JPH0336074B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel metal working oil composition, and more particularly 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. Metalworking oils that have been commonly used are:
Lubricating oil auxiliaries such as oiliness improvers, extreme pressure agents, rust preventives, and antioxidants are added to lubricating oil components such as fats, oils, mineral oils, or fatty acid esters, and this is O/W with an emulsifier.
It is usually supplied to the rolling processing department as a mold emulsion at a concentration of 1 to 20%, but due to recent rapid advances in rolling equipment and technology, for example in metal rolling,
As rolling speeds increase and mass production increases, the requirements for rolling oils such as lubrication, circulation stability, workability, and wastewater treatment properties are becoming increasingly severe. The current situation is that the development of However, conventional rolling oils using emulsifiers have various drawbacks and are 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; that is, increasing the stability of the emulsion reduces the amount of plate-out to the rolled material. However, if the amount of plate-out is not increased, the emulsion becomes unstable, which causes various problems during circulation. Furthermore, further improvements in lubricity and workability have been required for other metal working oils such as press oils and cutting oils. Therefore, the present inventor conducted research to solve the above-mentioned drawbacks of conventional emulsified metal working oils, and
Using a specific hydrophilic dispersant (a water-soluble anionic polymer compound), a lubricating oil component containing oil or wax at a temperature of 20 to 100°C is stably suspended and dispersed in water in a solid state below the melting point, By making it unstable when it is fed to the processing section, that is, above the melting point, we succeeded in improving the above drawback, and filed a patent application earlier (Japanese Patent Application Laid-Open No. 147593/1983).
issue). As a result of further research, the present inventor found that it can be used for metal processing under practically assumed high shear conditions, high speed and high pressure conditions with high processing speed and large reduction ratio, and can also be used for metal processing even under severe cutting conditions. In addition, we have found a metalworking oil composition that allows easy 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 it, the lubricating oil component is protected by the protective colloidal function of the polymer compound. It maintains a relatively large particle size and is stably dispersed in water, resulting in good circulation stability.Also, when it is supplied to the metal processing section and comes into contact with the metal workpiece, the large oil particles are dispersed together with the extreme pressure agent. Forming a thick and strong lubricating film on metal workpieces, and during long-term cyclical use.
The present invention was completed based on the discovery that a large particle size can be stably maintained even against the shearing force caused by stirring in the tank and the supply circulation pump. Therefore, the present invention provides (a) one or more lubricating oil components selected from the group consisting of fats and oils, mineral oils and fatty acid esters, and (b) the following general formula ()
The molecular weight obtained by polymerizing the monomer represented by
A metal working oil composition containing an anionic water-soluble polymer compound salt of 10 million to 10 million, and a metal working oil composition containing (c) an extreme pressure agent in addition to components (a) and (b). This is what we provide. (In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 1 to 3 carbon atoms, and m and n represent numbers of 0 to 3) Component (a) of the metal rolling oil composition of the present invention Examples of lubricating oil components include mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; whale oil, beef tallow, lard, rapeseed oil, castor oil, rice bran oil,
Animal and vegetable oils such as palm oil and coconut oil; 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. Examples include esters of 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 10 to 10 million, especially 10 to 10 million.
1 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 (i) to (x). (i) Phosphoric acid, phosphorous acid or their thio or ester compounds (ii) Alkyl, alkylaryl or allyl group with 1
(iii) mono- or diphosphonic acid esters having 1 to 8 hydroxyl groups, or thio compounds thereof; (iv) mono- or diphosphonic acids having an alkyl, alkylaryl, or allyl group having 1 to 8 carbon atoms, or thio compounds thereof, or derivatives thereof; Mono- or diphosphinic acid having an alkyl, alkylaryl or allyl group having 1 to 8 carbon atoms, or a thio compound thereof or a derivative thereof (v) Mono-, di- or triphosphonic acid containing a nitrogen atom (vi) A mono- or di- or triphosphonic acid having a carbon number of 1 to 8 (vii) Thiocarboxylic acid or salt thereof having an alkyl group, hydroxyalkyl group, alkylaryl group, or hydroxyalkylaryl group having 1 to 10 carbon atoms (viii) Organometallic zinc compound (ix) ) R'(-S) _-z R' [In the formula, z is an integer of 1 to 5, R' is a carbon number of 1 to
12 alkyl, alkylaryl, or allyl group] (x) Sulfur-containing organic heterocyclic compound, salt thereof, or derivative thereof Specific examples of this extreme pressure agent include the following. Examples of (i) include orthophosphoric acid, phosphorous acid,
Examples include mono- or diphosphoric acid esters of aliphatic, alicyclic or aromatic alcohols having 1 to 8 carbon atoms and orthophosphoric acid, or thio compounds thereof, or phosphite esters of the above-mentioned alcohols, or thio compounds thereof. Ru. An example of (ii) is 2-hydroxypropyl phosphate. For (iii), the general formula

