JPS59227980A - 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 water-sol. macromolecular compd. as essential ingredients, which has excellent circulation stability and lubricating properties, undergoes little changes with time and shows minimized entrapment of foreign substances. 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) at least one water-sol. macromolecular compd. selected from among cationic or amphoteric addition polymer, ring-opened polymer, polycondensate and natural polymer deriv. (B) are, e.g., phosphate of diethylaminoethyl methacrylate polymer, ring-opened polymer of ethyleneimine phosphate, epihalohydrin/amine polycondensate and cation-modified cellulose.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel metal working oil composition, more specifically, a novel metal working oil composition that is suitable for plastic working, cutting, grinding, etc. of metal containing a lubricating oil component and a water-soluble cationic polymer compound. The present invention relates to a metalworking oil composition useful as a lubricant during processing.

Conventionally used oil-based lubricants for the plastic working, cutting, and grinding of metals can be applied directly to the lubricated parts, or they can be emulsified by emulsifying the lubricant in water at a predetermined concentration using an emulsifier such as a surfactant. It is applied to the surface of the workpiece during processing. In other words, a liquid lubricant [F agent is characterized by the fact that it obtains a lubricating effect by depositing oil-based lubricating component particles emulsified with a surfactant or the like on the surface of the workpiece.Especially when water is used, A liquid lubricant used in the form of an emulsion is advantageous because of its cooling effect on heat generated during machining of a workpiece, and its economic efficiency due to the circulating use of the emulsion.

However, on the other hand, the use of surfactants as emulsifiers improves the stability of the emulsion (a).

Intermediate) Contamination such as metal powder and scum generated during metal processing is mixed into the emulsion.

(／→　Contamination of the surface of the workpiece due to these stains.

2) Decreased surface J load capacity of the contact lubricated surface of metal due to a decrease in the amount of lubricant emulsion particles that adhere to the surface of the workpiece due to the attempt to stabilize emulsification.

餠) Wastewater treatment properties of emulsions.

etc., it had some drawbacks in terms of emulsion management.

Therefore, after processing, a beautiful surface condition with no contamination of the surface of the workpiece due to lubricating oil, etc. can be obtained, and there is no contamination of metal powder, lubricant deterioration products, etc., or in other words, contamination is not entrained into the system. As a result, it is desired to develop a metalworking oil that does not contaminate the workpiece due to dirt, but at present no excellent lubricant having these effects has yet been found.

Therefore, the present inventors carried out sharpening and polishing in order to provide a metal working oil that eliminates the above-mentioned drawbacks of conventional emulsified lubricants using oily components. As a result, the inventors have discovered that the above object can be achieved by using a composition containing a specific cationic or amphoteric water-soluble polymer compound together with an oily lubricating oil component, and have completed the present invention.

That is, the present invention provides (a) one or more lubricating oil components selected from the group consisting of oils and fats, mineral oils, and fatty acid esters, and (b) containing nitrogen atoms in molecules with a molecular weight of 10 to 10 million. Metalworking oil containing as an essential component one or more water-soluble polymer compounds selected from cationic or zwitterionic addition polymers, ring-opening polymers, polycondensates, or natural polymer derivatives. A composition is provided.

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, cow's finger, liver fat, and rapeseed oil; Animal and vegetable oils such as castor oil, bran oil, palm oil, and coconut oil; fatty acids obtained from beef tallow, coconut oil, palm oil, and castor oil; aliphatic monohydric alcohols having 1 to 22 carbon atoms; ethylene glycol; Examples include esters with hentyl alcohol, pentaerythritol, etc. Each of these components may be used alone, or two types may be mixed and used. .

In addition, it is essential that the water-soluble polymer compound of component (b) contains a basic nitrogen atom or a cationic nitrogen atom;
Furthermore, the molecule may contain groups such as carboxylate, sulfonate, amide, and ester (for example, the following groups may be included).

(a) Homopolymers of salts or quaternary ammonium salts of nitrogen-containing monomers represented by the following general formulas (1) to (■), or copolymers of two or more thereof.

