JPS59227988A - Metal working oil composition with high detergency - Google Patents

Abstract

PURPOSE:To provide the titled compsn. contg. a lubricating oil component and a specified PH-adjusted polyalkyleneimine, which prevents buildup of scum and its migration into working oil, is useful for high-speed and high-pressure metal working and has excellent circulation stability, etc. for easier process control. CONSTITUTION:The metal working oil compsn. contains as essential ingredients (A) a lubricating oil component selected from among oil, fat, mineral oil and fatty acid ester, (B) polyalkyleneimine (deriv.) with an MW of 250-1,000 adjusted to a PH of 5.0 by the use of an acid. By hydrophilic action of the PH- adjusted polyalkyleneimine or by its performance as protective colloid, working oil is prevented against entrapment of scum and has high detergency upon deposited scum. Furthermore, the lubricating oil component is dispersed in water under a stabilized condition in a large particle diameter and oil particles with a large diameter form a thick and strong lubricating film on metal workpieces. The large particle diameter is maintained consistently over a long period of recycle use and disposal of waste water is accomplished quite readily.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel metalworking oil, more specifically, a cleaning oil containing a lubricating oil component and a polyalkyleneimine having a molecular weight of 250 or more and less than 1000 or a derivative thereof, which is obtained by the action of an acid. The present invention relates to a metal working oil composition with excellent properties.

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 supplied to the metal processing department at a concentration of 1 to 20% as a 0/W type emulsion using an emulsifier. With the advent of high-speed, mass production, the requirements for rolling oil are becoming increasingly severe in terms of lubricity, circulation stability, workability, wastewater treatment, working environment, etc., and we are fully meeting these demands. Currently, there is a need for the development of a rolling oil that can do this. 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, causing 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.
With long-term use, Pfril'l scum is formed, which is a mixture of metallic soap, decomposed products of lubricating oil components, etc., and metal powder.
Currently, it is unavoidable that scum be mixed into the emulsion, but metalworking oils that use emulsifiers can cause scum to be trapped in the oil and contaminate the oil. This can cause serious problems such as contamination of processing oil, deterioration of work efficiency, deterioration of work environment, and danger in terms of disaster prevention as these scum accumulates around processing parts, tank walls, and inside piping. It was occurring.

Therefore, the present inventor conducted research to solve the above-mentioned drawbacks of conventional emulsified metal working oils.
Using a specific hydrophilic dispersant (water-soluble anionic polymer compound), a lubricating oil component containing fat or wax at ℃
We succeeded in improving the above drawback by stably suspending and dispersing in water in a solid state below the melting point, and becoming unstable when feeding it to the processing section, that is, above the melting point. A patent application was filed in
No. 593).

Therefore, the present inventors conducted further research and found that the scum generated during machining does not accumulate around the machining area or get mixed into the machining oil (in addition, it has excellent properties for cleaning the workpiece). shows,
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 processing speed and high degree of processing, which are expected in practice, and which is easy to control the process such as liquid circulation stability, and the present invention completed.

More specifically, when using a specific polyalkylene, imine, or a derivative thereof whose pH has been adjusted to 50, dirt such as scum can be absorbed into 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 water, resulting in good circulation stability. If it comes into contact with the workpiece, large oil particles will spread thickly onto the metal workpiece.
Furthermore, during long-term circulation use, the large particle size can be stably maintained even against the shearing force of the tank agitation and supply circulation pump, and wastewater treatment is extremely easy. and so on, and completed the present invention.

That is, 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 (+3) a polyalkyleneimine or a derivative thereof having a molecular weight of 250 or more and less than 1000. The present invention provides a metal working oil composition with excellent cleanliness, which is characterized by containing as an essential component one or more selected from those obtained by the action of an acid.

