EP1394289A1

EP1394289A1 - Rust-preventive oil composition

Info

Publication number: EP1394289A1
Application number: EP02714499A
Authority: EP
Inventors: T. c/o Nippon Mitsubishi Oil Corp. SUGAWARA; Tadaaki c/o NIPPON MITSUBISHI OIL CORP. MOTOYAMA; Y c/o Nippon Petroleum Processing Co Ltd IWAMURA; Yukio c/o NIPPON MITSUBISHI OIL CORP. MATSUZAKI
Original assignee: Nippon Mitsubishi Oil Corp
Current assignee: Eneos Corp
Priority date: 2001-04-06
Filing date: 2002-04-05
Publication date: 2004-03-03
Anticipated expiration: 2022-04-05
Also published as: WO2002083986A1; EP1394289B1; EP1394289A4; ATE557078T1

Abstract

The rust preventive oil composition according to the present invention contains at least one kind of sulfonate of 1 to 10% by mass selected from a group consisting of an alkaline metal sulfonate, an alkaline earth-metal sulfonate (with the exception of barium sulfonate) and an amine sulfonate based on the total weight of the composition in at least one kind of base oil selected from a group consisting of a mineral oil and a synthetic oil, and the contents of barium, zinc, chlorine and lead are each 1000ppm by mass or less based on the total weight by element conversion of the composition, and the content of a compound having a group represented by the following general formula (1):

[wherein R¹ represents an alkyl group having 1 to 24 carbon atoms , R² represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 5 and n represents an integer of 1 to 6]
is 1000ppm by mass or less based on the total weight of the composition.

Description

Technical Field

The present invention relates to rust preventive oil compositions, and more particularly to a rust preventive oil composition which is useful for metal parts such as steel sheets and bearings.

Background Art

Conventionally, rust preventive oil compositions have been used for preventing parts from rust in a field of metal parts such as steel sheets and bearings. Particularly, rust preventive oil compositions containing a barium (Ba) type or a zinc (Zn) type rust prevention agent have an excellent rust prevention ability, and occupy a major position in the field. In addition, as described in Japanese Patent Laid Open No. HEI 9-279368 and the like, an art which uses a film forming agent together such as a derivative of alkylene oxide addition compound of an alkylphenol has been also known as the art to attain the better rust prevention ability of rust preventive oil compositions containing a calcium(Ca) type rust prevention agent.

