JPH068429B2 - Metal working oil - Google Patents

Description

TECHNICAL FIELD The present invention relates to a metalworking oil, and more specifically, it uses a polymerized oil obtained by polymerizing hydrogenated fish oil and has excellent lubricity, stability over time, and fish stability. The present invention relates to a metal working oil having an improved odor.

[Conventional technology]

Conventionally, metalworking oils such as cutting oils, grinding oils, rolling oils, press oils, and drawing oils are used as base oils for mineral oil or palm oil, beef tallow,
Animal and vegetable oils and fats such as lard and fatty acid esters are used. However, these base oils no longer fully satisfy the performance with the progress of metalworking technology, and in order to cover the performance, an oiliness improver, a surfactant, a rust inhibitor,
More additives such as extreme pressure additives and defoamers are blended and used.

As an attempt to improve the lubricity of the base oil without using additives, cold rolling oil for steel sheets (Japanese Patent Publication No. 51-6686) using modified fats and oils heat-treated in the presence of activated clay, unsaturated fatty acids were used. A cold rolling oil (Japanese Unexamined Patent Publication No. 60-81295), which uses an oil and fat containing partially hydrogenated triglyceride, has been reported.

[Problems to be solved by the invention]

On the other hand, fish oil is a liquid at room temperature, is easy to mix with other additives, is inexpensive, and suggests that it can be used as a base oil in various ways.

For example, fish oil has a history of being polymerized and used in the field of lubricating oil. However, while fish oil is the only domestic fat,
In recent years, the amount used has decreased. Unlike other animal and vegetable oils and fats, fish oil has a strong fish odor, complete deodorization is difficult, and even after deodorization, the odor returns with time, and highly unsaturated acids not contained in other oils and fats. This is because there are many technical problems to be solved, such as being unstable to heat because it contains a large amount of.

That is, it is difficult to use fish oil in the same manner as other animal and vegetable oils and fats according to the conventional technique.

For example, a polymerized oil of fish oil obtained by heat-treating fish oil has improved lubricity, but has a strong fish odor and cannot be practically used. The polymerized oil of deodorized and refined fish oil has a fishy odor over time, or is colored and has poor stability over time.

In addition, in the method of hydrogenation, when the degree of hydrogenation increases, the melting point rises and must be dissolved during handling, which limits its use and compatibilities with mineral oil, etc. Not only is odor and lubricity insufficient with hydrogenated products, but the cloud point also becomes high.For example, when compounded with mineral oil, it becomes cloudy at around 10 to 20 ° C. Product stability especially in low temperature regions There are problems such as lack of.

The present invention has been made in view of the above points, and an object thereof is to provide a metalworking oil having excellent lubricity, stability over time, and improved fish odor.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that by using a polymerized oil of hydrogenated fish oil, it is possible to obtain a metalworking oil having excellent lubricity, stability over time and fish odor. This led to the present invention.

That is, the present invention is a metalworking oil containing a polymerized oil having a viscosity of 80 to 3000 centipoise at 38 ° C. obtained by polymerizing hydrogenated fish oil having an iodine value of 60 to 110 by heating or oxidation.

The polymerized oil of the present invention is obtained by hydrogenating fish oil to an iodine value of 60 to 110, and then polymerizing it by heating or oxidation so as to have a viscosity of 80 to 3000 centipoise at 38 ° C.