Examples of the lubricating oil component (a) of the metalworking oil composition of the present invention include mineral oils such as spindle oil, press oil, turbine oil, and cylinder oil; whale oil, beef tallow, liver fat, rapeseed oil, and castor oil. , animal and vegetable oils such as bran oil, palm oil, coconut oil: ethylene glycol, fatty acids obtained from beef tallow, coconut oil, palm oil, castor oil, etc. and aliphatic monohydric alcohols having 1 to 22 carbon atoms. neopendel alcohol,
Examples include esters with pentaerythritol and the like. Each of these components may be used alone, or two types may be mixed and used.

The polyalkylene imine or its derivative as component (b) has a pH adjusted to 5.0 to 120, and a molecular weight in the range of 250 to 1,000.

The polyalkyleneimine mentioned here has 6 nitrogen atoms.
Examples include polyethyleneimine, polyalkyleneimine, and the like. Furthermore, substances with active hydrogen such as alcohols, phenols, amines, and carboxylic acids,
It is obtained by addition polymerization of ethyleneimine or propyleneimine, or by ammonolysis or amitrilysis 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 thus obtained is not a chain polyamine as represented by the following formula (1) (but is a branched compound having the skeleton of the above formula (2)).

-CH2-CH,, -NH- (1) The polyalkylene imine thus obtained contains 6 or more nitrogen atoms, and the number of primary nitrogen atoms, secondary nitrogen atoms and tertiary nitrogen atoms is The ratio of each is approximately 1:
Preferably, the ratio is in the range of 1:1 to 1:2:1.

More preferably, the polyethyleneimine has five or more consecutive skeletons shown in the following formula (3) in the molecule, and among them,
One or more of them has the skeleton shown in the above formula (2), and the terminal is OH and/or NH2.

Furthermore, the above-mentioned poly-alkyleneimine has excellent chemical reactivity similar to ordinary amines, and various derivatives can be synthesized from it. Representative examples are shown below.

(a) Reaction products with aldehydes and ketones (b
) Reaction products with alkyl halides (C) Reaction products with incyanates and thioisocyanates (d) Reaction products with active double bonds (
e) Reaction products with epihalohydrins (f)
Reaction products (g) with cyacamides, guanidines, urea, etc. Reaction products with carboxylic acids, acid anhydrides, acyl halides, etc. Also, as acids to act on these polyalkylene imines or their derivatives, organic acids, inorganic acids, etc. Acid is used. 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 (1) to ( The organic or inorganic phosphoric acid compounds shown in v) can be mentioned, but the use of other regulators is not prohibited. Among these pH adjusters, phosphoric acid compounds represented by the following (1) to (■) are preferred.

(1) Phosphoric acid, phosphorous acid, or thio or ester compounds thereof (11) Mono- or syringic acid esters having one or more hydroxyl groups in alkyl, alkylaryl, or allyl groups, or thio compounds thereof (iii) Number of carbon atoms: 1 Mono- or diphosphonic acid having ~8 alkyl, alkylaryl or allyl groups, or thio compounds thereof or derivatives thereof (1v) having 1 to 1 carbon atoms
Mono- or di- or di-phosphinic acids having 8 alkyl, alkylaryl or allyl groups or their thio compounds or their derivatives (v) Mono- or di- or tri-phosphonic acids containing a nitrogen atom Specific examples of the phosphoric acid compounds are as follows: is exemplified. Examples of (1) include orthophosphoric acid, phosphorous acid, aliphatic or alicyclic acids having 1 to 8 carbon atoms, or aromatic alcohols and orthophosphoric acid, mono- or G-syphosphoric acid esters, or thiosulfuric acid esters thereof. Examples include thio compounds such as G′i, a sulfurous acid ester with the above-mentioned alcohol, or a thio compound such as G′i. (1
Examples of 1) include 2-hydroxypropyl phosphate, which is a phosphonic acid represented by a ru group, an alkylaryl group, or an aryl group, such as methylphosphonic acid having 1 carbon atom, dimethylphosphonic acid having 8 carbon atoms, and n- Octylphosphonic acid, Moro-octylphosphonic acid, Benzylphosphonic acid, 2-ethylhexylphosphonic acid, Di-2-ethylhexylphosphonic acid, Dibenzylphosphonic acid, Phenylphosphonic acid, Diphenylphosphonic acid, 1-hydroxyethane diphosphonic acid Examples include acids and these thiophosphonic acids. Hydroxyethane diphosphonic acid is a compound represented by the following formula.

