JPH0336075B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel metalworking oil, more specifically, a metalworking oil with excellent cleanliness containing a lubricating oil component and a product obtained by the action of an acid on a polyalkyleneimine or a derivative thereof having a molecular weight of 250 or more and less than 1000. Regarding the composition. 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 metal processing department at a concentration of 1 to 20% as a mold emulsion, etc., but in the case of metal rolling, for example, rapid advances in rolling equipment and technology in recent years have led to faster rolling speeds and mass production. As a result, the requirements for rolling oil are becoming increasingly severe in terms of lubricity, circulation stability, workability, wastewater treatment, work environment, etc., and it is necessary to develop a rolling oil that can fully meet these demands. The current situation is that
However, rolling oil using conventional emulsifiers
There were various problems, and none of them were 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 metalworking oils such as press oils and cutting oils. In addition, high pressure to deform the metal during processing, resulting processing heat, moisture in the emulsion, lubricating oil components, and activated metal during processing are involved, and metal soaps and At present, so-called scum, which is a mixture of decomposition of lubricating oil components and metal powder, is generated, and it is unavoidable that it gets mixed into the emulsion. However, with metal working oil that uses an emulsifier, the scum is removed from the processing oil. These scum can be trapped in the machining oil and contaminate the machining oil, and these scum can accumulate around the machining parts, tank walls, inside piping, etc. This caused major problems such as deterioration of safety, deterioration of the working environment, and danger in terms of disaster prevention. Therefore, the present inventor conducted research to solve the above-mentioned drawbacks of conventional emulsified metal working oils, and
For fats and oils between 20 and 100℃, lubricating oil components containing wax are 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 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). Therefore, the present inventors conducted further research and found that scum generated during machining is less likely to accumulate around the machining area or get mixed into the machining oil, and also has excellent properties in terms of cleanliness of the workpiece. In addition, we have found a metalworking oil composition that can be used for metalworking under high-shear conditions and high-speed, high-pressure conditions with high working speed and high degree of workability, which are expected in practice, and which is easy to control the process such as liquid circulation stability. Completed the invention. More specifically, when a specific polyalkyleneimine or its derivative with a pH adjusted to 5.0 is used, dirt such as scum can be removed into the processing oil due to the hydrophilic effect or protective colloid function of the compound. The lubricating oil component maintains a large particle size and is stably dispersed in the water, resulting in good circulation stability.
In addition, when oil particles are supplied to the metal processing section and come into contact with the metal workpiece, the large oil particles form a thick and strong lubricating film on the metal workpiece. The present invention was completed after discovering that a large particle size can be stably maintained even against the shearing force of a supply circulation pump, and that wastewater treatment is extremely easy. That is, the present invention provides (a) one or two selected from the group consisting of fats and oils, mineral oils, and fatty acid esters.
Lubricating oil components with a molecular weight of 250 or more, and (b) a molecular weight of 250 or more.
A metalworking oil composition with excellent cleanliness, characterized by containing as an essential component one or more selected from those obtained by treating less than 1000 polyalkyleneimines or derivatives thereof with an acid. It provides: Examples of the lubricating oil component (a) of the metalworking oil composition of the present invention include mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; whale oil, beef tallow, lard, rapeseed oil, and castor oil. , 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, pentaerythol Examples include esters such as Each of these components may be used alone, or two types may be mixed and used. In addition, the polyalkyleneimine or its derivative as component (b) has a pH adjusted to 5.0 to 12.0,
Its molecular weight is in the range of 250 to 1000. The polyalkylene imine mentioned here includes polyalkylene imine having 6 or more nitrogen atoms, polypropylene imine, and the like. Furthermore, it refers to substances obtained by addition polymerization of ethyleneimine or propyleneimine to substances having active hydrogen such as alcohols, phenols, amines, and carboxylic acids, or by ammonolysis or aminolysis of dihalogenoalkanes. For example, polyethyleneimine can be easily obtained by adding ethyleneimine to polyethylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; It can also be obtained by polymerization using The polyethyleneimine obtained in this way is not a chain polyamine as shown in formula (1) below,
It is a branched compound having the skeleton of formula (2) above. −CH ₂ −CH ₂ −NH− (1) The polyalkylene imine thus obtained contains 6 or more nitrogen atoms, and the ratio of the numbers of primary nitrogen atoms, secondary nitrogen atoms, and tertiary nitrogen atoms is approximately 1:1:1 to 1, respectively. :2:1 is preferred. More preferably, the polyethyleneimine has five or more consecutive skeletons represented by the following formula (3) -CH ₂ -CH ₂ -N (3) in its molecule, and at least one of them has the above-mentioned structure. It has a skeleton shown in formula (2), in which less than 2 atoms are OH and/or NH ₂ . Furthermore, since the above-mentioned polyalkylene imine has excellent chemical reactivity similar to ordinary amines, various derivatives can be synthesized. Representative examples are shown below. (a) Reaction products with aldehydes and ketones (b) Reaction products with alkyl halides (c) Reaction products with isocyanates and thioisocyanates (d) Reactions with substances having active double bonds Products (e) Reaction products with epihalohydrins (f) Reaction products with cyanamides, guanidines, urea, etc. (g) Reaction products with carboxylic acids, acid anhydrides, acyl halides, etc. Also, these polyalkylene imines Organic acids and inorganic acids are used as the acid to act on the compound or its derivative. These include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and boric acid; lower fatty acids such as formic acid, acetic acid, and propionic acid; organic acids such as organic hydroxyl acids such as hydroxyacetic acid and hydroxypropionic acid; and the following () to (). The organic or inorganic phosphoric acid compounds shown in can be mentioned, but the use of regulators other than these is not prohibited. Among these PH regulators, phosphoric acid compounds represented by the following () to () are preferred. (i) Phosphoric acid, phosphorous acid or their thio or ester compounds (ii) Alkyl, alkylaryl or allyl group with 1
Mono- or di-phosphoric acid esters having 1 or more hydroxyl groups or thio compounds thereof (iii) Mono- or di-sulfonic acids having an alkyl, alkylaryl or allyl group having 1 to 8 carbon atoms or their thio compounds or derivatives thereof (iv) Mono- or disulfinic 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 Specific examples of this phosphoric acid compound include: The following are examples. Examples of (i) include orthophosphoric acid, phosphorous acid, mono- or diphosphoric acid esters of aliphatic, alicyclic or aromatic alcohols having 1 to 8 carbon atoms and orthophosphoric acid, or thio compounds thereof; Examples include phosphorous acid esters with the above alcohols or thio compounds thereof. An example of (ii) is 2-hydroxypropyl phosphate. For (iii), the general formula

