JP2001081490A - Lubricating oil for metal working - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricating oil that exhibits excellent lubricating properties when used in metal working by using a phosphorous ester having a (poly) alkylene group or the product of neutralization thereof with a basic compound. SOLUTION: A phosphorous ester represented by the formula is used. In the formula, R1, R2, and R3 are each H, a hydrocarbon group, or -(R4-O)n-R5 (wherein R4 in an alkylene; R5 is a hydrocarbon group; and n is a number of 1 or greater). Among them, the hydrocarbon group being R1, R2, R3, or R5 is desirably 6-36C alkyl or alkenyl; and R4 is a 2-4C alkylene. The moiety (R4O)n controls the oil or water solubility of the ester. When the lubricant is oil-soluble, it is desirable that it is added to a base oil such as a mineral oil, a synthetic oil, or a fat and oil and is used in an amount of, desirably, 0.01-30 wt.%. When the lubricant is water-soluble, it is desirable that the base is water and is added in an amount of 0.01-30 wt.%. This lubricant can be used in any types of metal workings including cutting, grinding, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphite-based metal working lubricant having a specific structure.

[0002]

2. Description of the Related Art Conventionally, in the field of metal working oils, extreme pressure agents have been used for the purpose of improving lubricity and workability. Typical extreme pressure agents are chlorine-based, sulfur-based, phosphorus-based and the like. However, although chlorine-based extreme pressure agents are excellent in workability, they may cause deterioration of the working environment such as skin rash and rust on metal, and are used as a cause of dioxin generation. The amount being reduced is decreasing. In particular, metal working oils often come into contact with workers' bodies, so chlorine-based extreme pressure agents tend to be avoided. Sulfur-based compounds are also excellent in lubricity and extreme pressure properties, but many have unique odors, and thus have many problems in metalworking applications that may come into contact with the human body. Phosphorus-based additives have been considered as alternatives to chlorine-based extreme pressure agents. Examples of the phosphorus-based additive include a phosphoric acid ester (salt) type, a phosphite ester (salt) type, a thiophosphoric acid ester (salt) type, and a phosphine type.

[0003] For example, JP-A-6-192676 discloses a plastic working oil composition containing a lubricating base oil containing an acidic phosphate ester amine salt such as lauryl acid phosphate cocoalkylamine salt. Also, JP-A-8
JP-134488 discloses a lubricating oil composition containing a base oil containing an acid phosphate amine salt such as a salt of octyl acid phosphate and diisotridecylamine, and a linear alkylamine. JP-A-11-131085
The publication discloses a phosphorus-based lubricating oil additive consisting of a reaction product of an acid phosphate ester and an amino alcohol.

[0004]

However, these phosphorus-based lubricants could not provide satisfactory extreme pressure performance. Therefore, the present inventors examined phosphite-based compounds instead of phosphate-based compounds, and found that a phosphite-based lubricant having a (poly) oxyalkylene group was used for metal working. The present inventors have found that they provide excellent lubricity as a lubricant, and have completed the present invention.

[0005]

That is, the present invention provides the following general formula (1):

[0006]

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[0007] {wherein, R ^1, R ² and R ³ is a hydrogen atom, a hydrocarbon group or the general formula ^{(2) - (R 4 -O} ) n -R 5 (2) ( wherein, R ⁴ Represents an alkylene group, R ⁵ represents a hydrocarbon group, and n represents a number of 1 or more.) However, at least one of R ¹ , R ² and R ³
One is a group represented by the general formula (2). A metal working lubricant comprising a phosphite represented by｝ or a neutralized product of the phosphite and a basic compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ and R ²
And R ³ represents a hydrogen atom, a hydrocarbon group or a group represented by the general formula (2). R ¹ , R ² and R ³ are each independent and may be the same or different. Where R ¹ ,
At least one of R ² and R ³ is a group represented by the general formula (2), and one or two of R ¹ , R ² and R ³ is a group represented by the general formula (2) Is preferred. Further, any one of R ¹ , R ² and R ³ is preferably a hydrogen atom. In the general formula (2), R
⁵ represents a hydrocarbon group.

The hydrocarbon groups represented by R ¹ , R ² and R ³ in the general formula (1) and R ⁵ in the general formula (2) include:
Examples include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group and the like. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, and secondary pentyl.
Neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary Dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2
-Hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl, etc. Is mentioned.

Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like. Examples of the aryl group include phenyl, toluyl, xylyl,
Cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, Examples include phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, and β-naphthyl groups. Examples of the cycloalkyl group and the cycloalkenyl group include, for example, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl,
Methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl,
Examples thereof include a methylcyclohexenyl group and a methylcycloheptenyl group. Among them, R ^{1 of} the general formula (1),
R ² and R ³ and the hydrocarbon group of R ^{5 in} the general formula (2) are
From the viewpoint of lubricity, an alkyl group or alkenyl group having 6 to 36 carbon atoms is preferable.

In the general formula (2), R ⁴ represents an alkylene group, preferably an alkylene group having 2 to 4 carbon atoms. The (R ⁴ —O) _n portion of the general formula (2) can be obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, long-chain α-olefin oxide, and styrene oxide. . When the (R ⁴ —O) _n portion is formed by adding an alkylene oxide or the like, R ⁴ is determined by the alkylene oxide or the like to be added. The polymerization form of the alkylene oxide or the like to be added is not particularly limited, and homopolymerization of one kind of alkylene oxide or the like, random copolymerization of two or more kinds of alkylene oxides or the like, block copolymerization or random /
It may be a block copolymer or the like. R ⁴ is most preferably an ethylene group or a propylene group, and when R ⁴ is two or more groups, one of them is preferably an ethylene group.

(R ⁴ —O) Controlling whether the lubricant for metalworking of the present invention is made oil-soluble or water-soluble by what kind of oxyalkylene chain constitutes the part of _n. Can be. If either the lubricant of the present invention is either water soluble an oil-soluble, it can not be said to have the relationship between the group represented by R ⁵ flatly, generally, to water-soluble, (R
^4- O) _n portion is an oxyalkylene chain obtained by addition polymerization of 8 to 10 mol or more of ethylene oxide, or 8 to 10
It is preferable to use an oxyalkylene chain formed by copolymerization of ethylene oxide and propylene oxide in moles or more. When the metal working lubricant of the present invention is made oil-soluble, the number of oxyethylene groups contained in the (R ⁴ —O) _n portion is set to 8 to 10 mol or less, or propylene oxide or butylene oxide is used. It is preferable to use an addition-polymerized oxyalkylene chain.

The phosphite represented by the general formula (1) can be used as it is, but may be neutralized with a basic compound. The degree of neutralization is not limited to the case where the phosphite represented by the general formula (1) and the basic compound are neutralized in the same amount, and of course, the amount of the basic compound is too small (partial neutralization).
And the basic compound may be in excess (excess neutralization). The neutralization method is not particularly limited, and may be a method of directly mixing the phosphite represented by the general formula (1) and the basic compound, or a method of separately adding and mixing them to the substrate.

Examples of the basic compound include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide; ammonia; methylamine, dimethylamine, ethylamine;
Diethylamine, (iso) propylamine, di (iso)
Propylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, 2-ethylhexylamine, di (2-ethylhexyl) amine, decylamine, didecylamine, dodecylamine, didodecylamine, tridecylamine, ditridecyl Amine, cetylamine, dicetylamine, cocoalkylamine, di (cocoalkyl) amine, alkylamine from soybean oil, di (alkyl from soybean oil) amine, alkylamine from tallow, di (alkyl from tallow) amine, oleylamine, dioleylamine,
Alkylamines such as stearylamine and distearylamine; polyalkylenepolyamines such as ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; monoethanolamine and N-methylmono Ethanolamine, N, N-dimethylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine, monopropanolamine,
Dipropanolamine, tripropanolamine, 2-
Amino-2-methyl-1-propanol, 2-amino-
2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ′, N′-tetrakis (hydroxyethyl) ethylenediamine, N, N,
Alkanolamines such as N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or alkylene oxide adducts thereof; N-butylmonoethanolamine, N-hexylmonoethanolamine, N-octylmonoethanolamine, N- Decyl monoethanolamine, N-cocoalkyl monoethanolamine, N
-Alkyl monoethanolamine derived from soybean oil, alkyl monoethanolamine derived from N-tallow, N-oleyl monoethanolamine, N-stearyl monoethanolamine, N-butyl diethanolamine, N-hexyl diethanolamine, N-octyl diethanolamine, N
-Decyldiethanolamine, N-cocoalkyldiethanolamine, N-soybean-derived alkyldiethanolamine, N-tallow-derived alkyldiethanolamine, N-
Oleyldiethanolamine, N-stearyldiethanolamine, N, N-dibutylmonoethanolamine,
N, N-dihexyl monoethanolamine, N, N-dioctyl monoethanolamine, N, N-didecyl monoethanolamine, N, N-bis (cocoalkyl) monoethanolamine, N, N-bis (alkyl derived from soybean oil) ) N-long chain alkyl alkanolamines such as monoethanolamine, N, N-bis (alkyl tallow) monoethanolamine, N-dioleyl monoethanolamine, N-distearyl monoethanolamine, and alkylene oxide addition thereof Objects and the like.