[Formula] or

[Formula] (R ₀ , R ₀ ' is an alkyl group, alkylaryl group, or allyl group having 1 to 8 carbon atoms), such as methylphosphonic acid having 1 carbon number, dimethylphosphonic acid to n having 8 carbon atoms. -octylphosphonic acid,
Di-n-octylphosphonic acid, benzylphosphonic acid, 2-ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, hydroxyethane diphosphonic acid, and these thiophosphonic acids Illustrated. Hydroxyethane diphosphonic acid is a compound represented by the following formula.

【formula】 For (iv), the general formula

[Formula] or

[Formula] (R ₀ and R ₀ ′ are the same as above) Phosphinic acid, for example, methylphosphinic acid with 1 carbon number, dimethylphosphinic acid with 8 carbon atoms
n-octylphosphinic acid, di-n-octylphosphinic acid, 2-ethylhexylphosphinic acid,
Examples include di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and these thiophosphinic acids. Examples of (v) include hexamethylphosphoric mono(or di)amide and nitrilotrismethylenephosphonic acid. Nitrilotrismethylenephosphonic acid is a compound represented by the following formula. Examples of (viii) include zinc dioctyl dithiophosphate, and examples of (ix) include octyl sulfide,
Examples of (x) include decyl disulfide and propyl trisulfide, and thiophene. The metal working oil composition of the present invention is prepared by blending each of the above components, and the amount of the lubricating oil component (a) is 99.8 to 60% of the total composition.
Weight% (hereinafter simply expressed as %), especially 99.8 to 70%,
The water-soluble polymer compound salt of component (b) is 0.1 to 20%, especially 0.1 to 10%, and the extreme pressure agent of component (c) is 0.1 to 10%, especially
0.1-5% is preferred. In addition to the above-mentioned components, various known additives such as rust preventive agents, oiliness improvers, antioxidants, etc. may be added to the metal working oil composition of the present invention, if necessary. The various additives mentioned above may be added in an amount of 0 to 2% and 0 to 20%, respectively, based on the total amount of the metal working oil composition as necessary.
%, 0 to 5%. Rust preventive agents include alkenylsuccinic acid and its derivatives, fatty acids such as oleic acid, esters such as sorbitan monooleate, and other amines; oiliness improvers include higher fatty acids such as oleic acid and stearic acid, and their Dibasic acids such as derivatives such as esters or dimer acids are used, and examples of antioxidants include phenolic compounds such as 2,4-di-t-butyl p-cresol, and aromatic amines such as phenyl α-naphthylamine. be done. 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 exhibits high lubrication performance through the action with the extreme pressure agent. In addition to providing a metalworking oil that exhibits minimal deterioration over time, it also has the following features: That is, although 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,
Since it does not have the ability to reduce the interfacial tension between water and oil and emulsify it, the lubricating oil components do not emulsify, and compared to metalworking oils that use conventional emulsifiers, they are less susceptible to dirt and oil that get mixed in during operation. It has the advantage of maintaining high lubricating properties as a metal working oil that is always clean and does not cause contaminants such as metal powder to be mixed into the metal working oil, that is, the so-called entrainment phenomenon. Also,
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 the metal-to-metal contact during machining, that is, the state of extreme pressure lubrication. The effect of extreme pressure agents that form a lubricating film on metal surfaces can be more effectively exerted, and the use of water-soluble polymer compound salts also has excellent wastewater treatment properties, making metal processing using conventional emulsifiers more effective. It has the excellent feature of creating a clean working environment, which is not found in oil. Although the mechanism of action of the water-soluble polymer compound of the present invention and the use of the extreme pressure agent has not been completely elucidated, it is thought to be roughly as follows. In other words, the water-soluble polymer compound salt completely and uniformly dissolved in the water layer adsorbs the particles of the lubricating oil component, which have become fine particles in response to mechanical shearing force, before coalescence begins, and the polymer compound salt The oil particles are made into relatively large particles by a kind of agglomeration effect, and furthermore, the large particles are stably dispersed in water by the steric and electroprotective colloidal action of the polymer compound salt. Next, an example will be given and explained. The metalworking oil compositions used in the examples are as follows. In addition, water-soluble polymer compound salts, extreme pressure agents,
The following emulsifiers were used. Water-soluble polymer compound salt (A): 2-acrylamide-
Polymer of Na salt of 2-methylpropanesulfonic acid (molecular weight 2000) Water-soluble polymer compound salt (B): 2-acrylamide-
Polymer of butylamine salt of 2-methylbutanesulfonic acid (molecular weight 100,000) Extreme pressure agent (1): Zinc phosphate extreme pressure agent (2): Triphenyl phosphite extreme pressure agent (3): Tridecyl phosphite electrode Pressure agent (4): 2-ethylhexyl acid phosphate Extreme pressure agent (5): Butylthiophosphinate Mg salt extreme pressure agent (6): Octylthiophosphinate sodium salt Extreme pressure agent (7): Thiobutyl Alcohol extreme pressure agent (8): dithioethyl zinc phosphate emulsifier: polyoxyethylene nonyl phenyl ether (HLB=7.8) antioxidant: 2,4-di-t-butyl p-cresol