[Formula] or

[Formula] Phosphonic acid represented by (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
Examples include -ethylhexylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, hydroxyethane diphosphonic acid, and these thiophosphonic acids. Hydroxyethane diphosphonic acid is a compound represented by the following formula.

【formula】 For (iv), the general formula

[Formula] or

Phosphinic acid represented by the formula (R ₀ and R′ ₀ are the same as above), such as methylphosphinic acid with 1 carbon number, dimethylphosphinic acid, n-octylphosphinic acid with 8 carbon atoms, di-n- Octylphosphinic acid, 2-ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and these thiophosphinic acids Illustrated. Examples of (v) include hexamethylphosphoric mono(or di)amide and nitrilotrismethylenephosphonic acid. Nitrilotrismethylenephosphonic acid is a compound represented by the following formula. When acid acts on polyalkylene imine,
The acid is preferably used so that the pH of the system is 5-12. The metal working oil composition of the present invention containing the above components has a lubricating oil component of 99.9 to 50% by weight (hereinafter expressed as %), particularly 99.9 to 70%, polyalkyleneimine or its derivative 0.1 to 20%, especially 0.1%. It is preferable to mix it so that it becomes -10%. In addition to the above-mentioned components, the metal working oil composition of the present invention with excellent cleanliness may contain various known additives, such as rust inhibitors, oiliness improvers, extreme pressure agents, antioxidants, surfactants, etc. Agents etc. can also be added. The various additives mentioned above may be added in an amount of 0 to 2%, 0 to 20%, and 0%, respectively, based on the total amount of the rolling oil composition as necessary.
It can be added at a rate of ~3%, 0-5%, and 0-3%. 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 esters or dimer acids which are derivatives, phosphorus compounds such as triphenyl phosphite and organometallic compounds such as zinc dialkydithiophosphate are used as extreme pressure agents, and organic metal compounds such as zinc dialkydithiophosphate are used as antioxidants. ,2,
Phenol compounds such as 4-di-t-butyl p-cresol, aromatic amines such as phenyl α-naphthylamine, etc. Furthermore, as surfactants, polyoxyethylene alkyl having an HLB in the range of 3.0 to 20.0, or Nonionic interfaces such as polyoxyethylene alkyl allyl ether, sorbitan esters, or derivatives thereof, glycerin monofatty acid ester, oxyethylene oxypropylene block polymer, alkyl amine, or ethylene diamine with ethylene oxide, or propylene oxide and ethylene oxide added. Examples include active agents, fatty acid soaps, anionic surfactants such as metal salts of alkylsulfonic acids, and amphoteric surfactants having an amino group and a carboxyl group. The metalworking oil composition of the present invention with excellent cleanliness can be prepared by simply mixing the above components at the time of use, or by preparing it as a solution with a water content of up to 80%.
It is used by diluting it with water. The thus obtained metalworking oil composition of the present invention with excellent cleanliness provides a stable particle size distribution with a relatively large particle size under stirring conditions with high shear force, has high lubrication performance, and has a low change over time. In addition to providing a metalworking oil with low oxidation, it also has the following features: That is, the polyalkyleneimine or its derivative used in the present invention itself has the ability to quickly adsorb to liquids and solid particles and make them hydrophilic.
Since water does not have the ability to lower the interfacial tension of oil and emulsify it, the lubricating oil components do not emulsify, and compared to metalworking oils that use conventional emulsifiers, they are less likely to be contaminated with oil or metals mixed in during operation. It has the advantage of maintaining high lubricating properties as a constantly clean metal working oil with little occurrence of the so-called entrapment phenomenon of foreign particles such as powder. In addition, due to the functions of the above components, it has excellent cleanliness against deposits of foreign substances such as dirty oil and metal powder, improves the dirtiness of the working environment, and has