JPS59227983A - Metal working oil composition - Google Patents

Abstract

PURPOSE:To provide a metal working oil compsn. contg. a lubricating oil component such as oil or fat and a specified anionic salt of water-sol. macromolecular compd. as essential ingredients, which is useful for high-speed and high-pressure metal working, has excellent lubricating properties and undergoes little change with time. CONSTITUTION:The metal working oil compsn. contains as essential ingredients (A) at least one lubricating oil component selected from among oil, fat, mineral oil and fatty acid ester and (B) an anionic salt of a water-sol. macromolecular compd. having an MW of 1,000-10,000,000 obtained by polymerization of a monomer of the formula (where R1, R2 and R3 are each 1-3C alkyl; m and n are each 0-3) and pref. (C) extreme-pressure agent (e.g. zinc phosphate or methylphosphonic acid). (B) are e.g. polymer of sodium 2-acrylamido-2-methylsulfonate and polymer of butylamine salt of 2-acrylamido-2-methylbutanesulfonic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal working oil composition containing a lubricating oil component and an anionic water-soluble polymer compound salt having a molecular weight of 10 to 10 million.

Conventionally, commonly used metalworking oils are made by adding lubricating oil auxiliaries such as oiliness improvers, extreme pressure agents, rust preventives, and antioxidants to lubricating oil components such as fats, mineral oils, or fatty acid esters. , this is usually made into an o/w type emulsion using an emulsifier.
Although it is supplied to the rolling processing department at a concentration of ~20%, for example, in the rolling of metals, rapid advances in rolling equipment and technology in recent years have led to higher rolling speeds and mass production. The requirements for rolling oils, such as lubricity, circulation stability, workability, and wastewater treatment properties, are becoming increasingly severe, and there is currently a need to develop rolling oils that can fully meet these demands. . However, rolling oil using conventional emulsifiers
It had various problems and was not satisfactory. In other words, with conventional rolling oil using emulsifiers, rolling lubricity is controlled by changing the type and amount of emulsifier added to increase or decrease the amount of oil that adheres to the rolling oil and the surface of the rolled material (plate-out amount). Ta. However, in rolling oils using such emulsifiers, the amount of plate-out and liquid circulation stability show contradictory tendencies; in other words, increasing the stability of the emulsion reduces the amount of plate-out on the rolled material. However, if the amount of plate-out is not increased, the emulsion becomes unstable, which causes various problems during circulation. Even though j'-3 is still used in other metal working oils such as press oil and cutting oil, further improvements in lubricity and workability have been required.

Therefore, the present inventor conducted research to solve the two drawbacks of conventional emulsified metalworking oils, and found that
°C, a lubricating oil component containing fat or wax is stably suspended and dispersed in water using a specific hydrophilic dispersant (water-soluble anionic polymer compound) in a solid state below the melting point,
By supplying the material to the processing section, i.e., at temperatures above the melting point, it becomes unstable, thereby successfully improving the above-mentioned drawbacks.
No. 7593).

As a result of further research, the present inventor found that it can be used for metal processing under practically assumed high shear conditions and high-speed, high-pressure conditions with fast processing speed and large reduction ratio, and that it can still be used for metal processing even under severe temperature and cutting conditions. We have found a metalworking oil composition that can be easily controlled in terms of process control such as liquid circulation stability.

More specifically, when a specific anionic water-soluble polymer compound salt is used or an extreme pressure agent is used in combination with this,
Due to the protective colloidal function of the polymer compound, the lubricating oil component maintains a relatively large particle size and is stably dispersed in water, resulting in good circulation stability. When in contact with the metal workpiece, large oil particles form a thick and strong lubricating film on the metal workpiece together with the extreme pressure agent.Furthermore, during long-term circulation use, oil particles with a large diameter form a strong lubricating film on the metal workpiece. The present invention was completed by discovering that a large particle size can be stably maintained even under force.

Therefore, the present invention provides (a) one or more lubricating oil components selected from the group consisting of oil iron, mineral oil, and fatty acid ester; and (1)) a monomer represented by the following general formula (I). - Molecular weight obtained by polymerizing keitai: 1000~]00
A metal working oil composition containing anionic water-soluble polymer compound salt and components (a) and (b) further containing (
C) 'A metalworking oil composition containing a layer pressure agent is provided.

