JP2005248264A - Rust prevention oil composition and rust prevention method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rust-preventing oil composition capable of forming an oil film having a uniform and sufficient thickness when applied to an object to be treated, and capable of sufficiently preventing the occurrence of rust without causing oil film breakage, And a rust prevention method using the rust prevention oil composition.
A rust containing a predetermined base oil and 1 to 40% by mass of a rust inhibitor based on the total amount of the composition, and having a kinematic viscosity at 40 ° C. of 100 to 1000 mm ² / s. Stop oil composition.
[Selection] Figure 1

Description

  The present invention relates to a rust prevention oil composition and a rust prevention method.

Conventionally, rust-preventing oil has been used to prevent the occurrence of rust in metallic parts such as automotive parts, cold-rolled steel sheets, the second half of hot rolling, plated steel sheets, bearing parts, architectural steel materials, precision parts, etc. (For example, refer to Patent Document 1).
JP-A-9-279368

  However, even with the above-described conventional rust preventive oil, rust generation may not be sufficiently prevented.

  Therefore, the present inventors first examined the cause of rust when conventional rust prevention oil was used. As a result, when conventional rust prevention oil is applied to a metal member, the oil film thickness varies depending on the application site, and the oil film is likely to be cut off. I found it.

  The present invention has been made in view of the above-described problems of the prior art, and can form an oil film having a uniform and sufficient thickness when applied to an object to be processed, without causing oil film breakage. It aims at providing the rust prevention oil composition which can fully prevent generation | occurrence | production, and the rust prevention method using the rust prevention oil composition.

  As a result of intensive studies to achieve the above object, the present inventors have determined that the content of the rust inhibitor in the rust preventive oil composition and the kinematic viscosity of the composition at 40 ° C. are within the specific ranges, respectively. Has been found to be solved, and the present invention has been completed.

That is, the rust preventive oil composition of the present invention contains a predetermined base oil and 1 to 40% by mass of a rust preventive agent based on the total amount of the composition, and has a kinematic viscosity at 40 ° C. of 100 to 1000 mm ² / s. It is characterized by being.

  Thus, by setting the content of the rust inhibitor in the rust preventive oil composition and the kinematic viscosity of the composition at 40 ° C. within the above ranges, respectively, a uniform and sufficient thickness when applied to the workpiece. Since the oil film is formed, the occurrence of rust can be sufficiently prevented without causing the oil film to break.

The rust prevention method of the present invention contains a predetermined base oil and 1 to 40% by mass of a rust inhibitor on the basis of the total amount of the composition, and has a kinematic viscosity at 40 ° C. of 100 to 1000 mm ² / s. It comprises a step of preparing a rust-preventing oil composition, and a step of heating the rust-preventing oil composition to have a kinematic viscosity of 50 mm ² / s or less and applying it to an object to be treated.

In this way, by heating the rust preventive oil composition of the present invention and setting its kinematic viscosity to 50 mm ² / s or less, the composition can be easily and reliably applied to a workpiece. In addition, since the applied composition becomes highly viscous by natural cooling to form a uniform and sufficient oil film, it is possible to sufficiently prevent the occurrence of rust without causing the oil film to break.

Conventionally, when performing rust prevention on a metallic member or the like, rust prevention oil having a kinematic viscosity at 40 ° C. of 1 to 30 mm ² / s is generally used from the viewpoint of workability when applied to a workpiece. Is used. However, with such a low-viscosity rust-preventing oil, unevenness in the thickness of the oil film is likely to occur and the oil film is likely to be cut off, so that the occurrence of rust cannot be sufficiently prevented.

  According to the rust preventive oil composition of the present invention, it is possible to sufficiently prevent the occurrence of rust without causing oil film breakage. In addition, according to the rust prevention method of the present invention, the rust prevention oil composition of the present invention can be easily and reliably applied to an object to be processed, and the excellent rust prevention by the rust prevention oil composition. Sex can be effectively obtained.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

As described above, the rust preventive oil composition of the present invention contains a predetermined base oil and 1 to 40% by mass of a rust preventive based on the total amount of the composition, and has a kinematic viscosity at 40 ° C. of 100 to 1000 mm ^2. / S.

  The base oil used in the present invention is not particularly limited as long as the kinematic viscosity of the rust preventive oil composition is within the above range, and may be either mineral oil or synthetic oil, and a mixture of mineral oil and synthetic oil Oil may be used.

  Specifically, as mineral oils, solvent degreasing, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogen removal from lubricating oil fractions obtained by atmospheric and vacuum distillation of crude oil Examples thereof include paraffinic or naphthenic mineral oil obtained by appropriately combining one or more purification means of chemical purification, sulfuric acid washing, and clay treatment.

  Moreover, polyolefin, alkylbenzene, etc. are used suitably as synthetic oil.

  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. In the case where the polyolefin is a copolymer of olefin monomers having different structures, the monomer ratio and the monomer arrangement in the copolymer are not particularly limited, and among random copolymers, alternating copolymers and block copolymers. Any of these may be used. The olefin monomer may be any of α-olefin, internal olefin, linear olefin, and branched olefin. Specific examples of such olefin monomers include ethylene, propylene, 1-butene, 2-butene, isobutene, linear or branched pentene (including α-olefin and internal olefin), linear Or branched hexene (including α-olefin and internal olefin), linear or branched heptene (including α-olefin and internal olefin), linear or branched octene (α-olefin) ), Linear or branched nonene (α-olefin, including internal olefin), linear or branched decene (including α-olefin, internal olefin), linear Alternatively, branched undecene (including α-olefin and internal olefin), linear or branched dodecene (including α-olefin and internal olefin), linear Or branched tridecene (including α-olefin and internal olefin), linear or branched tetradecene (including α-olefin and internal olefin), linear or branched pentadecene (α-olefin) ), Linear or branched hexadecene (α-olefin, including internal olefin), and mixtures thereof. Among these, ethylene, propylene, 1-butene, 2- Butene, isobutene, an α-olefin having 5 to 12 carbon atoms and a mixture thereof are preferably used. Further, among the α-olefins having 5 to 12 carbon atoms, 1-octene, 1-decene, 1-dodecene, a mixture thereof, and the like are more preferable.

  The above-mentioned polyolefin can be produced conventionally. Specifically, for example, it can be produced by a non-catalytic thermal reaction, and an organic peroxide catalyst such as benzoyl peroxide; aluminum chloride, aluminum chloride-polyhydric alcohol, aluminum chloride-titanium tetrachloride, chloride Friedel-Crafts type catalysts such as aluminum-alkyltin halides and boron fluoride; Ziegler type catalysts such as organic aluminum chloride-titanium tetrachloride and organic aluminum-titanium tetrachloride; aluminoxane-zirconocene, ionic compound-zirconocene A metallocene catalyst such as a catalyst; a Lewis acid complex catalyst such as an aluminum chloride-base catalyst, a boron fluoride-base catalyst, etc. Polyolefins can be produced.