R1 [In the formula, A is 10- or -+"JH-, +1. is 1-
Indicates an integer of 3, 8 is H or CH3, R2 and Mr. H
lCl-+3 or C,, I-1, is not shown] R8 [In the formula, R2, R3, and nl are the same as in the formula (1)] 1 [In the formula, R is the same as in the formula (1). The substitution position of pyridine is 2
or 4th position] R1 [In the formula, R1 and horse are the same as in formula (I). The substituent position of piperidine is the 2 or 4 position] R1 [In the formula, R2 and R3 are the same as in the formula (1)] Specific examples of these monomers include dimethylamine ethyl acrylate of the formula (1) 1-, diethylaminoethyl acrylate, dimethylaminoethyltuacrylate, diethylaminoethylmethacrylate-1, dimethylaminepropylacrylamide, diethylaminepropylacrylamide/dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide, etc.; dimethylamino of formula (It) Methylethylene, diethylaminomethylethylene, dimethylamine methylpropene, diethylaminomethylpropene, etc.; vinylpyridine of formula (ill), etc.; vinylpiperidine of formula q'111), vinyl-N-methylpiperidine, 4, (V) formula 0 % methylbenzylamine and the like.

Among homopolymers or copolymers of these monomers, the average molecular weight is 1. OOO~]0 million are used.

(1)) One or more of the nitrogen-containing monomers represented by formulas (1) to (■) or their salts or quaternary ammonium salts, and an α,β-unsaturated carboxylic acid or with one or more vinyl monomers selected from the group consisting of salts thereof or derivatives thereof, vinyl compounds containing sulfonic acid groups or salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms. Copolymer 1゜The vinyl monomers include, for example, vinylpyrrolidone, acrylonitrile; acrylic acid, methacrylic acid, maleic acid, or alkali metal salts of these acids, ammonium salts π, amide compounds or esterified t-vinyl Examples include sulfonic acid, methallylsulfonic acid, 2-acrylamidol 2-methylpropanesulfonic acid, p-styrenesulfonic acid, or alkali metal salts or ammonium salts of these acids. Among the copolymers with vinyl monomers, the average molecular weight is 10
00 to 1,000,000 is used.

(C-1) Polyethyleneimine salt or quaternary ammonium salt Easily obtained by adding ethyleneimine to polyethylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepencumine, and pentaethylenehexamine. It can also be obtained by polymerizing ethyleneimine, generally using an acidic catalyst. The polyethyleneimine thus obtained is not a chain polyamine like the following formula (1), but a branched compound having the skeleton of the above formula (2).

-CH, CH2-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 are approximately 1-
:I: Preferably, the ratio is in the range of 1 to 1:2:1.

(c-2) Salts or quaternary ammonium salts of derivatives of polyethyleneimine The following derivatives of polyethyleneimine ■ Reaction products with aldehydros and ketones ■ Reaction products with alkyl halides ■ Isocyanates, neoinone ane-1. ■ Reaction products with substances having active double bonds ■ Reaction products with epihalohydrins ■ Reaction products with soanamides, guanidines, urea, etc. ■ Carboxylic acids, acid anhydrides, amplifiers /・Reaction product with ride etc. (d) Salt or quaternary ammonium salt of polycondensate of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine.

Specifically, these repeating units are a polycondensate with polyethylene polyamine represented by the general formula (VID) and a polycondensate with polyoquinoethylene alkylamine represented by the general formula (IIID) with a molecular weight of 1000 to 1. 0.
000.000 is mentioned.

! OCR+-CONM-←R'NHe-R' NH
) (ulD4 [in the formula, R is a dimer monoacid residue or an alkylene group having 1 to 1 carbon atoms], R' is -CH, I:I(2-11], is a 2 to 7 [in the formula, R4 is the formula (same as SilD. R9 is a 7-alkyl group having 1 to 8 carbon atoms, R6 is H or CH3, R5
and R6ba1-], representing an integer of 0] Examples of the aliphatic dicarboxylic acids include dimer acid, adipic acid, etc., and polyethylene polyamines include:
Ethylenetriamine, triethylenetetramine, etc. can be used.

