JP4728157B2 - Cleaning and rust prevention oil composition - Google Patents

Description

  The present invention relates to a cleaning and rust-preventing oil composition having both a cleaning property and a rust-preventing property that can be used for metal processing and the like.

Metal parts are usually manufactured through metalworking processes such as cutting, grinding, and pressing, but metalworking oils used in metalworking often contain rusting factors because of extreme pressure. . If the corrosive factor remains on the surface of the part, it may cause rust if appropriate cleaning oil is applied and sufficient cleaning is not performed. Also, when assembling and inspecting metal parts with bare hands, fingerprints and sweat may adhere to the parts and cause rusting. Therefore, it is necessary to apply appropriate cleaning oil and perform sufficient cleaning. There is.
For this reason, it is customary to wash and remove these rust-causing factors with a low-viscosity cleaning oil such as NP-0 specified in “JIS K2246 rust prevention oil” and then apply an appropriate rust prevention oil. there were. As described above, two steps of the cleaning step and the rust prevention step are indispensable for the rust prevention treatment of the metal parts, and two kinds of treatment agents are necessary.
However, in general, the more the number of processes, the higher the cost, and the use of two types of treatment agents also imposes a heavy burden on the use of oil, etc., so that the treatment has both cleaning and rust prevention functions. Agents are in demand from the market.

  The problem of the present invention is that it is possible to unify the two processes of the cleaning process and the rust prevention process in a conventional metal processing process and the like, and it is possible to reduce the burden of oil management, An object of the present invention is to provide a cleaning and rust prevention oil composition having rust prevention properties.

In order to solve the above problems, it is necessary to first remove or suppress the corrosive factors described above by washing, but the washing performance is generally better as the viscosity of the washing oil is lower. On the other hand, the rust prevention property is better because the oil film becomes thicker as the viscosity of the rust prevention oil is higher. As a result of diligent research on a solution that satisfies these two conflicting requirements, the inventors of the present invention keep the 40 ° C. kinematic viscosity at 4 to ²⁰ mm ² / s and add a rust inhibitor and a required amount of water. As a result, it was found that a composition having both detergency and rust prevention properties can be obtained.
That is, according to the present invention, a base oil consisting of 40 mineral oil and / or synthetic oil of kinematic viscosity 1~18mm ² / s at ° C., and 40 mineral oil kinematic viscosity 55~130mm ² / s at ° C. and / or synthetic oils A cleaning and rust preventive oil composition having a kinematic viscosity at 40 ° C. of 4 to 20 mm ² / s (hereinafter sometimes abbreviated as the composition of the present invention). Is provided.

  The composition of the present invention contains a mineral oil and / or synthetic oil having the specific kinematic viscosity, a rust inhibitor, and water, and has a specific kinematic viscosity. In addition, the cleaning and rust prevention process for metal parts manufactured in can be unified, and the oil management burden can be reduced.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The composition of the present invention comprises a base oil consisting of mineral oil and / or synthetic oil.
As the mineral oil, for example, solvent debris, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, and the like for the lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of crude oil, Examples thereof include paraffinic or naphthenic mineral oil obtained by appropriately combining one or two or more purification means for sulfuric acid washing and clay treatment.
As the synthetic oil, for example, polyolefin and alkylbenzene are preferably used.

Examples of the polyolefin include those obtained by homopolymerization or copolymerization of olefin monomers having 2 to 16 carbon atoms, preferably 2 to 12 carbon atoms, and hydrides of these polymers.
When the polyolefin is a copolymer of olefin monomers having different structures, the monomer ratio and monomer arrangement in the copolymer are not particularly limited, and any of random copolymers, alternating copolymers, and block copolymers can be used. It may be.
The olefin monomer may be any of α-olefin, internal olefin, linear olefin, and branched olefin. Examples of such olefin monomers include ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, or these. The mixture of 2 or more types is mentioned. Among these, the pentene and the subsequent ones may be either linear or branched, and include α-olefins and internal olefins. Among these, ethylene, propylene, 1-butene, 2-butene, isobutene, an α-olefin having 5 to 12 carbon atoms, or a mixture thereof is preferably used. Further, among the α-olefins having 5 to 12 carbon atoms, 1-octene, 1-decene, 1-dodecene or a mixture thereof is more preferable.

  The polyolefin can be produced by a conventionally known method. For example, it can be produced by a non-catalytic thermal reaction, or an organic peroxide catalyst such as benzoyl peroxide; aluminum chloride, aluminum chloride-polyhydric alcohol, aluminum chloride-titanium tetrachloride, aluminum chloride-alkyltin Friedel-Crafts-type catalysts such as halides and boron fluorides; Ziegler-type catalysts such as organic aluminum chloride-titanium tetrachloride and organic aluminum-titanium tetrachloride; metallocenes such as aluminoxane-zirconocene and ionic compounds-zirconocene Type polyolefin; production of the desired polyolefin by homopolymerizing or copolymerizing the above olefin using a known catalyst such as Lewis acid complex type catalyst such as aluminum chloride-base, boron fluoride-base, etc. Can do.

Polyolefins obtained by such a method usually have double bonds, but in the present invention, so-called polyolefin hydrides obtained by hydrogenating double bond carbons in these polyolefins are used as base oils. It is preferable. When a polyolefin hydride is used, the thermal and oxidation stability of the resulting composition tends to be improved.
A hydride of a polyolefin can be obtained, for example, by hydrogenating a polyolefin with hydrogen in the presence of a known hydrogenation catalyst and saturating double bonds present in the polyolefin. In addition, when the olefin polymerization reaction is performed, by selecting the catalyst to be used, the olefin polymerization and the double bond existing in the polymer can be performed without passing through two steps such as olefin polymerization and polymer hydrogenation. It is also possible to complete the hydrogenation in one step.

An ethylene-propylene copolymer in a polyolefin; a copolymer obtained by polymerization of a butane-butene fraction made of a mixture of 1-butene, 2-butene and isobutene by-produced during naphtha pyrolysis, etc. 1-octene oligomers, 1-decene oligomers, 1-dodecene oligomers and hydrides thereof, and mixtures thereof are excellent in thermal and oxidation stability, viscosity-temperature characteristics, and low-temperature fluidity. In particular, a hydrogenated ethylene-propylene copolymer, a hydrogenated polybutene, a hydrogenated 1-octene oligomer, a hydrogenated 1-decene oligomer, a hydrogenated 1-dodecene oligomer, or a mixture thereof is more preferable.
Synthetic oils such as ethylene-propylene copolymers, polybutenes, and poly-α-olefins that are commercially available as base oils for lubricating oils are usually those whose double bonds are already hydrogenated. These commercially available products can also be used as the base oil.

As alkylbenzene, what has 1-4 C1-C40 alkyl groups in a molecule | numerator is preferable. Here, examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, Nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, octatriacontyl group, nonato Rear contyl group Tetracontyl group and the like, some of of these isomers include all isomers.
The alkyl group of the alkylbenzene may be linear or branched, but is preferably a branched alkyl group from the viewpoint of stability, viscosity characteristics, etc., and particularly easily available. Therefore, a branched alkyl group derived from an olefin oligomer such as propylene, butene, and isobutylene is more preferable.

  The number of alkyl groups in the alkylbenzene is preferably 1 to 4, but from the viewpoint of stability and availability, an alkylbenzene having one or two alkyl groups, that is, a monoalkylbenzene, a dialkylbenzene, or a mixture thereof is used. Most preferred. Moreover, as alkylbenzene, not only the alkylbenzene of a single structure but the mixture of the alkylbenzene which has a different structure may be sufficient.

The alkylbenzene can be produced, for example, using an aromatic compound as a raw material and using an alkylating agent and an alkylation catalyst. Here, as an aromatic compound used as a raw material, benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, or a mixture thereof is mentioned, for example.
Examples of the alkylating agent include lower monoolefins such as ethylene, propylene, butene, and isobutylene, preferably linear or branched olefins having 6 to 40 carbon atoms obtained by polymerization of propylene; wax, heavy C6-C40 linear or branched olefin obtained by thermal decomposition of oil, petroleum fraction, polyethylene, polypropylene, etc .; n-paraffin is separated from petroleum fractions such as kerosene, light oil, etc. And a linear olefin having 9 to 40 carbon atoms obtained by olefination, or a mixture thereof.
Examples of the alkylation catalyst include known catalysts such as Friedel-Crafts type catalysts such as aluminum chloride and zinc chloride; acidic catalysts such as sulfuric acid, phosphoric acid, silicotungstic acid, hydrofluoric acid, and activated clay. .