Disclosure of the Invention

However, it is worried about the aforementioned conventional rust preventive oil compositions that compounds such as an rust prevention agent and a film forming agent, and elements such as chlorine (Cl) mixed in the manufacturing process of the compounds have a malign influence on human body or ecosystem by themselves or by generating a certain substance through their disposition or incineration.
Therefore, in order to prevent the forgoing phenomenon, studies to achieve the adequately good rust prevention ability have been carried out without using the barium or zinc type rust prevention agent and the film forming agent such as alkyleneoxide addition compound of alkylphenol. However, any composition having the rust prevention ability equivalent to or better than conventional rust preventive oil compositions has not been developed yet.
Additionally, a good degreasing ability is required to rust preventive oils used for automobile bodies and appliance bodies which are degreased at a process using an alkaline degreasing agent. However, it has been technically difficult to achieve both the rust prevention and the degreasing ability at a high level.
Furthermore, rust preventive oils are usually applied on plate materials made of metals such as steel sheets for automobile bodies and appliance bodies when they are shipped. When a cleaning process is carried out for plate materials to remove foreign matters just before processing a press work, a cleaning oil having the rust prevention ability is sometimes used. Moreover, a cleaning process is carried out for bearing parts to remove foreign matters after processes, and rust preventive oils are applied after the cleaning, then the parts are shipped. The cleaning oil having the rust prevention ability is sometimes used.for the cleaning process. Although these cleaning oils having rust prevention ability (cleaning rust preventive oils) are required to have both an excellent foreign matter removing ability (hereinafter described as "cleaning ability") and an excellent rust prevention ability, it is technically difficult to achieve both ability adequately at the same time.
In view of the foregoing problems in the conventional technology, the object of the present invention is to provide rust preventive oil compositions which have the adequately good rust prevention ability without using the barium type or the zinc type rust prevention agent and the film forming agent such as an alkyleneoxide addition compound of alkylphenol, and is also to provide rust preventive oil compositions which is highly safe to human body or ecosystem.
As a result of extensive studies by the present inventors to achieve the above object, it has been found that the above object can be achieved by containing sulfonate of specific concentration which has a particular structure as an rust prevention agent, and by controlling each content of elements such as barium, zinc, chlorine and lead, and also the content of alkylene oxide addition compounds of alkylphenol at specific concentrations.
Namely, rust preventive oil compositions according to the present invention contain the following substances in at least one kind of base oil selected from mineral oils and synthetic oils; at least one kind of sulfonate selected from alkaline metal sulfonate, alkaline earth metal sulfonate (with the exception of barium sulfonate) and amine sulfonate in an amount of 1 to 10% by mass based on the total weight of the composition; barium, zinc, chlorine and lead wherein each element is in an amount of not more than 1000ppm by mass based on the total weight by element conversion of the composition; and a compound which has the group represented by the following formula (1):
is in an amount of not more than 1000ppm by mass based on the total weight of the composition. (Wherein R¹ represents an alkyl group having 1 to 24 carbon atoms, R² represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 5, and n represents an integer of 1 to 6.)
According to the present invention, sulfonate is preferably at least one kind of compound selected from the following group;
dialkylnaphthalene sulfonate having 14 to 30 total carbon atoms in two alkyl groups which are bonded to a naphthalene ring;
dialkylbenzene sulfonate in which two alkyl groups bonding to a benzene ring are each independently a straight chain alkyl group or a branched alkyl group having one side chain methyl group, and two alkyl groups have 14 to 30 total carbon atoms; and
monoalkylbenzene sulfonate having not less than 15 carbon atoms in an alkyl group bonding to a benzene ring.
In addition, according to the present invention, the content of monoalkylbenzene sulfonate which has one alkyl group having not more than 13 carbon atoms is preferably in an amount of not more than 1% by mass based on the total weight of the composition.
Furthermore, the content of alkylbenzene sulfonate which has an alkyl group derived from propylene oligomer is preferably in an amount of not more than 1% by mass based on the total weight of the composition.
Moreover, the rust preventive oil compositions according to the present invention comprise at least one kind of compound selected from the following groups (A) to (F) in an amount of preferably 1 to 20% by mass based on the total weight of the composition:
(A) a partial ester of polyhydric alcohol
(B) at least one kind of oxidized wax selected from alkaline metal salt of oxidized wax, alkaline earth metal salt of oxidized wax (with the exception of barium salt of oxidized wax) and amine salt of oxidized wax;
(C) esterified oxidized wax;
(D) at least one kind of lanoline fatty acid salt selected from alkaline metal salt of lanoline fatty acid, alkaline earth metal salt of lanoline fatty acid (with the exception of barium salt of lanoline fatty acid) and amine salt of lanoline fatty acid;
(E) esterified lanoline fatty acid; and
(F) at least one kind of fatty acid salt selected from alkaline metal salt of fatty acid, alkaline earth metal salt of fatty acid (with the exception of barium salt of fatty acid) and amine salt of fatty acid.
Furthermore, the total content of the compounds (A) to (F) is preferably in an amount of 20 to 500 parts by mass per 100 parts by mass of the sulfonate.
Additionally, the total content of the compounds (A), (C), (D) and (E) is preferably not more than 10% by mass based on the total weight of the composition.
Moreover, the rust preventive oil compositions according to the present invention have a kinematic viscosity of preferably 7 to 400mm²/s at 40° C.
Furthermore, the content of compounds having not more than 14 carbon atoms in base oils is preferably in an amount of not more than 20% by mass based on the total weight of the composition.
In addition, the content of aromatic components in base oils is preferably in an amount of not more than 50% by mass based on the total weight of the composition.
Moreover, the content of compounds having not more than 10 carbon atoms in base oils is.preferably in an amount of not more than 20% by mass based on the total weight of the composition.
Furthermore, the rust preventive oil compositions according to the present invention have a total base number of 1 to 20mgKOH/g, preferably the content of sulfonate and the total base number is represented by the following formula (2): TBN/CS≦3 (Wherein C_S represents a content [% by mass] of sulfonate, and TBN represents the total base number [mgKOH/g].)

Brief Description of the Drawings

Figure 1 is an explanatory drawing to illustrate an equipment used for a compatibility test of rust preventive oil compositions and resin materials in examples.

