquid. The condition is destroyed and the adhesion of oil components to the processed parts increases. Therefore, for example, to explain the case where the metal plastic working oil composition of the present invention is used as a rolling oil, it maintains a stable dispersion state at a temperature below the melting point of the oil or wax and rolls it. When the rolling oil is supplied to the biting part of the steel plate at a temperature higher than the melting point, the dispersion state is destroyed and a large amount of rolling oil adheres to the rolls and the steel plate, providing a good lubrication effect. Furthermore, the recovered rolling oil dispersion becomes a stable dispersion when cooled to a temperature below the melting point, so it can be recycled and used. The metal plastic working oil composition of the present invention can also be used for lubrication in press working, forging, extrusion, and the like. Furthermore, the metal plastic working oil composition of the present invention includes:
The ability to store and circulate at low temperatures saves energy and improves the working environment. Furthermore, since the particles are stored in a dispersed state, dirt such as scum and iron powder does not aggregate with the dispersed particles, and the dirt can be easily separated. Furthermore, since the dispersion state becomes unstable at temperatures above the melting point during lubrication, oil-water separation properties are improved and wastewater treatment properties are also excellent. The method for supplying the metal plastic working oil composition of the present invention to the processing section will be described below, taking as an example the case where it is supplied as rolling oil to a roll and a steel plate. First, the metal plastic working oil composition of the present invention, which is suspended in water such that the solid content is 0.1 to 40% by weight, more preferably 1 to 20% by weight, is heated at a temperature below the melting point of the oil or wax as a lubricating oil component. Store with mechanical stirring. Next, before supplying this, the dispersion state is made unstable by heating it to a temperature above the melting point using a heat exchanger, etc., and then it is supplied to the processing section, or by the friction between the roll and the steel plate and the heat of processing. The lubricating oil component is supplied to the hot machining area to make the dispersion state unstable and cause the lubricating oil components to adhere to the machining area. In addition, after lubrication, it is collected, cooled to below the melting point by natural cooling or a heat exchanger, and recycled for use. As mentioned above, the metal plastic working oil composition of the present invention has excellent features not found in conventional lubricants that meet the two desired conditions. Next, an example will be given and explained. The metal plastic working oil compositions shown in Table 1 were used in the Examples.

【table】

[Table] Example 1 Rolling test: (A) Rolling test method Rolling mill: 100mmφ x 150mm width, forged steel roll double rolling mill Material to be rolled: SPCC.SD (JIS.G3141) plate thickness 1mm
× Plate width 30mm Rolling speed: 1000m/min (B) Rolling oil supply method Mix the test oil and water to a specified concentration, and raise the temperature to above the melting point of one or more mixtures of oil and wax contained in the sample oil. The mixture is forcibly stirred while being heated, and further cooled to a predetermined temperature below the melting point of the above mixture while being forcibly stirred to prepare a dispersion. However, in the case of an emulsified oil agent used for comparison, it was prepared at the same temperature as the spray temperature. When spraying onto rolls and rolled materials, the spray temperature was controlled by a heat exchanger immediately before the gear pump inlet. Spray amount is 3.0/min
(Pressure 2.5Kg/cm ² ). The load during rolling with a rolling reduction of 50% was measured under the above conditions, and the unit width load at that time was determined. (C) Results Table 2 shows the results.

[Table] From the results in Table 2, when the composition of the present invention is used as a rolling oil, conventional fats and oils as shown in Comparative Examples (5) and (6) are used as a base oil, and this is mixed with an emulsifier. It showed superior rolling oil lubrication performance compared to emulsified rolling oil. Therefore, it can be seen that the method of preparing and supplying a dispersion liquid using a water-soluble dispersant as described above is very effective in improving the rolling oil lubrication performance. Example 2 Dispersion stability and oil adhesion test (a) Dispersion stability test Sample oil and water were mixed to a predetermined concentration, and one or more mixtures of fats and waxes contained in the sample oil were tested. The mixture is heated above the melting point, stirred for 5 minutes at 5000 rpm using a homomixer, and then heated or cooled to a predetermined temperature within 5 minutes at the same rotation speed. Furthermore, while stirring at a predetermined temperature and rotation speed of 500 rpm, the state after 1 hour was visually observed and the average particle size was measured using a Coulter counter. Evaluation methods were classified into the following three levels. ○: Uniformly dispersed layer with almost no separated floating substances observed in the top sweep. (Average particle size less than 10μ) △: Uniformly dispersed layer with a small amount of separated suspended matter observed in the upper layer. (Average particle size: 10 to 16 μm) ×: Most of the separated oil layer or solid aggregates are formed. (Average particle size of 16μ or more) (b) Oil adhesion test method Sample oil and water are mixed to a specified concentration and heated to a temperature above the melting point of one or a mixture of two or more of oils and waxes contained in the sample oil. The mixture is stirred using a homomixer at a rotational speed of 5000 rpm for 5 minutes, and then cooled to a predetermined temperature below the melting point of the above mixture within 5 minutes at the same rotational speed to prepare a dispersion. However, in the case of the emulsified oil agent used as a comparative product, it was prepared at the same temperature as the spray temperature. For the adhesion test, the above dispersion was heated to a predetermined temperature using a heat exchanger just before the inlet of the gear pump, and then sprayed onto the test piece for 2 seconds (pressure 1.0 atm, spray rate 1/min), and then allowed to cool to room temperature. and dried, and the amount of attached oil was measured gravimetrically. The test piece used was the same type as the one used in the rolling test, with dimensions of 50 mm width x 100 mm length, and surface roughness.
4.0 to 5.0μ, and was used after solvent degreasing in advance. (c) The results are shown in Table 3.