Base oil of mineral and / or synthetic oils used in the present invention, kinematic viscosity at 40 ℃ is 1~18mm ² / s, preferably 2-12 mm ² / s, more preferably a mineral oil of 4 to 6 mm ² / s and / Or a low-viscosity base oil made of synthetic oil and mineral oil and / or synthetic oil having a kinematic viscosity at 40 ° C. of 55 to 130 mm ² / s, preferably 70 to 115 mm ² / s, more preferably 85 to 100 mm ² / s. A mixture with a high viscosity base oil.
These low-viscosity base oil and high-viscosity base oil are each a mineral oil or a synthetic oil alone, or a combination of two or more mineral oils, two or more synthetic oils, at least one mineral oil and at least one synthetic oil. But you can. The mixing of the high-viscosity base oil contributes to the thickening of the coating film of the composition, the suppression of the increase in the amount taken out, and the optimization of the degreasing and spraying properties.

In the base oil used in the present invention, the blending amount of the low-viscosity base oil and the high-viscosity base oil is such that the kinematic viscosity at 40 ° C. of the composition of the present invention is 4 to ²⁰ mm ² / s. Although there is no particular limitation, the low viscosity base oil is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and the high viscosity base oil is preferably 5 to 70% by mass, based on the total amount of the composition. Preferably it is 5-50 mass%.

The rust inhibitor used in the composition of the present invention includes, for example, an oxidized wax salt, a carboxylic acid, a sulfonate, a carboxylate, an ester, a sarcosine compound, an amine, a boron compound, and a mixture thereof as a rust inhibitor. A compound selected from the group consisting of:
The oxidized wax salt is obtained by reacting an oxidized wax obtained by oxidizing a wax with at least one selected from alkali metals, alkaline earth metals (excluding barium) and amines, and the oxidized wax has an acidity. A salt obtained by neutralizing part or all of the group is preferred.
The oxidized wax used as a raw material for the oxidized wax salt is not particularly limited, but for example, oxidized wax such as paraffin wax, microcrystalline wax, petrolatum obtained by refining petroleum fraction, and polyolefin wax obtained by synthesis is oxidized. What is manufactured by doing is mentioned.
When the oxidized wax salt is an alkali metal salt, examples of the alkali metal used as a raw material include sodium and potassium. When the oxidized wax salt is an alkaline earth metal salt, examples of the alkaline earth metal used as a raw material include magnesium, calcium, barium and the like. When the oxidized wax salt is a heavy metal salt, examples of the heavy metal used as a raw material include zinc and lead. In addition, from the viewpoint of safety with respect to the human body and biological system, the oxidized wax salt is preferably not a barium salt or a heavy metal salt.

When the oxidized wax salt is an amine salt, examples of the amine include monoamines, polyamines, and alkanolamines.
Examples of the monoamine include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, monobutylamine, dibutylamine, tributylamine, monopentylamine, dipentylamine, Pentylamine, monohexylamine, dihexylamine, monoheptylamine, diheptylamine, monooctylamine, dioctylamine, monononylamine, monodecylamine, monoundecyl, monododecylamine, monotridecylamine, monotetradecylamine, mono Pentadecylamine, monohexadecylamine, monoheptadecylamine, monooctadecylamine, monononadecylamine, monoicosylamine , Monohenicosylamine, monodocosylamine, monotricosylamine, dimethyl (ethyl) amine, dimethyl (propyl) amine, dimethyl (butyl) amine, dimethyl (pentyl) amine, dimethyl (hexyl) amine, dimethyl (heptyl) Amine, dimethyl (octyl) amine, dimethyl (nonyl) amine, dimethyl (decyl) amine, dimethyl (undecyl) amine, dimethyl (dodecyl) amine, dimethyl (tridecyl) amine, dimethyl (tetradecyl) amine, dimethyl (pentadecyl) amine, Alkylamines such as dimethyl (hexadecyl) amine, dimethyl (heptadecyl) amine, dimethyl (octadecyl) amine, dimethyl (nonadecyl) amine, dimethyl (icosyl) amine, dimethyl (henicosyl) amine, dimethyl (tricosyl) amine;

  Monovinylamine, divinylamine, trivinylamine, monopropenylamine, dipropenylamine, tripropenylamine, monobutenylamine, dibutenylamine, tributenylamine, monopentenylamine, dipentenylamine, tripentenylamine, monohexenylamine, di Hexenylamine, monoheptenylamine, diheptenylamine, monooctenylamine, dioctenylamine, monononenylamine, monodecenylamine, monoundecenylamine, monododecenylamine, monotridecenylamine, monotetradecenylamine Cenylamine, monopentadecenylamine, monohexadecenylamine, monoheptadecenylamine, monooctadecenylamine, monononadecenylamine, monoicosenylamine, monohenicoseni Amines, mono DoCoMo cell alkenyl amines, alkenyl amines and mono- Trichoderma cell alkenyl amine;

  Dimethyl (vinyl) amine, dimethyl (propenyl) amine, dimethyl (butenyl) amine, dimethyl (pentenyl) amine, dimethyl (hexenyl) amine, dimethyl (heptenyl) amine, dimethyl (octenyl) amine, dimethyl (nonenyl) amine, dimethyl (nonenyl) amine Decenyl) amine, dimethyl (undecenyl) amine, dimethyl (dodecenyl) amine, dimethyl (tridecenyl) amine, dimethyl (tetradecenyl) amine, dimethyl (pentadecenyl) amine, dimethyl (hexadecenyl) amine, dimethyl (heptadecenyl) amine, dimethyl (octadecenyl) Monoamines having an alkyl group and an alkenyl group such as amine, dimethyl (nonadecenyl) amine, dimethyl (icocenyl) amine, dimethyl (henicocenyl) amine, dimethyl (tricosenyl) amine;

  Monobenzylamine, (1-phenyltyl) amine, (2-phenylethyl) amine (also known as monophenethylamine), dibenzylamine, bis (1-phenethyl) amine, bis (2-phenylethylene) amine (also known as diphenethylamine) Aromatic substituted alkylamines such as monocyclopentylamine, dicyclopentylamine, tricyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine, etc .; dimethylamine; dimethyl Monoamines having alkyl and cycloalkyl groups such as (cyclopentyl) amine, dimethyl (cyclohexyl) amine, dimethyl (cycloheptyl) amine; (methylcyclopentyl) amine, bis (methylcyclopentyl) amine, (dimethyl) (Lucyclopentyl) amine, bis (dimethylcyclopentyl) amine, (ethylcyclopentyl) amine, bis (ethylcyclopentyl) amine, (methylethylcyclopentyl) amine, bis (methylethylcyclopentyl) amine, (diethylcyclopentyl) amine, (methylcyclohexyl) Amine, bis (methylcyclohexyl) amine, (dimethylcyclohexyl) amine, bis (dimethylcyclohexyl) amine, (ethylcyclohexyl) amine, bis (ethylcyclohexyl) amine, (methylethylcyclohexyl) amine, (diethylcyclohexyl) amine, (methyl Cycloheptyl) amine, bis (methylcycloheptyl) amine, (dimethylcycloheptyl) amine, (ethylcycloheptylamine, (methylethylcycloheptyl) amine, (diethylcycloheptyl) And alkylcycloalkylamines such as amines, and all substituted isomers of these monoamines, including monoamines such as beef tallow amines derived from fats and oils.

  Examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, butylenediamine, dibutylenetriamine, Alkylene polyamines such as tributylenetetramine, tetrabutylenepentamine, pentabylenehexamine;

  N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-butylethylenediamine, N-pentylethylenediamine, N-hexylethylenediamine, N-heptylethylenediamine, N-octylethylenediamine, N-nonylethylenediamine, N-decylethylenediamine, N-undecyl, N-dodecylethylenediamine, N-tridecylethylenediamine, N-tetradecylethylenediamine, N-pentadecylethylenediamine, N-hexadecylethylenediamine, N-heptadecylethylenediamine, N-octadecylethylenediamine, N-nonadecylethylenediamine, N-icosylethylenediamine, N-henicosylethylenediamine, N-docosylethylenediamine, N N- alkylethylenediamine, such as Trichoderma sill ethylenediamine;

  N-vinylethylenediamine, N-propenylethylenediamine, N-butenylethylenediamine, N-pentenylethylenediamine, N-hexenylethylenediamine, N-heptenylethylenediamine, N-octenylethylenediamine, N-nonenylethylenediamine, N-decenylethylenediamine N-undecenyl, N-dodecenylethylenediamine, N-tridecenylethylenediamine, N-tetradecenylethylenediamine, N-pentadecenylethylenediamine, N-hexadecenylethylenediamine, N-heptadecenyl Ethylenediamine, N-octadecenylethylenediamine, N-nonadecenylethylenediamine, N-icosenylethylenediamine, N-henicocenylethylenediamine, N-docosenylethylene Amine, N- alkenyl ethylenediamine such as N- Trichoderma cell sulfonyl ethylenediamine;

  N-alkyldiethylenetriamine, N-alkenyldiethylenetriamine, N-alkyltriethylenetetramine, N-alkenyltriethylenetetramine, N-alkyltetraethylenepentamine, N-alkenyltetraethylenepentamine, N-alkylpentaethylenehexamine, N-alkenyl Pentaethylenehexamine, N-alkylpropylenediamine, N-alkenylpropylenediamine, N-alkyldipropylenetriamine, N-alkenyldipropylenetriamine, N-alkyltripropylenetetramine, N-alkenyltripropylenetetramine, N-alkyltetrapropylenepenta Min, N-alkenyltetrapropylenepentamine, N-alkylpentapropylenehexamine, N-alkenylpentapropylene Hexamine, N-alkylbutylenediamine, N-alkenylbutylenediamine, N-alkyldibutylenetriamine, N-alkenyldibutylenetriamine, N-alkyltributylenetetramine, N-alkenyltributylenetetramine, N-alkyltetrabutylenepentamine, N-alkyl or N-alkenylalkylene polyamines such as N-alkenyltetrabutylenepentamine, N-alkylpentabutylenehexamine, N-alkenylpentabutylenehexamine and the like, and all substituted isomers of these polyamines are also included. The polyamine here includes polyamines derived from fats and oils (such as beef tallow polyamine).

  Examples of the alkanolamine include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, and tri (n-propanol). ) Amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, tributanolamine, monopentanolamine, dipentanolamine, tripentanolamine, monohexanolamine, dihexanolamine, Monoheptanolamine, diheptanolamine, monooctanolamine, monononanolamine, monodecanolamine, monoundecanolamine, monododecano Amine, monotridecanolamine, monotetradecanolamine, monopentadecanolamine, monohexadecanolamine, diethylmonoethanolamine, diethylmonopropanolamine, diethylmonobutanolamine, diethylmonopentanolamine, dipropylmono Ethanolamine, dipropylmonopropanolamine, dipropylmonobutanolamine, dipropylmonopentanolamine, dibutylmonoethanolamine, dibutylmonopropanolamine, dibutylmonobutanolamine, dibutylmonopentanolamine, monoethyldiethanolamine, monoethyldi Propanolamine, monoethyldibutanolamine, monoethyldipentanolamine, monopropyldiethanolamine, monopropyl Dipropanolamine, monopropyldibutanolamine, monopropyldipentanolamine, monobutyldiethanolamine, monobutyldipropanolamine, monobutyldibutanolamine, monobutyldipentanolamine, monocyclohexylmonoethanolamine, monocyclohexyldiethanolamine, Examples include monocyclohexyl monopropanolamine, monocyclohexyl dipropanolamine, and all substituted isomers of these alkanolamines.

Among the above amines, monoamines are preferable in that they have good stain resistance. Among monoamines, monoamines having alkylamines, alkyl groups and alkenyl groups, monoamines having alkyl groups and cycloalkyl groups, cycloalkylamines and alkylcyclohexanes are preferred. Alkylamine is more preferred. Further, from the viewpoint of good stain resistance, an amine having 3 or more carbon atoms in the amine molecule is preferable, and an amine having 5 or more carbon atoms is more preferable.
The oxidized wax salt is preferably at least one selected from an alkali metal salt and an alkaline earth metal salt, more preferably an alkaline earth metal salt, from the viewpoint of rust prevention. Furthermore, among alkaline earth metal salts, calcium salts are particularly preferable from the viewpoint of safety.

Any carboxylic acid can be used as the rust preventive component, and preferred examples include fatty acids, dicarboxylic acids, hydroxy fatty acids, naphthenic acids, resin acids, oxidized waxes, and lanolin fatty acids.
The number of carbon atoms of the fatty acid is not particularly limited, but is preferably 6-24, more preferably 10-22. The 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.
Examples of such fatty acids include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecanoic acid. Saturated fatty acids such as icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid; hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, Unsaturated fatty acids such as hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, icosenoic acid, henicosenoic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid; or mixtures thereof; including all substituted isomers of these fatty acids It is done.

As the dicarboxylic acid, preferably a dicarboxylic acid having 2 to 40 carbon atoms, more preferably a dicarboxylic acid having 5 to 36 carbon atoms is used. Among these, dimer acid, alkyl or alkenyl succinic acid obtained by dimerizing an unsaturated fatty acid having 6 to 18 carbon atoms is preferably used.
Examples of the dimer acid include dimer acid of oleic acid. Among alkyl or alkenyl succinic acids, alkenyl succinic acid is preferable, and alkenyl succinic acid having an alkenyl group having 8 to 18 carbon atoms is more preferable.
As the hydroxy fatty acid, a hydroxy fatty acid having 6 to 24 carbon atoms is preferably used. The hydroxy fatty acid may have one or more hydroxy groups, but those having 1 to 3 hydroxy groups are preferably used. Examples of such hydroxy fatty acids include ricinoleic acid.
Naphthenic acid is a carboxylic acid in petroleum having a —COOH group bonded to a naphthene ring.
The resin acid refers to an organic acid present in a free state or as an ester in the natural resin.
The oxidized wax is obtained by oxidizing a wax. The wax used as the raw material is not particularly limited, and specific examples include paraffin wax obtained during refining of petroleum fractions, microcrystalline wax, petratum, and polyolefin wax obtained by synthesis.
Lanolin fatty acid is a carboxylic acid obtained by purifying, for example, hydrolysis of a waxy substance adhering to sheep wool.
Among these carboxylic acids, dicarboxylic acids are preferable, dimer acids are more preferable, and dimer acids of oleic acid are more preferable in terms of rust prevention properties, degreasing properties, and storage stability.

Preferable examples of the sulfonate as the rust preventive component include alkali metal sulfonate, alkaline earth metal sulfonate, and amine sulfonate. All sulfonates have sufficiently high safety for the human body and ecosystem, and can be obtained by reacting an alkali metal, alkaline earth metal or amine with sulfonic acid.
Examples of the alkali metal and alkaline earth metal constituting the sulfonate include the alkali metal and alkaline earth metal exemplified in the description of the alkali metal salt and alkaline earth metal salt of the oxidized wax, respectively. Calcium is preferred.
Examples of the amine constituting the sulfonic acid amine salt include the amines exemplified in the description of the amine salt of the oxidized wax.

  The said sulfonic acid can use the well-known thing manufactured by the conventional method. Specifically, from sulfonated alkyl aromatic compounds in the lubricating oil fraction of mineral oil, petroleum sulfonic acids such as mahogany acid produced as a by-product during white oil production, or from alkylbenzene production plants used as raw materials for detergents, etc. Synthesis of sulfonated alkylbenzene having linear or branched alkyl groups or sulfonated alkylnaphthalene such as dinonylnaphthalene obtained as a by-product or alkylating polyolefin with benzene And sulfonic acid. The molecular weight of these sulfonic acids is not particularly limited, but is preferably 100-1500, and more preferably 200-700.