The method for producing the phosphite represented by the general formula (1) may be a known method, for example, a method of dehydrating and condensing (poly) oxyalkylene ether and phosphorous acid. In the case of producing the phosphite represented by the general formula (1) by this method, if the amount of the (poly) oxyalkylene ether charged relative to the phosphorous acid is controlled, the resulting phosphite is esterified. The rate can be controlled. In addition, it can be manufactured by using a phosphorus chloride such as phosphorus trichloride as a raw material, but in the case of the present invention, since it is used as a lubricant for metal working, if chlorine atoms are mixed in as impurities, the corrosion of the metal may occur. It is more preferable to use the former phosphorous acid as a raw material because it may cause rust or rust. It is known that phosphites show the following equilibrium state in the case of, for example, diesters.

[0016]

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For convenience, the present invention is represented by the formula on the left as the general formula (1), but the compound of the formula on the left and the compound of the formula on the right are the same compound.

When the metalworking lubricant of the present invention is oil-soluble, mineral oil, synthetic oil or fat or the like is used as the lubricating base oil, and preferably 0.01 to 30% by weight of these lubricating base oils. , More preferably 0.1 to 20% by weight. In the case of water-solubility, water is used as a base material, and preferably 0.01 to 30% by weight, more preferably 0.1 to 30% by weight.
-20% by weight is used.

Mineral oil that can be used as a lubricating base oil is separated from natural crude oil and is produced by appropriately distilling, refining, and the like. Mineral oil is mainly composed of hydrocarbons (mostly paraffins), and also contains naphthenes, aromatics and the like. Base oils which have been subjected to hydrorefining, solvent dewaxing, solvent extraction, solvent dewaxing, hydrogen dewaxing, catalytic dewaxing, hydrocracking, alkali distillation, sulfuric acid washing, clay treatment, etc. are also preferably used. be able to.

The synthetic oil which can be used as the lubricating base oil is a chemically synthesized lubricating oil such as poly-α-olefin, polyisobutylene (polybutene), diester, polyol ester, and the like. Examples include phosphate esters, silicate esters, polyalkylene glycols, polyphenyl ethers, silicones, fluorinated compounds, alkylbenzenes and the like. Among them, poly-α-olefin, polyisobutylene (polybutene),
Diesters, polyol esters, polyalkylene glycols and the like can be used for general purposes.

The fats and oils which can be used as the lubricating base oil include, for example, linseed oil, eno oil, euca deer oil, olive oil, cocoa butter, kapok oil, white mustard oil,
Sesame oil, rice bran oil, safflower oil, shea nut oil, cinnamon oil, soybean oil, teaseed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil,
Vegetable fats such as cottonseed oil, coconut oil, wood wax, peanut oil, etc., animal fats such as horse fat, beef tallow, beef tallow, beef tallow, lard, goat fat, sheep fat, milk fat, fish oil, whale oil, etc. Hydrides.