Best Modes for Carrying Out the Invention

Preferable embodiments of the present invention will be described in more details below.
Rust preventive oil compositions according to the present invention comprise at least one kind of sulfonate selected from alkaline metal sulfonate, alkaline earth metal sulfonate (with the exception of barium sulfonate) and amine sulfonate in an amount of 1 to 10% by mass based on the total weight of the composition; barium, zinc, chlorine and lead in which each element is in an amount of not more than 1000ppm by mass based on the total weight by element conversion of the composition; and the compounds represented by the following general formula (1):
is in an amount of not more than 1000ppm by mass based on the total weight of the composition. (Wherein R¹ represents an alkyl group having 1 to 24 carbon atoms, R² represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 5, and n represents an integer of 1 to 6.)
All sulfonates according to the present invention are highly safe to human body or ecosystem, and are obtained by reactions of alkaline metal, alkaline earth metal (with the exception of barium) or amine with sulfonic acid.
The alkaline metals according to the present invention include sodium, potassium and the like, and alkaline earth metals include magnesium, calcium, and the like, and are preferably sodium, potassium and calcium.
The amines according to the present invention include monoamine, polyamine, alkanolamine, and the like. Specific examples of the above-mentioned monoamine include alkylamine such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine (includes all isomers), dipropylamine (includes all isomers), tripropylamine (includes all isomers), monobutylamine (includes all isomers), dibutylamine (includes all isomers), tributylamine (includes all isomers), monopentylamine (includes all isomers), dipentylamine (includes all isomers), tripentylamine (includes all isomers), monohexylamine (includes all isomers), dihexylamine (includes all isomers), monoheptylamine (includes all isomers), diheptylamine (includes all isomers), monooctylamine (includes all isomers), dioctylamine (includes all isomers), monononylamine (includes all isomers), monodecylamine (includes all isomers), monoundecylamine (includes all isomers), monododecylamine (includes all isomers), monotridecylamine (includes all isomers), monotetradecylamine (includes all isomers), monopentadecylamine (includes all isomers), monohexadecylamine (includes all isomers), monoheptadecylamine (includes all isomers), monooctadecylamine (includes all isomers), monononadecylamine (includes all isomers), monoeicosylamine (includes all isomers), monoheneicosylamine (includes all isomers), monodocosylamine (includes all isomers), monotricosylamine (includes all isomers), dimethyl(ethyl)amine, dimethyl(propyl)amine, (includes all isomers), dimethyl(butyl)amine (includes all isomers), dimethyl(pentyl)amine (includes all isomers), dimethyl(hexyl)amine (includes all isomers), dimethyl(heptyl)amine (includes all isomers), dimethyl (octyl) amine (includes all isomers), dimethyl(nonyl)amine (includes all isomers), dimethyl(decyl)amine (includes all isomers), dimethyl(undecyl)amine (includes all isomers), dimethyl(dodecyl)amine (includes all isomers), dimethyl(tridecyl)amine (includes all isomers), dimethyl(tetradecyl)amine (includes all isomers), dimethyl (pentadecyl) amine (includes all isomers), dimethyl(hexadecyl)amine (includes all isomers), dimethyl (heptadecyl)amine (includes all isomers), dimethyl(octadecyl)amine (includes all isomers), dimethyl(nonadecyl)amine (includes all isomers), dimethyl(eicosyl)amine (includes all isomers), dimethyl(heneicosyl)amine (includes all isomers) and dimethyl(tricosyl)amine (includes all isomers);
alkenylamine such as monovinylamine, divinylamine, trivinylamine, monopropenylamine (includes all isomers), dipropenylamine (includes all isomers), tripropenylamine (includes all isomers), monobutenylamine (includes all isomers), dibutenylamine (includes all isomers), tributenylamine (includes all isomers), monopentenylamine (includes all isomers), dipentenylamine (includes all isomers), tripentenylamine (includes all isomers), monohexenylamine (includes all isomers), dihexenylamine (includes all isomers), monoheptenylamine (includes all isomers), diheptenylamine (includes all isomers), monooctenylamine (includes all isomers), dioctenylamine (includes all isomers), monononenylamine (includes all isomers), monodecenylamine (includes all isomers), monoundecenylamine (includes all isomers), monododecenylamine (includes all isomers), monotridecenylamine (includes all isomers), monotetradecenylamine (includes all isomers), monopentadecenylamine (includes all isomers), monohexadecenylamine (includes all isomers), monoheptadecenylamine (includes all isomers), monooctadecenylamine (includes all isomers), monononadecenylamine (includes all isomers), monoeicosenylamine (includes all isomers), monoheneicosenylamine (includes all isomers), monodocosenylamine (includes all isomers) and monotricosenylamine (includes all isomers);
