JPH066712B2 - Lubricant - Google Patents

Description

TECHNICAL FIELD The present invention relates to a lubricating oil used as a metal working oil in metal working such as rolling, drawing, wire drawing, cutting, grinding and pressing.

[Conventional technology]

As a metalworking oil such as rolling oil, drawing oil, wire drawing oil, cutting oil, grinding oil, and press oil, animal and vegetable oils and fats, mineral oils, etc. or mixtures thereof have been added as necessary to improve oiliness, extreme pressure additives, and rust prevention. An agent, an antioxidant, an emulsifier, etc. added is used as it is or as an emulsion or aqueous solution of about 1 to 30%, and as a seed metal working oil, for example, a cold steel sheet containing a modified fat or oil heat-treated with activated clay. Hot-rolling oil (Japanese Examined Patent Publication No. 51-6686), a water-soluble cutting oil composition containing a salt of a polyhydroxy fatty acid obtained by hydrating an epoxidized fatty acid having an oxirane oxygen bonded to a double bond portion of an unsaturated fatty acid (JP-A-60-88096) and the like are known.

[Problems to be solved by the invention]

However, the cold rolling oil described in JP-B-51-6686, which mainly contains the modified fat and oil, has excellent lubricity,
Further, the modified fats and oils have improved hydrophilicity as compared with fats and oils, but they are still not sufficient, and when used as an emulsion, there are problems such as difficulty in emulsification, low emulsion stability, and easy separation. It was Meanwhile, JP-A-60-8809
The salt of polyhydroxy fatty acid used as the base oil of the cutting oil composition described in No. 6 is excellent in water solubility, but has a problem that the lubricity is not always sufficient. Furthermore, in recent years, the size and precision of processing machines have increased, the hardness of metal materials has increased, the speed and pressure of metal processing have increased, the accuracy of product processing surfaces has increased, and the amount of metal processing oil used to improve economic efficiency has been reduced. Although severer working conditions are required more and more, conventional metal working oils cannot cope with such severe conditions, and development of higher performance metal working oil has been desired.

[Means for solving problems]

The present invention has been made in view of the above points, and provides a lubricating oil having excellent hydrophilicity and lubricity, which exhibits excellent workability as it is or by mixing with other additives and used as a metal working oil. The purpose is to

The first lubricating oil in the present invention is obtained by polymerizing an animal or vegetable oil or fat having an unsaturated double bond, and the unsaturated double bond is added to the polymerized animal or vegetable oil or fat having an unsaturated double bond in the molecular chain. It is a compound obtained by ring-opening after conversion to introduce two hydroxyl groups per one double bond.

The polymerized animal or vegetable oil or fat is a polymerized oil having an unsaturated double bond obtained by polymerizing an oil or fat having an unsaturated double bond.
Examples of fats and oils having unsaturated double bonds include animal fats and oils, vegetable fats and oils, and examples of animal fats and oils include beef tallow, lard and the like, sardine oil, mackerel oil, saury oil, cod oil, tuna oil, squid oil and the like. Fish oil is used. As the vegetable oil, palm oil, rapeseed oil, soybean oil, castor oil and the like are used. For these oils and fats, nickel-based catalysts are used, and the pressure is 0.1 to 4.
It may be hydrogenated at 0 kg / cm ² ) and a temperature of about 160 to 200 ° C., but it is preferable to use one having an iodine value of 60 or more. It is also possible to use dehydrated castor oil obtained by dehydrating castor oil to increase unsaturated double bonds. The above-mentioned oils and fats may be crude oil obtained by squeezing oil from animals and plants, and the crude oil is treated with phosphoric acid, sulfuric acid, etc. for dewaxing, etc., and is a pre-purified oil having an increased triglyceride content, further an aqueous alkaline solution, active. Treat with white clay, activated carbon, etc., deoxidize,
A decolorized refined oil may be used. Examples of the method for polymerizing animal and vegetable fats and oils include an oxidative polymerization method and a thermal polymerization method. In the oxidative polymerization method, 150 to 20 while blowing air or oxygen.
Polymerization can be carried out by heating to 0 ° C. and reacting for 1 to 30 hours, and in the thermal polymerization method, polymerization can be carried out by heating to 250 to 300 ° C. and reacting for about 1 to 30 hours. The polymerized animal and vegetable oil having an unsaturated double bond thus obtained preferably has an iodine value of 40 or more and a viscosity at 40 ° C. of 100 to 2000 centistokes.