  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 hydride of polyolefin is used, the thermal / oxidative stability of the obtained rust preventive oil composition tends to be improved. The hydride of polyolefin can be obtained, for example, by hydrogenating polyolefin with hydrogen in the presence of a known hydrogenation catalyst and saturating double bonds existing 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.

  Among the polyolefins preferably used as a base oil in the present invention, an ethylene-propylene copolymer, polybutene (butane-butene fraction (by-product of 1-butene, 2-butene and A copolymer obtained by polymerization of a mixture of isobutene), 1-octene oligomer, 1-decene oligomer, 1-dodecene oligomer and their hydrides, and also a mixture thereof are heat / oxidative stability, viscosity- Preferred in terms of excellent temperature characteristics and low temperature fluidity, especially ethylene-propylene copolymer hydride, polybutene hydride, 1-octene oligomer hydride, 1-decene oligomer hydride, 1-dodecene oligomer hydride and These mixtures are more preferred. Synthetic oils such as ethylene-propylene copolymers, polybutenes, and poly-α-olefins that are commercially available as base oils for lubricants are usually those whose double bonds are already hydrogenated. In the invention, these commercially available products can also be used as the base oil.

  Moreover, as an alkylbenzene used suitably as a base oil concerning this invention, what has 1-4 C1-C40 alkyl groups in a molecule | numerator is preferable. Specific examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a propyl group (including all isomers), a butyl group (including all isomers), and a pentyl group ( All isomers included, hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (including all isomers) ), Decyl group (including all isomers), undecyl group (including all isomers), dodecyl group (including all isomers), tridecyl group (including all isomers), tetradecyl group (all ), Pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), octadecyl group (including all isomers) ), Nonadecyl group (including all isomers), icosyl group (including all isomers), heicosyl group (including all isomers), docosyl group (including all isomers), tricosyl group (all ), Tetracosyl group (including all isomers), pentacosyl group (including all isomers), hexacosyl group (including all isomers), heptacosyl group (including all isomers) , Octacosyl group (including all isomers), nonacosyl group (including all isomers), triacontyl group (including all isomers), hentriacontyl group (including all isomers), dotriacontyl group ( All isomers), tritriacontyl group (including all isomers), tetratriacontyl group (including all isomers), pentato Acontyl group (including all isomers), hexatriacontyl group (including all isomers), heptatriacontyl group (including all isomers), octatriacontyl group (including all isomers) ), Nonatoriacontyl group (including all isomers), tetracontyl group (including all isomers), and the like. Further, the alkyl group of the alkylbenzene according to the present invention may be linear or branched, but a branched alkyl group is preferable from the viewpoint of stability, viscosity characteristics, etc., and particularly easily available. In view of the above, branched alkyl groups derived from olefin oligomers such as propylene, butene and isobutylene are more preferred.

  The number of alkyl groups in the alkylbenzene used in the present invention is preferably 1 to 4, but from the viewpoints of stability and availability, alkylbenzene having one or two alkyl groups, that is, monoalkylbenzene, dialkylbenzene, Or a mixture thereof is 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 according to the present invention can be produced, for example, using an aromatic compound as a raw material and using an alkylating agent and an alkylation catalyst. Here, specific examples of the aromatic compound used as a raw material include benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, and mixtures thereof. Further, as the alkylating agent, specifically, a lower monoolefin such as ethylene, propylene, butene, and isobutylene, preferably a linear or branched olefin having 6 to 40 carbon atoms obtained by polymerization of propylene; C6-C40 linear or branched olefins obtained by thermal decomposition of wax, heavy oil, petroleum fractions, polyethylene, polypropylene, etc .; n-paraffins are separated from petroleum fractions such as kerosene and light oil And a straight-chain olefin having 9 to 40 carbon atoms obtained by olefinating it with a catalyst, and a mixture thereof. Furthermore, as alkylation catalysts in the alkylation, Friedel-Crafts type catalysts such as aluminum chloride and zinc chloride; acidic catalysts such as sulfuric acid, phosphoric acid, silicotungstic acid, hydrofluoric acid, activated clay, etc. A well-known catalyst is mentioned.

  In the present invention, the various base oils described above may be used alone, or two or more base oils may be mixed and used. Moreover, content of the said base oil in the rust prevention oil composition of this invention can be made into the remainder except a rust prevention agent. Moreover, the rust prevention oil composition of this invention can contain the other additive mentioned later, and can be made into the remainder except a rust prevention agent and another additive in that case.

  The rust inhibitor used in the present invention is not particularly limited, but sulfonates, carboxylic acids, carboxylates, esters, sarcosine, amines, and boron compounds are preferably used.

  Preferred examples of the sulfonate 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 constituting the sulfonate include sodium and potassium, and examples of the alkaline earth metal include magnesium, calcium and barium. Among these, sodium, potassium and calcium are preferable.