The lubricant for metal working of the present invention may be used for other lubricants.
Lubricants, such as oils, friction modifiers, extreme pressure agents, antioxidants
Agents, detergents, dispersants, viscosity index improvers, defoamers, rust prevention
Agent, pour point depressant, emulsifier, surfactant, rust inhibitor, preservative
Agent and the like. As an oil agent, for example,
Capric acid, caproic acid, pelargonic acid, caprylic acid,
Lauric acid, myristic acid, palmitic acid, stearin
Acid, oleic acid, linoleic acid, linolenic acid, arachiic acid
(C₂₀), Gadrenic acid (C_22F1), Behenic acid
(C_{twenty two}), Erucic acid (C_22F1), Lignoceric acid
(C_{twenty four}), Seracoleic acid (C _24F1), Serotoic acid (C
₂₆), Montanic acid (C₂₈), Melicic acid (C₃₀), Cello
Plastic acid (C₃₅), Ricinoleic acid, 12-hydro
Fatty acids such as xiestearic acid; dimer acid, glutar
Acid, adipic acid, pimelic acid, suberic acid, azelaine
Dicarboxylic acids such as acid, sebacic acid and dodecane diacid; lau
Lil alcohol, myristyl alcohol, palmitylua
Alcohol, stearyl alcohol, oleyl alcohol
Alcohols such as laurylamine, myristylamine,
Palmitylamine, stearylamine, oleylamine
Amines such as laurylamide, myristylamide, pal
Such as mitylamide, stearylamine, oleylamine, etc.
Amide; alkanolamine or N-long chain alkene as described above
Kill alkanolamines and the like. Alkano
Amine or N-long chain alkyl alkanolamine
May act as a rust or preservative

Examples of the friction modifier include capric acid (mono, di, tri) glyceride and caproic acid (mono, di, tri).
Di, tri) glyceride, caprylic acid (mono, di, tri)
Glyceride, lauric acid (mono, di, tri) glyceride, myristic acid (mono, di, tri) glyceride, palmitic acid (mono, di, tri) glyceride, stearic acid (mono, di, tri) glyceride, oleic acid (mono) ,
Esters such as di, tri) glyceride, ricinoleic acid or 12-hydroxystearic acid polycondensate, metal salts such as oxymolybdenum sulfide dialkyl dithiocarbamate, oxymolybdenum sulfide dialkyl dithiophosphate, zinc dialkyl dithiophosphate, zinc dialkyl dithiocarbamate, (Poly) glycerin ether such as (poly) glycerin oleyl ether and (poly) glycerin lauryl ether. Some of these compounds have antioxidant performance.

Examples of extreme pressure agents include sulfurized olefins,
Sulfurized paraffin, Sulfurized polyolefin, Sulfurized lard, Sulfurized fish oil, Sulfurized whale oil, Sulfurized soybean oil, Sulfurized pinene oil, Sulfurized phenol, Sulfurized alkylphenol, Sulfurized fatty acid, Dialkyl polysulfide, Dibenzyl disulfide, Diphenyl disulfide, Polyphenylene sulfide, Alkyl mercaptan, Alkylsulfone Acid, dithiocarbamate, 2,5-dimercapto-1,3,4-
Sulfur compounds such as thiadiazole derivative, thiuram disulfide, dialkyldithiophosphate dimer; butyl (thio, dithio) phosphate or phosphite, hexyl (thio, dithio) phosphate or phosphite, octyl (thio, dithio) phosphate or phosphite ,
2-ethylhexyl (thio, dithio) phosphate or phosphite, nonyl (thio, dithio) phosphate or phosphite, decyl (thio, dithio) phosphate or phosphite, lauryl (thio, dithio) phosphate or phosphite, myristyl (thio, Dithio) phosphate or phosphite, palmityl (thio, dithio) phosphate or phosphite, stearyl (thio, dithio) phosphate or phosphite, oleyl (thio, dithio) phosphate or phosphite, phenyl (thio, dithio) phosphate or phosphite ,
(Thio, dithio) phosphoric acid or phosphite compounds such as cresyl (thio, dithio) phosphate or phosphite. Some of these compounds have antioxidant performance.