Examples of the fish oil used in the present invention include sardine oil, cod oil, squid oil, herring oil, shark liver oil, blister shark oil, mackerel oil, and mixed fish oil obtained by mixing these fish oils. Although it may be used regardless of purification, it is preferable to use fish oil which is deoxidized with an aqueous solution of caustic soda and washed with water, decolorized with activated clay and activated carbon and purified by a conventional method.
The hydrogenation reaction is carried out using conventional hydrogenation conditions and catalysts. For example, a nickel-based catalyst is used in an amount of 0.2 to
1.0% by weight is used, hydrogenation reaction is carried out at a hydrogen pressure of 1.0 to 4.0 kg / cm ² at a temperature of 160 to 200 ° C., IV60 to 11
Fish oil hydrogenated to 0 is used as hydrogenated fish oil. When the IV of hydrogenated fish oil is 60 or less, the polymerization reaction is difficult to proceed, and the polymerized oil obtained with a high melting point of hydrogenated fish oil has poor compatibility with mineral oil, especially at low temperatures, and its lubricity is also insufficient. When the IV is 110 or more, a fishy odor remains in the obtained polymerized oil, and the odor becomes strong over time, which causes a problem particularly when used at high temperatures.

The method for producing a polymerized oil obtained by polymerizing hydrogenated fish oil used in the present invention (hereinafter referred to as “polymerized oil”) includes a method by heating or a method by oxidation, and the viscosity at 38 ° C. is 80 to 3000.
Polymerization reaction is performed within the range of centipoise (hereinafter referred to as “CP”). For example, in the method by heating, hydrogenated fish oil can be polymerized by heating the hydrogenated fish oil to 280 to 320 ° C. in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas and stirring at the same temperature for 2 to 30 hours. In the oxidation method, the reaction can be carried out by heating hydrogenated fish oil to 120 to 200 ° C and stirring at the same temperature for 2 to 30 hours while introducing oxygen or air.

Here, the polymerized oil of the present application preferably has a viscosity in the range of 80 to 3000 CP at 38 ° C. in terms of fish odor, lubricity, compatibility with mineral oil at low temperature, etc. It has some drawbacks such as a slight fishy odor, a residual odor over time, insufficient compatibility with mineral oil at low temperatures, and insufficient lubricity for recent high speed processing. . Further, when the viscosity is 3000 CP or more, the oiliness and solubility of the polymerized oil are reduced, and the formation of carbides and the like are observed, the lubricity is reduced, and the compatibility with mineral oil is reduced, which is not preferable.

The polymerized oil of the present invention can be used as it is, or can be used by adding it to other additives and an oiliness improver using it as a base oil,
It can also be used as a mixture with other animal and vegetable oils, esters, synthetic oils and mineral oils as oiliness improvers. Further, the metalworking oil of the present invention may be added with known lubricating oil additives such as extreme pressure additives, antioxidants, antifoaming agents, rust preventives, surfactants and the like depending on the purpose.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited thereto.

〔Example〕

Example 1 1000 g of purified fish oil (mixed fish oil mainly containing cod oil, IV 175) deoxidized and decolorized according to a conventional method was charged into an autoclave 2 made of stainless steel, a Ni-based catalyst was 0.4 Wt%, and a hydrogen pressure was 1.5 kg.
/ Cm ² , hydrogenation reaction at reaction temperature 160 ± 2 ℃, IV
980 g of 60 hydrogenated fish oil was obtained.

900 g of this hydrogenated fish oil was charged into a stainless steel 2 reaction kettle and stirred while blowing nitrogen gas.
Raise the temperature to 280 ℃ and react at the same temperature for 7 hours to obtain a viscosity of 1
800 g of polymerized oil of 000 CP was obtained.

The odor of the polymerized oil obtained (after polymerized oil production and after 30 days at 25 ° C), baking load (30 wt% spindle oil solution), and compatibility with mineral oil were measured, and the results are shown in Table-1 No. 2 Shown in.

The purified fish oil (IV 175) used above was hydrogenated in the same manner as above to obtain hydrogenated fish oil with IV of 50, 70, 80, 90, 100, 110 and 120, respectively, and heating it under nitrogen gas introduction. Polymerization gave a polymerized oil having a viscosity of about 1000 CP. Odor of the obtained polymerized oil,
The baking load and the compatibility with mineral oil were measured, and the results are shown in Table-1.
No. 1 and Nos. 3-8.

In Table 1, the polymerized oil obtained from the hydrogenated fish oil of IV50 has poor compatibility with mineral oil, and the polymerized oil obtained from the hydrogenated fish oil of IV110 has a bad odor. Is.