monoamine which has an alkyl group and an alkenyl group such as dimethyl(vinyl)amine, dimethyl(propenyl)amine (includes all isomers), dimethyl(butenyl)amine (includes all isomers), dimethyl(pentenyl)amine (includes all isomers), dimethyl(hexenyl)amine (includes all isomers), dimethyl(heptenyl)amine (includes all isomers), dimethyl(octenyl)amine (includes all isomers), dimethyl (nonenyl) amine (includes all isomers), dimethyl(decenyl)amine (includes all isomers), dimethyl(undecenyl)amine (includes all isomers), dimethyl(dodecenyl)amine (includes all isomers), dimethyl(tridecenyl)amine (includes all isomers), dimethyl(tetradecenyl)amine (includes all isomers), dimethyl(pentadecenyl)amine (includes all isomers), dimethyl(hexadecenyl)amine (includes all isomers), dimethyl(heptadecenyl)amine (includes all isomers), dimethyl(octadecenyl)amine (includes all isomers), dimethyl(nonadecenyl)amine (includes all isomers), dimethyl(eicosenyl)amine (includes all isomers), dimethyl(heneicosenyl)amine (includes all isomers) and dimethyl(tricosenyl)amine (includes all isomers);
aromatic substituted with alkylamine such as monobenzylamine, (1-phenylethyl)amine, (2-phenylethyl)amine (another name: monophenethylamine), dibenzylamine, bis(1-phenylethyl)amine and bis(2-phenylethylene)amine (another name: diphenethylamine);
cycloalkylamine having 5 to 16 carbon atoms such as monocyclopentylamine, dicyclopentylamine, tricyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine and dicycloheptylamine;
monoamine which has an alkyl group and a cycloalkyl group such as dimethyl(cyclopentyl)amine, dimethyl(cyclohexyl)amine and dimethyl(cycloheptyl)amine; and
alkylcycloalkylamine such as (methylcyclopentyl)amine (includes all isomers), bis(methylcyclopentyl)amine (includes all isomers), (dimethylcyclopentyl)amine (includes all isomers), bis(dimethylcyclopentyl)amine (includes all isomers), (ethylcyclopentyl)amine (includes all isomers), bis(ethylcyclopentyl)amine (includes all isomers), (methylethylcyclopentyl)amine (includes all isomers), bis(methylethylcyclopentyl)amine (includes all isomers), (diethylcyclopentyl)amine (includes all isomers), (methylcyclohexyl)amine (includes all isomers), bis(methylcyclohexyl)amine (includes all isomers), (dimethylcyclohexyl)amine (includes all isomers), bis(dimethylcyclohexyl)amine (includes all isomers), (ethylcyclohexyl)amine (includes all isomers), bis(ethylcyclohexyl)amine (includes all isomers), (methylethylcyclohexyl)amine (includes all isomers), (diethylcyclohexyl)amine (includes all isomers), (methylcycloheptyl)amine (includes all isomers), bis(methylcycloheptyl)amine (includes all isomers), (dimethylcycloheptyl)amine (includes all isomers), (ethylcycloheptyl)amine (includes all isomers), (methylethylcycloheptyl)amine (includes all isomers) and (diethylcycloheptyl)amine (includes all isomers). In addition, monoamines according to the present invention include monoamine (beef tallow amine, and the like) derived from fats.
Specific examples of polyamines according to the present invention include alkylenepolyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, butylenediamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine and pentabutylenehexamine;
N-alkylethylenediamine such as N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine (includes all isomers), N-butylethylenediamine (includes all isomers), N-pentylethylenediamine (includes all isomers), N-hexylethylenediamine (includes all isomers), N-heptylethylenediamine (includes all isomers), N-octylethylenediamine (includes all isomers), N-nonylethylenediamine (includes all isomers), N-decylethylenediamine (includes all isomers), N-undecylethylenediamine (includes all isomers), N-dodecylethylenediamine (includes all isomers), N-tridecylethylenediamine (includes all isomers), N-tetradecylethylenediamine (includes all isomers), N-pentadecylethylenediamine (includes all isomers), N-hexadecylethylenediamine (includes all isomers), N-heptadecylethylenediamine (includes all 'isomers), N-octadecylethylenediamine (includes all isomers), N-nonadecylethylenediamine (includes all isomers), N-eicosylethylenediamine (includes all isomers), N-heneicosylethylenediamine (includes all isomers), N-docosylethylenediamine (includes all isomers) and N-tricosylethylenediamine (includes all isomers);
N-alkenylethylenediamine such as N-vinylethylenediamine, N-propenylethylenediamine (includes all isomers), N-butenylethylenediamine (includes all isomers), N-pentenylethylenediamine (includes all isomers), N-hexenylethylenediamine (includes all isomers), N-heptenylethylenediamine (includes all isomers), N-octenylethylenediamine (includes all isomers), N-nonenylethylenediamine (includes all isomers), N-decenylethylenediamine (includes all isomers), N-undecenylethylenediamine (includes all isomers), N-dodecenylethylenediamine (includes all isomers), N-tridecenylethylenediamine (includes all isomers), N-tetradecenylethylenediamine (includes all isomers), N-pentadecenylethylenediamine (includes all isomers), N-hexadecenylethylenediamine, (includes all isomers), N-heptadecenylethylenediamine (includes all isomers), N-octadecenylethylenediamine (includes all isomers), N-nonadecenylethylenediamine (includes all isomers), N-eicosenylethylenediamine (includes all isomers), N-heneicosenylethylenediamine (includes all isomers), N-docosenylethylenediamine (includes all isomers) and N-tricosenylethylenediamine (includes all isomers); and
