JPH0737629B2 - Extreme pressure additive for water-soluble metal working oil - Google Patents

Description

TECHNICAL FIELD The present invention relates to an extreme pressure additive for a water-soluble metal working oil. More specifically, it has excellent extreme pressure and abrasion resistance, and has good compatibility with oiliness agents such as animal and vegetable oils, mineral oils and fatty acid esters, and extreme pressure additives for oily metal working oils and self-emulsifying power. The present invention relates to an extreme pressure additive for water-soluble metalworking oil.

[Conventional technology]

Conventionally, the sulfide of mackerel whale oil has been used as an extreme pressure additive for metalworking oils such as cutting oil, grinding oil, drawing oil, wire drawing oil, rolling oil, and casting oil. With the decline, catching is restricted, and due to the total ban on whaling, the use of matcha whale oil has become impossible. From the trends of such times, alternatives to mackerel whale oil have been devised. For example, (1) a sulfide of a mixture of lard and an olefin (Japanese Patent Publication No. 58-17797), (2) a wax ester derived from an unsaturated fatty acid and a saturated alcohol, and about 50-
A fat composition consisting of triglycerides having an iodine value of between 120 (Japanese Patent Publication No. 56-38618) is known.

[Disadvantages of conventional technology]

The sulfide of (1) has a drawback that the fatty acid chain length of lard used for sulfurization has a carbon number of up to 18 and that it has a low molecular weight, low lubricity and low extreme pressure due to the mixture of olefins. There is. The fat composition of (2) is a composition in which a specific wax ester and a triglyceride are mixed in a specific ratio, and physical properties such as iodine value, pour point, cloud point and the like are similar to those of mackerel oil. But,
In fact, natural whale oil is a mixture of triglyceride and wax ester, and its sulfide lubricity is inferior to that of whale oil.

Further, both the sulfide of (1) and the fat composition of (2) are considered only in terms of lubricity or extreme pressure, and have a drawback that the emulsifying property is extremely poor.

That is, in recent years, as a metal working oil, the working speed has been increased, and there has been a demand for improved lubricity, cooling performance, and savings in the amount of oil, and the amount of water-soluble metal working oil that is advantageous in these aspects is used. However, all of the conventionally known sulfide substances have high oil solubility, and a lubricating oil composition using this is emulsified in water to obtain a stable emulsified dispersion system or solubilized system. Needs to use a large amount of surfactant.

When used in a large amount of a surfactant, not only the lubricity is deteriorated, but also problems such as foaming at the time of use and deterioration of workability occur, and improvement thereof is strongly desired.

[Means for solving problems]

As a result of intensive studies conducted by the present inventors focusing on the above points, they have excellent extreme pressure properties, abrasion resistance, and self-emulsification properties,
The present invention has been accomplished by finding a sulfide substance as an additive suitable for both oil-based and water-soluble metal working oils.

That is, the present invention is 1 mol of animal and vegetable oil having an iodine value of 60 to 140, and saturated or unsaturated aliphatic alcohol having 4 to 24 carbon atoms.
It is obtained by transesterification with 0.5 to 4 mol and has a composition of (A) 5 to 90% by weight of triglyceride having an iodine value of 60 to 140, and (B) a general formula RCOOR '(where R is a carbon number of 11 to 11). 5 to 90% by weight of a fatty acid ester represented by 23 alkyl groups and / or alkenyl groups, R'is an alkyl group and / or alkenyl group having 4 to 24 carbon atoms, and (C) 12 to 24 carbon atoms.
Of saturated or unsaturated fatty acid glycerin monoester or glycerin diester 5 to 40% by weight of (A), (B), (C), and its iodine value is
It is an extreme pressure additive for water-soluble metalworking oils, characterized by sulfiding a mixture (D) of 60 to 110.