3 Lubricating oil which is component (a) of the metal rolling oil composition of the present invention (wherein, R3 represents an alkyl group having 1 to 3 carbon atoms, and m and n represent a number of O to 3) Ingredients include, for example, mineral oil such as spindle oil, machine oil, turbine oil, and cylinder oil; animal and vegetable oils such as whale oil, cow's finger, liver fat, rapeseed oil, castor oil, bran oil, palm oil, and coconut oil; Fats and oils include esters of fatty acids obtained from beef tallow, coconut oil, palm oil, castor oil, etc., and aliphatic monohydric alcohols having 1 to 22 carbon atoms, ethylene glycol, neopentyl alcohol, pentaerythritol, etc. Each of these components may be used alone, or two types may be mixed and used.

In addition, the anionic water-soluble polymer compound salt of component (b) has a molecular weight of 1,000 to 10,000,000, particularly 1,000 to 1,000,000.
One million is preferred. Examples of these salts include metal salts such as sodium, potassium, zinc, and calcium salts, and amine salts such as aliphatic amines.

Examples of the extreme pressure agent as component (C) include the following compounds (+) to (x).

(1) Phosphoric acid, phosphorous acid, or thio or ester compounds thereof (II) Mono- or syringic acid esters or thio compounds thereof having one or more hydroxyl groups in the alkyl, alkylaryl or allyl group (111) carbon number 1 Mono- or diphosphonic acid having ~8 alkyl, alkylaryl or allyl groups or thio compounds thereof or derivatives thereof (iv) carbon i1 ~
Mono- or di-phosphinic acid having 8 alkyl, alkylaryl or allyl groups or their thio compounds or derivatives thereof (V) Mono- or di- or triphosphonic acid containing a nitrogen atom (vl) Alkyl group having 1 to 8 carbon atoms or Thioalcohol (Vii) having an allyl group; Thiocarboxylic acid or salt thereof (vlil) having an alkyl group, hydroxyalkyl group, alkylaryl group, or hydroxyalkylaryl group having 1 to 10 carbon atoms; Organometallic zinc compound (ix) R'( S-R' [In the formula, Z i, il - an integer of 5, R' is the number of carbon atoms] - 1
(x) A sulfur-containing organic heterocyclic compound, a salt thereof, or a derivative thereof Specific examples of this extreme pressure agent include the following. (
Examples of 1) include orthophosphoric acid, phosphorous acid, and those having 1 to 1 carbon atoms.
Examples include mono- or silicic esters of aliphatic, alicyclic or aromatic alcohols and orthophosphoric acid or thio compounds thereof, or phosphorous esters of the above-mentioned alcohols or thio compounds thereof. (11) is 2
-Hydroxypropyl phosphate is exemplified. (+
: Phosphonic acid represented by D and Ro' is an alkyl group, alkylaryl group or allyl group having 1 to 8 carbon atoms,
For example, methylphosphonic acid having 1 carbon number, dimethylposponic acid to n-octylphosphonic acid having 8 carbon atoms, moro-octylphosphonic acid, benzylphosphonic acid, 2-ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid,
Examples include dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, hydroxyethanediphosphonic acid, and thiophosphonic acids thereof. Hydroxyethane diphosphonic acid is a compound represented by the following formula.

OHOHO] ((R, Examples of (V) include ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and these thiophosphinic acids. , hexamethylphosphoric mono(or di)amide,
Nitrilotrismethylenephosphonic acid is a compound represented by the following formula.

i(0-P-0 OH (v+:Q) Dioctyldithiophosphoric acid 1
Examples of (1×) F lead include octyl sulfide, decyl disulfide, and propyl trisulfide.

The metalworking oil composition of the present invention is prepared by blending the above-mentioned components, and the amount of the lubricating oil component (a) is 998 to 60% by weight (hereinafter simply ), especially 998 to 70%, (b)
The water-soluble polymer compound salt of the component is 01 to 20%, especially 0.
1 to 10%, and the extreme pressure agent of component (C) is preferably 0.1 to 10%, particularly 0.1 to 5%.

The metal working oil composition of the present invention contains the above components and, if necessary, various known additives, such as rust preventives, oiliness improvers,
Antioxidants and the like may also be added.

” 2. Various additives may be added to the total amount of the metal working oil composition as necessary, in amounts of 0 to 2, 0 to 20, 0 to 5, respectively.
It can be added at a ratio of

Rust inhibitors include alkenylco/phosphate and its derivatives, fatty acids such as oleic acid, esters such as sorbitan monooleate, and other amines, and oiliness improvers include oleic acid, stearic acid, etc. Dibasic acids such as higher fatty acids and their derivatives such as esters or dimer acids are used as antioxidants, phenolic compounds such as 2,4-di-t-butyl p-Vsolnato, and aromatic compounds such as phenyl α-naphthylamine. Examples include group amines and the like.