N-alkyl or N-alkenylalkylenepolyamine such as N-alkyldiethylenetriamine, N-alkenyldiethylenetriamine, N-alkyltriethylenetetramine, N-alkenyltriethylenetetramine, N-alkyltetraethylenepentamine, N-alkenyltetraethylenepentamine, N-alkylpentaethylenehexamine, N-alkenylpentaethylenehexamine, N-alkylpropylenediamine, N-alkenylpropylenediamine, N-alkyldipropylenetriamine, N-alkenyldipropylenetriamine, N-alkyltripropylenetetramine, N-alkenyltripropylenetetramine, N-alkyltetraprbpylenepentamine, N-alkenyltetrapropylenepentamine, N-alkylpentapropylenehexamine, N-alkenylpentapropylenehexamine, N-alkylbutylenediamine, N-alkenylbutylenediamine, N-alkyldibutylenetriamine, N-alkenyldibutylenetriamine, N-alkyltributylenetetramine, N-alkenyltributylenetetramine, N-alkyltetrabutylenepentamine, N-alkenyltetrabutylenepentamine, N-alkylpentabutylenehexamine and N-alkenylpentabutylenehexamine. Polyamine according to the present invention includes polyamine (beef tallow polyamine, and the like) derived from fats.
Furthermore, specific examples of alkanolamine according to the present invention include monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, tri(n-propanol)amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine (includes all isomers), dibutanolamine (includes all isomers), tributanolamine (includes all isomers), monopentanolamine (includes all isomers), dipentanolamine (includes all isomers), tripentanolamine (includes all isomers), monohexanolamine (includes all isomers), dihexanolamine (includes all isomers), monoheptanolamine (includes all isomers), diheptanolamine (includes all isomers), monooctanolamine (includes all isomers), monononanolamine (includes all isomers), monodecanolamine (includes all isomers), monoundecanolamine (includes all isomers), monododecanolamine (includes all isomers), monotridecanolamine (includes all isomers), monotetradecanolamine (includes all isomers), monopentadecanolamine (includes all isomers), monohexadecanolamine (includes all' isomers), diethylmonoethanolamine, diethylmonopropanolamine (includes all isomers), diethylmonobutanolamine (includes all isomers), diethylmonopentanolamine (includes all isomers), dipropylmonoethanolamine (includes all isomers), dipropylmonopropanolamine (includes all isomers), dipropylmonobutanolamine (includes all isomers), dipropylmonopentanolamine (includes all isomers), dibutylmonoethanolamine (includes all isomers), dibutylmonopropanolamine (includes all isomers), dibutylmonobutanolamine (includes all isomers), dibutylmonopentanolamine (includes all isomers), monoethyldiethanolamine, monoethyldipropanolamine (includes all isomers), monoethyldibutanolamine (includes all isomers), monoethyldipentanolamine (includes all isomers), monopropyldiethanolamine (includes all isomers), monopropyldipropanolamine (includes all isomers), monopropyldibutanolamine (includes all isomers), monopropyldipentanolamine (includes all isomers), monobutyldiethanolamine (includes all isomers), monobutyldipropanolamine (includes all isomers), monobutyldibutanolamine (includes all isomers), monobutyldipentanolamine (includes all isomers), monocyclohexylmonoethanolamine, monocyclohexyldiethanolamine, monocyclohexylmonopropanolamine (includes all isomers), monocyclohexyldipropanolamine (includes all isomers), and the like.
Among the aforementioned amines, monoamine is preferable because the amine has a good stain resistance. In addition, among monoamines, more preferable ones are alkylamine, monoamine having an alkyl group and an alkenyl group, monoamine having an alkyl group and a cycloalkyl group, cycloalkylamine and alkylcycloalkylamine. Furthermore, an amine having not less than 3 total carbon atoms in an amine molecule is preferable because the amine has a good stain resistance, and the amine having not less than 5 total carbon atoms is more preferable.
On the other hand, conventionally well-known sulfonic acid made by a common procedure can be used as sulfonic acid according to the present invention. Specific examples of sulfonic acid generally include petroleum sulfonic acids such as those made by sulfonation of an alkylaromatic compounds which are lubricant distillates of a mineral oil and so- called mahogany acid made as a by-product during a manufacturing of white oil, or synthetic sulfonic acids such as those made by sulfonation of alkylbenzenes having straight chain or branched alkyl groups and the one made by sulfonation of alkylnaphthalene such as dinonylnaphthalene. The alkylbenzene is obtained from a by-product at a manufacturing plant of alkylbenzene used for a raw material of cleaning oils, or is obtained by alkylation of benzene with polyolefin. No particular limitation is imposed on the molecular weight of sulfonic acid, however, the molecular weight is preferably 100 to 1500, and more preferably 200 to 700.
Among the above-mentioned sulfonic acid, at least one kind of compound selected from the following group is preferable,
namely, dialkylnaphthalene sulfonic acid having 14 to 30 total.carbon atoms in 2 alkyl groups that are bonded to a naphthalene ring;
dialkylbenzene sulfonic acid in which 2 alkyl groups bonding to a benzene ring are each independently a straight chain alkyl group or a branched alkyl group having one side chain methyl group, and also the total number of carbon atoms in 2 alkyl groups is 14 to 30; and
monoalkylbenzene sulfonic acid having not less than 15 carbon atoms in an alkyl group bonding to a benzene ring.
As described above, dialkylnaphthalene sulfonic acid preferably used according to the present invention has 14 to 30 total carbon atoms in 2 alkyl groups that are bonded to a naphthalene ring. When the total number of carbon atoms in 2 alkyl groups is less than 14, the demulsibility tends to be inadequate. On the other hand, when the total number thereof exceeds 30, the storage stability of the rust preventive oil composition tends to become poor. Additionally, 2 alkyl groups may be each independently a straight chain alkyl group or a branched alkyl group. Moreover, no particular limitation is imposed on the carbon number of each alkyl group as long as 2 alkyl groups have 14 to 30 total carbon atoms, however, the carbon number of each alkyl group is preferably 6 to 18.
