JPH10273687A - Rust inhibitor oil composition for plastic working - Google Patents

Abstract

(57) [Summary] [Problem] To provide an oil composition exhibiting excellent lubricity in plastic working and having rust-preventing ability. SOLUTION: A zinc dithiophosphate compound having at least one alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms and a rust inhibitor are mixed with mineral oil or synthetic oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust preventive oil composition for plastic working, and more particularly to press forming, bending forming, drawing forming, ironing forming, etc. for a steel plate, a stainless steel plate, a surface-treated steel plate or an aluminum alloy plate. Prior to plastic working, by applying to the plate material in advance, it functions as a rust-preventive oil during storage, and exhibits excellent lubricity during plastic working. .

[0002]

2. Description of the Related Art Lubricating oils for plastic working containing chlorine-based extreme pressure agents and sulfur-based extreme pressure agents have been widely used in the past because of their excellent extreme pressure properties. However, since these additives often have corrosive properties, even if a rust inhibitor is added to a plastic working lubricant containing these additives, a satisfactory rust inhibitor effect cannot be expected. .
And, in the case of applying rust-preventive oil for the purpose of rust prevention when preserving the sheet material, remove the rust-preventive oil prior to plastic working, and then apply the plastic working lubricant again. There is trouble to be. On the other hand, zinc alkyldithiophosphate compounds have been widely used in lubricants such as engine oils and hydraulic oils because of their excellent wear resistance and antioxidant properties. However, zinc alkyldithiophosphate compounds that have been practically used so far have an alkyl group having 8 or less carbon atoms, and have little effect on improving lubricity during plastic working of metal materials. Almost no additives are used as lubricating oil additives for plastic working.

[0003]

In recent years, the types and grades of sheet materials to be subjected to plastic working have been diversified, and the working shapes have been diversified. An object of the present invention is to provide an oil composition that can cope with such a trend.
Another object of the present invention is to provide an oil composition that exhibits high workability when performing plastic working on a difficult-to-work material such as a steel sheet, a stainless steel sheet, a surface-treated steel sheet, and an aluminum alloy sheet. Still another object of the present invention is to function as a rust preventive oil when storing a sheet material, as well as to provide good lubricity during processing, in contrast to the conventional plastic working lubricating oil which hardly exhibits a rust preventing effect. An object of the present invention is to provide a rust-preventive oil composition which is also used for plastic working.

[0004]

One of the rust-preventive oil compositions for plastic working according to the present invention comprises mineral oil and / or synthetic oil as a base oil, and (A) the following general formula (A) The zinc dithiophosphate compound represented by 1) is used in an amount of 0.5 to
50% by mass (In the above formula (1), R ¹ , R ² , R ³ and R ^{4 each} independently represent a hydrocarbon group, and R ¹ , R ² , R ³ and R 4
^At least one of ⁴ represents an alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms. ) And (B) 1 to 20% by mass of at least one rust inhibitor selected from the following (1) to (3): (1) oxide of wax or derivative thereof (2) polyhydric alcohol Partial ester (3) Lanolin or a derivative thereof is characterized in that it is contained. Another one is that the above-mentioned rust-preventive oil composition for plastic working is further added to (C) an alkali metal of sulfonic acid based on the total amount of the composition. A salt, an alkaline earth metal salt or an amine salt is contained in an amount of 1 to 20% by mass.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in more detail. The base oil in the present invention is a mineral oil and / or a synthetic oil. As a mineral oil, for example, a lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of crude oil, solvent removal, solvent extraction, hydrocracking, solvent dewaxing, contact dewaxing,
Paraffinic or naphthenic oils purified by appropriately combining hydrotreating, sulfuric acid washing, and clay treatments can be used. As synthetic oils, for example, poly α
-Olefin (polybutene, 1-octene oligomer,
Examples thereof include 1-decene oligomer, alkylbenzene, alkylnaphthalene, ester (however, excluding partial ester of polyhydric alcohol), polyoxyalkylene glycol, and polyphenyl ether. In the present invention, the kinematic viscosity of the base oil is not limited at all,
Kinematic viscosity at ℃ is 0.7~2000mm ² / s, preferably is used as the 0.7~1000mm ² / s. Of course, these mineral oils and synthetic oils may be used alone or in combination of two or more. Furthermore, a mixture of a solvent-level low-viscosity base oil (40 ° C. kinematic viscosity of 0.7 to ⁵ mm ² / s) and a medium-high viscosity base oil (40 ° C. kinematic viscosity of 6 to 2000 mm ² / s) is used in the present invention. Can also be used as a base oil.

