JPH0314895A - Rolling oil composition for metal - Google Patents

Abstract

PURPOSE:To prevent the contamination of the surface of material to be worked and the incorporation of contaminants into the system by using a specified water-soluble high molecular compound and a lubricating oil component comprising oil or fat, a mineral oil, or a fatty acid ester as constituents. CONSTITUTION:A lubricating oil component (A) comprising oil or fat, a mineral oil, or a fatty acid ester (e.g. a mixture of a beef tallow with a tallow fatty acid) is mixed with 0.01-0.1wt.% water-soluble high-molecular compound (B) selected from a cationic or amphoteric addition polymer, a ring-opening polymer, a polycondensation product, and a natural high molecular compound which contain N atoms in the molecule (e.g. a terpolymer of diethylaminoethyl acrylate borate, vinylpyrrolidone, and sodium acrylate in a molar ratio of 5:4:1) and having a molecular weight of 1,000 to 10,000,000; and 0-2wt.% rust preventive, 0-20wt.% oilness improver, 0-3wt.% extreme-pressure additive, 0-5wt.% antioxidant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel metal working oil composition, more specifically, a novel metal working oil composition which is suitable for plastic working, cutting, grinding, etc. of metals 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. That is, the liquid IQI'l agent is characterized in that it obtains a lubricating effect by adhering oily $4fir component particles emulsified with a surfactant etc. to the second surface of the workpiece. The liquid lubricant used as a lubricant is advantageous in terms of its cooling effect on the heat generated during machining of the workpiece, and its economical 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).

(b) 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.

(d) Does it occur to stabilize emulsification? A decrease in the load-bearing capacity of the metal contact lubricated surface due to a decrease in the amount of 1i1 beak component emulsion particles attached to the surface of the workpiece.

(E) Wastewater treatment of milk leakage.

etc., had many drawbacks in terms of emulsion management.

Therefore, after processing, a beautiful surface condition is obtained that prevents contamination of the surface of the workpiece by lubricating oil, etc., and contamination such as metal powder, lubricant deterioration products, etc.
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 found that the above object could be achieved by using a composition containing a 1'-mold ionic water-soluble polymer compound using a conventional oily component, and developed the present invention. completed.

That is, 4. The invention is directed to (a) cationic or zwitterionic addition polymers, open-term polymers, melon condensates, or natural polymer derivatives containing desired atoms in the molecules of oils, mineral oils, and fatty acids; The present invention provides a metal rolling oil composition containing as an essential component one or more water-soluble polymer compounds.

Examples of the lubricating oil component (a) of the metal processing composition of the present invention include mineral oils such as spindle oil, -Z'77 oil, turbine oil, and cylinder oil; whale oil, beef tallow, lard;
Animal and vegetable oils such as rapeseed oil, castor oil, bran oil, palm oil, coconut oil; fatty acids obtained from beef tallow, coconut oil, palm oil, castor oil, etc.; aliphatic alcohols with 1 to 22 carbon atoms; ethylene Examples include esters with glycol, neobentel alcohol, betaerythritol, and the like.

Each of these precepts may be 1fIIi, but two types may be mixed. It can also be used.

In addition, although 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, including the following.

(a) Homopolymers of salts or quaternary ammonium salts of nitrogen-containing monomers represented by the following general formulas (1) to (7), or copolymers of 281 or more thereof.

R, [wherein R is the same as in formula (I). The substitution position of pyridine is 2
or 4th position] R1 [wherein Rl and R2 are the same as in formula (I). The substituent position of piberidine is the 2nd or 4th position] R, U [In the formula, human represents 101 or 1 God 1, n represents an integer from 1 to 3, a represents H or CM, R2 and & is H1CH,
or C, l{,] R1 [In the formula, R,, R,, n, are the same as in formula (I)] R. ? In the formula, R1, Rt, R, are the same as in formula (I)] Specific examples of these monomers include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, Dimethylanoglovir acrylamide, diethylaminopropylacrylamide,
Dimethylaminopropyl methacrylamide, diethylaminopropyl methacrylamide, etc.; dimethylaminomethylethylene, diethylaminomethylethylene, dimethylaminomethylpropene, diethylaminomethylpropene, etc. of formula (■); vinylpyridine, etc. of formula (I); ) vinylbiperidine, vinyl-N-methylpiperidine, etc.; vinylbenzylamine of formula M, vinyl-N e N
- Dimethylbenzylamine and the like.

Among these homopolymers or copolymers, those having an average molecular weight of 10 to 10 million are used.