Furthermore, as described above, dialkylbenzene sulfonic acid preferably used according to the present invention is the one in which 2 alkyl groups bonding to a benzene ring are each independently a straight chain alkyl group or a branched alkyl group having one side chain methyl group, and also the total number of carbon atoms in 2 alkyl groups is 14 to 30. In the case of monoalkylbenzene sulfonic acid, when the carbon number of an alkyl group is not less than 15, the acid can be preferably used as described later. However, when the carbon number thereof is less than 15, the storage stability of the rust preventive oil composition tends to become poor. Furthermore, when monoalkylbenzene sulfonic acid having more than 3 alkyl groups is used, the storage stability of the rust preventive oil composition also tends to become poor. Still furthermore, when the alkyl group bonding to a benzene ring in dialkylbenzene sulfonic acid is a branched alkyl group which has a branched structure other than a side chain methyl group (for example, a branched alkyl group having a side chain ethyl group, and the like) and a branched alkyl group which has not less than 2 branched structures (for example, a branched alkyl group derived from propylene origomer, and the like), there is a fear of a malign influence on human body or ecosystem and a poor rust prevention ability. Furthermore, when the total carbon number in 2 alkyl groups bonding to a benzene ring in dialkylbenzene sulfonic acid is less than 14, demulsibility tends to become poor. On the other hand, when the total number thereof exceeds 30, the storage stability of the rust preventive oil composition tends to become poor. In addition, no particular limitation is imposed on the carbon number of each alkyl group as long as 2 alkyl groups have 14 to 30 total carbon atoms, however, the carbon number of each alkyl group is preferably 6 to 18.
Furthermore, monoalkylbenzene sulfonic acid preferably used according to the present invention is the compound having not less than 15 carbon atoms in one alkyl group which is bonded to a benzene ring as described above. When the carbon number in the alkyl group bonding to a benzene ring is less than 15, the storage stability of the obtained rust preventive oil composition tends to become poor. Furthermore, the alkyl group bonding to a benzene ring can be a straight chain or a branched, as long as the carbon number is not less than 15.
Specific examples of sulfonate obtained by using the above raw materials are as follows;
neutral (normal salt) sulfonate obtained by reacting base of alkaline metal (oxide of alkaline metal, hydroxide of alkaline metal, and the like), base of alkaline earth metal (oxide of alkaline earth metal, hydroxide of alkaline earth metal, and the like) or amine (ammonia, alkylamine, alkanolamine, and the like) with a sulfonic acid;
basic sulfonate obtained by heating the above neutral (normal salt) sulfonate with excess base of alkaline metal, base of alkaline earth metal or amine in the presence of water;
carbonateperbasic(ultrabasic)sulfonate obtained by reacting the above neutral (normal salt) sulfonate with base of alkaline metal, base of alkaline earth metal or amine in the presence of carbon dioxide gas;
borateperbasic(ultrabasic)sulfonate obtained by reacting the above neutral (normal salt) sulfonate with base of alkaline metal, base of alkaline earth metal or amine, and a boric acid compound such as boric acid and anhydrous boric acid, or obtained by reacting the above carbonateperbasic(ultrabasic)sulfonate with a boric acid compound such as boric acid and.anhydrous boric acid; and mixtures thereof.
In addition, when the above neutral (normal salt) sulfonate is synthesized, the targeted sulfonate can be obtained by adding chloride of the same alkaline metal, the same alkaline earth metal or the same amine as that for the targeted sulfonate as an accelerator, and also by conducting a exchange reaction wherein after preparing the neutral sulfonate (normal salt) of different alkaline metal, different alkaline earth metal or different amine from the targeted sulfonate, added is chloride of the same alkaline metal, the same alkaline earth metal or the same amine as that for the targeted sulfonate. However, chloride ion tends to be left in the sulfonate obtained by the aforementioned process. Therefore, in the present invention, it is preferable not to use the sulfonate obtained by the forgoing process or to carry out an adequate cleaning process for the obtained sulfonate. To be more precise, chlorine concentration in sulfonate is preferably not more than 200ppm by mass, more preferably not more than 100ppm by mass, even more preferably not more than 50ppm by mass, and most preferably not more than 25ppm by mass.
At least one kind of compound selected from the following group is preferably used;
dialkylnaphthalenesulfonate having 14 to 30 total carbon atoms in two alkyl groups which are bonded to naphthalene ring;
dialkylbenzenesulfonate in which 2 alkyl groups bonding to a benzene ring are each independently a straight chain alkyl group or a branched alkyl group having one side chain methyl group, and also the total number of carbon atoms in 2 alkyl groups is 14 to 30; and
monoalkylbenzenesulfonate in which an alkyl group bonding to a benzene ring has not less than 15 carbon atoms.