The component (A) in the present invention has 16 carbon atoms.
A zinc dithiophosphate compound having at least one of the above alkylaryl group or alkenylaryl group having 16 or more carbon atoms, and the compound has the following general formula (1)
It is represented by (In the above formula (1), R ¹ , R ² , R ³ and R ^{4 each} independently represent a hydrocarbon group, and R ¹ , R ² , R ³ and R 4
^At least one of ⁴ represents an alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms. In the component (A) of the present invention, at least one of R ^{1 to} R ^{4 in} the general formula (1) must be an alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms. The rest may be hydrocarbon groups having any number of carbon atoms. However, in terms of ease of handling and cost, the hydrocarbon group may have 30 or less carbon atoms, preferably 26 or less carbon atoms. Specific examples of such a hydrocarbon group include, for example, an alkyl group having 1 to 30 carbon atoms,
An alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, carbon Examples thereof include an alkenyl aryl group having 7 to 30 carbon atoms and an arylalkyl group having 7 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include:
Methyl group, ethyl group, n-propyl group, isopropyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched Heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group, linear or branched dodecyl Group, straight or branched tridecyl group, tetradecyl group, tetradecyl group, straight or branched tetradecyl group, straight or branched pentadecyl group, straight or branched hexadecyl group, straight or branched heptadecyl group , A linear or branched octadecyl group,
Straight or branched nonadecyl group, straight or branched icosyl group, straight or branched henicosyl group, straight or branched tricosyl group, straight or branched tetracosyl group, straight or branched Pentacosyl group, linear or branched hexacosyl group, linear or branched heptacosyl group,
A straight-chain or branched octakosyl group, a straight-chain or branched nonacosyl group, a straight-chain or branched triacontyl group and the like can be mentioned. Examples of the alkenyl group having 2 to 30 carbon atoms include an ethenyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, a linear or branched Branched hexenyl group, linear or branched heptenyl group, linear or branched octenyl group, linear or branched nonenyl group, linear or branched decenyl group, linear or branched A branched undecenyl group, a straight or branched dodecenyl group, a straight or branched tridecenyl group, a straight or branched tetradecenyl group, a straight or branched pentadecenyl group, a straight or branched hexadecenyl group, A straight-chain or branched heptadecenyl group, a straight-chain or branched octadecenyl group,
Straight or branched nonadecenyl group, straight or branched icosenyl group, straight or branched henicocenyl group, straight or branched tricosenyl group, straight or branched tetracosenyl group, straight or branched Pentacosenyl group, linear or branched hexacosenyl group, linear or branched heptacosenyl group, linear or branched octacosenyl group, linear or branched nonacosenyl group, linear or branched triaconenyl group And the like. Examples of the cycloalkyl group having 5 to 7 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the alkylcycloalkyl group having 6 to 30 carbon atoms include a methylcyclopentyl group (including all substituted isomers), a dimethylcyclopentyl group (including all substituted isomers), and an ethylcyclopentyl group (including all substituted isomers) ), Methylethylcyclopentyl group (including all substituted isomers), diethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (including all substituted isomers) Ethylcyclohexyl group (including all substituted isomers), methylethylcyclohexyl group (including all substituted isomers), diethylcyclohexyl group (including all substituted isomers), methylcycloheptyl Group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers) Including the body), including ethylcycloheptyl (all isomers), and the like methylethyl cycloheptyl group (including all isomers) is.
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the alkylaryl group having 7 to 30 carbon atoms include a tolyl group (including all substituted isomers), a xylyl group (including all substituted isomers), and an ethylphenyl group (including all substituted isomers). Linear or branched propylphenyl group (including all substituted isomers), linear or branched butylphenyl group (including all substituted isomers), linear or branched pentylphenyl group (including all substituted isomers) , A straight-chain or branched hexylphenyl group (including all substituted isomers), a straight-chain or branched heptylphenyl group (including all substituted isomers), a straight-chain or branched A branched octylphenyl group (including all substituted isomers), a linear or branched nonylphenyl group (including all substituted isomers), a linear or branched decylphenyl group (including all substituted isomers) including),
A linear or branched undecylphenyl group (including all substituted isomers), a linear or branched dodecylphenyl group (including all substituted isomers), a linear or branched tridecylphenyl group (including all substituted isomers) Straight-chain or branched tetradecylphenyl groups (including all substituted isomers), straight-chain or branched heptadecylphenyl groups (including all substituted isomers), Chain or branched hexadecylphenyl group (including all substituted isomers), linear or branched heptadecylphenyl group (including all substituted isomers), linear or branched octadecylphenyl group (including all substituted isomers) ), Linear or branched nonadecylphenyl groups (including all substituted isomers), linear or branched icosylphenyl groups (including all substituted isomers), linear Or branched hen A cosylphenyl group (including all substituted isomers), a linear or branched tricosylphenyl group (including all substituted isomers), a linear or branched tetracosylphenyl group (including all substituted isomers) And the like). Examples of the alkenylaryl group having 7 to 30 carbon atoms include an ethenylphenyl group (including all substituted isomers), a linear or branched propenylphenyl group (including all substituted isomers), a linear or A branched butenylphenyl group (including all substituted isomers), a linear or branched pentenylphenyl group (including all substituted isomers), a linear or branched hexenylphenyl group (including all substituted isomers) Isomers), linear or branched heptenylphenyl groups (including all substituted isomers), linear or branched octenylphenyl groups (including all substituted isomers), linear or branched A branched nonenylphenyl group (including all substituted isomers), a linear or branched decenylphenyl group (including all substituted isomers), a linear or branched undecenylphenyl group (including all substituted isomers) Including ), Linear or branched dodecenylphenyl groups (including all substituted isomers), linear or branched tridecenylphenyl groups (including all substituted isomers), linear or branched A tetradecenylphenyl group (including all substituted isomers), a linear or branched heptadecenylphenyl group (including all substituted isomers),
Straight or branched hexadecenyl phenyl group (including all substituted isomers), straight or branched heptadecenyl phenyl group (including all substituted isomers), straight or branched An octadecenylphenyl group (including all substituted isomers), a linear or branched nonadecenylphenyl group (including all substituted isomers), a linear or branched icosenylphenyl group (including all substituted isomers) Straight or branched henicocenyl phenyl group (including all substituted isomers), straight or branched tricosenyl phenyl group (including all substituted isomers) ), A linear or branched tetracosenylphenyl group (including all substituted isomers) and the like. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group (phenethyl group), a phenylpropyl group (including isomers of a propyl group), and a phenylbutyl group ( Butyl group isomers).