[Table] As is clear from the results in Table 3, the composition of the present invention is stable in a dispersed state below the melting point of a mixture of one or more of oils and waxes, and is stable when applied at temperatures above the melting point of the mixture. In the conditions,
It showed excellent performance with a large amount of adhesion. On the other hand, comparative products (1) to (6) either do not satisfy any of the performances or
Or, it does not satisfy either one of the performances and is not suitable for use in the composition of the present invention. Example 3 Dispersion circulation test Sample oil was mixed with water to a concentration of 5% by weight, and the mixture was heated to a temperature between 50°C and 65°C at which the sample oil melted uniformly, and the mixture was forcibly stirred. Under the stirring conditions, the liquid is cooled to a temperature of 25°C, 30°C, and 40°C to prepare a dispersion (liquid volume: 20 in a 30-volume tank). The dispersion liquid prepared in this manner is heated to a temperature of 50 to 65 degrees Celsius (50 to 65 degrees Celsius) just before the inlet of the gear pump using a heat exchanger, and then the spray nozzle (pressure
The oil was injected from 2.5 atm oil supply rate (3/min) onto an iron plate heated to 150°C. The recovered dispersion liquid is continuously cooled to 30°C through a heat exchanger while being forcedly stirred in a preliminary tank (capacity 2), and then returned to the original tank. This was repeated continuously for 48 hours, and the oil in the dispersion excluding the upper layer suspended matter was extracted and weighed, and the amount of decrease relative to the initial amount of oil was expressed as a percentage. At this time, 0.1% by weight of iron particles are precipitated at the bottom of the spray liquid receiving container based on the liquid used.
However, in the case of the emulsified oil used as a comparative product,
Since the emulsion was unstable at a liquid temperature of 30°C, the liquid temperature was kept at 60°C, the same as the spray temperature, and circulated. The results are shown in Table 4.

[Table] As is clear from Table 4, the cyclic stability performance obtained using the composition of the present invention and the spray coating method is compared to the normal cyclic stability performance obtained using the comparative products (5) and (6). showed that it is excellent. Example 4 Wastewater treatment test 3 g of sulfuric acid was added to a sample solution (1000 ml) above the melting point of a mixture of one or more types of fats and waxes prepared in the same manner as the oil adhesion test.
Stir for 2 minutes, then add calcium hydroxide to adjust the pH to 7, stir for 10 minutes, let stand for 30 minutes, collect the supernatant, and measure COD (potassium permanganate method). did. The results are shown in Table 5.

[Table] As is clear from the wastewater treatment test results in Table 5, the composition of the present invention generally has superior wastewater treatment properties compared to emulsified dispersions represented by comparative products (W) and (F). ing.

Claims (1)

[Claims] 1. One or more mixtures of two or more selected from the group consisting of fats and oils and waxes having a melting point of 20 to 100°C.
A lubricating oil component containing 100% by weight, and a molecular weight of 250 to 25000 in a proportion of 0.5 to 20% by weight relative to the lubricating oil component.
Olefin-maleic acid copolymer salt, acrylic acid or methacrylic acid-maleic acid copolymer salt,
One or more anionic water-soluble dispersants selected from the group consisting of homopolymer salts of acrylic acid or methacrylic acid or copolymer salts thereof, and aromatic compound sulfonic acid-formalin condensate salts A metal plastic working oil composition for cold rolling containing as an essential component. 2 The oil or wax content in the lubricating oil component is
The metal plastic working oil composition for cold rolling according to claim 1, wherein the amount is 30 to 100% by weight.