Examples of the amine include monoamine, polyamine, alkanolamine and the like. Specific examples of the monoamine include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine (including all isomers), dipropylamine (including all isomers), Propylamine (including all isomers), monobutylamine (including all isomers), dibutylamine (including all isomers), tributylamine (including all isomers), monopentylamine (all including all isomers) Including isomers), dipentylamine (including all isomers), tripentylamine (including all isomers), monohexylamine (including all isomers), dihexylamine (including all isomers) ), Monoheptylamine (including all isomers), diheptylamine (including all isomers) , Monooctylamine (including all isomers), dioctylamine (including all isomers), monononylamine (including all isomers), monodecylamine (including all isomers), monoundecyl ( Including all isomers), monododecylamine (including all isomers), monotridecylamine (including all isomers), monotetradecylamine (including all isomers), monopentadecylamine (Including all isomers), monohexadecylamine (including all isomers), monoheptadecylamine (including all isomers), monooctadecylamine (including all isomers), monononadecyl Amine (including all isomers), monoicosylamine (including all isomers), monohenicosylamine (including all isomers), monodocosylamine (Including all isomers), monotricosylamine (including all isomers), dimethyl (ethyl) amine, dimethyl (propyl) amine (including all isomers), dimethyl (butyl) amine (all Isomers), dimethyl (pentyl) amine (including all isomers), dimethyl (hexyl) amine (including all isomers), dimethyl (heptyl) amine (including all isomers), dimethyl ( Octyl) amine (including all isomers), dimethyl (nonyl) amine (including all isomers), dimethyl (decyl) amine (including all isomers), dimethyl (undecyl) amine (all isomers) ), Dimethyl (dodecyl) amine (including all isomers), dimethyl (tridecyl) amine (including all isomers), dimethyl (tetradecyl) ) Amine (including all isomers), dimethyl (pentadecyl) amine (including all isomers), dimethyl (hexadecyl) amine (including all isomers), dimethyl (heptadecyl) amine (including all isomers) ), Dimethyl (octadecyl) amine (including all isomers), dimethyl (nonadecyl) amine (including all isomers), dimethyl (icosyl) amine (including all isomers), dimethyl (henicosyl) amine Alkylamines such as (including all isomers), dimethyl (tricosyl) amine (including all isomers);
Monovinylamine, divinylamine, trivinylamine, monopropenylamine (including all isomers), dipropenylamine (including all isomers), tripropenylamine (including all isomers), monobutenylamine (Including all isomers), dibutenylamine (including all isomers), tributenylamine (including all isomers), monopentenylamine (including all isomers), dipentenylamine (all isomers) ), Tripentenylamine (including all isomers), monohexenylamine (including all isomers), dihexenylamine (including all isomers), monoheptenylamine (all isomers) ), Diheptenylamine (including all isomers), monooctenylamine (including all isomers), dioctenylamine (Including all isomers), monononenylamine (including all isomers), monodecenylamine (including all isomers), monoundecenyl (including all isomers), monododecenylamine (Including all isomers), monotridecenylamine (including all isomers), monotetradecenylamine (including all isomers), monopentadecenylamine (including all isomers), Monohexadecenylamine (including all isomers), monoheptadecenylamine (including all isomers), monooctadecenylamine (including all isomers), monononadecenylamine (all isomers) ), Monoicosenylamine (including all isomers), monohenicocenylamine (including all isomers), monodocosenylamine (including all isomers), Trichoderma cell (including all isomers) cycloalkenyl amines alkenyl amines, such as;
Dimethyl (vinyl) amine, dimethyl (propenyl) amine (including all isomers), dimethyl (butenyl) amine (including all isomers), dimethyl (pentenyl) amine (including all isomers), dimethyl ( Hexenyl) amine (including all isomers), dimethyl (heptenyl) amine (including all isomers), dimethyl (octenyl) amine (including all isomers), dimethyl (nonenyl) amine (all isomers) ), Dimethyl (decenyl) amine (including all isomers), dimethyl (undecenyl) amine (including all isomers), dimethyl (dodecenyl) amine (including all isomers), dimethyl (tridecenyl) Amine (including all isomers), dimethyl (tetradecenyl) amine (including all isomers), dimethyl (pen Decenyl) amine (including all isomers), dimethyl (hexadecenyl) amine (including all isomers), dimethyl (heptadecenyl) amine (including all isomers), dimethyl (octadecenyl) amine (all isomers) ), Dimethyl (nonadecenyl) amine (including all isomers), dimethyl (icosenyl) amine (including all isomers), dimethyl (henicosenyl) amine (including all isomers), dimethyl (tricosenyl) Monoamines having alkyl and alkenyl groups such as amines (including all isomers);
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
C5-C16 cycloalkylamines such as monocyclopentylamine, dicyclopentylamine, tricyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine;
Monoamines having an alkyl group and a cycloalkyl group, such as dimethyl (cyclopentyl) amine, dimethyl (cyclohexyl) amine, dimethyl (cycloheptyl) amine;
(Methylcyclopentyl) amine (including all substituted isomers), bis (methylcyclopentyl) amine (including all substituted isomers), (dimethylcyclopentyl) amine (including all substituted isomers), bis (dimethylcyclopentyl) ) Amine (including all substituted isomers), (ethylcyclopentyl) amine (including all substituted isomers), bis (ethylcyclopentyl) amine (including all substituted isomers), (methylethylcyclopentyl) amine ( All substituted isomers included), bis (methylethylcyclopentyl) amine (including all substituted isomers), (diethylcyclopentyl) amine (including all substituted isomers), (methylcyclohexyl) amine (all substituted isomers) Isomers), bis (methylcyclohexyl) amine (all substituted isomers) ), (Dimethylcyclohexyl) amine (including all substituted isomers), bis (dimethylcyclohexyl) amine (including all substituted isomers), (ethylcyclohexyl) amine (including all substituted isomers), bis (Ethylcyclohexyl) amine (including all substituted isomers), (Methylethylcyclohexyl) amine (including all substituted isomers), (Diethylcyclohexyl) amine (including all substituted isomers), (Methylcycloheptyl) ) Amine (including all substituted isomers), bis (methylcycloheptyl) amine (including all substituted isomers), (dimethylcycloheptyl) amine (including all substituted isomers), (ethylcycloheptylamine) (Including all substituted isomers), (methylethylcycloheptyl) amine (all substituted isomers) And alkyl cycloalkylamines such as (diethylcycloheptyl) amine (including all substituted isomers), etc. Monoamines also include monoamines derived from fats and oils (such as tallow amine). It is.

Specific examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, butylenediamine. , Alkylene polyamines such as dibutylene triamine, butylene tetramine, tetrabutylene pentamine, pentabylene hexamine;
N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine (including all isomers), N-butylethylenediamine (including all isomers), N-pentylethylenediamine (including all isomers), N -Hexylethylenediamine (including all isomers), N-heptylethylenediamine (including all isomers), N-octylethylenediamine (including all isomers), N-nonylethylenediamine (including all isomers) N-decylethylenediamine (including all isomers), N-undecyl (including all isomers), N-dodecylethylenediamine (including all isomers), N-tridecylethylenediamine (including all isomers) Including), N-tetradecylethylenediamine (including all isomers), -Pentadecylethylenediamine (including all isomers), N-hexadecylethylenediamine (including all isomers), N-heptadecylethylenediamine (including all isomers), N-octadecylethylenediamine (all isomers) N-nonadecylethylenediamine (including all isomers), N-icosylethylenediamine (including all isomers), N-henicosylethylenediamine (including all isomers), N-doco N-alkylethylenediamines such as silethylenediamine (including all isomers), N-tricosylethylenediamine (including all isomers);
N-vinylethylenediamine, N-propenylethylenediamine (including all isomers), N-butenylethylenediamine (including all isomers), N-pentenylethylenediamine (including all isomers), N-hexenylethylenediamine ( Including all isomers), N-heptenylethylenediamine (including all isomers), N-octenylethylenediamine (including all isomers), N-nonenylethylenediamine (including all isomers), N-decenylethylenediamine (including all isomers), N-undecenyl (including all isomers), N-dodecenylethylenediamine (including all isomers), N-tridecenylethylenediamine (including all isomers) All isomers), N-tetradecenylethylenediamine (including all isomers), N- Ntadecenylethylenediamine (including all isomers), N-hexadecenylethylenediamine (including all isomers), N-heptadecenylethylenediamine (including all isomers), N-octade Cenylethylenediamine (including all isomers), N-nonadecenylethylenediamine (including all isomers), N-icosenylethylenediamine (including all isomers), N-henicocenylethylenediamine N-alkenylethylenediamine such as (including all isomers), N-docosenylethylenediamine (including all isomers), N-tricosenylethylenediamine (including all isomers);
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-alkenyl alkylene polyamines such as N-alkenyltetrabutylenepentamine, N-alkylpentabylenehexamine, N-alkenylpentabylenehexamine and the like. The polyamine also includes polyamines derived from fats and oils (such as beef tallow polyamine).