  Among the above sulfonic acids, dialkylnaphthalenesulfonic acid in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30; the two alkyl groups bonded to the benzene ring are each a linear alkyl group or a side chain methyl group A dialkylbenzenesulfonic acid that is a branched alkyl group having one alkyl group and the total number of carbon atoms of the two alkyl groups is 14 to 30; and a monoalkylbenzenesulfone having 15 or more carbon atoms in the alkyl bonded to the benzene ring It is preferable to use at least one selected from the group consisting of acids.

In the preferred dialkylnaphthalene sulfonic acid, in which two alkyl groups bonded to the naphthalene ring have a total carbon number of 14 to 30, if the total carbon number of the two alkyl groups is less than 14, the demulsibility is not good. When it exceeds 30, the storage stability of the obtained rust preventive oil composition tends to be lowered. Each of the two alkyl groups may be linear or branched. Moreover, if the total carbon number of two alkyl groups is 14-30, there will be no restriction | limiting in particular about the carbon number of each alkyl group, However, As for carbon number of each alkyl group, 6-18 are respectively preferable.
In the preferred dialkylbenzenesulfonic acid, the two alkyl groups bonded to the benzene ring are each a branched alkyl group having one linear alkyl group or one side chain methyl group, and the total carbon of the two alkyl groups. In the case of monoalkylbenzenesulfonic acid having a number of 14 to 30, it can be suitably used as long as the alkyl group has 15 or more carbon atoms, as will be described later. When is used, the storage stability of the composition tends to decrease. Further, when an alkylbenzenesulfonic acid having 3 or more alkyl groups is used, the storage stability of the composition tends to decrease.

  A branched alkyl group in which the alkyl group bonded to the benzene ring of the dialkylbenzenesulfonic acid has a branched structure other than the side chain methyl group, such as a branched chain alkyl group having a side chain ethyl group, or two or more branched structures If the branched alkyl group has a branched chain, such as a branched alkyl group derived from an oligomer of propylene, the human body or the ecosystem may be adversely affected, and the rust prevention property tends to be insufficient. It is in. Further, if the total number of carbon atoms of two alkyl groups bonded to the benzene ring of the dialkylbenzene sulfonic acid is less than 14, the demulsibility tends to decrease, whereas if it exceeds 30, the storage stability of the composition decreases. Tend to. In addition, as long as the total number of carbon atoms of the two alkyl groups bonded to the benzene ring is 14 to 30, the number of carbon atoms of each alkyl group is not particularly limited, but the number of carbon atoms of each alkyl group is preferably 6 to 18 respectively. .

  As described above, the preferable monoalkylbenzenesulfonic acid has one alkyl group bonded to the benzene ring having 15 or more carbon atoms. When the number of carbon atoms of the alkyl group bonded to the benzene ring is less than 15, the storage stability of the resulting composition tends to decrease. Further, the alkyl group bonded to the benzene ring may be linear or branched as long as the carbon number is 15 or more.

Examples of the sulfonate obtained using the above raw materials include the following.
Alkali metal bases such as alkali metal oxides and hydroxides; alkaline earth metal bases such as alkaline earth metal oxides and hydroxides or amines such as ammonia, alkylamines and alkanolamines and sulfonic acids By heating a neutral (normal salt) sulfonate obtained by reacting with the above neutral (normal salt) sulfonate and an excess of an alkali metal base, an alkaline earth metal base or an amine in the presence of water. Basic sulfonate obtained; carbonate overbasic (superbasic) obtained by reacting the above neutral (normal salt) sulfonate with an alkali metal base, alkaline earth metal base or amine in the presence of carbon dioxide gas Sulphonate; the neutral (or normal salt) sulphonate is mixed with an alkali metal base, an alkaline earth metal base or amine and boric acid or anhydrous phosphate. Borate overbasic (superbasic) obtained by reaction with boric acid compounds such as uric acid, or by reaction of the above carbonate overbased (superbasic) sulfonates with boric acid compounds such as boric acid or boric anhydride. (Basic) sulfonate, or a mixture thereof.

  When producing the above neutral (normal salt) sulfonate, the same alkali metal, alkaline earth metal or amine chloride as the target sulfonate is added as a reaction accelerator, or an alkali metal different from the target sulfonate. It is also possible to prepare an alkaline earth metal or amine neutral (normal salt) sulfonate, and then add the same alkali metal alkaline earth metal or amine chloride as the target sulfonate to carry out the exchange reaction. Can be obtained. However, since chloride ions are likely to remain in the sulfonate obtained by such a method, the sulfonate obtained by such a method is not used in the present invention, or the sulfonate obtained by this method is not used. It is preferable to perform sufficient washing treatment such as washing with water. Specifically, the chlorine concentration in the sulfonate is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, preferably 50 ppm by mass or less, and 25 ppm by mass or less. It is particularly preferred.

  In addition, as the sulfonate, dialkylnaphthalene sulfonate in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30; the two alkyl groups bonded to the benzene ring are each a linear alkyl group or a side group. A dialkylbenzene sulfonate having a branched alkyl group having one chain methyl group and a total number of carbon atoms of the two alkyl groups of 14 to 30; and an alkyl bonded to the benzene ring having a carbon number of 15 or more It is preferable to use at least one selected from the group consisting of a certain monoalkylbenzene sulfonate.

In the present invention, among the above, it is more preferable to use one or more selected from neutral, basic and overbased alkali metal sulfonates and alkaline earth metal sulfonates; base number of 0 to 50 mgKOH / G, preferably 10-30 mg KOH / g neutral or near neutral alkali metal sulphonate or alkaline earth metal sulfonate and / or base number of 50-500 mg KOH / g, preferably 200-400 mg KOH / g (over) Particular preference is given to using basic alkali metal sulfonates or alkaline earth metal sulfonates. In addition, the mass ratio of the alkali metal sulfonate or alkaline earth metal sulfonate having a base number of 0 to 50 mgKOH / g and the alkali metal sulfonate or alkaline earth metal sulfonate having a base number of 50 to 500 mgKOH / g (the base number is 0). -50 mg KOH / g alkali metal sulfonate or alkaline earth metal sulfonate / base number 50-500 mg KOH / g alkali metal sulfonate or alkaline earth metal sulfonate) is preferably 0.1-30, more preferably 1-20. Especially preferably, it is 1.5-15.
Here, examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include barium, calcium and magnesium. Here, the base number is usually 6 to 30 of JIS K 2501 “Petroleum products and lubricating oil-neutralization number test method” in a state containing 30 to 70% by mass of a diluent such as lubricating base oil. Means the base number measured by the hydrochloric acid method in accordance with

  Examples of the carboxylic acid salt as the rust preventive component include alkali metal salts, alkaline earth metal salts, and amine salts of the carboxylic acid. Examples of the alkali metal, alkaline earth metal and amine constituting the carboxylate include the alkali metal, alkaline earth metal and amine exemplified in the description of the oxidized wax salt. Barium salt may be insufficiently safe for the human body and ecosystem.

Examples of the rust-preventing ester include partial esters of polyhydric alcohol, esterified oxidized wax, esterified lanolin fatty acid, alkyl or alkenyl succinate.
The partial ester of a polyhydric alcohol is an ester in which at least one of the hydroxyl groups in the polyhydric alcohol is not esterified and remains as a hydroxyl group, and any polyhydric alcohol as a raw material thereof can be used. However, the number of hydroxyl groups in the molecule is preferably 2 to 10, more preferably 3 to 6, and a polyhydric alcohol having 2 to 20 carbon atoms, more preferably 3 to 10 carbon atoms is suitable. Used for. Among these polyhydric alcohols, it is preferable to use at least one polyhydric alcohol selected from the group consisting of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitan, and it is more preferable to use pentaerythritol.

On the other hand, as the carboxylic acid constituting the partial ester, an arbitrary one is used, and the carbon number of the carboxylic acid is preferably 2 to 30, more preferably 6 to 24, and still more preferably 10 to 22. The carboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, and may be a linear carboxylic acid or a branched carboxylic acid.
Examples of such fatty acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, Saturated fatty acids such as hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, triacontanoic acid; Propenoic acid, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecene Unsaturated fatty acids such as, icosenoic acid, henicosenoic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic acid, heptacosenoic acid, octacosenoic acid, nonacosenic acid, triacontenoic acid; or a mixture thereof, these fatty acids Also included are all substituted isomers.