The animal and vegetable oils and fats having an iodine value of 60 to 140 used in the present invention include cod oil, sardine oil, mackerel oil, fish oils such as orange ruffy, and mixed fish oils containing these fish oils as main components, beef tallow, beef leg oil, pork fat. Animal fats such as coconut oil, castor oil, palm oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, rice bran oil, and other vegetable oils and fats, and these animal oils and vegetable oils are hydrogenated. And hydrogenated fats and oils having an iodine value of 60 to 140 are used, and at least one selected from them is used.

A fatty acid represented by the general formula (B) RCOOR '(wherein R is an alkyl group or alkenyl group having 11 to 23 carbon atoms and R'is an alkyl group or alkenyl group having 4 to 24 carbon atoms) used in the present invention. The ester is an ester of a saturated or unsaturated fatty acid having 12 to 24 carbon atoms and a saturated or unsaturated aliphatic alcohol having 4 to 24 carbon atoms, and has 12 to 24 carbon atoms to give a fatty acid residue portion of the fatty acid ester. Examples of saturated or unsaturated fatty acids include lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, behenic acid,
Examples include simple fatty acids such as erucic acid, arachidic acid, oleic acid, linoleic acid, linolenic acid and ricinoleic acid, and mixed fatty acids thereof.

4 to 24 carbon atoms used for transesterification with animal and vegetable oils and fats
Examples of the saturated or unsaturated aliphatic alcohol include a straight chain saturated alcohol having 4 to 24 carbon atoms, a side chain saturated alcohol having 4 to 24 carbon atoms having a side chain alkyl group having 1 to 8 carbon atoms, and natural fats and oils. Examples thereof include a reduced alcohol having 12 to 24 carbon atoms obtained by reducing a fatty acid obtained by decomposition or a synthetic alcohol containing a side chain alkyl group obtained by an oxo method or the like using an α-olefin as a raw material. For example, butanol, isobutanol, t-butanol, hexanol,
Octanol, isooctanol, lauryl alcohol, linoleyl alcohol, allyl alcohol, coconut oil reducing alcohol, beef tallow reducing alcohol, myristyl alcohol, cetanol, oleyl alcohol, stearyl alcohol, rapeseed oil reducing alcohol, fish oil reducing alcohol, hydrogenated fish oil reducing alcohol In addition, synthetic alcohols such as oxochol (manufactured by Nissan Chemical Industry Co., Ltd.), Dobanol (manufactured by Mitsubishi Petrochemical Co., Ltd.) and Dyador (manufactured by Mitsubishi Kasei Industry Co., Ltd.) can be mentioned.

The glycerin monoester and / or glycerin diester of (C) used in the present invention comprises glycerin and a carbon number of 12 to 24.
A saturated or unsaturated monoester or diester with a fatty acid and a mixture thereof, the saturated or unsaturated fatty acid having 12 to 24 carbon atoms to give a fatty acid residue portion of glycerin monoester or and glycerin diester, the above components The simple substance fatty acids and mixed fatty acids mentioned in (B) may be mentioned.

The mixture (D) used in the present invention comprises the above-mentioned triglyceride (A), the fatty acid ester (B) and the glycerin monoester or (C) glycerin diester, and preferably (A) :( B): (C) is mixed in a weight ratio of 5 to 90: 5 to 90: 5 to 40%.

To produce the mixture (D) by the alcoholysis reaction,
Animal and vegetable fats and oils with iodine value of 60 to 140 or hardened fats and oils thereof 1
Moles and 0.5 to 4 moles of a saturated or unsaturated aliphatic alcohol having 4 to 24, preferably 4 to 12 carbon atoms in the absence of a catalyst or an alkali catalyst such as caustic soda or caustic potash in a total amount of 0.005 ~ 0.1% by weight, preferably 0.01-0.05
In the presence of wt% 30-200 ℃, preferably 50-200 ℃,
The reaction is carried out for 0.5 to 6 hours, and the unreacted aliphatic alcohol is removed after the reaction to obtain a mixture (D).

The above reaction can be carried out in the presence of a nonpolar solvent such as benzene, toluene, xylene or the like in order to prevent coloring of the reaction product. After completion of the reaction, the catalyst and the glycerin formed in the reaction product are removed by washing with water, and the solvent and unreacted alcohol which are not removed by washing with water are removed by heating under normal pressure or reduced pressure to obtain a mixture (D).