  Further, as the alkanolamine, specifically, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, Tri (n-propanol) amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine (including all isomers), dibutanolamine (including all isomers), tributanolamine (all Isomers), monopentanolamine (including all isomers), dipentanolamine (including all isomers), tripentanolamine (including all isomers), monohexanolamine (all Isomers), di Xanolamine (including all isomers), monoheptanolamine (including all isomers), diheptanolamine (including all isomers), monooctanolamine (including all isomers), Monononanolamine (including all isomers), monodecanolamine (including all isomers), monoundecanolamine (including all isomers), monododecanolamine (including all isomers) ), Monotridecanolamine (including all isomers), monotetradecanolamine (including all isomers), monopentadecanolamine (including all isomers), monohexadecanolamine (including all isomers) All isomers), diethyl monoethanolamine, diethyl monopropanolamine (including all isomers), diethyl monobutanol amine (Including all isomers), diethylmonopentanolamine (including all isomers), dipropylmonoethanolamine (including all isomers), dipropylmonopropanolamine (including all isomers) ), Dipropylmonobutanolamine (including all isomers), dipropylmonopentanolamine (including all isomers), dibutylmonoethanolamine (including all isomers), dibutylmonopropanolamine (all ), Dibutylmonobutanolamine (including all isomers), dibutylmonopentanolamine (including all isomers), monoethyldiethanolamine, monoethyldipropanolamine (including all isomers) ), Monoethyldibutanolamine (including all isomers), monoethyldipenta Nolamine (including all isomers), monopropyldiethanolamine (including all isomers), monopropyldipropanolamine (including all isomers), monopropyldibutanolamine (including all isomers), Monopropyldipentanolamine (including all isomers), monobutyldiethanolamine (including all isomers), monobutyldipropanolamine (including all isomers), monobutyldibutanolamine (all isomers) ), Monobutyldipentanolamine (including all isomers), monocyclohexyl monoethanolamine, monocyclohexyldiethanolamine, monocyclohexylmonopropanolamine (including all isomers), monocyclohexyldipropanolamine ( Includes all isomers ), And the like.

  Among the amines described above, monoamines are preferable because they are more excellent in rust prevention. Among the 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. An amine having a total carbon number of 3 or more in the amine molecule is preferred because it is more excellent in rust prevention, and an amine having a total carbon number of 5 or more is more preferred.

  On the other hand, as the sulfonic acid according to the present invention, a conventionally known sulfonic acid produced by a conventional method can be used. 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. Although there is no restriction | limiting in particular about the molecular weight of these sulfonic acids, Preferably it is 100-1500, More preferably, the thing of 200-700 is used.

Among the above sulfonic acids,
Dialkylnaphthalenesulfonic acid wherein the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14-30;
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 a dialkylbenzene sulfone having a total carbon number of 14 to 30 of the two alkyl groups An acid; and a monoalkylbenzenesulfonic acid in which the alkyl bonded to the benzene ring has 15 or more carbon atoms,
It is preferable to use at least one selected from the group consisting of

  As described above, the dialkylnaphthalenesulfonic acid preferably used in the present invention has a total number of carbon atoms of two alkyl groups bonded to the naphthalene ring of 14 to 30. When the total number of carbon atoms of the two alkyl groups is less than 14, the demulsibility tends to be insufficient, and when it exceeds 30, the storage stability of the obtained rust preventive oil composition tends to be lowered. Note that 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, It is preferable that the carbon number of each alkyl group is 6-18, respectively.

  Further, as described above, the dialkylbenzenesulfonic acid preferably used in the present invention is a branched alkyl group in which two alkyl groups bonded to the benzene ring each have one linear alkyl group or one side chain methyl group. And the total number of carbon atoms of the two alkyl groups is 14-30. In the case of monoalkylbenzenesulfonic acid, it can be suitably used as long as the alkyl group has 15 or more carbon atoms, as will be described later. However, when a monoalkylbenzenesulfonic acid having an alkyl group having less than 15 carbon atoms is used, rust prevention oil is used. The storage stability of the composition tends to decrease. Also, when an alkylbenzene sulfonic acid having 3 or more alkyl groups is used, the storage stability of the rust preventive oil composition tends to decrease. Further, the alkyl group bonded to the benzene ring of the dialkylbenzenesulfonic acid has a branched alkyl group having a branched structure other than the side chain methyl group (for example, a branched alkyl group having a side chain ethyl group, etc.) or two A branched alkyl group having the above branched structure (for example, a branched alkyl group derived from an oligomer of propylene) may adversely affect the human body or ecosystem, and has rust prevention properties. It tends to be insufficient. Furthermore, if the total number of carbon atoms of the two alkyl groups bonded to the benzene ring of the dialkylbenzene sulfonic acid is less than 14, the demulsibility tends to be reduced. The stability tends to decrease. In addition, as long as the total carbon number of two alkyl groups couple | bonded with a benzene ring is 14-30, there will be no limitation in particular about the carbon number of each alkyl group, but carbon number of each alkyl group shall be 6-18, respectively. Is preferred.

  Furthermore, the monoalkylbenzene sulfonic acid preferably used in the present invention has one or more alkyl groups bonded to the benzene ring having 15 or more carbon atoms as described above. When the carbon number of the alkyl group bonded to the benzene ring is less than 15, the storage stability of the obtained rust preventive oil composition tends to be lowered. Further, the alkyl group bonded to the benzene ring may be linear or branched as long as the carbon number is 15 or more.

Specific examples of the sulfonate obtained using the above raw materials include the following. That is,
Alkali metal bases (alkali metal oxides, hydroxides, etc.), alkaline earth metal bases (alkali earth metal oxides, hydroxides, etc.) or amines (ammonia, alkylamines, alkanolamines, etc.) Neutral (normal salt) sulfonates obtained by reacting with sulfonic acids;
A basic sulfonate obtained by heating the 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;
Carbonate overbased (superbasic) sulfonate obtained by reacting the neutral (normal salt) sulfonate with an alkali metal base, alkaline earth metal base or amine in the presence of carbon dioxide;
Reaction of the neutral (normal salt) sulfonate with an alkali metal base, an alkaline earth metal base or amine, and a boric acid compound such as boric acid or boric anhydride, or the carbonate overbasing (superbase) A borate overbased (superbasic) sulfonate obtained by a reaction between a sulfonate and a boric acid compound such as boric acid or boric anhydride, and a mixture thereof.

  In addition, when producing the neutral (normal salt) sulfonate, the same alkali metal, alkaline earth metal or amine chloride as the target sulfonate as a reaction accelerator is added, After preparing a neutral (normal salt) sulfonate of a different alkali metal, alkaline earth metal or amine, the same alkali metal alkaline earth metal or amine chloride as the target sulfonate is added to carry out an exchange reaction. It is also possible to obtain the desired sulfonate. However, chloride ions are likely to remain in the sulfonate obtained by such a method. Therefore, in the present invention, the sulfonate obtained by such a method is not used, or the sulfonate obtained. 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.