Hydroxycarboxylic acid may be used as the carboxylic acid constituting the partial ester. The hydroxycarboxylic acid may be a saturated carboxylic acid or an unsaturated carboxylic acid, but a saturated carboxylic acid is preferred from the viewpoint of stability. Further, the hydroxycarboxylic acid may be a linear carboxylic acid or a branched carboxylic acid, but a linear carboxylic acid or 1 to 2 carbon atoms, more preferably 1 to 3 branched chains having 1 carbon atom. A branched carboxylic acid having 1 to 2, particularly preferably 1, is preferred.
The number of carbon atoms of the hydroxycarboxylic acid is preferably 2 to 40, more preferably 6 to 30, and still more preferably 8 to 24, from the viewpoint of achieving both rust prevention properties and storage stability.
The number of carboxylic acid groups that the hydroxycarboxylic acid has is not particularly limited, and may be either the hydroxycarboxylic acid monobasic acid or the polybasic acid, but the monobasic acid is preferable.
The number of hydroxyl groups that the hydroxycarboxylic acid has is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1 from the viewpoint of stability.
The bonding position of the hydroxyl group in the hydroxycarboxylic acid is arbitrary, but the carboxylic acid in which the hydroxyl group is bonded to the bonding carbon atom of the carboxylic acid group (α-hydroxy acid), or the main chain other than the bonding carbon atom of the carboxylic acid group. A carboxylic acid (ω-hydroxy acid) in which a hydroxyl group is bonded to an end carbon atom is preferable.

式中、Ｒ¹は水素原子、炭素数１〜３８のアルキル基または炭素数２〜３８のアルケニル基を示す。またＲ²は水素原子、炭素数１〜３８のアルキレン基または炭素数２〜３８のアルケニレン基を示す。 Preferable examples of the hydroxycarboxylic acid include an α-hydroxy acid represented by the formula (1) and an ω-hydroxy acid represented by the formula (2).

In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 38 carbon atoms, or an alkenyl group having 2 to 38 carbon atoms. R ² represents a hydrogen atom, an alkylene group having 1 to 38 carbon atoms, or an alkenylene group having 2 to 38 carbon atoms.

Examples of the alkyl group and alkenyl group represented by R ¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group Group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, octatriacontyl group, etc. Base Ethenyl group (vinyl group), propenyl group (allyl group), butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, Hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henycocenyl group, dococenyl group, tricocenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, octacocenyl group, nonacocenyl group, triacontenyl group, triacontenyl group, triacontenyl group Nyl group, dotriacontenyl group, tritriacontenyl group, tetratriacontenyl group, pentatriacontenyl group, hexatriacontenyl group, heptatriacontenyl group, octatriacone group Include alkenyl groups such as thenyl group, also it includes all of these isomers.

Examples of the alkylene group and alkenylene group represented by R ² include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, and dodecylene group. , Tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group, heicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacenelene group, heptacenelene group Group, nonacosylene group, triacontylene group, hentriacontylene group, dotriacontylene group, tritriacontylene group, tetratriacontylene group, pentatriacontylene group, hexatrine group Alkylene groups such as contylene, heptatriacetylene, and octatriacontylene; ethenylene (vinylene), propenyl (arylene), butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene , Decenylene group, undecenylene group, dodecenylene group, tridecenylene group, tetradecenylene group, pentadecenylene group, hexadecenylene group, heptadecenylene group, octadecenylene group, nonadecenylene group, icosenylene group, heicocenylene group, tricosenylene group, tricocenylene group, tricocenylene group, tricocenylene group, tricocenylene group, tricocenylene group, Group, heptacosenylene group, octacosenylene group, nonacosenylene group, triacontenylene group, hentriacontenylene group, dotriacontenylene Alkenylene groups such as tritriacontenylene group, tetratriacontenylene group, pentatriacontenylene group, hexatriacontenylene group, heptatriacontenylene group, octatriacontenylene group, etc., and all these isomers Also mentioned.

As a raw material containing such a hydroxycarboxylic acid, a lanolin fatty acid obtained by purifying a waxy substance adhering to sheep wool by hydrolysis or the like can be preferably used.
When hydroxycarboxylic acid is used as the constituent carboxylic acid of the partial ester, a carboxylic acid having no hydroxyl group may be used in combination. In addition, when the carboxylic acid which comprises partial ester contains both the hydroxy carboxylic acid and the carboxylic acid which does not have a hydroxyl group, the ratio of the hydroxy carboxylic acid to the whole quantity of constituent carboxylic acid has preferable 5-80 mass%. When the proportion of hydroxycarboxylic acid is less than 5% by mass, the rust prevention property tends to be insufficient. For the same reason, the proportion of the hydroxycarboxylic acid is more preferably 10% by mass or more, and further preferably 15% by mass or more. Moreover, when the ratio of the said hydroxycarboxylic acid exceeds 80 mass%, it exists in the tendency for storage stability and the solubility with respect to a base oil to become inadequate. For the same reason, the proportion of the hydroxycarboxylic acid is more preferably 60% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

The carboxylic acid having no hydroxyl group may be a saturated carboxylic acid or an unsaturated carboxylic acid. Of the carboxylic acids having no hydroxyl group, the saturated carboxylic acid may be either a straight chain carboxylic acid or a branched carboxylic acid, but a straight chain carboxylic acid or a branched chain having 1 or 2 carbon atoms, more preferably 1 carbon atom. 1-3 branched carboxylic acids are preferred, more preferably 1-2, even more preferably 1.
The number of carbon atoms of the saturated carboxylic acid having no hydroxyl group is preferably 2 to 40, more preferably 6 to 30, and still more preferably 8 to 24, from the viewpoint of achieving both rust prevention and storage stability. The number of carboxylic acid groups in the saturated carboxylic acid having no hydroxyl group is not particularly limited and may be either a monobasic acid or a polybasic acid, but a monobasic acid is preferable.
Among saturated carboxylic acids having no hydroxyl group, linear saturated carboxylic acids having 10 to 16 carbon atoms such as lauric acid and stearic acid are particularly preferred from the viewpoint of oxidation stability and stain resistance.

Among the carboxylic acids having no hydroxyl group, the unsaturated carboxylic acid may be either a linear carboxylic acid or a branched carboxylic acid, or a linear carboxylic acid or a branched chain having 1 or 2 carbon atoms, more preferably 1 carbon atom. -3, more preferably 1-2, and still more preferably 1 branched carboxylic acid.
Among carboxylic acids having no hydroxyl group, the number of carbon atoms of the unsaturated carboxylic acid is preferably 2 to 40, more preferably 6 to 30, and more preferably 8 to 24, from the viewpoint of achieving both rust prevention and storage stability. More preferably, 12-22 are especially preferable.

The number of carboxylic acid groups in the unsaturated carboxylic acid having no hydroxyl group is not particularly limited and may be either a monobasic acid or a polybasic acid, but a monobasic acid is preferred.
The number of unsaturated bonds of the unsaturated carboxylic acid having no hydroxyl group is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and more preferably 1 from the viewpoint of stability. Particularly preferred.
Among unsaturated carboxylic acids having no hydroxyl group, linear unsaturated carboxylic acids having 18 to 22 carbon atoms such as oleic acid are preferred from the viewpoint of rust prevention and solubility in base oils, and oxidation stability, From the viewpoint of solubility in base oil and stain resistance, branched unsaturated carboxylic acids having 18 to 22 carbon atoms such as isostearic acid are preferable, and oleic acid is particularly preferable.