The mixture (D) of the present invention preferably has an iodine value in the range of 60 to 110, and a sulfide substance obtained by sulfurizing the mixture has excellent extreme pressure properties and wear resistance. The extreme pressure resistance and wear resistance of (1) deteriorate, and when the iodine value is 110 or more, the oxidation stability and heat resistance decrease.

Further, the glycerin monofatty acid ester or glycerin difatty acid ester of the component (C) in the mixture (D) is 5 to 40
A sulfide substance having excellent extreme pressure property, abrasion resistance and self-emulsifying property can be obtained in the range of wt%, and when the content of the component (C) is 5% by weight or less, the extreme pressure property, abrasion resistance and self-emulsifying property are improved. No, 40
If it is more than 10% by weight, the lubrication performance such as extreme pressure property and wear resistance is not improved, and it is not economical.Furthermore, the compatibility of the obtained sulfide substance with mineral oil decreases, especially at low temperature, and the lubricating oil composition is May separate. The ranges of (A), (B), and (C) are preferably 30 to 70% by weight, 25 to 75% by weight, and 5 to 40% by weight, respectively.

The sulfurating substance of the present invention is sulfurized by adding sulfur to the mixture (D) according to a conventional method. The sulfurization reaction can be performed, for example, as follows.

To the mixture (D) at 150 to 200 ° C., 4 to 30% by weight of granular or powdery sulfur was added over 0.5 to 3 hours, and the mixture was stirred at the same temperature for 3 to 30 hours to carry out the reaction. After 90
Blow nitrogen gas or air at ~ 100 ° C to remove hydrogen sulfide. When a precipitate or the like is observed in the reaction product, the reaction product is filtered using Celite. The amount of sulfur at the time of sulfurization is less effective when the amount of sulfur is small, and is effective when it is large, but it is economically disadvantageous, and the range of 5 to 25% by weight is suitable in terms of performance and economically. There is.

The sulfurization reaction may be carried out in the presence of a basic catalyst by using mercaptans in addition to sulfur, and in this case, a sulfurized substance having less odor can be obtained.

The sulfide substance thus obtained is used as an extreme pressure additive for a water-soluble metalworking oil of the present invention, but its extreme pressure property and abrasion resistance are higher than those of conventional sulfide animal fats or sulfide fatty acid esters. Improved, and has self-emulsifying property,
Suitable as an extreme pressure or antiwear additive for oil-soluble or water-soluble lubricating oils.

The sulfide substance of the present invention is used for metal processing by dissolving in addition to mineral oil or animal and vegetable oil and emulsifying it as it is or in water, and as mineral oil, spindle oil, liquid paraffin, machine oil, gear oil As examples of animal and vegetable oils, rapeseed oil, castor oil, lard, beef tallow and the like can be mentioned, and 2 to 30% by weight of a sulfide substance is added to these oily substances for use.

The extreme pressure additive for the water-soluble metalworking oil of the present invention has excellent extreme pressure property, but the mechanism of action showing abrasion resistance is not clear, but unsaturated animal and vegetable oils and fatty acid esters and glycerin monofatty acid ester or and glycerin difatty acid It is considered that the sulfide with the ester acts as a complement within a specific range to exhibit excellent extreme pressure property or abrasion resistance and has emulsifying property.

〔Example〕

 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.

In the measurement examples, examples and comparative examples IV is iodine value, AV is acid value,%
Indicates% by weight.

Measurement Example In order to measure the composition ratio of (A), (B), and (C), the physical properties and the like of the sulfide of the mixture (D) prepared as described below were measured.