The metalworking oil composition of the present invention can be used by simply mixing the above components before use, or by preparing a concentrated solution with a water content of up to 80% and diluting it with water before use. .

The thus obtained metalworking oil composition of the present invention has a relatively large particle size and stable particle size distribution under stirring conditions with high shear force, and has high lubrication performance due to the action with the extreme pressure agent. In addition to providing a metalworking oil with little change over time, it also has the following features:

That is, the water-soluble polymer compound salt used in the present invention itself has the ability to quickly adsorb to liquids and solid particles and make them hydrophilic, but it has the ability to lower the interfacial tension between water and oil and emulsify it. Since it does not have the same properties, the lubricating oil components do not emulsify, compared to metalworking oils that use conventional emulsifiers.
It is an excellent metal working oil that maintains high lubrication properties as a constantly clean metal working oil that does not cause contaminants such as dirty oil or metal powder to get mixed into the metal working oil during operation, that is, the so-called entrainment phenomenon. There is a point. In addition, due to the functions of both of the above components, the dirt in the working environment is improved, and furthermore, the phenomenon of dirt entrapment is reduced, and the metal surface is further cleaned, which improves metal-to-metal contact during machining, that is, the state of extreme pressure lubrication. in,
Metalworking oil that uses conventional emulsifiers has excellent wastewater treatment properties due to the use of water-soluble polymer compound salts, which can more effectively demonstrate the effect of extreme pressure agents that form a lubricating film on metal surfaces. It has an excellent feature of realizing a clean working environment, which is not found in other systems.

Although the mechanism of action of the water-soluble polymer compound of the present invention and the extreme pressure agent used has not been completely elucidated, it is believed that the mechanism of action is approximately as follows. In other words, the water-soluble polymer compound salt completely and uniformly dissolved in the water layer or the particles of the lubricating oil component that have been micronized in response to mechanical shearing force are adsorbed before coalescence begins, and the polymer compound salt is The oil particles are formed into relatively large particles by a type of agglomeration, and the large particles are stably dispersed in water by the steric and electroprotective colloidal action of the polymer salt.

Next, an example will be given and explained.

The metalworking oil compositions used in the examples are as follows. The following water-soluble polymer compound salts, extreme pressure agents, and emulsifiers were used.

Water-soluble polymer compound salt (A): 2-Aku IJ) Reamide-2-#f propanesulfonic acid Na salt polymer (molecular weight 2000) Water-soluble polymer compound salt (B): 2-Aku IJ) Polymer of butylamine salt of raredo-2-methylbutanesulfonic acid (molecular weight 100,000) Extreme pressure agent (1): Zinc phosphate 11ifj pressure agent (2): ) Liphenyl phosphite extreme pressure agent (3): Tridene Ruphosphite extreme pressure agent (4):
2-Ethylhexyl acid phosphate extreme pressure agent (5); Butylthiophosphonic acid Mg salt 4M
Pressure Mll (G): Octylthiophosphine C
l1l Na base HE y-+l) (7):
Thiobutyl alcohol extreme pressure agent (8): dithioethyl zinc phosphate emulsifier: ho+)oxyethylene nonylphenyl ether () ILB = 7.8) Antioxidant = 2,4-di-t-butyl p-cresol mineral oil 85% oleic acid 5 Extreme pressure agent (1) 2 Triethanolamine 2 Emulsifier
5 Antioxidant 1 Comparative A2 Lubricating oil component Beef tallow 95% Beef tallow fatty acid 2 Emulsifier 2 Antioxidant 1 Comparative product System) 1 Comparative product 4 Lubricating oil component Beef tallow 92% Beef tallow fatty acid 2 Emulsifier 2 Antioxidant 1 Extreme pressure agent (dioctylthiophos triphonic acid) Comparative product A5 Lubricating oil component Mineral oil (spindle oil) 72-stearate octyl varnish 2゜Tyloleic acid 5 Emulsifier 2 Antioxidant 1 Comparative product 6 Lubricating oil component Mineral oil (spindle oil) 71% stearin [
Acid octyl ester 20 oleic acid
5 Emulsifier 2 Antioxidant 1 Extreme pressure agent (phosphorus type) 1 Comparative product A7 Lubricating oil component mineral oil (spindle oil) 71% stearic acid octyl ester 20 oleic acid
5 Emulsifier 2 Antioxidant 1 Extreme pressure agent (8) Comparative product 8 Lubricating oil component mineral oil (cylinder oil) 77 Tibentaerythritol tetrao 20 Leate emulsifier 2 Antioxidant 1 Comparative product A9 Lubricating oil component Mineral oil ( 76 Tipentaerythritol Tetrao 20 Leate Emulsifier 2 Antioxidant 1 Extreme Pressure Agent (8) 1 Example 1 Seizure Resistance Load Test (Falex Test Method) Measurement of anti-seizure load is based on ASTIVI standard D-3233 pressure load test(
It is mature according to the Farex test). The test samples were prepared by diluting each metalworking oil composition with water to a three-fold concentration and stirring this with a homomixer at a rotation speed of 10,000 rpm. To apply the test sample, apply the above stirring solution at 50 ml/min (pressure 0.
5 kg/cr? i), by using a gear pump under conditions of 50°C and applying it to the rotating pin at the center of the fixed block.