  In the partial ester of polyhydric alcohol and carboxylic acid, the proportion of unsaturated carboxylic acid in the constituent carboxylic acid is preferably 5 to 95% by mass. By making the ratio of unsaturated carboxylic acid 5 mass% or more, rust prevention property and storage stability can further be improved. For the same reason, the proportion of the unsaturated carboxylic acid is more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more. On the other hand, when the ratio of the unsaturated carboxylic acid exceeds 95% by mass, the air exposure property and the solubility in the base oil tend to be insufficient. For the same reason, the proportion of the unsaturated carboxylic acid is more preferably 80% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

Unsaturated carboxylic acids include both unsaturated carboxylic acids having a hydroxyl group and unsaturated carboxylic acids having no hydroxyl group, but the proportion of unsaturated carboxylic acid having no hydroxyl group in the total amount of unsaturated carboxylic acid Is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.
When the partial ester is a partial ester in which the proportion of the unsaturated carboxylic acid in the constituent carboxylic acid is 5 to 95% by mass, the iodine value of the partial ester is preferably 5 to 75, more preferably 10 to 60. 20 to 45 are more preferable. When the iodine value of the partial ester is less than 5, rust prevention properties and storage stability tend to be lowered. Moreover, when the iodine value of a partial ester exceeds 75, it exists in the tendency for the air exposure property and the solubility with respect to a base oil to fall.
The “iodine value” as used in the present invention means an iodine value measured by an indicator titration method of JIS K 0070 “acid value, saponification value, iodine value, hydroxyl value and unsaponified product value of a chemical product”.

Examples of the method for producing the partial ester include the following production methods (i), (ii), and (iii).
(i) a partial ester of a polyhydric alcohol and a hydroxycarboxylic acid, or a mixture of a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group, and a polyhydric alcohol and an unsaturated carboxylic acid having no hydroxyl group. Or a method of mixing a partial ester of a mixture of an unsaturated carboxylic acid having no hydroxyl group and a saturated carboxylic acid having no hydroxyl group so that the carboxylic acid composition in the mixture of the two satisfies the above conditions.
(ii) A carboxylic acid having a hydroxyl group and an unsaturated carboxylic acid having no hydroxyl group are mixed, or a saturated carboxylic acid having no hydroxyl group is further mixed so that the carboxylic acid composition of the partial ester obtained satisfies the above conditions. A method of mixing and performing a partial esterification reaction of the carboxylic acid mixture and a polyhydric alcohol.
(iii) a partial ester of a mixture of a hydroxycarboxylic acid and an unsaturated carboxylic acid having no hydroxyl group, or a mixture of these carboxylic acid and a saturated carboxylic acid having no hydroxyl group, the carboxylic acid composition is In order to satisfy the conditions, a partial ester of a polyhydric alcohol and a hydroxycarboxylic acid, or a mixture of a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group, or an unsaturated carboxylic acid having no polyhydric alcohol and a hydroxyl group A method of mixing a partial ester of an acid or a mixture of an unsaturated carboxylic acid having no hydroxyl group and a saturated carboxylic acid having no hydroxyl group.

In the case of the production method (i), for example, lanolin fatty acid is used as a mixture of a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group, and an carboxylic acid having 2 to 40 carbon atoms such as oleic acid as an unsaturated carboxylic acid having no hydroxyl group. Each of these unsaturated carboxylic acids can be preferably used. In this case, a partial ester (first partial ester) composed of a mixture of a polyhydric alcohol, a hydroxycarboxylic acid and a saturated carboxylic acid having no hydroxyl group, preferably a lanolin fatty acid, a polyhydric alcohol and a hydroxyl group. The content ratio of the unsaturated carboxylic acid, preferably a partial ester composed of oleic acid (second partial ester) is not particularly limited as long as the carboxylic acid composition ratio in the mixture of the two satisfies the above conditions, The proportion of the first partial ester in the total amount of the first and second partial esters is preferably 20 to 95 mass%, more preferably 40 to 80 mass%, and particularly preferably 55 to 65 mass%.
When the ratio of the first partial ester is less than 20% by mass or exceeds 95% by mass, rust prevention properties such as atmospheric exposure tend to be insufficient. Moreover, when the ratio of 1st partial ester exceeds 95 mass%, the solubility with respect to the base oil of the whole partial ester will fall, and it exists in the tendency for storage stability to become inadequate.

  The esterified oxidized wax refers to a product obtained by reacting an oxidized wax with alcohols to esterify some or all of the acidic groups of the oxidized wax. The oxidized wax used as the raw material for the esterified oxidized wax is the oxidized wax exemplified in the description of the oxidized wax salt; the alcohol is a linear or branched saturated monohydric alcohol having 1 to 20 carbon atoms. , Linear or branched unsaturated monohydric alcohols having 1 to 20 carbon atoms, polyhydric alcohols exemplified in the description of the ester, alcohols obtained by hydrolysis of lanolin, and the like.

The esterified lanolin fatty acid refers to a product obtained by reacting a waxy substance adhering to wool with a lanolin fatty acid obtained by purification such as hydrolysis and an alcohol. Examples of the alcohol used as a raw material for the esterified lanolin fatty acid include the alcohols exemplified in the description of the esterified oxidized wax, and among them, polyhydric alcohols are preferable, and trimethylolpropane, trimethylolethane, sorbitan, pentaerythritol, Glycerin is more preferred.
Examples of the alkyl or alkenyl succinic acid ester include esters of the alkyl or alkenyl succinic acid with a monohydric alcohol or a dihydric or higher polyhydric alcohol. Among these, esters of monohydric alcohols or dihydric alcohols are preferable.

The monohydric alcohol may be linear or branched, and may be saturated alcohol or unsaturated alcohol. The carbon number of the monohydric alcohol is not particularly limited, but an aliphatic alcohol having 8 to 18 carbon atoms is preferable.
As the dihydric alcohol, alkylene glycol and polyoxyalkylene glycol are preferably used. Examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, and decylene glycol.
Examples of the polyoxyalkylene glycol include those obtained by homopolymerizing or copolymerizing ethylene oxide, propylene oxide, and butylene oxide.
In the polyoxyalkylene glycol, when alkylene oxides having different structures are copolymerized, the polymerization form of the oxyalkylene group is not particularly limited, and either random copolymerization or block copolymerization may be used. Moreover, the polymerization degree of polyoxyalkylene glycol is not particularly limited, but is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.

The alkyl or alkenyl succinic acid ester may be a diester in which both of the two —COOH groups of the alkyl or alkenyl succinic acid are esterified (complete ester), or only one of the —COOH groups is esterified. Monoesters (partial esters) may be used, but monoesters are preferred because they are more excellent in rust prevention.
Among these esters, the use of esterified lanolin fatty acid is particularly preferred because it exhibits better rust prevention properties in the presence of water.

  As the sarcosine type compound which is the rust preventive component, a compound represented by any one of formulas (3) to (5) is preferably used. By containing at least one sarcosine type compound represented by the formulas (3) to (5) in the composition of the present invention, rust can be used without using heavy components such as wax, petrolatum, heavy base oil and the like. The stopping property can be further improved, and the rust preventing property can be maintained at a high level for a long time. For this reason, while being excellent in rust prevention property and its long-term maintenance property, the rust prevention oil composition advantageous in the suppression of the increase in taking-out amount, a degreasing property, and sprayability can be obtained.

R ³ —CO—NR ⁴ — (CH ₂ ) n —COOX (3)
^{(R 3 -CO-NR 4 -} (CH 2) n-COO) mY (4)
^{(R 3 -CO-NR 4 -} (CH 2) n-COO) m-Z- (OH) m '(5)
In each formula, R ³ represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, and n represents an integer of 1 to 4. In formula (3), X represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 1 to 30 carbon atoms. In formula (4), Y represents an alkali metal or an alkaline earth metal, m represents 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal. In the formula (5), Z is a residue excluding a hydroxyl group of a polyhydric alcohol having 2 or more valences, m is an integer of 1 or more, m ′ is an integer of 0 or more, and m + m ′ is a valence of Z.

In formulas (3) to (5), R ³ is an alkyl group or alkenyl group having 6 or more carbon atoms from the viewpoint of solubility in base oil, etc., preferably 7 or more carbon atoms, and 8 or more carbon atoms. More preferred. Further, from the viewpoint of storage stability and the like, it is an alkyl group or alkenyl group having 30 or less carbon atoms, preferably 24 or less carbon atoms, and more preferably 20 or less carbon atoms.
Examples of such alkyl and alkenyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Group, nonadecyl group, icosyl group and the like (these alkyl groups may be linear or branched); hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group An alkenyl group such as tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, etc. (These alkenyl groups may be linear or branched, and the position of the double bond is arbitrary. ) And the like.