Purified lard (IV = 65, AV = 0.7) 650 g, methyl oleate (IV = 86, AV = 0.5) 300 g, glycerol mono-beef tallow fatty acid ester and glycerin di-beef tallow fatty acid ester 60:40
% 50% mixture (IV = 40, AV = 0.7) was charged to a 2 round bottom flask (IV of mixture = 70) and 10% powdered sulfur with stirring.
0 g was added, the temperature was raised to 175 to 180 ° C, the reaction was carried out at the same temperature for 6 hours, then the mixture was cooled to 90 to 100 ° C, and nitrogen gas was bubbled through the reaction solution at the same temperature for 30 minutes. The produced hydrogen sulfide gas was removed to the outside of the system to obtain a sulfide substance having a sulfur content of 8%.

About the obtained sulfide substance, viscosity, friction coefficient, baking load,
Various physical properties such as compatibility with mineral oil and emulsifying property were measured, and the results are shown in No. 2 of Table-1.

Next, using A component (purified lard), B component (methyl oleate), and C component (60: 40% mixture of glycerin mono-beef fatty acid ester and glycerin di-beef fatty acid ester) used above, A, B, C A mixture D in which the mixing ratio of each component was changed was prepared, and this mixture D was sulfided under the same reaction conditions as described above so that the sulfur content was 8% to obtain a sulfide substance.

The mixing ratio of each component and various physical properties of the sulfide substance obtained therefrom were measured, and the results are shown in Table 1.

The measuring method of each physical property is as follows.

(1) Viscosity: With respect to the sulfide substance itself, the viscosity at a temperature of 99 ° C. was measured using a B-type viscometer.

(2) Sample: In the following measurement, 10% by weight of the above-mentioned sulfide substance was added to 60 spindle oil, and the dissolved substance was used for the measurement.

(3) Friction coefficient (μ): With a pendulum type oil friction tester,
The coefficient of friction at room temperature was measured.

(4) Baking load: Rotation speed with a high-speed four-ball friction tester
The pressure (kg / cm ² ) at the time of baking was measured by continuously increasing the pressure under the conditions of 600, 1500 rpm and temperature at room temperature.

(5) Compatibility with mineral oil: Each sample was allowed to stand at 0 ° C for 14 days, and the condition after standing was observed to determine the compatibility with mineral oil as follows.

○: transparent, Δ: cloudy, ×: separated into two layers.

(6) Emulsifying property: 20% of sulfide substance to 60 spindle oil
80 g of the added and dissolved product and 720 g of pure water were placed in a tall beaker of 1 and rapidly stirred for 5 minutes using a homomixer, and then allowed to stand for 3 minutes, after which the amount of separated oil layer was measured. , Shown as a percentage of the amount of oil charged.

As a result of the following, as shown in Table-1, (A) 5 to 90% by weight,
(B) 5 to 90% by weight, (C) 5 to 40% by weight are excellent, and those out of this range are high friction coefficient, low seizure load, The viscosity is high, the compatibility with mineral oil is poor, the emulsifying property is poor, or the performance of a plurality of items is poor, and it cannot be put to practical use.

Example 1 900 g of hydrogenated fish oil (IV = 90, AV = 0.51), 130 g of isooctyl alcohol and 0.3 g of caustic soda were charged, reacted at 110 to 115 ° C. for 2 hours, cooled, and the reaction mixture was washed with 1500 g of water. To remove caustic soda, then water and unreacted isooctyl alcohol are distilled off under reduced pressure to give triglyceride (IV87) 43.8% hydrogenated fish oil fatty acid isooctyl ester.
25.3%, glycerin monohydrogenated fish oil fatty acid ester 6.7
%, Glycerol dihydrogenated fish oil fatty acid ester 24.1% (IV = 85, AV = 1.5).

75 g of powdered sulfur was added to 500 g of this mixture and sulfided under the same reaction conditions as in the measurement example to obtain a sulfided substance having a sulfur content of 11.0%.

Table 2 shows various physical properties of the obtained sulfide substances.

Example 2 445 g of refined lard (IV = 65, AV = 0.31), rapeseed oil (IV =
101, AV = 0.52) 455 g, isobutyl alcohol 390 g and caustic potash 0.3 g were charged and reacted at 100 to 110 ° C for 3 hours, then caustic soda was washed off with water, and then water and unreacted isobutyl alcohol were distilled off under reduced pressure. Glycerin trifatty acid ester (IV69) 36.3%, fatty acid isobutyl ester 47.2%, glycerin monofatty acid ester 8.3%, glycerin difatty acid ester 8.4% (IV = 77, AV
= 1.2) was obtained.

