JPH0522753B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a metalworking oil, and more specifically, it is a metalworking oil with excellent emulsion stability and lubricity that can be used for both aqueous and non-aqueous metalworking oils. This relates to metal working oil. [Prior art] Metalworking oils include, for example, cutting oil, grinding oil,
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 oiliness improvers, surfactants, rust inhibitors, extreme pressure additives, and antifoaming agents in the base oil.The oiliness improvers include: Generally, natural or synthetic compounds such as higher fatty acids, higher fatty acid esters, animal and vegetable oils, dimer acids, trimer acids, and polybutene are used. However, it is not fully satisfied in terms of lubricity, and in order to improve its performance, more additives are added. Additionally, in addition to the base oil, water-soluble metalworking oils contain oiliness improvers, but in order to emulsify or solubilize these oil components, large amounts of several types of surfactants must be 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. [Means for Solving the Problems] That is, the present invention provides an iodine value in the range of 30 to 10,000 centipoise at 38.8°C, which is obtained by reacting maleic anhydride with refined fish oil and an iodine value of 120 obtained by refining fish oil. Maleated refined fish oil with viscosity A
(hereinafter referred to as "maleated oil"), or ester B of a maleated fish oil obtained by reacting the maleated oil with a monohydric alcohol or a polyhydric alcohol (hereinafter referred to as "maleated oil ester"). Metalworking oils containing maleated oils or maleated oil esters, as well as maleated oils or maleated oil esters, base oils of animal and vegetable fats and mineral oils, additives, emulsifiers and There are some things that are a mixture. The maleated oil or maleated oil ester of the present invention is prepared by first deoxidizing and decolorizing fish oil using a conventional method, and then adding maleic anhydride to purified fish oil with an iodine value of over 120, either without a catalyst or with a known catalyst for maleation. It can be obtained by reacting at 150 to 250°C using The type of fish oil used in the present invention is not limited as long as it is not significantly oxidized or polymerized. Conventionally, fish oil has a unique odor that comes from the fish body and fish oil itself, which is called fish oil odor.
By maleating it, the odor can be suppressed or changed to a very weak odor, and even when used, the odor can be reduced to such an extent that no fishy odor is felt. Types of fish oils include sardine oil, flounder oil, mackerel oil, saury oil, shark oil, squid oil, seaweed oil, etc., and those derived from these raw material oils with an iodine value of over 120 are used. Among these fish oils, a mixture of sardine oil, mackerel oil, saury oil, etc. may also be used. The reaction molar ratio of refined fish oil and maleic anhydride is determined by the viscosity of the maleated oil or maleated oil ester.
30 to 10,000 centipoise (hereinafter "cp") at 38.8℃
There is no particular limitation as long as it falls within the range of 0.1 maleic anhydride per 1 mole of refined fish oil
A product obtained by reacting 4.0 mol from If the number of moles of maleic anhydride is 0.1 to 0.5 moles, the lubricating performance will decrease somewhat. Moreover, at 2.5 to 4.0 moles, the lubricating performance is sufficient, but the compatibility with mineral oil and animal and vegetable oils and fats decreases, but both can be used satisfactorily for practical purposes. As the number of moles of maleic anhydride increases relative to 1 mole of fish oil, the viscosity of the resulting product increases, and products with viscosities in the range of 30 to 1000 cp (38.8°C) can be used. Especially within this range 40~
A range of 2000 cp (38.8°C) is most preferable in terms of compatibility with other fats and oils and lubricity. The viscosity
If it is less than 30 cp, the compatibility is good, but the lubricity is insufficient and a fishy odor remains. Also, if the viscosity exceeds 10,000 cp, the compatibility with other fats and mineral oils will be low.
It can be used practically. In addition, for the maleated oil obtained above, maleated oil ester obtained by esterifying the carboxyl group derived from maleic acid in the molecule with a monohydric alcohol or polyhydric alcohol can also be used in the same way as the maleated oil. However, the esterification reaction is carried out by a conventional method, and when heated to 60 to 180°C in the presence of an acidic or alkaline catalyst, esters are generated. Examples of the monohydric alcohol used here include methanol, butanol, octanol, and the like. Further, examples of the polyhydric alcohol include ethlene glycol, propylene glycol, sorbitol, diglycerin, and the like. Further, adducts obtained by adding ethylene oxide to the above-mentioned alcohols can also be used. [Function] The higher the concentration of the maleated oil or its ester 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, It is preferable to mix at least 4% of maleated oil or its ester from the viewpoint of lubricity in metal processing, and if it is less than this, the effect will be significantly reduced. Furthermore, since the maleated oil or its ester used in this application has self-emulsifying properties, when used as a water-based metal processing oil, the amount of surfactant used is extremely small, making it economical. In addition, 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 or its ester of the present invention is blended with mineral oil or synthetic lubricating base oil, or with animal or vegetable oil or fat, exhibit extremely excellent lubricity. Although it is known to maleate common animal and vegetable oils and fats, the product is complex and it is also known that several reactions occur. In particular, in the case of fish oil containing a large amount of highly unsaturated fatty acids, it is presumed that the reactions and reaction products thereof are even more different from those of other animal and vegetable oils and fats. However, it is currently not possible to completely analyze or analyze the reaction and reaction products. However, as a result of repeated studies, it was discovered that the features of the present invention can be obtained if the viscosity range is limited as in the present invention. The maleated oil and its ester of the present invention can be used alone as a base oil for metal working oil or as an oiliness improver, but may be mixed in advance with other animal and vegetable oils, esters, synthetic oils, and mineral oils for the same purpose. May be used for Further, known lubricating oil additives such as extreme pressure additives, antioxidants, antifoaming agents, surfactants, etc. can be freely added to the lubricating oil composition of the present invention for their purposes. [Example] The present invention will be specifically described below with reference to Examples. Example 1 900g of purified fish oil (AV0.5) of IV130 and 34g of maleic anhydride were charged into a 2-four-necked flask equipped with a condenser, stirrer, thermometer, and _N2 gas inlet tube, and heated at 200 to 210℃. After heating and stirring for 4 hours, unreacted maleic anhydride was distilled off under reduced pressure to obtain an acid value of 20 and a viscosity of
933.6 g of maleated oil of 120 cp (38.8°C) was obtained. Example 2 Using 900 g of purified fish oil (AV 0.3) of IV 130 and 57 g of maleic anhydride, maleation was performed in the same manner as in Example 1 to obtain 945 g of maleated oil with an acid value of 29.3 and a viscosity of 150 cp.
I got it. Example 3 Using 900 g of purified fish oil (AV 0.4) of IV 150 and 120 g of maleic anhydride, maleation was performed in the same manner as in Example 1 to obtain maleated oil with an acid value of 61.1 and a viscosity of 440 cp.
Obtained 1002g. Example 4 Using 900 g of IV175 purified fish oil (AV0.5) and 300 g of maleic anhydride, maleation was carried out in the same manner as in Example 1 to obtain 1125 g of maleated oil having an acid value of 121.6 and a viscosity of 1380 cp. Example 5 400 g of maleated oil obtained in Example 4, 180 g of butanol, 120 g of toluene, and para-toluenesulfonic acid (hereinafter referred to as "PTSA") as a catalyst.
0.4g into a test tube with condenser, stirrer, thermometer and _N2
The mixture was placed in a four-necked flask (No. 1) equipped with a gas introduction tube, and heated at 100 to 130° C. with stirring to reflux and remove the water produced by the reaction. The end point of the response was the point at which almost no water came out. Thereafter, the reaction system was cooled to 50° C., the catalyst was neutralized, and unreacted butanol and toluene were distilled off under reduced pressure to obtain 505.4 g of maleated oil ester with an acid value of 3.5. Example 6 240 g of the maleated oil obtained in Example 4, 21.9 g of trimethylolpropane, and 105 g of toluene were charged into a 1-four-necked flask equipped with the same equipment as used in Example 5, and heated and stirred at 120°C for 4 hours. After cooling to about 40℃, add octyl alcohol 262.2
g and 0.48 g of PTSA as a catalyst were added thereto, and the reaction product water was separated and removed at 110 to 130° C. while heating and stirring again. Furthermore, after neutralizing the catalyst, unreacted octyl alcohol and toluene are distilled off under reduced pressure, and the acid value is
5.7, 383.5 g of maleated oil ester was obtained. Example 7 400 g of maleated oil obtained in Example 1 and 60 g of oleyl alcohol 4 mole adduct of oleyl alcohol
was placed in a four-necked flask equipped with a condenser, stirrer, thermometer, and _N2 inlet tube, and heated and stirred at 120°C for 5 hours to prepare a maleated oil ester with an acid value of 17.4.
Obtained 460g. The maleated oils or maleated oil esters obtained in Examples 1 to 7 were blended alone or as a blend as shown in Table 1, and the performance was evaluated by carrying out a load-bearing capacity test, a ring compression test, and a rolling test. I went.