As a method of introducing a hydroxyl group into the double bond portion of the polymerized animal or vegetable oil or fat, the polymerized animal or vegetable oil or fat is reacted with a peroxide such as peracetic acid or hydrogen peroxide to epoxidize the double bond portion, and then the epoxy group There may be mentioned a method in which is a hydroxyl group.
About 0.5 to 10 wt% of the above-mentioned peroxide is added to polymerized animal and vegetable oils and fats having unsaturated double bonds, and formic acid, phosphoric acid, sulfuric acid, etc. are used as catalysts at 60 to 80 ° C for 2 hours. By reacting to some extent, an epoxy group can be introduced into the double bond portion of polymerized animal and vegetable oils and fats. After completion of reaction, 1
The first lubricating oil of the present invention is obtained by dehydration at about 00 to 120 ° C. Epoxy group is an unstable group, usually the reaction product obtained by epoxidation, the epoxy group is almost completely hydroxyl group in the process such as water produced by the reaction or purification by washing with water, the purpose of the present invention All epoxy groups may not necessarily be hydroxyl groups as long as they do not interfere, and some spoxy groups may remain.

The second lubricating oil of the present invention is obtained by polymerizing an animal or vegetable oil or fat having an unsaturated double bond, and an unsaturated double bond is added to the polymerized animal or vegetable oil or fat having an unsaturated double bond in the molecular chain. A polyoxyalkylene ether introduced by reacting an alkylene oxide with the hydroxyl group of a hydroxylated polymerized animal and vegetable oil / fat (the above-mentioned first lubricating oil) after ring opening after introduction to introduce two hydroxyl groups per double bond. It is a compound having a group. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like, and these may be added alone, or two or more kinds may be randomly added or block-added. It is preferable to add 1 to 10 wt% of the alkylene oxide to the polymerized animal and vegetable oil. The hydroxyl group to which the alkylene oxide is added is usually a hydroxyl group introduced into the double bond portion of a polymerized animal or vegetable oil or fat having an unsaturated double bond, but the raw material oil or fat of the polymerized animal or vegetable oil or fat has a hydroxyl group, such as castor oil. In the case of fats and oils, alkylene oxide may be added to the hydroxyl group to introduce a polyoxyalkylene ether group. The first lubricating oil also has a hydroxyl group and thus is excellent in hydrophilicity, but by adding an alkylene oxide to form a polyoxyalkylene ether group, the hydrophilicity can be further enhanced.

Both the first lubricating oil and the second lubricating oil preferably have a viscosity at 40 ° C. of 80 to 3000 centistokes, but 100 to 2000 in terms of handling in the manufacturing process.
The one having a centistokes is preferable, the one having a viscosity of 400 to 3000 centistokes is preferable from the viewpoint of lubricating performance, and the one having a viscosity of 100 to 2000 centistokes is preferable in consideration of both handling and lubricity in the manufacturing process.

The lubricating oil of the present invention is as it is or if necessary mixed with animal and vegetable fats and oils, fatty acid esters, mineral oils, extreme pressure additives, antioxidants, surfactants, rust preventives, defoaming agents and the like, rolling oil,
Used for metal working oils such as drawing oil, wire drawing oil, cutting oil, grinding oil, press oil. The lubricating oil of the present invention has excellent hydrophilicity,
Emulsions or aqueous solutions can be easily prepared without using an emulsifier or an extremely small amount of an emulsifier, and the emulsion or aqueous solution can be easily prepared, and the stability of the dispersion state of the emulsion or the dissolved state of the aqueous solution is excellent. There is.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples.
In addition, as the raw material fats and oils used in Examples and Comparative Examples, all crude oils were used unless otherwise specified.