(e) Dihaloalkane-polyalkylenepolyamine polymer.

Specifically, di/-roalkanes such as 1,2-dichloroethane, 1゜2-dibromoethane, 1,3-dichloropro/; and polyalkylenes having two or more tertiary amine groups in the molecule. It is a polymer that is a quaternary ammonium salt with polyamine, and its average molecular weight is 100.
Examples include 0 to 100,000.

Examples of the polyalkylene polyamines mentioned above include the following.

(f) Shrimp...rohydrin-amine polycondensate.

Specifically, examples include those in which the repeating unit is represented by the following general formula (kaku) and the average molecular weight is 10 million to 10 million.

-EO-CH2CH-)- [In the formula, R7- represents a methyl group or an ethyl group.

Xo represents a halogen ion] (g) Salt of chitosan or cationically modified product of starch or cellulose.

The polymers of (a) to (f) above have an average molecular weight of 1
000 to 1,000,000 is more preferable.

Although the mechanism of action of the water-soluble cationic polymer compounds and water-soluble amphoteric polymer compounds (a) to (g) above has not been completely elucidated, it is thought to be roughly as follows. In other words, the dissolved water-soluble cationic or zwitterionic polymer compound completely uniformly adsorbs the particles of the lubricating oil component, which have been micronized in response to mechanical shearing force, before coalescence begins. However, the polymer compound makes the oil particles into large particles by a kind of coagulation effect, and furthermore, the large particles are stably dispersed in water by the steric and electrically protective colloidal effect of the polymer compound.

This is because, in the case of the water-soluble anionic polymer compound disclosed in JP-A-55-1.47593, its agglomerating effect on oil particles is weak, so that it is rendered safe as a protective colloid as a fine particle. This is different from the fact that fine oil particles cannot be recovered into large particles.

These hydric cationic or bivalent ionic polymer compounds can be used alone or in combination of two or more,
It is preferable to mix this in an amount of 0.1 to 10% by weight based on the total amount of the metal working oil composition.

In addition to the above-mentioned components, the metal working oil composition of the present invention may contain various known additives, such as rust preventives, oiliness improvers,
4. It is also possible to add iron pressure agents, antioxidants, etc.

The various additives mentioned above may be added in an amount of 0 to 2%, 0 to 20%, 0 to 3%, and 0 to 5%, respectively, based on the total amount of the rolling oil composition as necessary.
%.

As rust inhibitors, alkenylsuccinic acid and its derivatives,
Fatty acids such as oleic acid, esters such as norbitan monooleate, or other amine necks, etc. are used as oiliness improvers. However, as extreme pressure agents, phosphorus compounds such as tricresyl phosphate and metal compounds such as zinc dialkyldithiophosphate are still used as extreme pressure agents.
Examples include phenolic compounds such as di-t-butyl p-cresol, aromatic amines such as phenyl α-naphthylamine, and the like.

The metalworking oil composition of the present invention can be prepared by simply mixing the above-mentioned lubricating oil component and a water-soluble polymer compound, or by preparing it as a concentrated solution with a moisture content of up to 80% and adding it to the water at the time of use. Used by dilution.

The thus obtained metal rolling oil composition of the present invention can be prepared by incorporating the above-mentioned specific water-soluble cationic or zwitterionic polymeric compound, so that the metal rolling oil composition of the present invention can be improved by the action of the protective colloidal function of the polymeric compound. Since the lubricating oil component maintains a large particle size and is stably dispersed in water, circulation stability is improved (if it is still supplied to the metal processing section and comes into contact with the metal workpiece, large oil particles will be released). The present invention provides a metal working oil that forms a thick and strong lubricating film on metal workpieces, has high lubrication performance, and exhibits little change over time, and has the following features: 7. Although it has the ability to make water and oil hydrophilic, it does not have the ability to emulsify by lowering the interfacial tension between water and oil, so the lubricating oil components do not emulsify and cannot be used with conventional metalworking oils using emulsifiers. In comparison, it has the advantage of being a metal processing oil that is always clean and retains the so-called high moisturizing properties, with less of the so-called entrapment phenomenon of foreign substances such as dirt oil and metal powder mixed in during processing. Also,
The functions of both of the above ingredients improve the dirtiness of the working environment.
It also has excellent wastewater treatment properties, and has an excellent feature that creates a clean working environment, which is not found in conventional metalworking oils that use emulsifiers.