The component (A) of the present invention comprises R ¹ , R ² , R in the above general formula (1) from the viewpoint of workability during plastic working.
It is necessary that at least one of ³ and R ⁴ is an alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms, and preferably, among R ¹ , R ² , R ³ and R ⁴ Two, more preferably three, most preferably R ¹ , R ² , R ³ and R
It is desirable that all of ^{4 be} an alkylaryl group having 16 or more carbon atoms and / or an alkenylaryl group having 16 or more carbon atoms. The upper limit of the number of carbon atoms of the alkylaryl group having 16 or more carbon atoms and the alkenylaryl group having 16 or more carbon atoms is not particularly limited, but the number of carbon atoms is usually 30 or less, preferably 26 or less in terms of ease of handling and cost. It is. Among the alkylaryl groups having 16 or more carbon atoms, an alkylphenyl group in which at least one alkyl group having 10 to 24 carbon atoms is bonded to a phenyl group is preferable from the viewpoint of more excellent workability during plastic working, and 10 carbon atoms. An alkylphenyl group in which an alkyl group of from 21 to 21 is bonded to at least one phenyl group,
An alkylphenyl group in which at least one alkyl group having 10 to 18 carbon atoms is bonded to a phenyl group is most preferred. Further, among alkenylaryl groups having 16 or more carbon atoms,
For the same reason, an alkenylphenyl group having at least one alkenyl group having 10 to 24 carbon atoms bonded to a phenyl group is preferable, and an alkenylphenyl group having at least one alkenyl group having 10 to 21 carbon atoms bonded to the phenyl group is more preferable. An alkenylphenyl group having at least one alkenyl group having 10 to 18 carbon atoms bonded to a phenyl group is most preferred. In the present invention, one of the zinc dithiophosphate compounds included in the general formula (1) defined above can be used alone, or two or more can be used in combination.

The lower limit of the content of the component (A) in the oil composition of the present invention is 0.5% by mass, preferably 1% by mass, more preferably 2% by mass, and most preferably 3% by mass, based on the total amount of the composition. On the other hand, the upper limit of the content is 50% by mass, preferably 40% by mass based on the total amount of the composition.
When the content of the component (A) is less than 0.5% by mass based on the total amount of the composition, the effect of adding lubricity is not exhibited. On the other hand, when the content exceeds 50% by mass based on the total amount of the composition, The resulting addition effect of improving lubricity is not suitable in terms of cost, which is not preferred. The zinc dithiophosphate compound represented by the above general formula (1) is a neutral salt, but when it is produced, a basic zinc dithiophosphate compound is usually produced as a by-product. This basic salt, which is a by-product, may be contained in the oil composition of the present invention as long as it is in the range of 0 to 150 parts by weight based on 100 parts by weight of the neutral salt. However, even in that case, the content of the zinc dithiophosphate compound (neutral salt) represented by the general formula (1) must be in the range of 0.5 to 50% by mass based on the total amount of the composition.

The component (B) in the present invention is one or more compounds selected from the following (1) to (3). (B1) Oxide of wax or derivative thereof (B2) Partial ester of polyhydric alcohol (B3) Lanolin or derivative thereof The oxide of wax referred to in the above component (B1) is obtained at the time of refining petroleum fraction. Those manufactured by oxidizing wax such as paraffin wax, microcrystalline wax, petrolatum, and polyolefin wax obtained by synthesis are used. Also,
As the derivative, salts and esters modified are used. With the salts of the oxide of the wax, the above-mentioned oxide of the wax is reacted with an alkali metal such as sodium and potassium, an alkaline earth metal such as magnesium, calcium, and barium, and a salt or a base such as an amine, It refers to a product obtained by neutralizing a part or all of the acidic groups of a wax oxide to form a salt. The wax oxide is obtained by esterifying the wax oxide by reacting an alcohol with the wax oxide to esterify a part or all of the acidic groups of the wax oxide. Point. The saponification value, total acid value and metal content of the component (B1) are optional, but are specified in JIS K 2503 from the viewpoint that the composition is excellent in storage stability, oxidation stability, water displacement and rust prevention. Saponification value 50-1
Those having properties of 00 mg KOH / g and a total acid value defined in JIS K 2501 of 2 to 20 mg KOH / g are preferably used.