Examples 1 to 7 1800 g of oils and fats shown in Table 1 were charged in a three-necked four-necked flask equipped with a stirrer, a cooler, and a thermometer, and heated and stirred at 180 ° C. for 2 hours while sucking air, and then polymerization shown in the table I got oil. Then cool to 80 ° C. and
5% hydrogen peroxide solution and formic acid as catalyst 1% of the total amount charged
The mixture was added, heated and stirred at 80 ° C. for 2 hours, washed twice with water after completion of the reaction, and then dehydrated at 120 ° C. to obtain a compound as a lubricating oil. In Examples 5 to 7, potassium hydroxide was further used as a catalyst, and the alkylene oxides shown in Table 1 were added to give lubricating oils. The properties of these lubricating oils are
Shown in the table.

Examples 8 to 14 The same flask as in Examples 1 to 7 was charged with 1800 g of the fats and oils shown in Table 1, and the mixture was heated at 300 ° C. under a nitrogen gas atmosphere at 3 ° C. for 3 hours.
The mixture was heated and stirred for a period of time to obtain a polymerized oil shown in Table 1. Then, in the same manner as in Examples 1 to 7, 35% hydrogen peroxide solution in the amount shown in Table 1 was reacted, and after the reaction was completed, the compound was washed with water and dehydrated to obtain a lubricating oil. In Examples 11 to 12, potassium hydroxide was further used as a catalyst, and the alkylene oxides shown in Table 1 were added to give lubricating oils. The properties of these lubricating oils are shown in Table 2.

Comparative Example 1 The polymerized fish oil obtained by polymerizing the fish oil shown in Table 1 by the same method as in Examples 1 to 7 was used as a lubricating oil. The properties of this lubricating oil (polymerized fish oil) are shown in Table 2.

Comparative Example 2 1800 g of fish oil shown in Table 1, 35% hydrogen peroxide solution 90
and 18 g of formic acid were charged in the same flask as in the example, and 8
The hydroxylated fish oil obtained by heating and stirring at 0 to 90 ° C. for 2 hours was used as a lubricating oil. The properties of the obtained lubricating oil (hydroxylated fish oil) are shown in Table 2.

Examples 15 to 19 and Comparative Examples 3 to 4 Processing oils having the formulations shown in Table 3 were stirred as a 15% emulsion with a homomixer (8000 rpm) and maintained at 80 ° C. while being circulated by a gear pump while being nozzle (1/4). KS
A00480) rolled steel plate (SPC-C-SB, 1 x
50 × 150 mm) was sprayed so that the amount of oil adhered was about 1.5 g / m ² ) and then rolled under the following conditions.
Before rolling, draw two lines with a spacing of 50 mm in advance on the steel sheet. After rolling, the spacing between the two lines is 167 mm (reduction ratio 70
%) Was measured with a load cell to compare rolling performance. The results are shown in Table 3.

Rolling test conditions Rolling mill: 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 SB 1 mm × 50 mm × 150 mm Examples 20 to 24, Comparative Examples 5 to 6 Using cutting oils having the compositions shown in Table 4 as cutting oils, cutting resistance values when cut under the following conditions are shown. It was measured. Further, the roughness of the cut surface in the cutting direction was measured with a stylus type roughness measuring machine. The results are also shown in Table 4.

Cutting test conditions Cutting machine: 3 ton vertical internal drawing broaching machine Cutting tool: Maximum depth of preparation per blade is 0.05 mm, width 7
mm, blade interval 8 mm, key broach tool with material SKH55 Work material: S-45C Cutting speed: 2 m / min. Examples 25 to 28, Comparative Example 7 Processing oil having the composition shown in Table 5 was applied to both sides of the aluminum plate.
It was applied so as to have an adhesion amount of g / m ² , and a deep drawing test of an aluminum plate was performed under the following conditions, and drawing loads at the time of drawing with various drawing ratios were measured. The results are shown in Table 5.

Deep drawing test conditions Testing machine: High-speed deep drawing test machine (manufactured by Tokyo Testing Machine Co., Ltd.),
Punch diameter 32mm, die diameter 35mm, processing speed 1m / mi
n. Processed material: Aluminum disc with a thickness of 1 mm (JIS A110
0.0), diameter 62.4mm to diameter 66.4mm for each sample oil
Six discs each having a diameter increasing by 0.8 mm were processed, and a test from a drawing ratio of 1.95 to a drawing ratio of 2.075 was performed.