(bl) 1 of the nitrogen-containing monomer or its salt or quaternary ammonium salt represented by the above general formulas ([) to (7)]
species or two or more species, α,β monounsaturated carboxylic acid or its salt or its derivative, sulfonic acid group-containing vinyl compound or its salt, acrylonitrile, vinylpyrrolidone, and aliphatic olefin having 2 to 20 carbon atoms. A copolymer with one or more vinyl monomers selected from the group consisting of:

Examples of the vinyl monomer include vinylpyrrolidone, acrylonitrile; acrylic acid, methacrylic acid, maleic acid, and acetic acid of these acids. Potassium gold IAim, ammonium salts, amide compounds and esterified products; vinylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-styrenesulfonic acid or alkali metal salts of these acids; Examples include ammonium salts. The average molecular weight of the copolymer of the nitrogen-containing monomer and the vinyl monomer is 10.
00 to 10 million are used.

(c-1) Polyethyleneimine salt or quaternary ammonium salt Easily obtained by adding ethyleneimine to polyethylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenebentamine, and pentaethylenehexamine. It can also be obtained by polymerizing the parent ethyleneimine, generally using an acidic catalyst. The polyetherenimine thus obtained is not a chain-like borian as shown in formula (1) below, but is a compound having a branched structure having the skeleton shown in formula (2) above.

-Cf{t-CI{, -N}I- {1) The polyalkyleneimine thus obtained contains 6 or more nitrogen atoms, including a primary nitrogen atom, a secondary nitrogen atom, and a tertiary nitrogen atom. The ratio of the number of nitrogen atoms is approximately 1:
Preferably, the ratio is in the range of 1:1 to 122:1.

(c-2) Salts or quaternary ammonium salts of polyethyleneimine derivatives The following derivatives of polyethyleneimine ■ Reaction products with aldehydes and ketones ■ Reaction products with alkyl halides ■ Incyanates, Reaction products with neoisocyanates■ Reaction products with substances having an active binary bond■ Reaction products with shrimp halohydrins? Reaction products with cyanamides, guanidines, urea, etc. (d) Reaction products with carboxylic acids, acid anhydrides, acyl halides, etc. (d) I1'li Aliphatic dicarboxylic acids and polyetherene polyamine or diborioxy Salts or quaternary ammonium salts of polycondensates with ethylene alkylamines.

Specifically, those repeating units are polycondensates with polyethylene borian represented by the general formula ~ D and general formula ~
A polycondensate with dibolyoxyethylene alkylamine represented by the molecular weight iooo~10.000.0
0 0 can be mentioned.

{QC -R, -CONI{-+R'-NH←R'-
Nf{-} ■n4 [In the formula, R4 is a dimer acid residue or an alkyl group having 1 to 10 carbon atoms, R' is 1CHCH2-, and 2 to 7 [In the formula, R is 'Same as ID * 'j'-a charcoal R
a1 to 8 (D alkyl group, R is H or Ckls,
nS and Hiki indicate a number from 1 to 10] Examples of the aliphatic dicarboxylic acids include dimer acid, adivic acid, etc., and polyethylene polyamines include:
Diethylenetriamine, triethylenetetrimine, etc. can be used.

(e) Dihaloalkane-borealkyleneboryamine polymer.

Specifically, dihaloalkanes such as 1,2-dichloroethane, 1,2-dipromeethane, and 1,3-dichloropropane, and polyalkylenebolyamines having two or more tertiary amino groups in the molecule. It is a polymer which is a quaternary ammonic salt of
There are 10 million things to list.

Examples of the polyalkylene polyamines mentioned above include the following.

(f) Epihalohydrin-amine polycondensate.

Specifically, the repeating unit is represented by the following general formula (2) and the average molecular weight is 10 to 10 million.

[In the formula, R7~& represents a methyl group or an ethyl group.

X0 represents a halogen ion] (g) Salt of chitosan or cationically modified product of starch or cellulose.

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

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. That is, the water-soluble cationic or zwitterionic polymer compound completely and uniformly dissolved in the water layer adsorbs the particles of the lubricating oil component, which have been made into fine particles in response to mechanical shearing force, before coalescence begins. The polymer compound forms large particles by coagulating oil particles together, and the large particles are stably dispersed in water by the steric and electrically protective colloidal action of the polymer compound.

This is because in the case of the water-soluble anionic polymer compound disclosed in JP-A-5-5-147593, it has a weak aggregation effect on oil particles, so it is stabilized as a protective colloid as a fine particle, and once it is made fine, it is stabilized as a protective colloid. This is different from recovering oil particles into larger particles.

These water-soluble cationic or zwitterionic polymer compounds can be used alone or in a mixture of two or more, and the amount of these water-soluble cationic or zwitterionic polymer compounds is 0.000% relative to the total amount of the metal sword loe oil composition. 1~10i
It is preferable to mix it so that it is adjusted to Lt%.