The component (B2) is a partial ester of a polyhydric alcohol. As the polyhydric alcohol used herein, any one can be used, but 2 to 10, preferably 3 to
2 to 20 carbon atoms having 6 hydroxyl groups, preferably 3 to 2 carbon atoms
Ten polyhydric alcohols are preferably used. Among them, in the present invention, it is more preferable to use one or more polyhydric alcohols selected from glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitan. As the acid constituting the partial ester, any acid can be used, but usually a fatty acid having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms is used. Such a fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Specifically, for example, hexanoic acid (including all isomers), heptanoic acid (including all isomers), octanoic acid (including all isomers), nonanoic acid (including all isomers), Decanoic acid (including all isomers), undecanoic acid (including all isomers), dodecanoic acid (including all isomers), tridecanoic acid (including all isomers), tetradecanoic acid (including all isomers) Body)
Pentadecanoic acid (including all isomers), hexadecanoic acid (including all isomers), heptadecanoic acid (including all isomers), octadecanoic acid (including all isomers), nonadecanoic acid (including all isomers) Icosanoic acid (including all isomers), heicosanoic acid (including all isomers), docosanoic acid (including all isomers), tricosanoic acid (including all isomers), tetracosane Saturated fatty acids such as acids (including all isomers); hexenoic acid (including all isomers), heptenoic acid (including all isomers), octenoic acid (including all isomers), nonenic acid (including Decenoic acid (including all isomers), undecenoic acid (including all isomers), dodecenoic acid (including all isomers), tridecenoic acid (including all isomers) ), Tetradece Acid (including all isomers),
Pentadecenoic acid (including all isomers), hexadecenoic acid (including all isomers), heptadecenoic acid (including all isomers), octadecenoic acid (including all isomers), nonadecenoic acid (including all isomers) Icosenoic acid (including all isomers), heicoicenoic acid (including all isomers), docosenoic acid (including all isomers), tricosenoic acid (including all isomers), tetracocene Unsaturated fatty acids such as acids (including all isomers); and mixtures thereof. Here, the partial ester means an ester which remains in the form of a hydroxyl group in which at least one or more of the hydroxyl groups in the polyhydric alcohol is not esterified. As the component (B2), for example, glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, glycerin didodecanoate (glycerin dilaurate), glycerin diisolaurate, glycerin monotetradecanoate (glycerin) Glycerin monoisomyristate, glycerin ditetradecanoate (glycerin dimyristate), glycerin diisomyristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, glycerin Dihexadecanoate (glycerin dipalmitate), glycerin diisopalmitate, glycerin monooctadecanoate (glycerin monostearate), glycerin monoisostearate Glycerin dioctadecanoate (glycerin distearate), glycerin diisostearate, glycerin monooctadesenoate (glycerin monooleate), glycerin monoisooleate, glycerin dioctadecenoate (glycerin dioleate) Glycerin partial esters such as glycerin diisooleate; trimethylolethane monododecanoate (trimethylolethane monolaurate), trimethylolethane monoisolaurate, trimethylolethanedidodecanoate (trimethylolethanedilaurate), Trimethylolethanediisolaurate, trimethylolethane monotetradecanoate (trimethylolethane monoisomyristate), trimethylolethane monoisomyristate, trimethylo Ethaneditetradecanoate (trimethylolethanedimyristate), trimethylolethanediisomyristate, trimethylolethanemonohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylol Ethanedihexadecanoate (trimethylolethanedipalmitate), trimethylolethanediisopalmitate, trimethylolethane monooctadecanoate (trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylol Ethanedioctadecanoate (trimethylolethanedistearate), trimethylolethanediisostearate, trimethylolethane monooctadecenoate (trimethylolethane monostearate) Oleate),
Trimethylolethane partial esters such as trimethylolethane monoisooleate, trimethylolethanedioctadecenoate (trimethylolethanedioleate), and trimethylolethanediisooleate; trimethylolpropane monododecanoate (trimethylol) Propane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropanezide decanoate (trimethylolpropanedilaurate), trimethylolpropanediisolaurate, trimethylolpropanemonotetradecanoate (trimethylolpropane monomyristate) ), Trimethylolpropane monoisomyristate, trimethylolpropaneditetradecanoate (trimethylolpropanedimyristate), trimethylol Lopandiisomyristate, trimethylolpropane monohexadecanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisopalmitate, trimethylolpropane dihexadecanoate (trimethylolpropane dipalmitate), trimethylol Propane diisopalmitate, trimethylolpropane monooctadecanoate (trimethylolpropane monostearate), trimethylolpropane monoisostearate, trimethylolpropane dioctadecanoate (trimethylolpropane distearate), trimethylol Propane diisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate),
Trimethylolpropane partial esters such as trimethylolpropane monoisooleate, trimethylolpropanedioctadecenoate (trimethylolpropanedioleate), and trimethylolpropanediisooleate; pentaerythritol monododecanoate (pentaerythritol mono) Laurate), pentaerythritol monoisolaurate, pentaerythritol didodecanoate (pentaerythritol dilaurate), pentaerythritol diisolaurate, pentaerythritol tridodecanoate (pentaerythritol trilaurate), pentaerythritol triisolaurate, penta Erythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomer State, pentaerythritol tetra decanoate (pentaerythritol myristate), pentaerythritol iso myristate,
Pentaerythritol tritetradecanoate (pentaerythritol trimyristate), pentaerythritol triisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol dihexadecano Ethate (pentaerythritol dipalmitate), pentaerythritol diisopalmitate, pentaerythritol trihexadecanoate (pentaerythritol tripalmitate), pentaerythritol triisopalmitate,
Pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol dioctadecanoate (pentaerythritol distearate), pentaerythritol diisostearate, pentaerythritol trioctadecano Ethate (pentaerythritol tristearate), pentaerythritol triisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate), pentaerythritol monoisooleate, pentaerythritol dioctadecenoate (pentaerythritol dioleate) Ethate), pentaerythritol diisooleate, pentaerythritol trioctadecenoate (pentaerythritol) Pentaerythritol partial esters such as tall trioleate) and pentaerythritol triisooleate; sorbitan monododecanoate (sorbitan monolaurate), sorbitan monoisolaurate, sorbitan didodecanoate (sorbitan dilaurate), sorbitan diisolaurate , Sorbitan tridodecanoate (sorbitan trilaurate),
Sorbitan triisolaurate, sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan monoisomyristate, sorbitan ditetradecanoate (sorbitan dimyristate), sorbitan diisomyristate, sorbitan tritetradecanoate ( Sorbitan triisomyristate), sorbitan triisomyristate, sorbitan monohexadecanoate (sorbitan monopalmitate), sorbitan monoisopalmitate, sorbitan dihexadecanoate (sorbitan dipalmitate), sorbitan diisopalmitate,
Sorbitan trihexadecanoate (sorbitan tripalmitate), sorbitan triisopalmitate, sorbitan monooctadecanoate (sorbitan monostearate), sorbitan monoisostearate, sorbitan dioctadedecanoate (sorbitan distearate) , Sorbitan diisostearate, sorbitan trioctadecanoate (sorbitan tristearate),
Sorbitan triisostearate, sorbitan monooctadecenoate (sorbitan monooleate), sorbitan monoisooleate, sorbitan dioctadecenoate (sorbitan dioleate), sorbitan diisooleate, sorbitan trioctadecenoate (Sorbitan trioleate), sorbitan partial esters such as sorbitan triisooleate, and mixtures thereof are preferably used. In particular, monoesters such as glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, glycerin monotetradecanoate (glycerin monomyristate),
Glycerin monoisomyristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, glycerin monooctadecanoate (glycerin monostearate), glycerin monoisostearate, glycerin monooctadecenoate (Glycerin monooleate), glycerin monoisooleate; trimethylolethane monododecanoate (trimethylolethane monolaurate), trimethylolethane monoisolaurate, trimethylolethane monotetradecanoate (trimethylolethane mono) Myristate), trimethylolethane monoisomyristate, trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethanemo Isopalmitate, trimethylolethane monooctadecanoate (trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate Ethates: trimethylolpropane monododecanoate (trimethylolpropane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropane monotetradecanoate (trimethylolpropane monomyristate), trimethylolpropane monoisomyristate , Trimethylolpropane monohexadecanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisopalmitate, trimethylo Lepropane monooctadecanoate (trimethylolpropane monostearate), trimethylolpropane monoisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate; penta Erythritol monododecanoate (pentaerythritol monolaurate), pentaerythritol monoisolaurate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomyristate, pentaerythritol monohexadecanoate ( Pentaerythritol monopalmitate, pentaerythritol monoisopalmitate, pentaerythritol monooctadecanoate (pen Taerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate), pentaerythritol monoisooleate; sorbitan monododecanoate (sorbitan monolaurate), sorbitan mono Isolaurate, sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan monoisomyristate, sorbitan monohexadecanoate (sorbitan monopalmitate), sorbitan monoisopalmitate, sorbitan monooctadecanoate (sorbitan) Monostearate), sorbitan monoisostearate, sorbitan monooctadecenoate (sorbitan monooleate),
Sorbitan monoisooleate; and mixtures thereof are more preferably used.