Dialkylnaphthalene sulfonates in which the total number of carbon atoms of the two alkyl groups bonded to the naphthalene ring is 14 to 30;
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 a dialkylbenzene sulfone having a total carbon number of 14 to 30 of the two alkyl groups Acid salts; and monoalkylbenzenesulfonates in which the number of carbon atoms of the alkyl bonded to the benzene ring is 15 or more,
It is preferable to use at least one selected from the group consisting of

  Any carboxylic acid can be used, and preferred examples include fatty acids, dicarboxylic acids, hydroxy fatty acids, naphthenic acids, resin acids, oxidized waxes, and lanolin fatty acids. The fatty acid here is a fatty acid having 6 to 24 (more preferably 10 to 22) carbon atoms. Here, the fatty acid used in the present invention may be a saturated fatty acid or an unsaturated fatty acid, and may be a linear fatty acid or a branched fatty acid. Specific examples of such fatty acids include hexanoic acid (including all isomers), heptanoic acid (including all isomers), octanoic acid (including all isomers), nonanoic acid (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), pentadecanoic acid (including all isomers), hexadecanoic acid (including all isomers), heptadecanoic acid (including all isomers), octadecanoic acid (all isomers) ), Nonadecanoic acid (including all isomers), icosanoic acid (including all isomers), heicosanoic acid (including all isomers), docosanoic acid (including all isomers), tricosane Acid (all isomeric Saturated fatty acids such as tetracosanoic acid (including all isomers); hexenoic acid (including all isomers), heptenoic acid (including all isomers), octenoic acid (including all isomers) ), Nonenoic acid (including all isomers), decenoic acid (including all isomers), undecenoic acid (including all isomers), dodecenoic acid (including all isomers), tridecenoic acid (all ), Tetradecenoic 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), henicosenoic acid (including all isomers), docosenoic acid (all Including isomers) And mixtures thereof; (including all isomers) tricosenoic acid, (including all isomers) tetracosenoic acid unsaturated fatty acids such as.

  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. Specific 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. Specific examples of such hydroxy fatty acids include ricinoleic acid and the like.

  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 (hydrolyzing, etc.) a waxy substance adhering to sheep wool.

  Examples of the carboxylate include alkali metal salts, alkaline earth metal salts, and amine salts of the carboxylic acids described above. Examples of the alkali metal, alkaline earth metal, and amine here include the alkali metal, alkaline earth metal, and amine exemplified in the description of the sulfonic acid. Barium salt may be insufficiently safe for the human body and ecosystem.

  Carboxylic acid salts can be used in combination with other rust inhibitors, but when an oxidized wax salt and a lanolin fatty acid salt are used in combination with a sulfonic acid sodium salt, sodium salts are used as the oxidized wax salt and the lanolin fatty acid salt, respectively. It is preferable.

  Examples of the esters include partial esters of polyhydric alcohols, esterified oxidized waxes, esterified lanolin fatty acids, alkyl or alkenyl succinic acid esters, and the like.

  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. Can be used, but the number of hydroxyl groups in the molecule is preferably 2 to 10 (more preferably 3 to 6) and the number of carbon atoms is 2 to 20 (more preferably 3 to 10). Alcohol is preferably used. Among these polyhydric alcohols, it is more preferable to use at least one polyhydric alcohol selected from the group consisting of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitan.

  On the other hand, any acid can be used as the acid constituting the partial ester, but fatty acids having 6 to 24 carbon atoms (more preferably 10 to 22 carbon atoms) are preferred. Here, the fatty acid used in the present invention 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 the fatty acids exemplified in the description of the carboxylic acid.

Specific examples of partial esters of polyhydric alcohols obtained using the above polyhydric alcohols and acids include glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, and glycerin didodecanoate. (Glycerol dilaurate), glycerol diisolaurate, glycerol monotetradecanoate (glycerol monomyristate), glycerol monoisomyristate, glycerol ditetradecanoate (glycerol diisomyristate), glycerol diisomyristate, glycerol mono Hexadecanoate (glycerol monopalmitate), glycerol monoisopalmitate, glycerol dihexadecanoate (glycerol dipalmitate), glycerol diisopalmitate, glycerol monooctadecanoate Glycerin monostearate), glycerin monoisostearate, glycerin dioctadecanoate (glycerin distearate), glycerin diisostearate, glycerin monooctadecenoate (glycerin monooleate), glycerin monoisooleate, Glycerin partial esters such as glycerin dioctadecenoate (glycerin dioleate), glycerin diisooleate;
Trimethylol ethane monododecanoate (trimethylol ethane monolaurate), trimethylol ethane monoisolaurate, trimethylol ethane didodecanoate (trimethylol ethane dilaurate), trimethylol ethane diisolaurate, trimethylol ethane monotetra Decanoate (trimethylolethane monomyristate), trimethylolethane monoisomyristate, trimethylolethaneditetradecanoate (trimethylolethanedimyristate), trimethylolethanediisomyristate, trimethylolethanemonomyristate Decanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylolethanedihexadecanoate (trimethylolethanedi) Lumitate), trimethylol ethane diisopalmitate, trimethylol ethane monooctadecanoate (trimethylol ethane monostearate), trimethylol ethane monoisostearate, trimethylol ethane dioctadecanoate (trimethylol ethane distea) Rate), trimethylol ethane diisostearate, trimethylol ethane monooctadecenoate (trimethylol ethane monooleate), trimethylol ethane monoisooleate, trimethylol ethane dioctadecenoate (trimethylol ethanediolate) Trimethylolethane partial esters such as trimethylolethanediisooleate;
Trimethylolpropane monododecanoate (trimethylolpropane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropane didodecanoate (trimethylolpropane dilaurate), trimethylolpropane diisolaurate, trimethylolpropane monotetra Decanoate (trimethylolpropane monomyristate), trimethylolpropane monoisomyristate, trimethylolpropane ditetradecanoate (trimethylolpropane dimyristate), trimethylolpropane diisomyristate, trimethylolpropane monohexa Decanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisopalmitate, trimethylolpropane dihexadeca (Trimethylolpropane dipalmitate), trimethylolpropane diisopalmitate, trimethylolpropane monooctadecanoate (trimethylolpropane monostearate), trimethylolpropane monoisostearate, trimethylolpropane dioctadecano (Trimethylolpropane distearate), trimethylolpropane diisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate, trimethylolpropane dioctadeceno Trimethylolpropane partial esters such as acrylate (trimethylolpropane dioleate), trimethylolpropane diisooleate;
Pentaerythritol monododecanoate (pentaerythritol monolaurate), pentaerythritol monoisolaurate, pentaerythritol didodecanoate (pentaerythritol dilaurate), pentaerythritol diisolaurate, pentaerythritol tridodecanoate (pentaerythritol trilaurate) Rate), pentaerythritol triisolaurate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomyristate, pentaerythritol ditetradecanoate (pentaerythritol dimyristate), pentaerythritol diisostate Myristate, Pentaerythritol Tritetradecanoate (Pentaerythritol Trimilli Tate), pentaerythritol triisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol dihexadecanoate (pentaerythritol dipalmitate), pentaerythritol di Isopalmitate, pentaerythritol trihexadecanoate (pentaerythritol tripalmitate), pentaerythritol triisopalmitate, pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol Dioctadecanoate (pentaerythritol distearate), pentaerythritol diisostearate Pentaerythritol trioctadecanoate (pentaerythritol tristearate), pentaerythritol triisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate), pentaerythritol monoisooleate, pentaerythritol dioctaate Pentaerythritol partial esters such as decenoate (pentaerythritol dioleate), pentaerythritol diisooleate, pentaerythritol trioctadecenoate (pentaerythritol trioleate), 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 trimyristate) 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 dioctadecanoate (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 trio) Benzoate), sorbitan partial esters, such as sorbitan triisostearate oleate,
Alternatively, a mixture of these is preferably used. Among these, glycerol monododecanoate (glycerol monolaurate), glycerol monoisolaurate, glycerol monotetradecanoate (glycerol monomyristate), glycerol monoisomyristate, and glycerol monohexadeca are monoesters. Noate (glycerol monopalmitate), glycerol monoisopalmitate, glycerol monooctadecanoate (glycerol monostearate), glycerol monoisostearate, glycerol monooctadecenoate (glycerol monooleate), glycerol monoiso Oleate; trimethylolethane monododecanoate (trimethylolethane monolaurate), trimethylolethane monoisolaurate, trimethylolethane monotetradecanoate Trimethylolethane monomyristate), trimethylolethane monoisomyristate, trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylolethane monooctadecanoate ( Trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate; trimethylolpropane monododecanoate (tri Methylolpropane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropane monotetradecanoate (trimethylolpropane monomyristate) , Trimethylolpropane monoisomyristate, trimethylolpropane monohexadecanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisopalmitate, trimethylolpropane monooctadecanoate (trimethylolpropane monostearate) , Trimethylolpropane monoisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate; pentaerythritol monododecanoate (pentaerythritol monolaurate), pentaerythritol Monoisolaurate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoi Somyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol monooctaate Decenoate (pentaerythritol monooleate), pentaerythritol monoisooleate; sorbitan monododecanoate (sorbitan monolaurate), sorbitan monoisolaurate, sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan Monoisomyristate, sorbitan monohexadecanoate (sorbitan monopalmitate), sorbitan monoisopalmitate , Sorbitan octadecanoate (sorbitan monostearate), sorbitan monoisostearate, sorbitan mono-octadecenoate (sorbitan monooleate), sorbitan monoisostearate oleate, or it is preferable to use a mixture thereof.