According to the present invention, the content of sulfonate is in an amount of 1 to 10% by mass based on the total weight of the rust preventive oil composition as described above. When the content of sulfonate is less than 1% by mass, the rust prevention ability is inadequate. Consequently, due to a similar reason, the content of sulfonate is preferably in an amount of not less than 2% by mass based on the total weight of the rust preventive oil composition, and more preferably not less than 4% by mass. On the other hand, when the content of sulfonate according to the present invention exceeds 10% by mass, an improvement effect of the rust prevention ability is not proportional to the content of sulfonate. Thus, due to a similar reason, the content of sulfonate is preferably in an amount of not more than 9% by mass based on the total weight of the rust preventive oil composition, and more preferably not more than 8% by mass.
In addition, the sulfonate content according to the present invention represents a net content of sulfonate. More specifically, in the case 'of neutral (normal salt) sulfonate, the content of neutral sulfonate itself is that of sulfonate, and in the case of basic sulfonate, carbonateperbasic(ultrabasic)sulfonate and borateperbasic(ultrabasic)sulfonate, the content of sulfonate is that of neutral (normal salt) sulfonate excluding the basic salt excessively contained.
Furthermore, according to the present invention, the solution made by dissolving the forgoing sulfonate into carrier oil at 20 to 60% by mass may be also used, and it is commercially available. When this kind of sulfonate is used, the prescribed amount of sulfonate is adjusted by weighing the amount of above-mentioned solution that contains the prescribed amount of net sulfate (for example, in the case of 50% by mass solution, use the above-mentioned solution twice as much as the prescribed amount of sulfate).
In the rust preventive oil composition according to the present invention, each element of barium, zinc, chlorine and lead is in an amount of not more than 1000ppm by mass based on the total weight by element conversion of the composition. When any element among these elements is in an amount of more than 1000ppm by mass, safety to human body or environment such as ecosystem becomes inadequate. Then, due to a similar reason, the content of barium, zinc, chlorine and lead is preferably in an amount of not more than 500ppm by mass, more preferably not more than 100ppm by mass, even more preferably not more than 50ppm by mass, furthermore preferably not more than 10ppm by mass, and most preferably not more than 5ppm by mass.
In addition, the content of elements is the value measured by the following method. More specifically, the content of barium, zinc and lead means the content [ppm by mass] based on the total weight of the composition, and is measured based on 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)"; and the content of chlorine means the content [ppm by mass] based on the total weight of the composition, and is measured in accordance with "IP PRPOSED METHOD AK/81 Determination of chlorine - Microcoulometery oxidative method". Detection limit of each element by the above-mentioned measurement is generally 1ppm by mass.
Furthermore, in the rust preventive oil compound according to the present invention, the compound which has a group represented by the following general formula (1):
is in an amount of not more than 1000ppm by mass based on the total weight of the composition, wherein R¹ represents an alkyl group having 1 to 24 carbon atoms, R² represents an alkylene group having 2 to 4 carbon atoms, m represents an integer of 1 to 5, and n represents an integer of 1 to 6. When the compound having the group represented by the above-mentioned formula (1) is in an amount of more than 1000ppm by mass, safety to human body or environment such as ecosystem becomes inadequate. In addition, due to a similar reason, the compound having the group represented by the above-mentioned formula (1) is preferably in an amount of not more than 500ppm by mass, more preferably not more than 100ppm by mass, even more preferably not more than 50ppm by mass, furthermore preferably not more than 10ppm by mass, and most preferably not more than 5ppm by mass.
The compounds which have the group represented by the above-mentioned general formula (1) include the following general formula (3) to (5): A - H A - R³
wherein A represents a group represented by general formula (1), R³ represents a hydrocarbon group having 1 to 24 carbon atoms or an acyl group having 1 to 24 carbon atoms.
In addition, when elements such as barium, zinc, and chlorine, and the compound having the group represented by the above-mentioned formula (1) are contained in raw materials of sulfonate or base oils used in the present invention, or when elements and the compound get mixed in raw materials at. the manufacturing process of the rust preventive oil composition, the above-mentioned elements and the compound can be removed by refining raw materials or the rust preventive oil compound by common procedures. Furthermore, in the manufacturing process of base oils and additives used in the present invention, the incorporation of these elements and the compounds into the rust preventive oil compound can be avoided by carrying out the following things; i.e., not to share manufacturing facilities used for the manufacturing process of the other base oils and additives; to clean facilities when these are used for the manufacturing process of the other base oils and additives; and to use sulfonate of lower chloride concentration as explained in the manufacturing process of the above-mentioned sulfonate.
