JPH0532990A - Metallic plastic working oil composition and extreme-pressure additive for metallic plastic working oil - Google Patents

Abstract

PURPOSE:To obtain the subject new composition, containing a dialkyl polythiophosphate and capable of exhibiting excellent performance in shearing, deep drawing, drawing work, etc., of stainless steel sheets without containing any chlorinated paraffins. CONSTITUTION:The objective composition containing a dialkyl polythiophosphate prepared by reacting (A) a dialkyl dithiophosphate (salt) composed of a product of reaction between a mixed aliphatic alcohol composed of preferably (i) 85-95wt.% 7-10C aliphatic alcohol and i6C aliphatic alcohol and (ii) phosphorus pentasulfide or its alkaline metallic salt or ammonium salt with (B) a sulfur chloride preferably composed of sulfur monochloride as an extreme-pressure additive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel metal-plastic working oil composition such as punching oil, squeezing oil, drawing oil and the like, and an extreme pressure additive used therein. More specifically, a plastic working oil composition containing no chlorinated paraffin that exhibits excellent performance in plastic working such as shearing, drawing, and drawing of a stainless steel plate, and an extreme pressure additive used for the same

[0002]

[0003]

2. Description of the Related Art Conventionally, in plastic working such as shearing, drawing, and drawing of a steel sheet, frictional damage (seizure) between a die or die and the steel sheet is prevented, quality of processed products is improved, and tool wear is increased. For the purpose of suppression, metal plastic working oil compositions containing extreme pressure additives such as punching oil, drawing oil and drawing oil are used.

At that time, generally, the type of extreme pressure additive used also changes depending on the type of steel sheet. For example, carbon steel and galvanized steel sheets often use sulfur-based extreme pressure additives and chlorine-based extreme pressure additives, and stainless steel sheets use only chlorine-based extreme pressure additives.

Examples of the sulfur-based extreme pressure additives include sulfurized fats and oils, sulfurized olefins, dialkyl polysulfides and the like. Further, examples of the chlorine-based extreme pressure additive include chlorinated paraffin, chlorinated fatty acid, and chlorinated fatty acid ester.

[0006]

However, the metal plastic working oil composition containing the chlorine-based extreme pressure additive is liable to rust in the processed product due to chlorine, and chlorine gas is generated during welding, which causes work Its use is being restricted because it may damage the environment. Therefore, for plastic working of carbon steel sheets and galvanized steel sheets, metal plastic working oil compositions containing sulfur-based extreme pressure additives as "dechlorination" have become mainstream. However, regarding the plastic working of the stainless steel sheet, since the stainless steel sheet is hard and has a large adhesive property, the metal plastic working oil composition containing the sulfur-based extreme pressure additive,
Seizure, so-called "galling" cannot be prevented,
Still, a metal plastic working oil composition containing a chlorine-based extreme pressure additive, particularly a chlorinated paraffin, is frequently used.

As described above, in the plastic working of a stainless steel sheet, a metal plastic working oil composition which is free from rust due to chlorine in place of the metal plastic working oil composition containing chlorinated paraffin, and which prevents galling, and Finding the extreme pressure additive to use is an extremely difficult task.

[0008]

Therefore, the present inventors have
As a result of intensive studies to solve such a difficult problem, as an alternative to chlorinated paraffin, a metal plastic working oil composition containing an extreme pressure additive composed of dialkyl polythiophosphate was found. The present invention has been completed by discovering that it is a metal plastic working oil composition that is effective in plastic working of stainless steel plates and has no problem of rust caused by chlorine.

That is, the present invention relates to a metal plastic working oil composition characterized by containing a dialkyl polythiophosphate, and a metal plastic working oil characterized by comprising a dialkyl polythiophosphate. An extreme pressure additive for use is also provided.