excellent wastewater treatment properties, making it more effective than conventional It has the excellent feature of creating a clean working environment, which is not found in metalworking oils that use emulsifiers. Although the function of the composition of the present invention, particularly the use of polyalkyleneimine or its derivatives, has not been completely elucidated, it is thought to be roughly as follows. In other words, polyalkyleneimine or its derivatives uniformly dissolved in the water layer quickly adsorbs dirt such as dirt oil and metal powder, makes the surface hydrophilic, and also acts as a steric and electrically protective colloid. The dirt can be stabilized as particles, and furthermore, can be brought into a fluid state by these actions, so that these stains can be easily moved by slight mechanical force, such as liquid flow rate, spray pressure, etc. As a result, it is thought that the dirt accumulated around the processing area, on the tank wall, inside the pipes, etc. can be easily removed. In this case, from the viewpoint of densely covering the particle surface, polyalkyleneimine or a derivative thereof having a relatively low molecular weight in the range of 250 or more and less than 1000 is preferable. On the other hand, similar to the mechanism for these dirt components, particles of the lubricating oil component, which have been made into fine particles in response to mechanical shearing force on the lubricating oil component, are adsorbed before coalescence begins, and the polymer compounds of the lubricating oil component are The oil particles are formed into large particles by a type of aggregation, and the large particles are stably dispersed in water by the steric and electroprotective colloidal effects of the polymer compound. In the case of the water-soluble anionic polymer compound disclosed in JP-A No. 55-147593, it has a weak aggregation effect on oil particles, so it is stabilized as a protective colloid as a fine particle, and once the oil has been refined, it becomes This is different from not being able to recover particles into larger particles. Next, an example will be given and explained. The metalworking oil compositions used in the examples are as follows. The following were used as polyethyleneimine, antioxidant, extreme pressure agent, surfactant, fatty acid ester, and emulsifier. Polyethyleneimine: (1) Polyethyleneimine with a molecular weight of 250 is treated with phosphoric acid.
PH = 7.0 (2) Polyethyleneimine with a molecular weight of 250 and ethylphosphonic acid with PH = 6.0 (3) Polyethyleneimine with a molecular weight of 250 with butylphosphinic acid with PH = 8.5 (4) Molecular weight 300 (5) Polyethyleneimine with a molecular weight of 300 and butyraldehyde added in an amount of 10% by weight based on the polyethyleneimine.
(6) A polyurea reaction product of polyethyleneimine with a molecular weight of 300 and myristyl isocyanate in an amount of 5% by weight based on the polyethyleneimine was reacted with phosphoric acid to a pH of 8.0. 8.5 (7) Polyethyleneimine with a molecular weight of 600 adjusted to pH=10 with 2-ethylhexyl acid phosphate (8) Polyethyleneimine with a molecular weight of 600 adjusted to PH=10 with phosphoric acid
(9) Polyethyleneimine with a molecular weight of 600 and PH = 8.0 with hydroxyethane diphosphonic acid (10) Polyethyleneimine with a molecular weight of 600 and PH = 6.0 with nitrilotrismethylenephosphonic acid (11) ) Polyethyleneimine with a molecular weight of 600 adjusted to PH=6.0 with hydroxyacetic acid (12) Polyethyleneimine with a molecular weight of 600 adjusted to PH=6.0 with boric acid
= 9.0 (13) Polyethyleneimine with a molecular weight of 300 is reacted with acetic anhydride to give a concentration of 50% by weight to the polyethyleneimine, and the pH is adjusted to 7.0 with phosphoric acid (14) Polyethyleneimine with a molecular weight of 900 is reacted with hydroxyethane diamine. PH = 8.5 with phosphonic acid Antioxidant; 2-4-di-t-butyl-p-cresol extreme pressure agent; Triphenyl phosphite surfactant (1); Polyoxyethylene nonyl phenyl ether ( HLB=10.6) Surfactant (2); Oxyethylene oxypropylene block polymer (wt% of ethylene oxide
= 40%, molecular weight ≒ 2500) Surfactant (3); 5 moles of ethylene oxide added to laurylamine Fatty acid ester; Emulsifier in 2-ethylhexyl stearate comparative example; Polyoxide ethylene nonyl phenyl ether (HLB = 7.6 )