Test method Viscosity: The viscosity at 38 ° C. was measured with a B-type viscometer.

Baking load: Shell type high-speed four-ball friction tester Ball 1/2 inch Measuring temperature 70 ° C Vertical shaft speed 800 rpm Sample polymer oil: 60 spindle oil (wt ratio 30:70) mixed oil Compatibility with mineral oil: polymer oil Dissolve 30 in 60 spindle oil and
After making a wt% solution and leaving it at 0 ° C. for 7 days, the degree of separation was visually judged.

◯: Good, Δ: Slightly separated or a little precipitate in the lower part, ×: Separated into two layers Odor: After polymerization reaction, the odor after standing to cool for 30 days at room temperature was It was judged according to the standard.

◯: No fish odor Δ: Slight fish odor ×: Violent fish odor Example 2 Deoxidized and decolorized refined fish oil (mixed fish oil mainly containing cod, IV
170) 10 kg was charged into a stainless steel 20 autoclave, hydrogenated at 0.4 wt% Ni-based catalyst, hydrogen pressure 1.8 kg / cm ² , reaction temperature 160 ± 2 ° C., hydrogenation of IV85.5, AV0.60. 9.5 kg of fish oil was obtained.

1000g of this hydrogenated fish oil was charged into a stainless steel 2 reaction kettle, stirred while blowing air, heated to 160 ° C in 30 minutes, polymerized at the same temperature for 1.5 hours, and viscosity (38 ° C) 10
980 g of 0 CP polymerized oil was obtained.

The odor, baking load, and compatibility with mineral oil of the obtained polymerized oil were measured, and the results are shown in No. 3 of Table-2.

Further, using the hydrogenated fish oils of IV85.5 and AV0.60 obtained by the above hydrogenation reaction, polymerization was carried out in the same manner as above and the viscosity (38
℃) 70CP, 80CP, 500CP, 1000CP, 2000CP, 3000CP, 3
300 CP of polymerized oil was synthesized, and the odor, baking load, and compatibility with mineral oil of the obtained polymerized oil were measured in the same manner as in Example 1, and the results are shown in Table 2, Nos. 1, 2 and 4 to 8. Shown in.

In Table 2, among the polymerized oils of hydrogenated fish oil (No. 1 to 8), those with a viscosity of 70CP have good compatibility with mineral oil and bad odor, and those with a viscosity of 3300CP have compatibility with mineral oil. However, both are out of the scope of the present invention.

Comparative Examples 1 and 2 The purified fish oil (IV 170) used in Example 2 was hydrogenated in the same manner as in Example 2 to synthesize hydrogenated fish oils of IV8.7 (Comparative Example 1) and IV85.5 (Comparative Example 2). And then measuring its physical properties,
The results are shown in Nos. 9 and 10 of Table-2.

Comparative Examples 3 and 4 The purified fish oil (IV 170) used in Example 2 was polymerized in the same manner as in Example 2 to synthesize polymer oils having a viscosity of 38 ° C. of 500 CP (Comparative Example 3) and 1200 CP (Comparative Example 4). Various physical properties of the obtained polymerized oil were measured, and the results are shown in Nos. 11 and 12 of Table-2.

Example 3 A hydrogenation reaction was carried out in the same manner as in Example 1 using purified fish oil (mixed fish oil mainly containing cod, IV 170.2) and purified fish oil (mixed fish oil mainly containing sardine, IV 175.6) to obtain hydrogen. Heat-polymerization of the added fish oil under the same conditions as in Example 1, or Example 2
Polymerized oils A to D shown in Table 3 by oxidative polymerization under the same conditions as
Got

Using the obtained polymerized oils A to D as sample oils, the following cutting test was performed to evaluate the lubricating performance in the cutting process. The results are shown in Table-4.

As a comparative example, rapeseed oil (IV 104.4) was used for the same cutting test.