In formulas (3) to (5), R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms. From the viewpoint of storage stability and the like, it is an alkyl group having 4 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms.
In the formulas (3) to (5), n is an integer of 4 or less, preferably 3 or less, more preferably 2 or less, from the viewpoint of storage stability.
In formula (3), the alkyl group or alkenyl group represented by X has 30 or less carbon atoms, preferably 20 or less carbon atoms, and more preferably 10 or less carbon atoms from the viewpoint of storage stability. Examples of such alkyl groups or alkenyl groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups and the like (these alkyl groups). May be linear or branched); alkenyl groups such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, etc. (these alkenyl groups are linear) Or may be branched, and the position of the double bond is arbitrary). Moreover, it is preferable that it is an alkyl group from the point of being excellent in rust prevention property. X is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. More preferably, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is even more preferable.

  In the formula (4), examples of the alkali metal or alkaline earth metal represented by Y include sodium, potassium, magnesium, calcium, and barium. Among these, alkaline earth metals are preferable because they are more excellent in rust prevention. In addition, in the case of barium, there is a risk that the safety to the human body and the ecosystem will be insufficient.

In the formula (5), examples of the polyhydric alcohol represented by Z include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, divalent alcohols such as dimer diol; glycerin, 2- (hydroxymethyl) -1,3-propanediol, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1 , 2,3-propanetriol, 2-methyl-2,3,4-butyl Tantriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4 -Trihydric alcohols such as dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane; pentaerythritol, erythritol, 1, 2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, sorbitan Tetrahydric alcohols such as adonitol, arabitol, xylitol, triglycerin, etc .; dipentaerythritol , Sorbitol, mannitol, iditol, inositol, dulcitol, talose, hexavalent alcohols such as allose; polyglycerol or dehydration condensation product thereof.
In the formula (5), m and m ′ mean that all of the hydroxyl groups of the polyhydric alcohol of Z may be substituted, or only a part thereof may be substituted.

  As the sarcosine type compounds represented by the formulas (3) to (5), only one kind of compound selected from these may be used alone, or a mixture of two or more kinds of compounds may be used. . Among these, at least one compound selected from the formulas (3) and (4) is preferable from the viewpoint of more excellent rust prevention.

  Examples of the rust-preventing component include amines exemplified in the description of the oxidized wax salt, and examples of the boron compound include calcium borate.

In the composition of the present invention, one of the above rust inhibitors may be used alone, or two or more of the same kind of rust inhibitors may be used in combination. May be used in combination of two or more.
As the rust inhibitor used in the composition of the present invention, a sulfonate or an ester is preferable from the viewpoint of exhibiting superior rust preventive properties under the coexistence of water, and a sulfonate and an ester are used in combination. It is more preferable.
In addition to the above rust inhibitors, alcohols typified by higher aliphatic alcohols; phosphoric acid monoesters, phosphoric acid diesters, phosphite esters, (sub) phosphoric acid derivatives typified by their amine salts, etc. Can also be included as a rust inhibitor.

In the production of the rust inhibitor, a chlorine bleach may be used for the purpose of decoloring. In the present invention, a non-chlorine compound such as hydrogen peroxide is used as the bleach, or the bleaching is performed. Preferably no treatment is performed. In addition, chlorine compounds such as hydrochloric acid may be used for the hydrolysis of fats and oils, and in this case, it is also preferable to use a non-chlorine acid or basic compound. Furthermore, it is preferable to subject the resulting compound to a sufficient washing treatment such as washing with water.
The chlorine concentration of the rust inhibitor is not particularly limited as long as it does not impair the properties of the composition of the present invention, but is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, still more preferably 50 ppm or less, particularly preferably. It is 25 mass ppm or less.

In the composition of the present invention, the content in the case of using a rust inhibitor other than carboxylic acid is not particularly limited, but from the viewpoint of rust prevention, it is preferably 0.1% by mass or more, more preferably, based on the total amount of the composition. Is 0.5% by mass or more, more preferably 1.0% by mass or more. Further, the content of the rust inhibitor other than the carboxylic acid is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% on the basis of the total amount of the composition from the viewpoint of degreasing and storage stability. It is below mass%.
In the composition of the present invention, the content in the case of using a carboxylic acid as a rust inhibitor is not particularly limited, but from the viewpoint of rust prevention properties, it is preferably 0.01% by mass or more, more preferably, based on the total amount of the composition. It is 0.03 mass% or more, More preferably, it is 0.05 mass% or more. If the content of carboxylic acid is less than the lower limit, the effect of improving rust prevention by the addition may be insufficient. The carboxylic acid content is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.2% by mass or less, based on the total amount of the composition. If the carboxylic acid content exceeds the upper limit, the solubility in the base oil becomes insufficient, and the storage stability may be reduced.

The composition of the present invention contains water as an essential component. As the water here, any water such as industrial water, tap water, ion-exchanged water, distilled water, activated carbon or water treated with a general household water purifier can be used.
In the composition of the present invention, the content of water is usually 0.1 to 20% by mass based on the total amount of the composition. The lower limit of the content is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and most preferably 0.8% by mass or more from the viewpoint of detergency. . In addition, the upper limit of the content is 20% by mass or less, preferably 15% by mass or less, and preferably 10% by mass or less, from the viewpoint that the composition of the present invention exhibits liquid stability that does not cause two-layer separation or the like. Is more preferable and 5% by mass or less is most preferable.

The lower limit of the kinematic viscosity at 40 ° C. of the composition of the present invention is 4 mm ² / s or more, preferably 5 mm ² / s or more, and more preferably 6 mm ² / s or more. If the kinematic viscosity is less than the lower limit value, the oil film cannot be maintained, which may cause a problem in rust prevention. The upper limit of the kinematic viscosity at 40 ° C. of the composition of the present invention is not more than 20 mm ² / s, preferably not more than 18 mm ² / s, more preferably at most 15 mm ² / s. If the kinematic viscosity exceeds the upper limit, the detergency may be reduced.

  In the composition of this invention, you may contain another additive as needed. Specifically, for example, paraffin wax having a remarkable effect of improving the rust-preventing property in an acidic atmosphere; sulfurized oil, sulfurized ester, long-chain alkyl zinc dithiophosphate, tricresyl phosphate having a remarkable effect of improving press moldability or lubricity Phosphate esters such as fate, fats and oils such as lard, fatty acids, higher alcohols, calcium carbonate, potassium borate; phenolic or amine antioxidants for improving antioxidant performance; benzotriazole or its derivatives, thiadiazole, Corrosion inhibitors such as benzothiazole for improving corrosion prevention performance; Wetting agents such as diethylene glycol monoalkyl ether; Film-forming agents such as acrylic polymer, paraffin wax, micro wax, slack wax, polyolefin wax, petrolatum; Le silicone, fluorosilicone, antifoaming agents such as polyacrylates, surfactants or mixtures thereof. In addition, although content of said other additive is arbitrary, the sum total of content of these additives is 10 mass% or less on the basis of the composition whole quantity of this invention.

In the composition of the present invention, the contents of barium, zinc, chlorine and lead are each in terms of elements, and are preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 100 ppm by mass as the total composition standard. ppm or less, even more preferably 50 mass ppm or less, even more preferably 10 mass ppm or less, particularly preferably 5 mass ppm or less, and most preferably 1 mass ppm or less. If the content of any one of these elements exceeds 1000 ppm by mass, there is a possibility that safety to the environment such as the human body or the ecosystem is insufficient.
In addition, content of the element in this invention means the value measured by the following method. That is, the contents of barium, zinc and lead are ASTM D 5185-95 "Standard Test Method for Determination of Additive Elements, Wear Metals, and Contaminants in Used Lubricating Oils and Determination of Selected Elements in Base Oils by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) ”; the chlorine content is the content based on the total amount of the composition measured according to the“ IP PROPOSED METHOD AK / 81 Determination of chlorine? Microcoulometry oxidative method ”(mass ppm) ). The detection limit of each element in the measurement method is usually 1 ppm by mass.

  The base number of the composition of the present invention is not particularly limited, but is preferably 1 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, still more preferably 2 mgKOH / g or more, particularly preferably 3 mgKOH from the viewpoint of rust prevention. / G or more. From the viewpoint of storage stability, the base number is preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, still more preferably 10 mgKOH / g or less, and particularly preferably 8 mgKOH / g. Here, the base number is JIS K 2501 “Petroleum products and lubricating oils—Test method for neutralization number”. The base number (mgKOH / g) measured by the hydrochloric acid method according to the above.