The component (B3) of the present invention is lanolin or a derivative thereof. Lanolin (wool fat) as used herein refers to one obtained by purifying a waxy substance that adheres to wool hair. In the present invention, such lanolin may be used as it is, or may be used as a derivative thereof.
Derivatives include alkali metal salts, alkaline earth metal salts or esters. Alkali metal salts or alkaline earth metal salts, lanolin, sodium, potassium and other alkali metals and magnesium, calcium,
Oxides of alkaline earth metals such as barium, by reacting with a base such as a hydroxide, a part or all of the fatty acid component contained in lanolin is a metal salt, and lanolin fatty acid ester, Lanolin and alcohol, preferably polyhydric alcohol, more preferably glycerin,
It refers to a product obtained by reacting trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitan to esterify a part or all of the fatty acid component contained in lanolin. In the present invention, the saponification value and the total acid value of the above lanolin fatty acid ester are optional,
The saponification value of 20 to 220 mgKOH / g specified in JIS K2503 and JIS in view of excellent storage stability, oxidation stability, water displacement property and rust prevention property of the composition.
K 2501 total acid value 1-20 mgKOH / g
Those having the following properties are preferably used. The component (B) of the present invention includes the component (B1) and the component (B2) described above.
A mixture in which two or more compounds selected from the component and the component (B3) are mixed at an arbitrary ratio can also be preferably used. The lower limit of the compounding amount of the component (B) in the plastic working and rust preventive oil composition of the present invention is 1% by weight, preferably 2% by weight based on the total amount of the composition, while the upper limit of the compounding amount is 20% by weight, preferably 10%, based on the total amount
% By weight. When the amount of the component (B) is less than 1% by weight based on the total amount of the composition, the rust-preventive property is reduced. On the other hand, when the amount is more than 20% by weight based on the total amount of the composition, the processability is reduced. , Respectively, is not preferred.