  The esterified oxidized wax refers to a product obtained by reacting an oxidized wax with an alcohol to esterify part or all of the acidic groups of the oxidized wax. Here, as the oxidized wax used as a raw material of the esterified oxidized wax, the oxidized wax exemplified in the description of the carboxylate; the alcohols are linear or branched having 1 to 20 carbon atoms. Examples thereof include saturated monohydric alcohols, 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 lanolin fatty acid obtained by purifying (hydrolyzing, etc.) a waxy substance adhering to sheep wool and an alcohol. Here, examples of the alcohol used as a raw material for the esterified lanolin fatty acid include alcohols exemplified in the description of the esterified oxidized wax, and among them, polyhydric alcohols are preferable, and trimethylolpropane, trimethylolethane, and sorbitan. , Pentaerythritol and glycerin are more preferable.

  Examples of the alkyl or alkenyl succinic acid ester include esters of the above-described alkyl or alkenyl succinic acid with a monohydric alcohol or a dihydric or higher polyhydric alcohol. Among these, esters of monohydric alcohols and dihydric alcohols are preferable.

  The monohydric alcohol here may be a linear or branched one, and may be a saturated alcohol or an unsaturated alcohol. Moreover, although carbon number in particular of monohydric alcohol is not restrict | limited, C8-C18 aliphatic alcohol is used preferably.

  As the dihydric alcohol, alkylene glycol and polyoxyalkylene glycol are preferably used. Specific 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 homopolymerization or copolymerization of a certain group side such as ethylene oxide, propylene oxide, 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 may be random copolymerization or block copolymerization. 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 two —COOH groups of the alkyl or alkenyl succinic acid are esterified (complete ester), or only one of the —COOH groups is an ester. Monoester (partial ester) may be used, but monoester is preferable from the viewpoint of more excellent rust prevention.

  Moreover, as sarcosine, the compound represented by either of the following general formula (1)-(3) is used preferably.

R ¹ —CO—NR ² — (CH ₂ ) _n —COOX (1)
(Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, X is hydrogen, an alkyl group having 1 to 30 carbon atoms, or (C 1-30 alkenyl group, n represents an integer of 1-4)
[R ¹ —CO—NR ² — (CH ₂ ) _n —COO] _m Y (2)
Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, Y is an alkali metal or alkaline earth metal, and n is 1 An integer of ˜4, m is 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.
^{[R 1 -CO-NR 2 -} (CH 2) n -COO] m -Z- (OH) m '(3)
(Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, and Z is a hydroxyl group of a polyhydric alcohol having 2 or more valences) And m represents an integer of 1 or more, m ′ represents an integer of 0 or more, m + m ′ represents a valence of Z, and n represents an integer of 1 to 4.)
In general formulas (1) to (3), R ¹ represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms. From the viewpoint of solubility in base oil, the alkyl group or alkenyl group must have 6 or more carbon atoms, preferably 7 or more carbon atoms, and more preferably 8 or more carbon atoms. Further, from the viewpoint of storage stability and the like, it is necessary that the alkyl group or alkenyl group has 30 or less carbon atoms, preferably 24 or less carbon atoms, and more preferably 20 or less carbon atoms. Specific examples of such alkyl groups and alkenyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Alkyl groups such as heptadecyl group, octadecyl group, nonadecyl group, icosyl group (these alkyl groups may be linear or branched); hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group Group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group and the like alkenyl groups (these alkenyl groups may be linear or branched, and the position of the double bond) Are also optional)

In general formulas (1) to (3), R ² represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of storage stability and the like, it is necessary that the alkyl group has 4 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms. In general formulas (1) to (3), n represents an integer of 1 to 4. From the viewpoint of storage stability and the like, it is necessary to be an integer of 4 or less, preferably 3 or less, and more preferably 2 or less.

  In general formula (1), X represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 1 to 30 carbon atoms. The alkyl group or alkenyl group represented by X needs to have 30 or less carbon atoms from the viewpoint of storage stability, preferably 20 or less carbon atoms, and preferably 10 or less carbon atoms. More preferred. Specific examples of such an alkyl group or alkenyl group include alkyl groups such as 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, and a decyl group. (These alkyl groups may be linear or branched); alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group (these alkenyl groups) May be linear or 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 hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms, and more preferably hydrogen or an alkyl group having 1 to 20 carbon atoms. It is more preferable that it is hydrogen, and it is still more preferable that it is a C1-C10 alkyl group.