【table】

【table】

【table】

【table】

[Table] Comparative product No. 1 Lubricating oil ingredients Beef tallow 95% Beef fatty acid 2 Emulsifier 2 Antioxidant 1 Comparative example No. 2 Lubricating oil ingredient Beef tallow 94% Beef fatty acid 2 Extreme pressure agent 1 Emulsifier 2 Antioxidant 1 Comparison Product No. 3 Lubricating oil component Mineral oil (cylinder oil) 77% Pentaerythritol tetraoleate 20 Emulsifier 2 Antioxidant 1 Comparative product No. 4 Lubricating oil component Mineral oil (cylinder oil) 76% Pentaerythritol tetraoleate 20 Pole Pressure agent 1 Emulsifier 2 Antioxidant 1 Comparative product No. 5 Lubricating oil component Mineral oil (spindle oil) 72% Stearic acid octyl ester 20 Oleic acid 5 Emulsifier 2 Antioxidant 1 Comparative product No. 6 Lubricating oil component Mineral oil ( Spindle oil) 71% Stearic acid octyl ester 20 Oleic acid 5 Extreme pressure agent 1 Emulsifier 2 Antioxidant 1 Example 1 Cleanliness test To prepare the test sample, dilute each metalworking oil composition with water to a 3% concentration. This was carried out by stirring at 10,000 rpm for 60 minutes using a homomixer at a temperature of 60°C. In the cleanliness test, 5 g of cold-rolled oil scum was uniformly applied to a surface-cleaned steel plate (70 x 100 x 0.2 mm), and the above dispersion was sprayed onto the scum-coated plate (pressure 1.0 Kg/cm ² ). I did it. The cleanliness was evaluated by visual inspection, with 5 being the most heavily contaminated surface with almost no scum removed from the surface, and 1 being the most heavily contaminated surface with almost no scum removed. A stepwise comparison method was used.

【table】

[Table] Example 2 Anti-Seizure Load Test (Farex Test Method) The anti-seizure load was measured in accordance with ASTM standard D-3233 pressure load test (Farex 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°C.
The coating was applied to the rotating pin at the center of the fixed block using a gear pump under these conditions. The results are shown in Table 3.

【table】

[Table] Example 3 Seizure load test (Soda four-ball test method) Seizure load measurement is based on the Defense Agency provisional standard.
It was conducted according to the NDSXXK2740 oil film strength test method (Soda four-ball test method). 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, use a gear pump to spray the above stirred solution at a spray rate of 0.5/min (pressure: 0.5 kg/cm ² ) and a sample solution temperature of 50°C.
3 from below the 3 test steel balls fixed with ball holders
The coating was applied to the rotating steel ball above through the center space of each contact point. The results are shown in Table 4.

[Table] Example 4 Particle size measurement To prepare the test sample, each metal working oil composition was diluted with water to a concentration of 3%, the temperature was set to 60°C, and the mixture was stirred for 60 minutes at 10,000 rpm using a homomixer. That's what I did. The particle size of the test sample was measured by the Coulter counter method using a 200 μm aperture. The results are shown in Table 5.

[Table] *Difficult to measure due to separation of oily substances.
Example 5 Wastewater treatment test After adding ±3 g of bread sulfate to the test solution (1) prepared in the same manner as in Example 2, the mixture was stirred for 2 minutes, and 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 6.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (a) one or more lubricating oil components selected from the group consisting of fats and oils, mineral oils, and fatty acid esters; and (b) polyalkyleneimine or derivatives thereof having a molecular weight of 250 or more and less than 1000. A metalworking oil composition with excellent cleanliness, characterized in that it contains as an essential component one or more selected from those obtained by reacting with an acid. 2. The metalworking oil composition with excellent cleanliness according to claim 1, wherein the polyalkyleneimine is polyethyleneimine. 3 The amount of polyalkyleneimine in the lubricating oil component
The metal working oil composition with excellent cleanliness according to claim 1, wherein the amount is 0.1 to 20% by weight.