In the present invention, as described above, by adding a predetermined amount of the component (A) and the component (B) to the base oil, a plastic working and rust preventing oil composition excellent in workability and rust resistance can be obtained. Although it can be obtained, an alkali metal salt, an alkaline earth metal salt or an amine salt of sulfonic acid can be added as the component (C) for the purpose of further improving the rust preventive performance. Examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include magnesium, calcium, and barium. Examples of the amine include ammonia; an alkylamine having an alkyl group having 1 to 3 carbon atoms, such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, and tripropylamine; monomethanolamine Alkanolamines having an alkanol group having 1 to 3 carbon atoms, such as dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monoethanolamine, dipropanolamine, and tripropanolamine. The component (C) is not particularly limited in its production method, and any component produced by any method can be used. For example, a molecular weight of 100 to
Alkali metal salts, alkaline earth metal salts, amine salts, and mixtures thereof of alkyl aromatic sulfonic acids obtained by sulfonating 1500, preferably 200 to 700 alkyl aromatic compounds can be used. As the alkyl aromatic sulfonic acid here,
Generally, sulfonated alkyl aromatic compounds in lubricating oil fractions of mineral oil and by-products during the production of white oil,
Petroleum sulfonic acid such as so-called mahoganic acid, for example, alkyl benzene having a linear or branched alkyl group, which is obtained as a by-product from an alkyl benzene production plant used as a raw material for detergents or obtained by alkylating polyolefin to benzene. Synthetic sulfonic acids such as sulfonated ones and sulfonated alkylnaphthalenes such as dinonylnaphthalene are exemplified. As the component (C), the above-mentioned alkyl aromatic sulfonic acid, a base of an alkali metal (such as an oxide or hydroxide of an alkali metal), and a base of an alkaline earth metal (such as an oxide or a hydroxide of an alkaline earth metal) So-called neutral (normal salt) sulfonate obtained by reacting with the above-mentioned amines (ammonia, alkylamine, alkanolamine, etc.); neutral (normal salt) sulfonate;
A so-called basic sulfonate obtained by heating an excess of an alkali metal base, an alkaline earth metal base or an amine in the presence of water; a neutral (normal salt) sulfonate in the presence of carbon dioxide gas. base,
So-called carbonate overbased (ultrabasic) obtained by reacting with alkaline earth metal bases or amines
Sulfonates; neutral (normal salt) sulfonates are reacted with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (ultrabasic) ) Sulfonates and boric acid compounds such as boric acid or the like, and so-called borate overbased (ultra-basic) sulfonates produced by reacting the compounds; and mixtures thereof. The total chlorine number of the component (C) is optional. Usually, the value of the total base number by the perchloric acid method specified in JIS K2501 is 0 to 700 mg KOH.
/ G, preferably in the range from 0 to 600 mg KOH / g. In the rust-preventive oil composition for plastic working of the present invention, the content of the component (C) is 1% by mass or more based on the total amount of the composition.
Preferably, it is 2% by mass or more. (C)
When the content of the component is less than 1% by mass, the effect of improving rust prevention cannot be expected. Further, the content of the component (C) is desirably 20% by mass or less, preferably 15% by mass or less. Then, the base number of the component (C) (mgK
OH / g) and its content (% by mass) are 50 mgK
OH / g or less is desirable.

In the oil composition of the present invention, known lubricating oil additives can be used alone or in combination of several kinds in order to further enhance various performances. These additives include, for example, lubricity improvers represented by sulfurized oils and fats, phosphates such as tricresyl phosphate, oils and fats such as lard oil, fatty acids, and the like; 2,6-di-tert-butyl- p-cresol, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,
4'-bis (2,6-di-tert-butylphenol),
Antioxidants represented by 4,4'-thiobis (6-tert-butyl-o-cresol); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, micro wax, slack wax, polyolefin wax, etc. Water displacing agents such as fatty acid amine salts; zinc dithiophosphate compounds (excluding those represented by the above general formula (1)); graphite, fluorinated graphite, molybdenum disulfide, boron nitride, polyethylene Solid lubricants such as powders; corrosion inhibitors such as amines, alkanolamines, amides and carboxylic acids; metal deactivators such as benzotriazole and thiadiazole; defoamers such as methyl silicone, fluoro silicone and polyacrylate; No. The content when these known additives are used in combination can be arbitrarily selected, but is usually adjusted so that the total content of these known additives is 0.1 to 10% by weight based on the total amount of the composition.

The rust-preventive oil composition for plastic working of the present invention, in which the components (A) and (B) are added to the base oil, and if necessary, the component (C) and other additives, is used. There is no particular limitation on (40 ° C.). However, the kinematic viscosity (40 ° C.) is preferably in the range of 1.5 to 500 mm ² / s, and more preferably in the range of ² to 200 mm ² / s, from the viewpoint of handling convenience and the amount taken out when immersion oil is applied. Is more preferable. Further to oiled steel plate, considering also the slip suppression when winding the steel sheet into a coil, kinematic viscosity (40 ° C.) is preferably in the range of 2~50mm ² / s, 2~25mm ² / More preferably, it is in the range of s.

The rust-preventive oil composition for plastic working according to the present invention includes, for example, ordinary steel plates, stainless steel plates, hot-dip galvanized steel plates, alloyed hot-dip galvanized steel plates, electro-galvanized steel plates, and electro-zinc-iron alloy-plated steel plates , Electric zinc-nickel alloy plated steel sheet, double-layer plated steel sheet, plastic processing of surface-treated steel sheet such as turn sheet, specifically, press forming, bending forming, drawing forming, ironing is particularly preferably used in iron forming and the like. is there. In addition to plastic working of steel sheets, stainless steel sheets and surface-treated steel sheets, plastic working of non-ferrous metal sheets such as aluminum and aluminum alloys, for example, press forming, bending forming, drawing forming,
It is also suitably used in ironing and the like.