  In the general formula (2), Y represents an alkali metal or an alkaline earth metal, and specific examples include sodium, potassium, magnesium, calcium, barium and the like. 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 general formula (2), m represents 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.

  In general formula (3), Z represents the residue except the hydroxyl group of the polyhydric alcohol more than bivalence. Specific examples of such polyhydric alcohols 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, dimer diol Divalent alcohols such as 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- 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 Le, sorbitol, mannitol, iditol, inositol, dulcitol, talose, hexavalent alcohols such as allose, polyglycerin or their dehydrated condensates and the like.

  In the general formula (3), m is an integer of 1 or more, m ′ is an integer of 0 or more, and m + m ′ is the same as the valence of Z. That is, all of the hydroxyl groups of the polyhydric alcohol of Z may be substituted, or only a part thereof may be substituted.

  Among the sarcosine represented by the general formulas (1) to (3), it may be at least one compound selected from the general formulas (1) and (2) from the viewpoint of more excellent rust prevention properties. preferable. Moreover, only 1 type of compound chosen from general formula (1)-(3) may be used independently, and the mixture of 2 or more types of compounds may be used.

  Examples of the amine include the amines exemplified in the description of the sulfonate.

  In addition, examples of the boron compound include calcium borate.

  In the production of the above compound, a chlorine bleach may be used for the purpose of decolorization. In the present invention, a specific chlorine compound such as hydrogen peroxide is used as the bleach, or a decoloration treatment is performed. It is preferable not to carry out. In addition, chlorine compounds such as hydrochloric acid may be used for the hydrolysis of fats and oils. 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.

  Further, the chlorine concentration of the above compound is not particularly limited as long as it does not impair the properties of the rust preventive oil composition, but is preferably 200 ppm by mass or less, more preferably 100 ppm by mass or less, Preferably it is 50 ppm or less, Most preferably, it is 25 mass ppm or less.

  In the rust preventive oil composition of the present invention, one of the above rust inhibitors may be used alone, or two or more may be mixed and used. However, it is preferable to use sulfonate in combination with at least one selected from carboxylic acid, carboxylate, ester, sarcosine, amine, and boron compound because higher rust-preventing properties can be obtained. Furthermore, the rust inhibitor used in combination with the sulfonate is preferably at least one selected from esters, carboxylic acids and carboxylates, and used in combination with esters and carboxylic acids and / or carboxylates. Is more preferable. In addition, as the ester herein, a partial ester of polyhydric alcohol and a partial ester of alkenyl succinic acid are preferable, and as the carboxylic acid, fatty acid, dimer acid and alkenyl succinic acid are preferable, and as the carboxylate, a fatty acid salt, Lanolin fatty acid salts and oxidized wax salts are preferred.

  The content of the rust inhibitor in the rust inhibitor composition of the present invention is required to be 1 to 40% by mass as described above, preferably 2 to 30% by mass, more preferably 5 to 20% by mass. . When the content of the rust inhibitor is less than 1% by mass, sufficient rust preventive properties cannot be obtained. Moreover, even if content of a rust inhibitor exceeds 40 mass%, the rust prevention property corresponding to content cannot be obtained.

  Moreover, in the rust prevention oil composition of this invention, you may contain another additive as needed. Here, specific examples of other additives used in the present invention include, for example, paraffin wax having a remarkable effect of improving the rust-preventing property in an acidic atmosphere; Fats and oils, sulfurized esters, phosphate esters such as long-chain alkyl zinc dithiophosphates, tricresyl phosphates, fats and oils such as pork fats, fatty acids, higher alcohols, calcium carbonate, potassium borate; phenols to improve antioxidant performance Or amine antioxidants; corrosion inhibitors for improving corrosion prevention performance (benzotriazole or its derivatives, thiadiazole, benzothiazole, etc.); wetting agents such as diethylene glycol monoalkyl ether; acrylic polymers, paraffin wax, microwax , Slack wack , Polyolefin waxes, film-forming agents such as petrolatum; methyl silicone, fluorosilicone, antifoaming agents such as polyacrylates, water-soluble spoilage factors water and surfactant to remove, and mixtures thereof. In addition, rust inhibitors other than sulfonates according to the present invention, specifically, alkyl or alkenyl succinic acid (including anhydride) and derivatives thereof, dimers of unsaturated fatty acids such as oleic acid, etc. Other polar group-containing carboxylic acids, such as dicarboxylic acids, hydroxy fatty acids, mercapto fatty acids, etc .; carboxylic acids such as oxidized waxes; metals of carboxylic acids such as fatty acids, naphthenic acids, resin acids, alkenyl succinic acids, amino acid derivatives, etc. Carboxylates such as salts (sodium, potassium, calcium, magnesium, aluminum, zinc, lead, etc.) and amine salts (monoamine, tallow amine, polyamine, alkanolamine, etc.) Alcohols represented by higher aliphatic alcohols; phosphoric acid monoesters, phosphoric acid diesters, phosphorus It is also possible to incorporate boron compounds, esters, represented by these amine salts (nitrite) phosphoric acid derivatives. In addition, although content of said other additive is arbitrary, it is preferable that the sum total of content of these additives is 10 mass% or less on the basis of rust prevention oil composition whole quantity.

  Further, in the rust preventive oil composition of the present invention, the barium, zinc, chlorine and lead contents are each converted to elements, preferably 1000 ppm by mass or less, more preferably 500 ppm, based on the total amount of the rust preventive oil composition. The mass ppm or less, more preferably 100 mass ppm or less, still more preferably 50 mass ppm or less, still 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 in accordance with" IP PRPOSED METHOD AK / 81 Determination of chlorine-Microcoulometery oxidative method ". Mass ppm]. The detection limit of each element in the above measurement method is usually 1 mass ppm.

The kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention needs to be 100 to 1000 mm ² / s as described above. When the kinematic viscosity at 40 ° C. of the rust preventive oil composition is less than 100 mm ² / s, the oil film of the coating film is likely to break, and sufficient rust preventive properties cannot be obtained. For the same reason, the kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention is preferably 200 mm ² / s or more, more preferably 300 mm ² / s or more, still more preferably 400 mm ² / s or more, particularly preferably. 500 mm ² / s or more. On the other hand, if the kinematic viscosity exceeds 1000 mm ² / s, it cannot be put into practical use in terms of workability. For the same reason, the kinematic viscosity at 40 ° C. of the rust preventive oil composition of the present invention is preferably 900 mm ² / s or less, more preferably 800 mm ² / s or less. In addition, in the rust prevention method of the present invention described later, the rust prevention oil composition of the present invention is heated so that its kinematic viscosity is 50 mm ² / s or less, thereby realizing easy and reliable application to an object to be treated. Although it becomes possible, heating at a higher temperature is required to reduce the viscosity of the rust preventive oil having a kinematic viscosity at 40 ° C. exceeding 1000 mm ² / s. The deterioration of the oil is promoted and its performance is impaired.