Examples of the phenolic antioxidant include 2,6-di-tert.-butylphenol (hereinafter, tert.-butyl is abbreviated as t-butyl),
2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t
-Butyl-4-ethylphenol, 2,4-dimethyl-
6-t-butylphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4'-
Bis (2-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-
t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4 '
-Isopropylidenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-
Cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-isobutylidenebis (4,6-dimethylphenol),
2,6-bis (2'-hydroxy-3'-t-butyl-
5'-methylbenzyl) -4-methylphenol, 3-
t-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole, stearyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, 3- (4-hydroxy-3 Oleyl, 5-di-t-butylphenyl) propionate, dodecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3,5-di-t -Butylphenyl) decyl propionate, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis {3- (4-hydroxy-3,5)
-Di-t-butylphenyl) propionyloxymethyldimethane, 3- (4-hydroxy-3,5-di-t-
Butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid and glycerin monooleyl ether, 3- (4-hydroxy-3,5-diethyl ―
(t-butylphenyl) propionic acid butylene glycol ester, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid thiodiglycol ester, 4,4′-thiobis (3-methyl-6-t -Butylphenol), 4,4'-thiobis (2-methyl-6-)
t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-
Butyl-α-dimethylamino-p-cresol, 2,6
-Di-t-butyl-4- (N, N'-dimethylaminomethylphenol), bis (3,5-di-t-butyl-4)
-Hydroxybenzyl) sulfide, tris ｛(3,
5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl diisocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Isocyanurate, 1,3,5-tris (3,5-di-
t-butyl-4-hydroxybenzyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl} sulfide, 1,3,5-tris (4-t -Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4-t)
-Butyl-3-hydroxybenzyl sulfide), 6
-(4-hydroxy-3,5-di-t-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine, 2,2-thio-２diethyl-bis-3-
(3,5-di-t-butyl-4-hydroxyphenyl)｝ propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinamide), 3,5-di -T-butyl-4-hydroxy-
Benzyl-phosphate diester, bis (3-methyl-4-
(Hydroxy-5-t-butylbenzyl) sulfide,
3,9-bis [1,1-dimethyl-2- {β- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4- (Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid} glycol ester, etc. No.

Examples of the amine antioxidant include, for example, 1
-Naphthylamine, phenyl-1-naphthylamine, p
-Naphthylamine-based antioxidants such as -octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine and phenyl-2-naphthylamine; N, N'-diisopropyl-p-phenylenediamine , N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl- p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-
1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine,
Phenylenediamine antioxidants such as phenylhexyl-p-phenylenediamine and phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p,
p'-di-t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p '
-Didodecyldiphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine and the like Diphenylamine-based antioxidants; phenothiazine, N-methylphenothiazine,
Examples include phenothiazine antioxidants such as N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazine carboxylate, and phenoselenazine.

Examples of the sulfur-based antioxidants include dioctylthiodipropionate, didecylthiodipropionate, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, laurylstearylthiodipropionate. Pionate, dimyristylthiodipropionate, distearyl-β,
β'-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-stearyl Thiopropionic acid) pentaerythritol tetraester, (3
-Oleylthiopropionic acid) pentaerythritol tetraester, 2-mercaptobenzimidazole, 2
-Mercaptomethylbenzimidazole, 2-benzimidazole disulfide, dilauryl sulfide, amylthioglycolate and the like.

Examples of the metal salt antioxidant include nickel dithiocarbamate, zinc-2-mercaptobenzimidazole and the like. As the detergent or rust inhibitor, for example, calcium sulfonate, calcium phenate, calcium salicylate, magnesium sulfonate, magnesium phenate, magnesium salicylate, barium sulfonate, barium phenate,
And barium salicylate. Examples of the dispersant include polyalkenyl succinic monoimide or bisimide, polyalkenyl succinic monoimide or bisimide boric acid modified product, polyalkenyl succinic ester, benzylamine and the like. Examples of the viscosity index improver include poly (meth) acrylate, polyisobutylene, polystyrene, ethylene-propylene copolymer, styrene-isobutylene copolymer and the like.

Examples of the surfactant include polyethylene glycol, polyethylene glycol monoalkyl (aryl) ether, polyethylene glycol dialkyl (aryl) ether, polyoxyethylene polyoxypropylene copolymer, polyol ester, polyether polyol, alkanolamide, Examples thereof include alkylbenzene sulfonic acid and petroleum sulfonate. These surfactants may also act as an oil agent or an emulsifier.