The composition of the present invention can achieve all of rust prevention, degreasing, storage stability and cleanability at a high level and can be suitably used as a rust prevention oil for various metal members. . The metal member that is the object to be treated is not particularly limited, and specifically, cold-rolled steel sheets, hot-rolled steel sheets, high-tensile steel sheets, galvanized steel sheets, etc. used for automobile bodies and electrical product bodies, for tinplate Examples thereof include metal plate materials such as an original plate, an aluminum alloy plate, and a magnesium alloy plate, and further bearing components such as a rolling bearing, a tapered rolling bearing, and a needle bearing, a steel material for construction, and a precision component.
As conventional rust prevention oil for such metal members, intermediate rust prevention oil used in the process of processing metal members, shipping rust prevention oil used for rust prevention at the time of shipment, press working There are cleaning rust preventive oils used in the cleaning process for removing foreign matters prior to delivery or for removing foreign matters prior to shipment at the metal plate manufacturer, but the cleaning and rust preventing oil composition of the present invention is used for all these applications. can do.

The method for applying the composition of the present invention to the object to be treated is not particularly limited. For example, the composition can be applied to a metal member by a method such as spraying, dropping, transfer using a felt material, electrostatic oiling, or the like. Among these coating methods, the spray method is preferable because the oil film thickness can be made uniform by coating in a fine mist. The application apparatus when applying the spray method is not particularly limited as long as it can atomize the composition of the present invention. For example, any of an air spray type, an airless spray type, and a hot melt type can be applied. .
In the coating step, it is preferable to provide a draining step using a centrifuge or a draining step by leaving for a long time after an excessive cleaning and rust prevention oil composition is applied.

When the composition of the present invention is used as a cleaning oil, the surface of a metal member is satisfactorily cleaned by supplying a large excess amount of the composition of the present invention by spraying, showering, dip coating or the like. Rust can be prevented. Furthermore, if necessary, surface cleaning with a roll brush or the like is also performed after the metal processing step, so that the efficiency of removing foreign matters can be increased.
When performing cleaning using the composition of the present invention, it is preferable to perform surface treatment of the metal member with a ringer roll or the like to adjust the amount of oil adhering to the surface of the metal member.

Regardless of the application method of the composition of the present invention, it is preferable to recover, circulate and reuse the cleaning and rust preventive oil composition applied in excess on the metal member. In the circulation of the composition of the present invention, it is preferable to remove foreign matters mixed in the circulation system.
For example, a foreign substance can be removed by providing a filter in the middle of the circulation path of the composition of the present invention, preferably just before the composition of the present invention is ejected toward a metal member. Moreover, a magnet can be provided in the bottom part of the tank which stores the composition of this invention, and foreign materials, such as abrasion powder, can also be adsorbed | sucked and removed by magnetic force.
There is a concern that the performance of the composition of the present invention that is reused in such a process may be deteriorated due to the incorporation of oil from the previous process. Therefore, when reusing the composition of the present invention, the kinematic viscosity and density measurement, copper plate corrosion test, rust prevention property test, etc. are regularly performed on the used oil to control its properties. Accordingly, it is preferable to perform oil replenishment, drain disposal, tank cleaning, oil purification operation, and the like.

For discarded oils, use the oils as they are or with a solvent or low-viscosity base oil, and use them in lines where the required performance for cleaning and rust prevention oil compositions is low compared to the lines used before disposal. As a result, the total amount of oil used can be reduced.
When the composition of the present invention is stored in a tank, it is preferably replenished according to the amount of decrease in the composition in the tank. In that case, it may not necessarily be the same composition as the composition filled in the initial stage, and a composition or the like in which the additive for increasing the performance desired to be strengthened may be replenished as occasion demands. Or conversely, the cleaning ability of the cleaning and rust preventive oil composition may be maintained by replenishing a composition having a reduced viscosity by a method such as reducing the content of the high viscosity base oil.

  When the composition of the present invention is used in a cleaning process for removing foreign matters prior to shipment in a metal plate manufacturer, the metal plate may be wound up in a coil shape immediately after the cleaning process or shipped as a sheet material. Is possible. According to this method, there is a merit that the amount of foreign matter attached is small and cleaning can be performed easily and reliably even when a cleaning process using a cleaning rust prevention oil is performed immediately before the pressing process in pressing. As a matter of course, a rust-preventing treatment may be performed in two stages by providing a step of applying rust-preventing oil again after the step of washing with the cleaning rust-preventing oil at the steel plate manufacturing site.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
Examples 1-8, Comparative Examples 1-4
In Examples 1 to 8 and Comparative Examples 1 to 4, cleaning and rust preventive oil compositions having the compositions shown in Table 1 were prepared using the base oils and additives shown below, respectively.
(Base oil)
Base oil 1: mineral oil base oil having a kinematic viscosity at 40 ° C. of 1.5 mm ² / s 2: mineral oil base oil having a kinematic viscosity at 40 ° C. of 6.2 mm ² / s 3: kinematic viscosity at 40 ° C .: 93.0 mm ² / S mineral oil
(Anti-rust agent)
Anticorrosive agent 1: Na dinonyl naphthalene sulfonate Anticorrosive agent 2: Ethylenediamine sulfonate Anticorrosive agent 3: Lanolin fatty acid partial ester of pentaerythritol
(water)
Distilled water
(Other additives)
Other additives 1: Di-t-butyl-p-cresol as an antioxidant Other additives 2: Benzotriazole as a metal deactivator Other additives 3: Dicyclohexylamine EO adduct as a surfactant

The following evaluation tests were conducted on the cleaning and rust prevention oil compositions of Examples 1 to 8 and Comparative Examples 1 to 4. The results are shown in Table 1.
(Wet test)
The test was carried out in accordance with JIS K 2246 5.34 “Wet Test Method”, and the value was expressed as the number of hours during which the evaluation standard, Class A (degree of rusting was 0%) could be maintained.
(Fingerprint removability test)
The test was performed in accordance with JIS K 2246 5.31 “Fingerprint removability test”, and the case where no rust was generated was indicated by a circle.
(Fingerprint suppression test)
Perform the test in the following steps.
(1) A fingerprint removal test of JIS K 2246 5.31 is performed on the cleaned test piece (the same as the wet test), and an artificial fingerprint liquid is printed.
(2) The test piece on which the fingerprint is printed is dip-coated in the sample oil, and then drained for 24 hours.
(3) Evaluate the presence or absence of rust when the test piece is suspended in the same manner as the wet test and kept for 2 weeks in a high-humidity thermostat adjusted to 50 ° C and relative humidity 95%. The case where there is no mark is indicated by a circle.
(Separation stability)
After preparing the rust prevention oil composition, it was kept in a thermostatic bath adjusted to 25 ° C. for 24 hours, and the presence or absence of water separation was evaluated.
From the results shown in Table 1, when the cleaning and rust preventive oil composition does not contain water, fingerprint removability and fingerprint suppression are poor (Comparative Example 1), and when the viscosity is too low, the fingerprint removability is poor (Comparative Example 2). It can be seen that if the viscosity is too high, the fingerprint suppression is poor (Comparative Example 3), and if there is too much water, water separation occurs (Comparative Example 4).

Claims (4)

A base oil consisting of kinematic viscosity 1~18mm ² / s mineral and / or synthetic oils, as well as 40 mineral oil kinematic viscosity 55~130mm ² / s at ° C. and / or synthetic oils at 40 ° C., and rust inhibitors, water A washing and rust prevention oil composition having a kinematic viscosity at 40 ° C. of 4 to 20 mm ² / s.   The rust preventive agent is at least one compound selected from the group consisting of oxidized wax salts, carboxylic acids, sulfonates, carboxylates, esters, sarcosine type compounds, amines and boron compounds. Anti-rust oil composition. The cleaning and rust prevention oil composition according to claim 1 or 2, wherein the water content is 0.1 to 20% by mass based on the total amount of the composition. The cleaning and rust preventive oil composition according to any one of claims 1 to 3, further comprising a dicyclohexylamine EO adduct as a surfactant.