Next, an example will be given and explained.

The metalworking oil compositions used in the examples are as follows. A water-soluble cationic or zwitterionic polymer compound is expressed as a "water-soluble polymer compound," and q is indicated by weight.

Table 1 ■ Extreme pressure agent triphenyl phosphite surfactant (emulsifier) Polyoxyethylene nonylphenyl ether (l (L
B = 10.6) Antioxidant 2.4-Di-t-butyl p-cresol and below Overmill Table 2-2 (Target) Table 2-3 (%) Comparative product 1 Lubricating oil component Beef tallow 94 Beef tallow power 1 Go fatty acid.

Emulsifier 2 Antioxidant 1 Comparative product 2 Lubricating oil component beef tallow 94%
2 Extreme pressure agent 1 Emulsifier 1i11 2 Antioxidant 1 Comparative product 3 Lubricating oil component mineral oil (cylinder oil) 72 pentaerythritol tetraoxygen 1-20 Emulsifier 2 Antioxidant 1 Comparative product 4 Lubricating oil component mineral Oil (cylinder oil) 72 pentaerythritol tetraoleate) 20
Extreme pressure agent 1 Emulsifier 2
Antioxidant 1 Comparative product Tsuta 5 Lubricating oil component Mineral oil (spindle oil) 67 Stearic acid octyl ester 20 Oleic acid 5 Emulsifier 2 Antioxidant 1 Comparative product Bian 6 Lubricating oil component Mineral oil (spindle oil) 67 Stearly AM, Octyl Ester 20
Oleic acid 5 Extreme pressure agent 1 Emulsifier 2 Antioxidant 1 Example 1 ■ Seizure load test) (Faresox test 1 test method) lIII
Measurement of seizure load is performed using A S TM 1'J1. Case D −
It was conducted in accordance with the 3233 pressure load test (Faresox test). To prepare the test samples, each metalworking oil composition was diluted with water to 3 degrees, and then mixed with a homomixer at a rotational speed of 10. This was done by stirring at OO rpm. To apply the test sample, spray 50 ml of ``double fi:e 4'' P solution for 7 minutes (pressure 0.5 kg/
ai), 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.

Margin below Table 3 Margin below Example 2 Burning load test (Soda four-ball test method) Burning 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.
diluted to the highest concentration and mixed with a homomixer at 10 revolutions.
．． This was done by stirring at 000 rpm. To apply the test sample, pour the above stirring solution into a spray V, g O, 5
A 7 minutes (pressure 0.5 kg/cnt), sample solution temperature 5
Using a gear pump under the condition of 0°C, the upper rotating steel ball (・'' Yes.

The results are as shown in Table 4. 1-1 Margin below Table 4 Margin below Example 3 After adding 3J of sulfuric acid bread to the test solution (stone) prepared in the same manner as in Example 2 of the wastewater treatment test, The mixture was stirred for 1 minute, and then Ca (OH)2 was added to adjust the pI-I to 7.0, followed by stirring for 10 minutes. Next, after standing for 30 minutes, the supernatant was collected, and C0D (KMn
O4 method) was measured. The results are shown in Table 5.