OCH30 II I II HO-P -C-P -OH 1l OHOHOH Phosphinic acid, such as methylphosphinic acid with 1 carbon number, dimethylphosphinic acid to 8σ] n-octylphosphinic acid, di-n-octylphosphinic acid, 2 Examples include -ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and these thiophosphinic acids. (
As for v), hexamethylphosphoric mono(
Or, nitrilotrismethylenephosphonic acid is a compound represented by the following formula, exemplified by diamide and nitrilotrismethylenephosphonic acid.

0I■ When an acid is applied to the polyalkylene imine, it is preferable to use the acid so that the pH of the system becomes 5 to 12.

The metal working oil composition of the present invention containing the above components has a lubricating oil component of 999 to 50% by weight (hereinafter referred to as "part"), particularly 999 to 50% by weight of the lubricating oil component.
99-70, polyalkyleneimine or its derivative 0
It is preferable to mix the oil composition in an amount of 1 to 20%, particularly 0.1 to 10%. In addition to the above-mentioned components, the metal working oil composition of the present invention with excellent cleanliness may contain various known components as needed. Additives such as rust preventive agents, oiliness improvers, extreme pressure agents, antioxidants, surfactants, etc. may also be added. The above various additives may be added to the total amount of the rolling oil composition as necessary. 0-2 staff, 0-20 staff, 0-3 chi, 0-5
%, 0 to 3%.

Rust inhibitors include alkenylcono-phosphates and their 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 its derivatives such as esters or dibasic acids such as dimer acids; as extreme pressure agents, phosphorus compounds such as triphenyl phosphite; and organometallic compounds such as zinc dialkyldithiophosphate; as antioxidants ,2,4
- Phenol compounds such as di-t-butyl p-cresol, aromatic amines such as phenyl α-naphthylamine, etc. Furthermore, as surfactants, HLB is 30 to 20.
Polyoxyethylene alkyl in the range of 0, or polyoxyethylene alkyl allyl ether, sorbitan esters, or derivatives thereof, chunonoserine monofatty acid ester, oxyethylene oxypropylene block polymer, alkyl amine, or ethylene diamine with ethylene oxide, or propylene oxide and ethylene oxide. Examples include nonionic surfactants such as σ), anionic surfactants such as fatty acid soaps and metal salts of alkylsulfonic acids, and amphoteric surfactants having an amine 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 a concentrated solution with a water content of up to 80% and diluting it with water at the time of use. used by

The thus obtained metalworking oil composition of the present invention (σ-) with excellent cleanliness has a relatively large particle size and stable particle size distribution under stirring conditions with high shear force, and has high lubrication performance. In addition to providing a processing oil with little change over time, it also has the following features.