The results are shown in Table 2.

Table 2 Example 2 Seizure load test (Soda four-ball test method) Seizure load measurement is based on the Defense Agency provisional standard NDS XXK27.
40 oil film strength test method (Soda four-ball test method). To prepare the test sample, mix each metalworking oil composition with water for 30 minutes.
% concentration and mix it with a homomixer at 10 revolutions.
．． This was done by stirring at 000 rpm. The test sample was applied by spraying the above stirred solution at a spray amount of 0.5 for 7 minutes (pressure: 05 k!9/cr?i), and sample solution temperature: 5
Using a gear pump at 0°C, the coating was applied from below three test steel balls fixed with ball holders to the rotating steel ball above through the space at the center of the three contact points.

The results are shown in Table 3.

Below is a margin Table 3 Example 3 Wastewater treatment test Test liquid (1 stone) prepared in the same manner as in Example 2 was added with sulfuric acid pan ±
After adding 3 g, the mixture was stirred for 2 minutes, and further Ca(OR)2 was added to adjust the pH to 7.0, followed by stirring for 10 minutes. Then, after standing for 30 minutes, the subnatant liquid was collected and the C0D (KMnO, method) was measured. The results are shown in Table 4.

1. Margin Table 4

Claims (1)

[Scope of Claims] 1. One or more lubricating oil components selected from the group consisting of fats and oils, mineral oils and fatty acid esters, and (
b) It is characterized by containing as an essential component an anionic water-soluble polymer compound salt having a molecular weight of 10 million to 10 million obtained by polymerizing a monomer represented by the following general formula (I). Metalworking oil composition. 1 (3 (wherein, R, R, and R3 represent an alkyl group having 1 to 3 carbon atoms, and m and n represent numbers of 0 to 3) 2. Anionic water-soluble polymer compound The amount of salt is 0.1 to 0.1 of the total composition.
20. The metalworking oil composition according to claim 1, which has a weight ratio of 20% by weight. 3. One or more lubricating oil components selected from the group consisting of fats and oils, mineral oils and fatty acid esters; (b) obtained by polymerizing a monomer represented by the following general formula (I); A metalworking oil composition characterized by containing an anionic water-soluble polymer compound salt having a molecular weight of 1,000 to 10,000, and (c) an extreme pressure agent as essential components. (In the formula, R2 and R3 represent an alkyl group having 1 to 3 carbon atoms, and m and n represent numbers of 0 to 3). The metal working oil composition according to claim 3, which is any one of the compounds. (1) Phosphoric acid, phosphorous acid, or thio or ester compounds thereof (ii) Mono- or silicic acid esters having one or more hydroxyl groups in alkyl, alkylaryl, or allyl groups, or thio compounds thereof (+ii) Carbon Numbers 1-8
Mono- or diphosphonic acid having an alkyl, alkylaryl or allyl group or a thio compound thereof or a derivative thereof (1v) Mono- or diphosphinic acid having an alkyl, alkylaryl or allyl group having 1 to 8 carbon atoms or a thio compound thereof or derivatives thereof (V) mono-, di-, or triphosphonic acid containing a nitrogen atom (vi) thioalcohol having an alkyl group or allyl group having 1 to 8 carbon atoms, argyl group having 1 to 12 carbon atoms, hydroxyalkyl sulfiocarboxylic acid or its salt having an alkylallyl group, an alkylaryl group, or a hydroxyalkylaryl group (viii) Organometallic zinc compound (ix) Indicates an alkyl, alkylaryl or allyl group having 1 to 12 carbon atoms] (X) Sulfur-containing organic heterocyclic compound or its radical or its derivative 5 The amount of the anionic water-soluble polymer compound salt is the total composition The metal working oil composition according to claim 3, which has a weight ratio of 0.1 to 20. 6. The metalworking oil composition according to claim 3, wherein the amount of the extreme pressure agent is 01 to 10 parts by weight of the total composition.