【table】

【table】

[Table] Comparative product No. 1 Mineral oil 85% Oleic acid 5 Extreme pressure agent (1) 2 Triethanolamine 2 Emulsifier 5 Antioxidant 1 Comparative product No. 2 Lubricating oil ingredients Beef tallow 95% Beef tallow fatty acid 2 Emulsifier 2 Antioxidant Agent 1 Comparative product No. 3 Lubricating oil component Beef tallow 94% Beef tallow fatty acid 2 Emulsifier 2 Antioxidant 1 Extreme pressure agent (phosphate ester type) 1 Comparative product No. 4 Lubricating oil component Beef tallow 92% Beef tallow fatty acid 2 Emulsifier 2 Antioxidant 1 Extreme pressure agent (dioctylthiophosphonic acid) 3 Comparative product No. 5 Lubricating oil component Mineral oil (spirdled oil) 72% Stearic acid octyl ester 20 Oleic acid 5 Emulsifier 2 Antioxidant 1 Comparative product No. 6 Lubrication Oil component Mineral oil (spindle oil) 71% Stearic acid octyl ester 20 Oleic acid 5 Emulsifier 2 Antioxidant 1 Extreme pressure agent (phosphorus type) 1 Comparative product No. 7 Lubricating oil component Mineral oil (spindle oil) 71% Stearic acid Octyl ester 20 Oleic acid 5 Emulsifier 2 Antioxidant 1 Extreme pressure agent (8) 1 Comparative product No. 8 Lubricating oil component mineral oil (cylinder oil) 77% Pentaerythritol tetraoleate 20 Emulsifier 2 Antioxidant 1 Comparative product No. .9 Lubricating oil component Mineral oil (cylinder oil) 76% Pentaerythritol tetraoleate 20 Emulsifier 2 Antioxidant 1 Extreme pressure agent (8) 1 Example 1 Anti-seizure load test (Farex test method) Measurement of anti-seize load The test was conducted in accordance with ASTM standard D-3233 pressure load test (Falex test). The test samples were prepared by diluting each metal working oil composition with water to a concentration of 3% and stirring this with a homomixer at a rotation speed of 10,000 rpm. To apply the test sample, spray the above stirred solution at a rate of 50 ml/min (pressure: 0.5 kg/cm ² ), and at a dispersion temperature of 50 ml/min.
The coating was applied to the rotating pin at the center of the fixed block using a gear pump at ℃. The results are shown in Table 2.