70 g of powdered sulfur was added to 500 g of this mixture, and sulfurization was performed under the same reaction conditions as in the measurement example to obtain an extreme pressure additive for water-soluble metalworking oil having a sulfur content of 9.9%.

Table 2 shows various physical properties of the obtained sulfide substances.

Example 3 Rapeseed oil (IV = 101, AV = 0.35) 700 g and palm oil (IV5
1, IV0.25) 300g mixed fats and oils (IV86, AV0.32), isooctyl alcohol 286g and caustic soda 0.15g were charged, reacted at 110-120 ° C for 4 hours, cooled, and washed with water. Caustic soda was removed, and then water and unreacted isooctyl alcohol were distilled off under reduced pressure to give triglyceride (IV90) 47.2% and fatty acid isooctyl ester 2
Mixture of 3.0%, glycerin monofatty acid ester 13.6%, glycerin difatty acid ester 16.2% (IV = 76, AV = 1.
8) got.

80 g of powdered sulfur was added to 500 g of this mixture and sulfided under the same reaction conditions as in the measurement example to obtain a sulfided substance having a sulfur content of 12.0%.

Table 2 shows various properties of the obtained sulfide substance.

Comparative Examples 1 and 2 Purified lard (IV = 65, AV = 0.38) as Comparative Example 1 and purified mackerel whale oil (IV = 82, AV = 0.4) as Comparative Example 2 under the same reaction conditions as in Example 1, respectively. Each physical property value of the sulfided substance obtained by sulfided to a content of 8% is shown in Table-2.

Comparative Example 3 400 g of rapeseed oil (IV = 101, AV = 0.5) and 600 g of tallow fatty acid butyl ester (IV = 40, AV = 0.4) were charged (I of the mixture).
V = 40.4, AV = 0.5) and 120 g of powdered sulfur were added and sulfided under the same reaction conditions as in Example 1 to obtain a sulfided substance having a sulfur content of 8.2%.

Table 2 shows various physical properties of the obtained sulfide substances.

〔The invention's effect〕

As described above, the extreme pressure additive for a water-soluble metalworking oil of the present invention is a glycerin monoester of a triglyceride, a fatty acid ester, and a fatty acid obtained by transesterification of an animal and vegetable oil / fat with an iodine value of 60 to 140 and an aliphatic alcohol, or And a glycerin diester in a specific ratio to obtain a mixture, which is a sulfurized substance obtained by sulfurizing the mixture. The sulfurized substance has excellent extreme pressure and abrasion resistance, and is compatible with an oiliness agent. It has good self-emulsification property and can be widely used as an extreme pressure additive for oil-based and water-soluble metal working oils. The extreme pressure and abrasion resistance of the industrial oil can be enhanced, or the same performance can be exhibited with a small amount of addition, and there are effects such as excellent economical efficiency.

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Claims (1)

[Claims] 1. A mole of an animal or vegetable oil having an iodine value of 60 to 140 and a saturated or unsaturated aliphatic alcohol having 4 to 24 carbon atoms.
5 to 9 triglyceride having an iodine value of 60 to 140 and having a composition of (A) obtained by transesterification with 5 to 4 mol
0% by weight, (B) general formula RCOOR '(where R is a carbon number of 11 to
23 alkyl groups and / or alkenyl groups, R ′ has 4 carbon atoms
5 to 90% by weight of a fatty acid ester represented by (alkyl group and / or alkenyl group of 24 to 24), and (C) 5 to 40% by weight of glycerin monoester or glycerin diester of saturated or unsaturated fatty acid having 12 to 24 carbon atoms. (A),
It consists of (B) and (C), and its iodine value is 60-110.
An extreme pressure additive for water-soluble metal working oils, which is characterized by sulfiding the mixture (D).