  The rust prevention oil composition of the present invention having the above-described structure enables formation of an oil film having a uniform and sufficient thickness on the object to be treated, and sufficiently prevents the occurrence of rust without causing oil film breakage. It is possible to do that. The method for applying the rust-preventing oil composition to the object to be processed is not particularly limited. For example, the rust-preventing oil composition may be applied at room temperature. Is feasible.

That is, in the rust prevention method of the present invention, the rust preventive oil composition of the present invention is heated to have a kinematic viscosity of 50 mm ² / s or less and applied to an object to be treated. In this way, by heating the rust preventive oil composition of the present invention and setting its kinematic viscosity to 50 mm ² / s or less, the composition can be easily and reliably applied to an object to be treated.

The object to be treated in the rust prevention method of the present invention is not particularly limited, and is suitably applied to metallic members such as automobile parts, cold-rolled steel sheets, hot-rolled latter half, plated steel sheets, bearing parts, architectural steel materials, precision parts, and the like. can do. Further, the method for applying the heated composition to the object to be treated is not particularly limited, but it is desirable to apply it in a fine mist from the point of making the oil film thickness uniform. The application apparatus in this case is not particularly limited as long as it can atomize rust preventive oil having a kinematic viscosity of 50 mm ² / s or less. For example, any of an air spray type, an airless spray type, a hot melt type, etc. is applicable. Is possible.

FIG. 1 is an explanatory view showing an example of a coating apparatus preferably used in the rust prevention method of the present invention. In FIG. 1, a tank 1 contains a rust preventive oil composition (hereinafter simply referred to as “rust preventive oil”) 100 of the present invention. The tank 1 is provided with a heater 2 and a thermocouple 3, and the heater 2 and the thermocouple 3 are electrically connected to the temperature controller 4, respectively. Thereby, the rust prevention oil 100 accommodated in the tank 1 is heated to a temperature at which the kinematic viscosity is 50 mm ² / s or less. Further, during the heating, the rust preventive oil 100 is sufficiently stirred by the stirring bar 5 provided in the tank 1.

The rust preventive oil 100 heated in this way is drawn to the line L1 by the pump 6 and supplied to the spray 7. And the application | coating to the to-be-processed object 10 of the rust prevention oil 100 is performed by spraying the atomized anti-rust oil 100 toward the to-be-processed object 10 arrange | positioned facing the nozzle of the spray 7. FIG. At this time, in order to atomize the rust preventive oil 100 in the spray 7, the kinematic viscosity of the rust preventive oil 100 may be maintained at 50 mm ² / s or less by heating the line L 1, the spray 7, or the like as necessary. preferable. Although the heating temperature varies depending on the type of the rust preventive oil 100, etc., it is preferable that the temperature range, for example, 50 to 100 ° C. The upper limit of the heating temperature is not particularly limited, but the oxidative stability of the rust preventive oil 100 In view of this point, overheating should be avoided. Furthermore, heating to a temperature exceeding the flash point of rust prevention oil should be avoided because of the risk of fire. In addition, the atomization of the rust preventive oil 100 can be performed not only by managing the kinematic viscosity between the tank 1 and the spray 7 but also by controlling the application pressure, the nozzle tip, and the like.

  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 1-5, Comparative Examples 1-2]
In Examples 1 to 5 and Comparative Examples 1 and 2, rust prevention oil compositions were prepared using the base oils and additives shown below, respectively.

(Base oil)
Base oil 1: mineral oil (kinematic viscosity at 40 ° C .: 100 mm ² / s)
Base oil 2: mineral oil (kinematic viscosity at 40 ° C .: 500 mm ² / s)
Base oil 3: mineral oil (kinematic viscosity at 40 ° C .: 750 mm ² / s)
Base oil 4: mineral oil (kinematic viscosity at 40 ° C .: 1000 mm ² / s)
Base oil 5: mineral oil (kinematic viscosity at 40 ° C .: 10 mm ² / s)
Base oil 6: mineral oil (kinematic viscosity at 40 ° C .: 85 mm ² / s)
(Additive)
A1: Calcium sulfonate A2: Pentaerythritol monooleate A3: Oxidized paraffin calcium flame Next, the following evaluation tests were performed on the rust preventive oil compositions of Examples 1 to 5 and Comparative Examples 1 and 2.

[Sag test of coating film]
Using the coating apparatus shown in FIG. 1, the rust-preventing oil composition was heated and applied to a 30 mm × 350 mm test piece. At this time, in Examples 1 to 5 and Comparative Example 2, the rust preventive oil composition was heated to a temperature of 50 mm ² / s. Each heating temperature is shown in Table 1. Moreover, about the comparative example 1, the application | coating of the rust prevention oil composition was performed at room temperature, without heating.

  Next, each test piece after coating was held vertically and left at room temperature for 24 hours in a sealed state so as not to be affected by wind. Then, the test piece was cut | disconnected every 100 mm from the lower end, the three test pieces of a lower test piece, a middle test piece, and an upper test piece were obtained, and the oil coating amount of each test piece was measured by weight. And using the obtained measured value, the oil distribution amount distribution rate in each part of the test piece was obtained according to the following formula. The obtained results are shown in Table 1.

(Oil coating amount distribution ratio in each part of test piece [%]) = (Oil coating amount of upper, middle or lower test piece) / (Total oil application amount of upper, middle and lower test piece)
[Rust prevention test]
In the same manner as in the sagging property test of the coating film, each rust preventive oil composition was applied to the test piece, left at room temperature for 24 hours, and the test piece was cut to obtain an upper test piece, a middle test piece, and a lower test piece. Got. About these three test pieces, rust prevention property was evaluated in accordance with JIS K 2246 “Salt spray test method”. The obtained results are shown in Table 1. In Table 1, A means "no rust", B means "slight rust", and C means "rust".

  Moreover, about Examples 1-5, the standing time at room temperature was 48 hours, and the same rust prevention test was further implemented. The obtained results are shown in Table 1.

It is explanatory drawing which shows an example of the coating device used in this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Tank, 2 ... Heater, 3 ... Thermocouple, 4 ... Temperature controller, 5 ... Stirrer, 6 ... Pump, 7 ... Spray, 10 ... To-be-processed object, 100 ... Rust prevention oil.

Claims (2)

A rust-preventing oil composition comprising a predetermined base oil and 1 to 40% by mass of a rust inhibitor on the basis of the total amount of the composition, and having a kinematic viscosity at 40 ° C. of 100 to 1000 mm ² / s . A step of preparing a rust-preventing oil composition containing a predetermined base oil and a rust inhibitor of 1 to 40% by mass based on the total amount of the composition and having a kinematic viscosity at 40 ° C. of 100 to 1000 mm ² / s; ,
Heating the rust preventive oil composition to have a kinematic viscosity of 50 mm ² / s or less, and applying to the object to be treated;
A rust prevention method comprising:

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