That is, although 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, it emulsifies by lowering the interfacial tension between water and oil. Because it does not have the ability to emulsify the lubricating oil components, compared to metalworking oils that use conventional emulsifiers, it is less likely to trap dirt, oil, metal powder, and other impurities that get mixed in during operation. It has the advantage of maintaining high lubrication properties as a metalworking oil that is always clean and has little clogging. In addition, due to the functions of the above ingredients, it has excellent cleanliness against deposits of dirt and foreign substances such as oil and metal powder, improves the dirtiness of the working environment, and has excellent wastewater treatment properties. It has the excellent feature of realizing 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:
Polyalkyleneimine or its derivatives uniformly dissolved in the water layer quickly adsorbs dirt such as oil and metal powder, making the surface hydrophilic, and also acts as a steric and electrically protective colloid. These stains can be stabilized as particles, and furthermore, can be brought to a state where they are produced, making it possible to easily move these stains with a 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 made into thick particles by a kind of aggregation, and the large particles are stably dispersed in water by the steric and electrically protective colloidal action of the polymer compound. In the case of the water-soluble anionic polymer compound disclosed in JP-A No. 55-147593, the agglomerating effect on oil particles is weak, so the fine particles are stabilized as protective colloids, and once the oil particles are 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: (]) Polyethyleneimine with a molecular weight of 250 is purified with phosphoric acid.
H = 7.0 (2) Polyethyleneimine with a molecular weight of 250 adjusted to pH = 6.0 with ethylphosphonic acid (3) Molecular weight 25
pH = 0 polyethyleneimine with butylphosphinic acid
(4) Polyethyleneimine with a molecular weight of 300 was diluted with diethyl acid phosphate to pH = 9.
．． (5) Polyethyleneimine with a molecular weight of 3'QIO is reacted with butyraldehyde to give a concentration of 10% by weight based on the polyethyleneimine, and the pH is adjusted to 80 with phosphoric acid.(6) Myristyl is added to polyethyleneimine with a molecular weight of 300. A polyurea reaction product containing 5% by weight of isocyanate based on polyethyleneimine was adjusted to pH=5 with phosphoric acid.
(7) Polyethyleneimine with a molecular weight of 600 was adjusted to pH 85 with 2-ethylhexylua/radphosphate.
= 10 (8) Polyethyleneimine with a molecular weight of 600 is purified with phosphoric acid.
(9) Polyethyleneimine with a molecular weight of 600 was adjusted to pH = 8.0 with hydroxyethane diphosphonic acid (lO) Polyethyleneimine with a molecular weight of 600 was adjusted to pH = 6.0 with nitrilotrisnotylenephosphonic acid. (1) Polyethyleneimine with a molecular weight of 600 was adjusted to pH = 6.0 with hydroxyacetic acid (12) Polyethyleneimine with a molecular weight of 600 was adjusted to pH = 6.0 with boric acid.
(13) Polyethyleneimine with a molecular weight of 300 was reacted with acetic anhydride to give a concentration of 50% by weight to the polyethyleneimine, and the pH was adjusted to 7.0 with phosphoric acid (14) Polyethylene with a molecular weight of 900 Imine adjusted to pH=8.5 with hydroxyethane diphosphonic acid; Antioxidant; 2,4-di-t-butyl-p-cresol extreme pressure agent; Triphenylbosphite surfactant (1); Polyoxy Ethylene nonyl phenyl ether (HLB=IO,6) surfactant (3)
; Fatty acid ester obtained by adding 5 moles of ethylene oxide to laurylamine; Emulsifier in 2-ethylhexyl stearate comparative example; Polyoxyethylene nonylphenyl ether (HLB-7, 6) Table 1-] Table (H) Table 2 (%) Table 1-3 (%) Comparative product name 1 Lubricating oil component Beef tallow 95% beef tallow fatty acid 2 Emulsifier 2 Antioxidant 1 Comparative product A2 Lubricating oil component Beef tallow 94% Beef tallow fatty acid 2 Extreme pressure Agent 1 Emulsifier 2 Antioxidant 1 Comparative product A3 Lubricating oil component Mineral oil (cylinder oil) 77% Emulsifier 2 Antioxidant 1 Comparative product/164 Lubricating oil component Mineral oil (Cylinder oil 76 Thipentaeris 1
Tan-Lutetra 2゜oleate extreme pressure agent] Emulsifier 2 Antioxidant 1 Comparative product A5 Lubricating oil component Mineral oil (spindle oil) 72% stearic acid octyl ester 20 Oleic acid
5 Emulsifier 2 Antioxidant l Comparison product store 6 Lubricating oil component mineral oil (spindle oil) 7゛1% stearic acid octyl ester 20 Oleic acid
5 Extreme pressure agent 1 Emulsifier 2 Antioxidant □ Example 1 To prepare the cleanliness test sample, each metalworking oil composition was diluted with water to a concentration of 3 parts, brought to a temperature of 60°C, and homogenized. This was done by stirring with a mixer at 10.00 rpm for 60 minutes. The cleanliness test was conducted using a surface-cleaned steel plate (70 x 10
0x0.2 mm) uniformly coated with cold rolling oil scum 57
Spray the above dispersion onto this scum coated plate (
The pressure was 1.0 kq/cni).