In addition to the above-mentioned precepts, the metal working oil composition of the present invention may contain various known additives, such as rust preventives, oiliness improvers, etc.
Extreme pressure agents, antioxidants, etc. can also be added.

Each of the above-mentioned additives can be used in amounts of 0 to 2%, 0 to 20%, O to 3%, and O to 5%, respectively, based on the total rolling oil composition as required.
Complementary training can be provided at a rate of 1.

As rust preventive agents, alkenylconocitric acid and its derivatives, fatty acids such as oleic acid, esters such as sorbitan monooleate, or their amines, etc. are used.As oiliness improvers, high grade agents such as oleic acid and stearic acid are used. Dibasic acids such as fatty acids and their derivatives, esters or dimer acids, and extreme pressure agents such as phosphorus compounds such as tricresyl phosphate and organometallic compounds such as zinc dialkyldithiophosphate, are effective in preventing oxidation. As an agent, 2.4-
Examples include phenolic compounds such as di-t-butyl p-cresol and aromatic amines such as phenyl α-naphthylamine.

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 up to the level of SOS in AIill 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. The lubricating oil component maintains a 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 gold-filled workpiece, large oil particles are dispersed. It forms a thick and strong lubricating film on metal workpieces, has high lubrication performance, and provides a metal working oil with little change over time, and has the following five features. In other words, although it is used in the present invention and has the ability to make it hydrophilic, it is desirable to have the ability to emulsify by lowering the interfacial tension between water and oil, so it is not possible to use a conventional emulsifier without emulsifying the lubricating oil components. Compared to conventional metalworking oils, this oil has the advantage of maintaining high slip properties as a constantly clean metalworking oil that is less prone to the so-called entrapment phenomenon of impurities such as dirty oil and metal powder that get mixed in during processing. There is. In addition, the above-mentioned functions of both cutting oils reduce dirt in the working environment and have excellent wastewater treatment properties, creating a cleaner working environment that cannot be seen with conventional metalworking oils that use emulsifiers. It has special 5W ridges.

Next, an example will be given and explained. The metalworking oil used in the Examples + [i] components are as follows. Water-soluble cationic or zwitterionic polymer compounds are expressed as ``water-soluble polymer compounds'' and are expressed in terms of weight.

First surface pressure agent triphenyl phosphite surfactant (emulsifier) Polyoxyethylene nonyl phenyl ether (1 {L
B=1 0.6) Antioxidant 4-di-t-butyl p-cresol 1・゛Margin Table 2-1 Table 2-3 Table 2-2 Comparative product &l Lubricating oil ingredients Beef n beef tallow fatty acid emulsifier oxidation Inhibitor Comparison Product A2 Lubricating Oil Ingredients Beef Tallow Fatty Acid Pressure Agent Emulsifier Antioxidant Comparison Product 3 @ Lubricating Oil Ingredient Mineral Oil (Cylinder Oil) Pentaerythritol Tetraoleate Emulsifier Antioxidant Comparative Product A4 Lubricating Oil Ingredient Mineral Oil (cylinder oil) Pentaerythritol tetraoleate Extreme pressure agent Emulsifier Antioxidant Comparative product Hire 5 Lubricating oil component Mineral oil (Spindle oil) Stearic oil Octyl ester Oleic acid Emulsifier Antioxidant Comparative product iP5 6 @ Lubricating oil component Mineral Oil (spindle oil) Sudeary acid scutyl ester oleic acid Extreme pressure agent No. 3 Emulsifier Antioxidant Example 1 Anti-seizure load test (Falex test method) Measurement of anti-seize load is ASTM standard D-3233 pressure load test (Falex test). To prepare the test samples, each metalworking oil composition was diluted with water to three different concentrations, and mixed with a Bomo mixer at a rotational speed of 10. This was done by stirring at OOO rpm. To apply the test sample, spray the above stirred solution at a rate of 50-/min (pressure: 0.5'Kg/f).
fl), using a gear pump at a dispersion temperature of 50° C., and applying it to a rotating bottle in the center of a fixed block.

The results are shown in Table 3.

Below 1-bu0 Below margin Example 2 Seizure load test (Soda four-ball test method) Seizure load measurement is based on the Defense Agency provisional standard NDS XXK27
40 oil film strength test method (Soda four-ball test method). To prepare the test sample, mix each metalworking oil composition with water for 30 minutes.
Dilute it to a high concentration and mix it with a homomixer at 10 revolutions.
．． This was done by stirring at 000 rpm. To apply the test sample, spray the above stirred solution.
Using a gear pump under the conditions of 5-13/min (pressure o.sky/cit) and sample solution temperature of 50°C, the center of three contact points from below of three test steel balls fixed with ball holders was measured. This was done by throwing the cloth through the space above onto the rotating steel ball.

