JPH0473477B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metalworking oil, and more specifically, to a metalworking oil with excellent emulsion stability and lubricity that can be used for both aqueous and non-aqueous metalworking oils. . Metalworking oils include cutting oils, grinding oils,
Water-soluble metal working oil used in water-based systems, oil-soluble metal working oil used in non-aqueous (oil-based) systems, depending on the name and usage depending on the processing method, such as rolling oil, press oil, drawing oil, plastic working oil, etc. There are various ways of classification. Such metal working oil compositions contain various additives such as oil property improvers, surfactants, rust inhibitors, extreme pressure additives, and antifoaming agents in the base oil. As oiliness improvers, natural or synthetic compounds such as higher fatty acids, higher fatty acid esters, animal and vegetable oils, dimer acids, trimer acids, and polybutenes are generally used. However, it is not fully satisfied in terms of lubricity, and in order to improve its performance, more additives are added. In addition to the base oil, oiliness improvers are added to water-soluble metalworking oils, but in order to emulsify or solubilize these oil components, large amounts of several types of surfactants are not used. A stable emulsified dispersion or solubilized system cannot be obtained. Emulsification or solubilization with a large amount of surfactant not only reduces the lubricity but also generates a large amount of foam during use, which causes undesirable problems in the processing process. The present invention was developed as a result of studies aimed at solving these drawbacks of conventional metal working oils. In other words, in the present invention, fish oil is hydrogenated to increase its iodine value.
50-120 hydrogenated fish oil is obtained by reacting it with maleic anhydride. Metalworking oils containing maleated hydrogenated fish oils (hereinafter referred to as "maleated oils") having a viscosity in the range of 40 to 20000 centipoise at 38.8°C, consisting of 100% maleated oils, as well as maleated oils. Some products are made by mixing synthetic oils with base oils such as animal and vegetable fats and mineral oils, additives, and emulsifiers. The higher the concentration of the maleated oil of the present invention, the higher the lubricity obtained, but when used in combination with animal and vegetable oils, mineral oils, other oiliness improvers, and extreme pressure additives, A content of at least 4% is preferable from the viewpoint of lubricity in metal processing, and if the content is less than this, the effect will be significantly reduced. Furthermore, since the maleated oil used in this application has self-emulsifying properties, when used as a water-based metalworking oil, the amount of surfactant used is extremely small, which is not only economical but also , a metalworking oil with significantly less foaming can be obtained. On the other hand, oil-soluble metalworking oils and lubricating oils in which the maleated oil of the present invention is blended with mineral oil or synthetic lubricating base oil, or with animal or vegetable oil, exhibit extremely excellent lubricity. The features of the present invention are particularly achieved by maleating semi-hydrogenated fish oil which has been hydrogenated to an appropriate range. Fish oil has a history of being polymerized and used in the field of lubricants, but although fish oil is the only domestically produced oil, its usage has been decreasing in recent years. This is because fish oil, unlike other animal and vegetable oils, has a strong fishy odor, is difficult to completely deodorize, and contains a large amount of polyunsaturated acids, which are not found in other fats and oils, making it unstable to heat. This is because there are still many technical issues that need to be resolved. The maleated oil of the present invention is produced by firstly processing refined fish oil using a hydrogenation catalyst in a conventional manner to achieve an iodine value of 50 to 50.
It is obtained by hydrogenating to 120° C. and then reacting maleic anhydride at 150 to 250° C. without a catalyst or using a known catalyst for maleation. The type of fish oil used in the present invention is not limited as long as it is not significantly oxidized or polymerized. However, fish oil purified by conventional methods is preferred. The hydrogenation reaction is carried out using conventional hydrogenation conditions and catalysts. For example, using a nickel-based catalyst of 0.2 to 1.0% by weight based on oil and fat, hydrogen pressure of 1.0
The hydrogenation reaction is carried out at ~4.0 Kg/cm ² and a temperature of 160-200°C. The iodine value after hydrogenation is 50-120, preferably 60-100. If the iodine value (hereinafter referred to as "IV") is less than 50, the maleation reaction will be difficult to proceed, the resulting maleated fish oil will have a high melting point, and its lubricity will not be sufficient. When the IV is 120 or more, the fishy odor is so strong that industrial production is limited. The reaction molar ratio of hydrogenated fish oil and maleic anhydride is 0.1 to 1 mole of hydrogenated fish oil to 0.1 to 1 mole of maleic anhydride.
4.0 mol, preferably 0.5 to 2.5 mol reacted, is suitable for use as a metalworking fluid. If the number of moles of maleic anhydride is 0.1 to 0.5 moles, the lubricating performance will decrease somewhat. Also, at 2.5 to 4.0 mol,
Although it has sufficient lubricating performance, its compatibility with mineral oil and animal and vegetable oils and fats decreases, but it can be used satisfactorily for practical purposes. A viscosity in the range of 40 to 20,000 has the best compatibility with other oils and fats and mineral oil, and has excellent lubricity. If the viscosity is less than 40, the compatibility with other oils is good, but the lubricity is not sufficient, and if the viscosity is more than 2000, the compatibility with other oils, fats, and mineral oils is low, and therefore constant lubricity is not achieved. I can't. It is generally known to maleate animal and vegetable oils and fats, but it is also known that the product is complex and that several types of reactions occur. In particular, when maleating hydrogenated fish oil obtained by hydrogenating fish oil containing a large amount of highly unsaturated acids, the reaction products are estimated to be different and more complex than other animal and vegetable oils. are doing. However, the reaction and reaction products have not been completely analyzed. However, as a result of repeated studies, it was discovered that the features of the present invention can be obtained if the maleated oil reaches a viscosity as limited as the present invention. This application is based on this invention. The maleated oil of the present invention can be used alone as a base oil for metal working oil or as an oiliness improver, but it can be mixed in advance with other animal and vegetable oils, esters, synthetic oils, and mineral oils. May be used for this purpose. Furthermore, known lubricating oil additives, such as extreme pressure additives, antioxidants, antifoaming agents, surfactants, etc., may be optionally added for that purpose to the lubricating oil compositions of the present invention. The present invention will be specifically explained below with reference to Examples. Example 1 Refined fish oil with an iodine value of 175 was treated with a Ni-based catalyst of 0.4 using a conventional method.
%, hydrogenated at a hydrogen pressure of 1.5Kg/cm ² and a temperature of 160±2℃,
Hydrogenated fish oil with an iodine value of 91 and an acid value of 0.5 was obtained. After reacting 1 mole of hydrogenated fish oil with 0.5 mole of maleic anhydride at 180°C for 3 hours using a 33-necked flask, excess maleic anhydride was distilled off under reduced pressure to give an acid value of 84.7 and a viscosity of 430 (centipoise: 38 centipoise). A maleated oil was obtained. Example 2 Iodine value 61 obtained under the same conditions as Example 1,
After reacting 1 mole of hydrogenated fish oil with an acid value of 0.5 and 2 moles of maleic anhydride at 190°C for 2 hours using a 33-necked flask, excess maleic anhydride was distilled off under reduced pressure to obtain an acid value of 102, A maleated oil with a viscosity of 1276 centipoise was obtained. Example 3 Iodine value 71 and acid value 0.5 obtained under the conditions of Example 1
1 mole of maleic anhydride to 1 mole of hydrogenated fish oil
After reacting for 5 hours at 170°C using a three-necked flask, excess maleic anhydride was distilled off under reduced pressure to obtain a maleated oil with an acid value of 67.7 and a viscosity of 320 centipoise. Example 4 Maleated oils obtained in Examples 1 to 3 are shown in Table-1.
The emulsifying properties and lubrication performance were evaluated using either a single product or a combination product as shown in the figure below. As a comparative example, beef tallow with an emulsifier added was used.