* 1 Viscosity measured at 40 ° C with a Canon Fenske viscometer * 2 Ratio of the weight of alkylene oxide added to the weight of the raw material * 3 The odor measured immediately after production and after standing at room temperature for 30 days was measured according to the following criteria.

No animal or plant odor, no fish odor ○ Some animal or plant odor, some fish odor ・ ・ △ Severe animal and plant odor, fish odor, etc. × * 4 30 parts by weight of sample 60-spindle oil 70 parts by weight After mixing with 1 part, the mixture was allowed to stand at 0 ° C. for 7 days, and then the state of separation was observed and judged according to the following criteria.

No separation ・ ・ ・ ・ ○ Slight separation or some precipitation on the bottom ・ ・ ・ ・ △ Separation into two layers ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ × * 5 Shell type high-speed four-ball friction Test steel balls by testing machine 1
The measurement was performed under the conditions of 1/2 inch, a measurement temperature of 50 ° C., and a vertical shaft rotation speed of 600 rpm.

* 6 Polyoxyethylene (8 mol) noniphenyl ether surfactant * 7 Sulhol 430 (manufactured by Matsumura Oil Research Institute) was used as an emulsifying agent and a rust preventive.

〔The invention's effect〕

As described above, the first lubricating oil of the present invention has a structure in which a hydroxyl group is introduced into the double bond portion of a polymerized animal or vegetable oil or fat having an unsaturated double bond, thereby improving lubricity, hydrophilicity and stability. In addition to being excellent, even if a crude oil such as fish oil is used as a raw material, it has almost no odor, so that it can be produced using an inexpensive crude oil, and an excellent lubricating oil can be provided at a low cost. Further, the second lubricating oil of the present invention has a structure in which an alkylene oxide is added to the first hydroxyl group portion to introduce a polyoxyalkylene ether group, so that the second lubricating oil has excellent performance of the first lubricating oil, and further It has excellent hydrophilicity.

The lubricating oil of the present invention as it is or mixed with animal and vegetable oils, mineral oils and other additives, rolling oil, drawing oil, wire drawing oil,
It is used as a metal working oil such as cutting oil, grinding oil, and press oil, and the metal working oil using the lubricating oil of the present invention has various effects such as excellent workability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 103: 00 Z 9159-4H 105: 18) C10N 20:02 30:00 A 8217-4H 30: 06 40:22 40:24 Z 8217-4H 60:04 60:06 70:00 (72) Inventor Tsugio Okita 5-7-4 Nakashizu, Sakura City, Chiba Prefecture (72) Inventor Akio Nakajima Matsudo City, Chiba Prefecture 17-6 Jobandaira Jinya-mae (72) Inventor Shoji Ogihara 6-1, Fujigaoka, Konan-shi, Aichi 60-310 Konan housing complex (56) References JP-A-56-109296 (JP, A) JP-A-60-88096 ( JP, A) JP-B-31-4942 (JP, B1)

Claims (4)

[Claims] 1. A polymerized vegetable oil / fat obtained by polymerizing an animal / vegetable oil / fat having an unsaturated double bond, and having an unsaturated double bond remaining in the molecular chain, is epoxidized with an unsaturated double bond and then subjected to ring opening. Then, a lubricating oil having two hydroxyl groups introduced per one double bond. 2. The lubricating oil according to claim 1, which has a viscosity at 40 ° C. of 80 to 3000 centistokes. 3. A polymerized animal / vegetable oil / fat obtained by polymerizing an animal / vegetable oil / fat having an unsaturated double bond, and having an unsaturated double bond remaining in its molecular chain, is subjected to epoxidation of the unsaturated double bond, followed by ring opening. Then, the lubricating oil is characterized by having a polyoxyalkylene ether group introduced by reacting an alkylene oxide with a hydroxyl group of a hydroxylated polymerized animal and vegetable oil / fat in which two hydroxyl groups are introduced per one double bond. 4. The lubricating oil according to claim 3, which has a viscosity at 40 ° C. of 80 to 3000 centistokes.