[0016]

EXAMPLES Hereinafter, the content of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these contents. [Synthesis Example 1] Put p into a 2 liter glass four-necked flask.
-(2,4,6-trimethylnonyl) phenol 1.7
4 mol, 0.4 mol of phosphorus pentasulfide and 360 g of xylene
And stirred at 143 ° C. for 2 hours under a nitrogen atmosphere. After the reaction mixture was filtered to remove insolubles, the filtrate was heated to 95 ° C.
And dried under vacuum with p- (2,4,6-trimethylnonyl)
Phenyldithiophosphoric acid, containing impurities, yield 105%
I got it. Next, 250 g of this product was placed in a 2 liter glass four-necked flask under a nitrogen atmosphere, and about
The solution was dissolved in 00 ml with heating and stirring at 50 ° C., and 0.24 mol of zinc oxide and 0.3 g of acetic acid were added thereto.
Stirred at C overnight. After completion of the reaction, the reaction solution was extracted with hexane, washed well with saturated saline, and the solution was dried over anhydrous sodium sulfate. The obtained product has 1 carbon atom.
94% of a neutral salt (represented by the following formula) of a zinc dithiophosphate compound having an alkylphenyl group of 8 and 5% of a basic salt
And 1% of other impurities, but were subjected to the test without further purification. R ¹ : p- (2,4,6-trimethylnonyl) phenyl group [Synthesis Example 2] Except that p- (n-decyl) phenol was used instead of p- (2,4,6-trimethylnonyl) phenol Is a compound having 1 carbon atom in the same manner as in Synthesis Example 1.
A zinc dithiophosphate compound having 6 alkyl groups was synthesized. The obtained product is composed of 95% of a neutral salt (expressed by the following formula) of a zinc dithiophosphate compound having an alkylphenyl group having 16 carbon atoms, 4% of a basic salt, and 1% of other impurities.
However, the mixture was subjected to the test without further purification. R ¹ : p- (n-decyl) phenyl group [Synthesis Example 3] Synthesis Example 1 except that p- (4-decenyl) phenol was used instead of p- (2,4,6-trimethylnonyl) phenol. By the same method as described above, a zinc dithiophosphate compound having an alkenyl group having 16 carbon atoms was synthesized. The obtained product was a mixture of 95% of a neutral salt (expressed by the following formula) of a zinc dithiophosphate compound having an alkenylphenyl group having 16 carbon atoms, 4% of a basic salt, and 1% of other impurities. However, it was subjected to the test without further purification. R ¹ : p- (4-decenyl) phenyl group [Synthesis Example 4] 0.53 mol of potassium hydroxide was added to 900 m
The solution dissolved in 1 l of water is placed in a 2 liter glass four-necked flask, and cooled to 5 ° C. while stirring, and p- (2,
A solution in which 250 g of (4,6-trimethylnonyl) phenol was dissolved in about 80 ml of tetrahydrofuran was added dropwise. 100 ml of tetrahydrofuran is further added,
Add 0.27 mol of zinc chloride dissolved in water and add 3
Stir vigorously for hours. After completion of the reaction, the reaction solution was extracted with hexane, washed well with saturated saline, and the solution was dried over anhydrous sodium sulfate. The obtained product was composed of 50% of a neutral salt (represented by the following formula) of a zinc dithiophosphate compound having an alkylphenyl group having 18 carbon atoms, and 45% of a basic salt.
%, And 5% of other impurities, but were subjected to the test without further purification. R ¹ : p- (2,4,6-trimethylnonyl) phenyl group [Synthesis Example 5] The number of carbon atoms was calculated in the same manner as in Synthesis Example 1 except that n-octyl alcohol was used instead of n-dodecyl alcohol. A zinc dialkyldithiophosphate compound having an alkyl group of 8 was synthesized. The obtained product is composed of 93% of a neutral salt (expressed by the following formula) of a zinc dithiophosphate compound having an alkyl group having 8 carbon atoms, and 6% of a basic salt.
%, And 1% of other impurities, but were subjected to the test without further purification. R ¹ : n-octyl group