The metal working lubricant of the present invention can be used for all kinds of metal working. Examples of the types of metal processing that can be used include, for example, cutting, grinding, wire drawing, rolling, forging, pressing,
Examples include extrusion, bending, drawing, stretching, ironing, roll forming, shearing, rotation, elongation, drawing, and pressing. Metals to which the lubricant for metal working of the present invention is applied include iron, aluminum, titanium, magnesium, copper, zinc, manganese, alloys thereof (for example, stainless steel, brass, etc.) or alloys of these with silicon, etc. Although not limited, a good effect is exhibited particularly when iron, aluminum, and stainless steel are used.

[0031]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following examples, “%” is based on weight unless otherwise specified.

(Production Example 1) 2 mol of phosphorous acid was added to 3 mol of polyoxyethylene (2) lauryl ether, and
The reaction was carried out for 5 hours while dehydrating at 0 to 150 ° C. to obtain a phosphite of the present invention product 1 shown in Table 1 below. Similarly, various polyoxyalkylene alkyl ethers were reacted with phosphorous acid to obtain phosphites of inventive products 2 to 7 shown in Table 1 below. Furthermore, the phosphite of the product 1 of the present invention and the alkylamine shown in Table 1 were mixed to obtain amine salts of the phosphites of the products 8 and 9 of the present invention.

[0033]

[Table 1]

(Example 1) A mixture of the lubricating base oil and the lubricants of the present invention 1 to 9 and comparative products 1 to 4 shown in Table 1 was used as a sample, and the load applied to the ball was varied. Then, a load resistance test was performed. That is, the wear scar diameter (mm) of the ball at each load was measured using a high-speed four-ball testing machine under the following conditions. <Test conditions> Lubricating base oil: Refined mineral oil (viscosity at 40 ° C: 18.3 mm
² / s) Time: 10 seconds Rotation speed: 1,500 rpm Temperature: Room temperature Sample addition amount: 3% based on lubricating base oil The results are shown in Table 2.

[0035]

[Table 2]

(Production Example 2) Polyoxyethylene (10)
The product 1 of the present invention of Production Example 1 except that lauryl ether was used.
In the same manner as in the above method, a phosphite of product 10 of the present invention shown in Table 3 below was obtained. Similarly, the phosphites of the present invention products 11 to 14 shown in Table 3 below and the present invention product 1
The amine salts of the phosphites 5 and 16 were obtained.

[0037]

[Table 3]

Example 2 Inventive product 10 shown in Table 3 in water
Using a mixture of the lubricants of Nos. 1 to 16 and Comparative Products 5 to 7 as a sample, a load resistance test was performed by changing the load applied to the ball in various ways. That is, the wear scar diameter (m) of the ball at each load was measured using a high-speed four-ball testing machine under the following conditions.
m) was measured. <Test conditions> Base material: water Time: 2 seconds Rotation speed: 1,500 rpm Temperature: room temperature Sample addition amount: 3% based on base material These results are shown in Table 4.

[0039]

[Table 4]

From the results of Examples 1 and 2, the phosphite ester-based metal working lubricant of the present invention is a phosphate ester-based lubricant (comparative products 2 and 4 to 7) or (poly) oxyalkylene. It was found that, compared to phosphite-based lubricants having no group (Comparative Products 1 and 3), excellent lubricity was exhibited in both oil-based and water-based metal working oils.

[0041]

The effect of the present invention is to provide an excellent lubricating metal working lubricant comprising a phosphite having a (poly) oxyalkylene group or a neutralized product thereof with a basic compound. is there.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Naoto Namiki 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F-term (reference) 4H104 AA01Z BH02C BH05C BH06C DA02A DA06A EB02 FA01 FA02 LA03 PA21 QA01

Claims (3)

[Claims] 1. The following general formula (1): In the formula, R ¹ , R ² and R ³ are a hydrogen atom, a hydrocarbon group or the following general formula (2) — (R ⁴ —O) _n —R ⁵ (2) (wherein R ⁴ is an alkylene group R ⁵ represents a hydrocarbon group, and n represents a number of 1 or more.) However, at least one of R ¹ , R ² and R ³
One is a group represented by the general formula (2). A metal working lubricant comprising a phosphite represented by｝ or a neutralized product of the phosphite and a basic compound. 2. The metal working lubricant according to claim 1, wherein R ⁵ is an alkyl group or an alkenyl group having 6 to 36 carbon atoms. 3. The metal working lubricant according to claim 1, wherein R ⁴ is an alkylene group having 2 to 4 carbon atoms.