Margin below Table 5

Claims (1)

[Scope of Claims] (]) (a) one or more 4■ lubricating oil components selected from the group consisting of fats and oils, mineral oils, and fatty acid esters; and (b) in molecules with a molecular weight of 10 to 10 million. The essential ingredient is one or more water-soluble bacterial molecular compounds selected from cationic or zwitterionic addition polymers, ring-opening polymers, polycondensates, and natural polymer derivatives containing a nitrogen atom. A metal-working oil paper characterized by containing: 1) an acid substance; (2) The water-soluble polymer compound is a polymeric compound selected from the group consisting of the following (a) to (g). thing. (a) A homopolymer of a salt of a nitrogen monomer or a quaternary ammonium salt represented by the following general formulas (1) to (V), or a copolymer of two or more thereof. [In the formula, A is 10- or -Nl-I-, nl is 1 to 3
represents an integer, R8 is H or CH, & and R1 is H
, CH3 or C2 represents] R8 [In the formula, R,, R, , R3, nl are the same as in formula (I)]
R1 [wherein, R1 is the same as in formula (I). The substitution position of pyridine is 2
or 4th place] ■, [In the formula, R1 and ■2 are the same as in the formula (■). The substituent position of piperidine is the 2 or 4 position] R1 [In the formula, 1S R, and R3 are the same as in formula (I)] (l)) Nitrogen-containing monomers represented by the general formulas (1) to (■) or one or more quaternary ammonium salts, and α
, a vinyl monomer selected from the group consisting of β-unsaturated carbon dioxide or a salt thereof or a derivative thereof, a sulfonic acid group-containing vinyl compound or its derivatives, acrylonitrile, vinylpyrrolidone, and an aliphatic olefin having 2 to 2° of carbon atoms. 1 or a copolymer with 211 or more. (C) Salt or quaternary ammonium salt of polyethyleneimine or its derivative. ((1) Salt or quaternary ammonium salt of a polycondensate of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine. (e) Dihaloalkane-polyalkylene polyamine polymer. (f) Shrimp halohydrin- Amine polycondensate. (g) Salt of chit-zan, starch or cellulose, or cation-modified products thereof. (3) Water-soluble cationic polymer compound or water-soluble amphoteric polymer compound having a molecular weight of 1000 to 1 .000,0
00. The metal working oil composition according to claim 1 or 2, which is (4) the α, β-unsaturated carboxylic acid copolymerized with the nitrogen-containing premature compound is acrylic acid, ivy acrylic [Shun] or maleic acid, and the salt thereof is an alkali metal or ammonium;
The metalworking oil composition according to claim 2 or 3, wherein the derivative is an argylamide, an alkyl ester or acrylonitrile. (5) The sulfonic acid group-containing vinyl compound copolymerized with the nitrogen-containing monomer is vinyl sulfonic acid, methallyl sulfone,
2-acrylamido-2-methylpropanesulfonic acid,
or p-styrenesulfonic acid, and the metal working oil composition according to claim 2 or 3, wherein the salt thereof is an alkali metal or ammonium. (6) The repeating unit of the ring-opening polymer of ethyleneimine has the following general formula (VD [wherein, R2 is an integer of 1 to 5, I]3 is O' to 5-41
[indicating number] Claim 2 or 3
The metallurgical oil composition described in 1. (7) The repeating unit of the polycondensate of aliphatic dicarboxylic acid and polyethylene polyamine has the following general formula (1'1-+OC
R, -CON1((-R'-NI(+Ti-R'-NI
-I-3- (Vllll [wherein, J-7, is a dimer acid residue or an alkyl/7 group having 1 to 1° carbon atoms, R
' is -CH2Cf (2-1+1. +a 2~7 (7
) represents an integer] Claim 2 or 3
The metal working oil composition described in . (8) The repeating unit of the polycondensate of aliphatic dicarboxylic acid and dipolyoquine ethylene alkylamine has the following general formula
I [In the formula, R4 is the same as the formula (VID. R6 is a carbon number of 1 to 8
alkyl group, mount is H or CHl, R5 and) are 1 to 1
Indicates an integer of 0] Claim 2 or 3
The metal working oil composition described in . (9) The repeating unit of the epihalohydrin-amine polycondensate has the following general formula (lx), -(0-C1(2C1(+8) [wherein, R7 to R0 are CH3 or C21-I, and Xo is a halogen ion 2 or 3 of the claims, which is
The metal working oil composition described in . (10) The amount of the water-soluble cationic polymer compound or the water-soluble imageable ionic polymer compound in the entire composition is from O, ] to 10 to 4 parts. The metal working oil composition according to any one of the items.