The cleanliness was evaluated by visual inspection, with 5 being the most heavily contaminated surface with almost no scum removed from the surface, and J being the most heavily contaminated surface with almost no scum removed. A stepwise comparison method was used.

Table 2 Example 2 Seizing resistance load test (Falex test method) The seizing resistance was measured in accordance with ASTM standard D-3233 pressure load test (Falex test). Preparation of the test sample is
Each metal working oil composition was diluted with water to a concentration of 3.5 L, and this was stirred using a homomixer at a rotational speed of 10.00 rpm. To apply the test sample, spray the above stirred solution in an amount of 50 ml for 11 minutes (pressure 0.5 ky/c).
nI), a gear pump was used at a dispersion temperature of 50° C., and the dispersion was applied to a rotating pin at the center of a fixed block.

The results are shown in Table 3.

Table 3 Example 3 Seizure load test (Soda four-ball test method Seizure load measurement is based on Defense Agency provisional standard NDSXXK274
The test was conducted according to the 0 oil film strength test method (Soda four-ball test method). To prepare the test samples, each metalworking oil composition was diluted with water to a concentration of 3 parts, and mixed with a homomixer at a rotational speed of 1.
This was done by stirring at 0.00 rpm. The test sample was applied using a gear pump at a spray amount of o5ti (pressure: 05kg101) and a sample solution temperature of 50°C, and applied to three test steel balls from the bottom fixed with a ball holder. The method was to apply it to the two rotating steel balls through the space between them at the point of contact.

The results are shown in Table 4.

Table 4 Example 4 To prepare the sample for particle size measurement, each metal working oil composition was diluted with water to a concentration of 3%, the temperature was 60°C, and a homomixer was used at a rotation speed of 10.00 rpm for 60 minutes. This was done by stirring. The particle size of the test sample was measured using the Coulter counter method, with a diameter of 200 μm. - It was carried out using char.

The results are shown in Table 5.

Table 5 * Difficult to measure due to separation of oily substances.

Example 5 Wastewater treatment test After adding sulfuric acid bread earth 3y' to the test liquid (lt) prepared in the same manner as in Example 2, it was stirred for 2 minutes, and then Ca(OH)2 was added to adjust the pH to 7. The mixture was stirred for 10 minutes. Next, after standing still for 30 minutes, the subnatant liquid was collected and COD (KMnO4
method) was measured.

The results are shown in Table 6.

Table 6 Procedural Amendment (Voluntary) 6 July 22, 1980 Kazuo Wakasugi, Director General of the Patent Office1, Disclosure of the Case, Patent Application No. 103629 of 19882, Concerned about the cleanliness of the name of the invention Metalworking oil composition 3, relationship to the amended person case Applicant address 1-14-1o, Kayabacho, Nihonbashi, Chuo-ku, Tokyo Name (091) Kao Soap Co., Ltd. Representative Maru 1) Yoshibe Address 1-1-2-4 Marunouchi, Chiyoda-ku, Tokyo, Agent address: 113-go, Nihonbashi Ningyocho, Chuo-ku, Tokyo (10
3) The application to be amended, the content of the amendment, "(Patent application pursuant to the proviso to Article 38 of the Patent Act)" written on page 1 of the application, and the addition of " The statement "Number of inventions 2" is deleted.

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 (
1)) Cleanliness characterized by containing as an essential component one or more selected from those obtained by reacting acid with polyalkyleneimine or its derivatives having a molecular weight of 25 or more and less than 1000. Excellent metalworking oil composition. 2. A metalworking oil composition with excellent cleanliness according to claim 1, wherein the polyalkyleneimine is polyethyleneimine. 3 The amount of polyalkyleneimine is 01 to 2 of the lubricating oil component.
The metal working oil composition with excellent cleanliness according to claim 1, which has a weight coefficient of 0.