[Table] 1 Emulsifying property Emulsification separation degree and ESI were measured for Nos. 1, 3, and 7 in Table 1, and are shown in Table 2.

[Table] 1 Emulsification separation test method Add 5% solution of each sample to tall beaker 1.
A sample of 800 ml was prepared, stirred for 5 minutes using a homomixer, and left to stand.The amount of separated oil layer was measured after an elapsed time of 2 minutes and 5 minutes, and expressed as a percentage of the amount of sample oil charged. 2 ESI (Emulsification Stability Index) Add 5% solution of each sample to 1 tall beaker.
Make 800ml and use a homo mixer at room temperature for 5 minutes.
After stirring for a minute, immediately collect 300ml into a separating funnel.
After 100 ml of each emulsion was taken out from the upper and lower layers, the oil content (%) in each was measured, and the ESI was calculated using the following formula. ESI% = Lower layer oil content (%) / Upper layer oil content (%) x 100 Next, as a test of lubrication performance, a load carrying capacity test, a ring compression test, and a rolling test were conducted. The method was as described below. The results are shown in Table-3, Table-
4. Shown in Figure-1. 2 Load-bearing capacity test Shell-type high-speed four-ball friction tester 1/2 inch ball Measurement temperature 50±2℃ Vertical rotation speed 1500rpm

【table】

【table】 3 Ring compression test Compression load 80t Ring dimensions: outer diameter 20mm, inner diameter 10mm Thickness: 5mm Measurement temperature: normal temperature

[Table] 4 Rolling test Rolling mill: Four-roll rolling mill Work roll diameter 150mm Width 140mm Backup roll diameter 250mm Width 140mm Roll material: Chrome steel Roll circumferential speed: 30m/min Rolling material: SPC-C Thickness 0.60mm × Width 50 mm × Length 150 mm Method for measuring rolling performance Draw two lines at a 50 mm interval (l ₁ ) on the steel plate before rolling, roll this, measure the interval after rolling (l ₂ ), and then The rolling reduction ratio was calculated using the formula. Rolling ratio (%)=l ₂ −l ₁ /l ₂ ×100 Further, the rolling load (ton) at that time was measured using a load cell. Lubricating method: At 5% (weight) concentration of the sample, it was stirred with a homochimiser at 50°C to form an emulsion, and during rolling, the biting part of the steel plate and the rolls were sprayed with oil and rolled. 5 Results i The results in Table 2 show that Examples 1 and 3 of the present invention are semi-tight emulsions and exhibit extremely high emulsion stability even without the addition of an emulsifier, whereas emulsion stability is poor with beef tallow alone. However, in order to make it equivalent to Examples 1 and 3, the emulsifier should be added at 1.7%.
need to be added. The results of the load-bearing capacity shown in Table 3 and the friction coefficient shown in Table 4 show that all the products containing the maleated oil of the present invention have both load-bearing capacity and friction coefficient compared to the target samples (beef tallow and rapeseed oil). This shows that it has excellent lubricity. From the results of the rolling test shown in Figure 1, Examples Nos. 1 to 6 of the present invention all showed superior rolling performance compared to No. 7 (beef tallow). It is recognized that there is a significant difference in rolling performance even if the emulsion stability is the same.

[Brief explanation of the drawing]

The drawing is a rolling performance comparison chart showing the rolling performance of the compositions shown in Table 1 in terms of the relationship between rolling load (ton) and rolling reduction (%).

Claims (1)

[Claims] 1. A metalworking oil characterized by containing a maleated product of hydrogenated fish oil having a viscosity of 40 to 20,000 centipoise at 38.8°C obtained by reacting hydrogenated fish oil with an iodine value of 50 to 120 and maleic anhydride.