Cutting test method Dissolve sample oil in 60 spindle oil to make 20wt% solution,
Using this solution, the cutting resistance value was measured by a vertical internal drawing broach tester, and the roughness of the cut surface was measured in the cutting direction by a stylus type roughness measuring machine to evaluate the lubricating performance during cutting.

Cutting condition Tester: 3ton vertical inner surface drawing broaching machine Tool: Max. 0.05mm per blade, width 7mm, pitch 8mm, key broaching tool with material SKH55 Work material: S-45C Cutting speed: 2m / min Example 4 Polymerized oils A to D obtained in Example 3 were used as sample oils, and the sample oils were dissolved in paraffinic mineral oil (Nisseki turbine oil 32) to prepare a 3 wt% solution. The lubricating performance of this solution in the aluminum deep drawing test was evaluated by a high speed deep drawing tester. The results are shown in Figure 1.

As a comparative example, a deep drawing test of aluminum was conducted in the same manner as above using a 3 wt% paraffinic mineral oil solution of oleic acid.

Test condition Tester: Deep drawing tester manufactured by Tokyo Tester Co., Ltd. Punch diameter 32mmφ, Die diameter 35mmφ, Processing speed 1m / sec. Processing material: One sample using aluminum plate (JIS A1100.0 thickness 1mm) Diameter 62.4 mmφ (drawing ratio 1.95) to 68.0 per oil
8 points up to mmφ (drawing ratio 2.125) (diameter increase rate 0.8m
m) test sample oil application amount: 1 g / m ³ , applied to both sides of processed material Example 5 Polymerized oils A to D obtained in Example 3 were used as sample oils, and the following rolling test was performed to perform lubrication performance in rolling. Was evaluated. The results are shown in Figure 2.

As a comparative example, beef tallow (IV48.5) was used to perform a rolling test in the same manner as above.

Rolling test method Draw two lines with a spacing of 50 mm (l ₁ ) on the steel sheet before rolling,
After applying the sample oil to this steel plate, rolling it and rolling it, 2
The interval (l ₂ ) between the lines was measured, and the rolling reduction was calculated by the following formula. The rolling load (ton) at that time was measured with a load cell.

The rolling test conditions are as follows.

Rolling machine: Four-stage rolling mill Work roll Diameter 150 mm x Width 140 mm Backup roll Diameter 250 mm x Width 140 mm Roll material Chrome steel roll peripheral speed 30 m / min Rolling material: SPC-C Thickness 0.6 mm x Width 50 mm x Length 150 mm Sample oil coating amount: 1 g / m ² [Effect of the invention] As described above, the metalworking oil of the present invention contains the polymerized oil of hydrogenated fish oil, and the fish oil is hydrogenated to a certain IV. After that, the polymerized oil polymerized in a specific viscosity range is used as a base oil or an oiliness improver, and the present invention has a higher lubricity than beef tallow, which is conventionally used as a base oil for metalworking oils. Because it is excellent, it can be used for metal processing such as metal cutting, grinding, rolling, pressing, drawing, etc. to obtain a processed product with a good finished surface, exhibiting good performance with a small usage amount and being excellent in economic efficiency. Further, it has little odor such as fish odor, can be used for metal working under high temperature and can improve working environment, and no odor is generated or coloring even when the metal working oil of the present invention is left for a long time. Etc. have good effects such as good stability over time, high storability and high commercialability.

[Brief description of drawings]

FIG. 1 ... A load-drawing ratio correlation diagram showing the results of a deep drawing test of aluminum according to Example 4 of the present invention. Fig. 2 ... A load-reduction ratio correlation diagram showing rolling test results according to Example 5 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10N 30:08 40:20 Z 8217-4H

Claims (1)

[Claims] 1. A metalworking oil comprising a polymerized oil having a viscosity of 80 to 3000 centipoise at 38 ° C. obtained by polymerizing hydrogenated fish oil having an iodine value of 60 to 110 by heating or oxidation.