The results are shown in Table 4.

Margins below Table A! Example 3 Wastewater Treatability Test Add 3i of sulfuric acid to the test liquid (1 ml) prepared in the same manner as in Example 2. After adding m, the mixture was stirred for 2 minutes, and then Ca(OH)2 was added to adjust the pH to 7.0, followed by stirring for 10 minutes. Next, after standing for 30 minutes, the supernatant was collected, and COD (Kfvln
O, method) was measured. The results are shown in Table 5.

Margin below No. table

Claims (10)

[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) cations containing nitrogen atoms in molecules with a molecular weight of 10 to 10 million. It is characterized by containing as an essential component one or more water-soluble polymer compounds selected from neutral or zwitterionic addition polymers, ring-opening polymers, polycondensates, and natural polymer compounds. Metal rolling oil composition. (2) The metal rolling oil composition according to claim 1, wherein the water-soluble polymer compound is a polymer compound selected from the group consisting of the following (a) to (g). (a) Homopolymers of salts or quaternary ammonium salts of nitrogen-containing monomers represented by the following general formulas (I) to (V), or copolymers of two or more thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, A represents -O- or -NH-, n_1 represents an integer from 1 to 3, R_1 represents H or CH_3, R_2 and R
_3 indicates H, CH_3 or C_2H_5] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R_1, R_2, R_3, n_1 are formula (I)
Same as] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, R_1 is the same as in formula (I). The substitution position of pyridine is the 2nd or 4th position] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) [In the formula, R_1 and R_2 are the same as in formula (I). The substitution position of piperidine is the 2nd or 4th position] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) [In the formula, R_1, R_2, and R_3 are the same as in formula (I)]
(b) One or two salts or quaternary ammonium salts of nitrogen-containing monomers represented by the above general formulas (I) to (V)
and α, β-unsaturated carboxylic acid or its salt, or its amide, ester, or acid anhydride;
One vinyl monomer selected from the group consisting of sulfonic acid group-containing vinyl compounds or salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms.
species or copolymers with two or more species. (c) Polyethyleneimines or salts thereof or quaternary ammonium salts. (d) Salt or quaternary ammonium salt of a polycondensate of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine. (e) Dihaloalkane-polyalkylenepolyamine polymer. (f) Epihalohydrin-amine polycondensate. (g) Cationized starch, cationized cellulose, chitosan salt or chitosan quaternary salt. (3) The molecular weight of the water-soluble cationic polymer compound or the water-soluble amphoteric polymer compound is 1000 to 1,000.0
00. The metal rolling oil composition according to claim 1 or 2, which is (4) The α,β-unsaturated carboxylic acid copolymerized with the nitrogen-containing monomer is acrylic acid, methacrylic acid, maleic acid, or an alkyl amide, alkyl ester, or acrylonitrile thereof, and the salt thereof is an alkali metal salt or The metal rolling oil composition according to claim 2 or 3, which is an ammonium salt. (5) The sulfonic acid group-containing vinyl compound copolymerized with the nitrogen-containing monomer is vinyl sulfonic acid, methallyl sulfonic acid, 2
-Acrylamido-2-methylpropanesulfonic acid or p-styrenesulfonic acid, and the metal rolling 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 is the following general formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) [In the formula, n_2 is an integer from 1 to 5, and n_3 is 0 to [indicates an integer of 5]
The metal rolling oil composition described in 2. (7) The repeating unit of the polycondensate of aliphatic dicarboxylic acid and polyethylene polyamine has the following general formula (VII) ▲ Formula,
There are chemical formulas, tables, etc. ▼ (VII) [In the formula, R_4 is a dimer acid residue or an alkylene group having 1 to 10 carbon atoms, R' is -CH_2CH_2-, and n_4 is an integer from 2 to 7] Represented by Claim 2 or 3 which is
The metal rolling oil composition described in 2. (8) The repeating unit of the polycondensate of aliphatic dicarboxylic acid and dipolyoxyethylene alkylamine has the following general formula (V
III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VIII) [In the formula, R_4 is the same as formula (VII). R_5 is carbon number 1
-8 alkyl group, R_6 is H or CH_3, n_5 and n_6 are integers of 1 to 10] Claim 2 or 3
The metal rolling oil composition described in 2. (9) The repeating unit of the epihalohydrin-amine polycondensate is the following general formula (IX) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IX) [In the formula, R_7 to R_9 are CH_3 or C_2H_5,
The metal rolling oil composition according to claim 2 or 3, wherein X^■ represents a halogen ion. (10) Any one of claims 1 to 9, wherein the amount of the water-soluble cationic polymer compound or the water-soluble zwitterionic polymer compound is 0.1 to 10% by weight based on the total composition. The metal rolling oil composition described in 2.