Examples 1 to 9 and Comparative Examples 1 to 6
The rust-preventive oil composition for plastic working of Examples 1 to 9 was prepared with the composition shown in Table 1. For comparison, according to the composition shown in Table 2, when component (A) was not used (Comparative Example 1), when zinc dithiophosphate compound having an alkyl group having 8 carbon atoms was used (Comparative Example 2), chlorinated paraffin was used. (Comparative Example 3), using lard sulfide (Comparative Example 4), using only sulfonate without using component (B) as a rust inhibitor (Comparative Example 5), and using rust inhibitor A composition was also prepared when no agent was used (Comparative Example 6). In addition, each component used is as follows. Base oil Base oil 1: Paraffin solvent refined mineral oil (kinematic viscosity 25 mm ²
/ S (@ 40 ° C) Base oil 2: Paraffin solvent refined mineral oil (kinematic viscosity 6.5 mm)
² / s (@ 40 ° C) Base oil 3: Naphthenic hydrocarbon solvent (Kinematic viscosity 1.8 mm
² / s (@ 40 ° C.) Base oil 4: Paraffin solvent refined mineral oil (kinematic viscosity 80 mm ²
/ S (@ 40 ° C.)) (A) Component A1: The product obtained in Synthesis Example 1 (94% by mass of a neutral salt,
A mixture of 5% by mass of a basic salt and 1% by mass of other impurities) A2: The product obtained in Synthesis Example 2 (95% by mass of a neutral salt,
A mixture of 4% by mass of a basic salt and 1% by mass of other impurities) A3: The product obtained in Synthesis Example 3 (95% by mass of a neutral salt,
A mixture of 4% by mass of a basic salt and 1% by mass of other impurities) A4: The product obtained in Synthesis Example 4 (50% by mass of a neutral salt,
(Blend of 45% by mass of basic salt and 5% by mass of other impurities) (B) Component B1: Oxidized paraffin Ba salt (Saponification value 65 mg KOH
/ G, total acid value 4.0 mgKOH / g, Ba content 5.0
B2: sorbitan monooleate B3: lanolin fatty acid pentaerythritol ester (saponification value 100 mg KOH / g, total acid value 5 mg KOH)
/ C) Component C1: Neutral barium salt of petroleum sulfonic acid (total base number (perchloric acid method) 4 mg KOH / g) C2: Carbonate of petroleum sulfonic acid Overbased calcium salt (total base number (per Chloric acid method) 400 mg KOH / g) Other components D1: The product obtained in Synthesis Example 5 (neutral salt 93% by mass,
D2: Chlorinated paraffin (chlorine content: 50% by mass) D3: Lard sulfide (sulfur content: 10% by mass) Examples 1 to 9 and comparison The compositions of Examples 1 to 6 were evaluated for performance by the tests described below, and the results are shown in Tables 1 and 2. [Cylindrability test] The SPCD material specified in JIS G 3141 “Cold rolled steel sheet and steel strip” was used as a test plate material, and a cylinder formability test was performed by the following method. The sample oil was spray-coated on the surface of the test plate at a rate of ² g / m ² , the drawing ratio was 2.2, and the wrinkle holding force was from 0.5 tf to 0.25.
The molding was performed by increasing the value by tf, and the maximum wrinkle pressing force at which no break occurred was measured. In the cylindrical molding, as the wrinkle pressing force is increased, the generation of wrinkles is suppressed, but the fracture is more likely to occur. Therefore, the larger the maximum wrinkle pressing force is, the higher the breaking prevention effect is and the more excellent the workability is. [Anti-rust test] The test was carried out in accordance with a "salt spray test" defined in JIS K 2246 "Anti-rust oil".
However, as the material of the test piece, a cold rolled steel plate was used as JIS grade SPCE material.
/ M ² , spray drying and left to dry at room temperature for 12 hours. When no rusting was observed for 6 hours or more (A class), the score was 5, and when rusting was observed for 4 to 6 hours, when rusting was observed for 4 or 3 to 4 hours. Was evaluated according to a five-point evaluation method in which rust was observed within 1 to 2 hours, score was 2, and rust was observed within 1 hour.
The higher the rating, the better the rust resistance.

[0018]

[Table 1]

[0019]

[Table 2]

As shown in the results of the performance evaluation test in Table 1,
The plastic working and rust preventive oil composition of the examples according to the present invention has extremely good performance of excellent workability and rust prevention. On the other hand, Comparative Examples 1 to 4
As described above, the component (A) of the present invention is not used,
When a zinc dithiophosphate compound having an alkyl group having 8 carbon atoms is used instead of the component (A), chlorinated paraffin is used, or sulfide of lard is used, as shown in Table 2, The performance is significantly inferior to the compositions of the examples, clearly indicating the superiority of the compositions of the invention. Also,
Comparative Examples 5 and 6 are cases in which the component (B) is not used, but are inferior in rust prevention and do not satisfy the object of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10N 40:20 (72) Inventor Dai Kazuka 8 Chidori-cho, Naka-ku, Yokohama-shi Japan Central Oil Research Institute (72) Invention Person Yukio Matsuzaki 8 Chidori-cho, Naka-ku, Yokohama, Japan Central Research Laboratory of Petroleum Corporation

Claims (2)

[Claims] 1. A mineral oil and / or a synthetic oil as a base oil,
Based on the total amount of the composition, 0.5 to 50% by mass of (A) a zinc dithiophosphate compound represented by the following general formula (1): (In the above formula (1), R ¹ , R ² , R ³ and R ^{4 each} independently represent a hydrocarbon group, and R ¹ , R ² , R ³ and R 4
^At least one of ⁴ represents an alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms. ) And (B) 1 to 20% by mass of at least one rust inhibitor selected from the following (1) to (3): (1) oxide of wax or derivative thereof (2) polyhydric alcohol Partial ester (3) Lanolin or a derivative thereof. 2. A mineral oil and / or a synthetic oil as a base oil,
Based on the total amount of the composition, 0.5 to 50% by mass of (A) a zinc dithiophosphate compound represented by the following general formula (1): (In the above formula (1), R ¹ , R ² , R ³ and R ^{4 each} independently represent a hydrocarbon group, and R ¹ , R ² , R ³ and R 4
^At least one of ⁴ represents an alkylaryl group having 16 or more carbon atoms or an alkenylaryl group having 16 or more carbon atoms. (B) 1 to 20% by mass of at least one rust inhibitor selected from the following (1) to (3) (1) Wax oxide or derivative thereof (2) Polyhydric alcohol portion Ester (3) A rust-preventive oil composition for plastic working, comprising 1 to 20% by mass of lanolin or a derivative thereof and (C) an alkali metal salt, alkaline earth metal salt or amine salt of sulfonic acid.