As the base oil of the metal plastic working oil composition of the present invention, various mineral oils and synthetic oils can be used. Examples of mineral oils include distillate oil obtained by distilling paraffin-based crude oil, naphthene-based crude oil, etc. under atmospheric pressure, or distilling the atmospheric distillation residue under reduced pressure, or refinement thereof Oils such as solvent refined oil, hydrogenated refined oil, dewaxed oil and the like can be mentioned. Further, as the synthetic oil, polyolefin, polyglycol ester, phosphate ester,
Silicone oil, alkyldiphenyl, dibasic ester and the like can be mentioned.

The dialkyl polythiophosphate to be contained in the above base oil in the present invention is obtained by adding a solvent such as n-hexane, toluene or xylene to 2 mol of dialkyl dithiophosphoric acid or a salt thereof and adding 1 mol of sulfur chloride to 30 mol. It is obtained by dropping at -60 ° C, and after dropping, reacting at 40-60 ° C for 4-9 hours to remove by-products and distilling off the solvent. Examples of sulfur chloride include sulfur monochloride and sulfur dichloride, among which sulfur monochloride is preferable.

As the dialkyldithiophosphoric acid or salt thereof used here, for example, 4 mol of aliphatic alcohol and 1 mol of phosphorus pentasulfide are reacted at 40 to 100 ° C. until the generation of hydrogen sulfide stops, and unreacted. Those obtained by filtering out phosphorus pentasulfide, alkali metal salts, ammonium salts thereof and the like can be mentioned. The alkali metal salt of dialkyldithiophosphoric acid is obtained by adding an alcohol solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or lithium hydroxide to the dialkyldithiophosphoric acid obtained as described above at room temperature. The ammonium salt of dialkyldithiophosphoric acid can be obtained by adding ammonium gas to the above dialkyldithiophosphoric acid at 10 to 50 ° C.
It is obtained by blowing in.

Examples of the aliphatic alcohol used to obtain the dialkyldithiophosphoric acid include, for example, methyl alcohol.
, Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-
Butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, 2 -Octyl alcohol, n-decyl alcohol and the like may be mentioned alone or as a mixture, but mixed aliphatic alcohols having an average number of carbon atoms of 4 to 10, especially aliphatic alcohols having 7 to 10 carbon atoms. Mixed aliphatic alcohols consisting of alcohols and aliphatic alcohols having 6 or less carbon atoms are preferred, and 85 to 95% by weight of 2-ethylhexyl alcohol and 6 carbon atoms are particularly preferred.
It is preferable to use a mixed aliphatic alcohol containing the following aliphatic alcohol in an amount of 15 to 5% by weight, because it is excellent in extreme pressure and solubility in the base oil, and a small amount of additive is effective.

The amount of these dialkyl polythiophosphates used is such that the content in the metal plastic working oil composition to which they are added is 1 to 40% by weight, preferably 5 to 20% by weight.
Is the range.

The metal plastic working oil composition of the present invention contains, in addition to the above-mentioned components, various additives such as alkenyl succinic acid, oxidized paraffin, calcium sulfonate, and the like.
Sorbitan monooleate, dicyclohexylamine,
Anti-rust agent such as acidic phosphate ester, oil and fat, higher saturated fatty acid, higher unsaturated fatty acid, higher fatty acid monoalkyl ester, phosphate ester, oiliness improver such as alcohol, sulfurized oil and fat, sulfurized olefin, dialkyl polysulfide, etc. extreme pressure Additives can also be added.

[0016]

EXAMPLES The present invention will be specifically described with reference to Examples and Test Examples below.

Example 1 In a 2 l flask connected to a hydrogen sulfide absorber, 432 g of 2-ethylhexyl alcohol and n-butyl alcohol were added.
48 g (4 mol mixed weight ratio 90:10 as mixed aliphatic alcohol) and 222 g (1 mol) of phosphorus pentasulfide were charged, stirred and reacted at 80 ° C. for 6 hours to obtain dialkydithiophosphoric acid.