【table】

【table】 (1) Load-bearing capacity test Shell-type high-speed four-ball friction tester 1/2 inch ball Measurement temperature 50±2℃ Vertical shaft rotation speed 1500rpm

【table】

【table】 (2) Ring compression test Compression load 80t Ring dimensions: outer diameter 20mm inner diameter 10mm Thickness 5mm Measurement temperature: normal temperature

[Table] (3) Rolling test Rolling mill: Four-high roll rolling machine Backup roll: Diameter 250mm x Width 140mm Roll material: Chrome steel Roll circumferential speed: 30m/min Rolling material: SPC-C Thickness 0.6mm x Width 50mm x length 150mm Measurement temperature: Method for measuring cold rolling performance Draw two lines at a 50mm interval ( ₁ ) on the steel plate before rolling, roll this, measure the interval after rolling ( ₂ ), and then The rolling reduction ratio was determined from the formula. Rolling ratio = ₂ − ₁ / ₂ × 100 In addition, the rolling load (ton) at that time was measured using a load cell. Regarding the amount of oil applied to the test steel plates, each sample was dissolved in a solvent of a certain concentration in advance, and the oil was applied so that the total amount was 1 g/m ² , and after drying, it was subjected to the test. Incidentally, sample No. 10 was prepared as a 5% emulsion and stirred in a homomixer, and a steel plate was immersed in it and then subjected to a test. The results are shown in Figure 1.

[Brief explanation of drawings]

The drawing is a rolling performance comparison diagram showing the relationship between rolling load (ton) and rolling reduction (%) using the composition shown in Table 1. Numbers 1 and 3 to 10 in the drawing are shown in Table 1, respectively. These are rolling oils having compositions No. 1, 3 to 10 shown in No. 1.

Claims (1)

[Claims] 1 Maleated fish oil A having a viscosity of 30 to 10,000 centipoise at 38.8°C obtained by reacting maleic anhydride with purified fish oil having an iodine value of over 120,
or ester B of a maleated fish oil obtained by reacting the maleated fish oil A with a monohydric alcohol or a polyhydric alcohol.