[Table] Example 2 Seizure load test (Soda four-ball test method) Seizure load measurement is based on the Defense Agency provisional standard NDS
XXK2740 Oil film strength test method (Soda four-ball test method)
I followed the instructions. The test samples were prepared by diluting each metal working oil composition with water to a concentration of 3% and stirring this with a homomixer at a rotation speed of 10,000 rpm. The test sample was applied using a gear pump at a spray rate of 0.5/min (pressure: 0.5 Kg/cm ² ) and a sample solution temperature of 50°C, using the above stirring solution over three test steel balls fixed with a ball holder. The coating was applied from below to the rotating steel ball above through the space at the center of the three contact points. The results are shown in Table 3.

[Table] Example 3 Wastewater treatment test After adding 3 g of aluminum sulfate to the test solution (1) prepared in the same manner as in Example 2, it was stirred for 2 minutes, and further Ca
(OH) ₂ was added to adjust the pH to 7.0, and the mixture was stirred for 10 minutes. Then, after standing for 30 minutes, collect the subnatant liquid and COD
(KMnO ₄ method). The results are shown in Table 4.

【table】

【table】

【table】

Claims (1)

[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) a metal characterized by containing as an essential component an anionic water-soluble polymer compound salt with a molecular weight of 10 million to 10 million obtained by polymerizing a monomer represented by the following general formula () Processed oil composition. (In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 1 to 3 carbon atoms, and m and n represent numbers of 0 to 3.) 2 The amount of anionic water-soluble polymer compound salt is ,
The metalworking oil composition according to claim 1, wherein the amount is 0.1 to 20% by weight of the total composition. 3. One or more lubricating oil components selected from the group consisting of fats and oils, mineral oils and fatty acid esters,
(b) Contains an anionic water-soluble polymer compound salt with a molecular weight of 10 million to 10 million obtained by polymerizing the monomer represented by the following general formula (), and (c) an extreme pressure agent as essential components. A metal working oil composition characterized by: (In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 1 to 3 carbon atoms, and m and n represent numbers of 0 to 3.) 4 The extreme pressure agent is the following (I) to (X) The metal working oil composition according to claim 3, which is any of the compounds represented by the following. (i) Phosphoric acid, phosphorous acid or their thio or ester compounds (ii) Alkyl, alkylaryl or allyl group with 1
(iii) mono- or diphosphonic acid esters having 1 to 8 hydroxyl groups, or thio compounds thereof; (iv) mono- or diphosphonic acids having an alkyl, alkylaryl, or allyl group having 1 to 8 carbon atoms, or thio compounds thereof, or derivatives thereof; Mono- or diphosphinic acid having an alkyl, alkylaryl or allyl group having 1 to 8 carbon atoms, or a thio compound thereof or a derivative thereof (v) Mono-, di- or triphosphonic acid containing a nitrogen atom (vi) A mono- or di- or triphosphonic acid having a carbon number of 1 to 8 Thioalcohol having an alkyl group or allyl group (vii) Thiocarboxylic acid or salt thereof having an alkyl group, hydroxyalkyl group, alkylaryl group or hydroxyalkylaryl group having 1 to 12 carbon atoms (viii) Organometallic zinc compound (ix) ) R'(-S) _-z R' [In the formula, z is an integer of 1 to 5, R' is a carbon number of 1 to
12 alkyl, alkylaryl or allyl group] (x) Sulfur-containing organic heterocyclic compound or salt thereof or derivative thereof 5 The amount of the anionic water-soluble polymer compound salt is
The metalworking oil composition according to claim 3, wherein the amount is 0.1 to 20% by weight of the total composition. 6. The metalworking oil composition according to claim 3, wherein the amount of the extreme pressure agent is 0.1 to 10% by weight of the total composition.