Then, 300 ml of toluene was added to this,
135 g (1 mol) of sulfur monochloride was added dropwise at 50 ° C or lower,
The mixture was reacted at 60 ° C. for 4 hours, washed with water, the by-product hydrochloric acid was removed, and the toluene was distilled off to obtain a dialkyl polythiophosphate.

Obtained dialkyl polythiophospher
Was added to 90 parts by weight of 150 spindle oil to obtain a metal plastic working oil composition (A-1) of the present invention.

Example 2 433 g of 2-ethylhexyl alcohol and 59 g of n-amyl alcohol (4 mol as mixed aliphatic alcohol,
A dialkyl polythiophosphate was obtained in the same manner as in Example 1 except that the mixing weight ratio of 88:12) was used, and the metal plastic working oil composition (A-2) of the present invention was then similarly obtained.
Got

Example 3 In a 2 liter flask connected to a hydrogen sulfide absorber, 432 g of 2-ethylhexyl alcohol and 48 g of isobutyl alcohol (4 mol as mixed aliphatic alcohol, mixing weight ratio 90:10) and five were added. 222 g (1 mol) of phosphorus sulfide was charged, stirred and reacted at 80 ° C. for 6 hours to obtain dialkyldithiophosphoric acid. Next, add 3 parts of this dialkyldithiophosphoric acid.
The mixture was transferred to a L flask and 560 g of a 20 wt% caustic potash solution in ethyl alcohol was added dropwise at room temperature, followed by stirring at room temperature for 2 hours to obtain a potassium salt of dialkyldithiophosphoric acid.
Next, 300 ml of toluene was added thereto, 135 g (1 mol) of sulfur monochloride was added dropwise at 50 ° C or lower, and the mixture was reacted at 60 ° C for 4 hours. After that, dialkyl polythiophosphate was obtained, and then a metal plastic working oil composition (A-3) of the present invention was obtained in the same manner as in Example 1.

Example 4 Dialkyldithiophosphoric acid obtained in the same manner as in Example 3 was used.
After blowing 34 g (2 mol) of ammonia gas at -40 ° C, 300 ml of toluene was further added, and 135 g (1 mol) of sulfur monochloride was added dropwise at 50 ° C or lower, and reacted at 60 ° C for 4 hours to produce a by-product. Ammonium chloride was removed by filtration, and toluene was distilled off to obtain a dialkyl polythiophosphate, and then, in the same manner as in Example 1, a metal plastic working oil composition (A-4) of the present invention was obtained. .

Example 5 520 g (4 mol) of 2-ethylhexyl alcohol instead of mixed aliphatic alcohol consisting of 432 g of 2-ethylhexyl alcohol and 48 g of isobutyl alcohol
A dialkyldithiophosphoric acid was obtained in the same manner as in Example 3 except that was used. Then, a dialkyl polythiophosphate was obtained in the same manner as in Example 4 except that this dialkyl dithiophosphoric acid was used, and then the metal plastic working oil composition (A-4) of the present invention was obtained in the same manner as in Example 1. Obtained.

Test Example 1 Metal plastic working oil compositions (A-
1) to (A-5) and chlorinated paraffin (chlorine content 5
0% by weight) 10 parts by weight and 150 parts by weight of spindle oil 90, 150 parts by weight of a plastic working oil composition (B-1), 10 parts by weight of sulfide sulfide (sulfur content 15% by weight) and 150 parts of spindle oil 90 An extreme pressure effect test (high-speed four-ball test) and a rust test were conducted in order to see the extreme pressure effect and the rust resistance of the metal plastic working oil composition (B-2) consisting of 10 parts by weight. The results are shown in Table 1.

The high speed four-ball test and the rusting test were conducted under the following test conditions. High-speed four-ball test equipment: High-speed four-ball test test Rotating ball: Stainless steel (SUS304) ball for ball bearing 1/2 inch (JIS class 1) Fixed ball: Chrome steel ball for ball bearing 1/2 inch (JIS
Advanced) Vertical shaft rotation speed: 500 rpm Loading method: 5 minutes at each load Here, extreme pressure property was evaluated by the galling load on the surface of the stainless steel ball.

Rust test water addition: 0.1 part by weight to 100 parts by weight of sample oil Test piece: Stainless steel plate (SUS304, 25
X 60 x 0.5 mm) Test piece dipping method: Half-immersing test piece vertically in sample oil Temperature: 100 ° C Time: 3 hours Here, regarding the rust resistance, the surface of the unsoaked part of the test piece The presence or absence of rust was evaluated.

[0027]

[Table 1]

[0028]

As described above, since the metal plastic working oil composition and the extreme pressure additive for metal plastic working oil of the present invention have no problem of rust due to chlorine and are effective in plastic working of stainless steel sheets, Instead of the conventional metal plastic working oil composition containing chlorinated paraffin which is a chlorine-based extreme pressure additive, it can be used as a metal plastic working oil composition effective for plastic working of stainless steel sheets.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10N 40:24 Z 8217-4H

Claims (14)

[Claims] 1. A metal plastic working oil composition comprising a dialkyl polythiophosphate. 2. A dialkyl polythiophosphate,
The composition according to claim 1, which is obtained by reacting dialkyldithiophosphoric acid or a salt thereof with sulfur chloride. 3. A dialkyldithiophosphoric acid or a salt thereof is a compound obtained by reacting a mixed aliphatic alcohol having an average number of carbon atoms of 4 to 10 with phosphorus pentasulfide, or an alkali metal salt or ammonium salt thereof. The composition according to 2. 4. A dialkyldithiophosphoric acid or its salt is a mixed aliphatic alcohol composed of an aliphatic alcohol having 7 to 10 carbon atoms and an aliphatic alcohol having 6 or less carbon atoms and phosphorus pentasulfide. The composition according to claim 2, which is obtained by reacting with or an alkali metal salt or ammonium salt thereof. 5. The composition according to claim 4, wherein the aliphatic alcohol having 7 to 10 carbon atoms is 2-ethylhexyl alcohol. 6. The composition according to claim 4, wherein the content of the aliphatic alcohol having 7 to 10 carbon atoms in the mixed aliphatic alcohol is 85 to 95% by weight. 7. The composition according to claim 2, 3, 4, 5, or 6, wherein the sulfur chloride is sulfur monochloride. 8. An extreme pressure additive for metal plastic working oils, which comprises a dialkyl polythiophosphate. 9. A dialkyl polythiophosphate,
The extreme pressure additive according to claim 8, which is obtained by reacting dialkyldithiophosphoric acid or a salt thereof with sulfur chloride. 10. A dialkyldithiophosphoric acid or a salt thereof,
The extreme pressure additive according to claim 9, which is obtained by reacting a mixed aliphatic alcohol having an average number of carbon atoms of 4 to 10 with phosphorus pentasulfide, or an alkali metal salt or ammonium salt thereof. 11. A dialkyldithiophosphoric acid or a salt thereof,
A mixture of an aliphatic alcohol having 7 to 10 carbon atoms and an aliphatic alcohol having 6 or less carbon atoms with a mixed aliphatic alcohol to react with phosphorus pentasulfide, or an alkali metal salt thereof. The extreme pressure additive according to claim 9, which is an ammonium salt. 12. An aliphatic alcohol having 7 to 10 carbon atoms.
The polymer is 2-ethylhexyl alcohol.
The extreme pressure additive described. 13. The extreme pressure additive according to claim 11 or 12, wherein the content of the aliphatic alcohol having 7 to 10 carbon atoms in the mixed aliphatic alcohol is 85 to 95% by weight. 14. The extreme pressure additive according to claim 9, 10, 11, 12, or 13, wherein the sulfur chloride is sulfur monochloride.