Base oils that are used for the rust preventive oil composition of the present invention include a mineral oil, a synthetic oil, and mixtures thereof.
Specific examples of a mineral oil according to the present invention include a paraffin type or a naphthenic type oil obtained by suitably combining one or more than two refining processes selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydro-refining, sulfuric acid washing, and clay treatment, which are applied to lubricant distillates obtained by atmospheric distillation or vacuum distillation of crude oil. Furthermore, specific examples of synthetic oil include polyolefin, alkylbenzene, and the like.
Specific examples of polyolefin according to the present invention include homopolymer or copolymer of olefin monomer having 2 to 16 carbon atoms, preferably 2 to 12 carbon atoms, and hydride of these polymers, and the like. In addition, when polyolefin is copolymer of olefin monomer that has a different structure, no particular limitation is imposed on a monomer ratio and monomer arrangement of the copolymer, and any of random copolymer, alternating copolymer and block copolymer may be used. Furthermore, any of α-olefin, internal olefin, straight chain olefin and branched olefin may be used as the above-mentioned olefin monomer. Specific examples of the olefin monomer include ethylene, propylene, 1-butene, 2-butene, isobutene, straight chain or branched pentene (includes α-olefin and internal olefin), straight chain or branched hexene (includes α-olefin and internal olefin), straight chain or branched heptene (includes α-olefin and internal olefin), straight chain or branched octene (includes α-olefin and internal olefin), straight chain or branched nonene (includes α-olefin and internal olefin), straight chain or branched decene (includes α-olefin and internal olefin), straight chain or branched undecene (includes α-olefin and internal olefin), straight chain or branched dodecene (includes α-olefin and internal olefin), straight chain or branched tridecene (includes α -olefin and internal olefin), straight chain or branched tetradecene (includes α -olefin and internal olefin), straight chain or branched pentadecene (includes α -olefin and internal olefin), straight chain or branched hexadecene (includes α -olefin and internal olefin). and mixtures thereof. Among them, ethylene, propylene, 1-butene, 2-butene, isobutene, α-olefin having 5 to 12 carbon atoms and mixtures thereof are preferably used.
Furthermore, among α -olefin having 5 to 12 carbon atoms, 1-octene, 1-decene, 1-dodecen and mixtures thereof are more preferable.
The above-mentioned polyolefin can be obtained by conventionally well-known processes. More concretely, the polyolefin can be manufactured by non-catalytic thermal reaction, and also, the objective polyolefin can be manufactured by the homopolymerization or the copolymerization of the above-mentioned olefin with well-known catalysts such as; an organic peroxide catalyst such as benzoyl peroxide; a Friedel-Crafts catalyst such as aluminum chloride, an aluminum chloride-polyhydric alcohol type, an aluminum chloride-titanium 'tetrachloride type, an aluminum chloride-alkyl-tin halide type and boron fluoride; a Ziegler catalyst such as an organic aluminum chloride-titanium tetrachloride type and an organic aluminum-titanium tetrachloride type; a metallocene catalyst such as an aluminoxane-zirconocene type and an ionic compound-zirconocene type; and a Lewis acid complex catalyst such as an aluminum chloride-base type and a boron fluoride-base type.
The polyolefin obtained by these processes generally has double bonds. However, according to the present invention, so-called hydrides of a polyolefin in which double bond carbons are hydrogenated are preferable to use as a base oil. When a hydride of a polyolefin is used, the heat and the oxidation stability of obtained rust preventive oil composition tends to be' improved. In addition, a hydride of a polyolefin is obtained by saturating double bonds in the polyolefin through hydrogenating the polyolefin with hydrogen in the existence of well-known hydrogenation catalysts. Furthermore, when a polymerization reaction of an olefin is carried out, the polymerization of the olefin and the hydrogenation of double bonds in the polymer can be accomplished by one process, instead of taking 2 processes by selecting a catalyst to be used.
Among the polyolefin preferably used as the base oil according to the present invention, an ethylene-propylene copolymer, polybutene (a copolymer obtained by a polymerization of butane-butene fractions (a mixture of 1-butene, 2-butene and isobutene) which are by-products upon naphtha thermal cracking), 1-octene oligomer, 1-decene oligomer, 1-dodecene oligomer, and hydrides thereof, and furthermore, mixtures thereof are preferable because they are excellent in the heat and oxidation stability, viscosity-temperature property, and low temperature fluidity, and particularly, ethylene-propylene copolymer hydride, polybutene hydride, 1-octene oligomer hydride, 1-decene oligomer hydride, 1-dodecene oligomer hydride, and mixtures thereof are more preferable. In addition, synthetic oils which are commercially available as base oils for lubricants such as ethylene-propylene copolymer, polybutene and poly- α -olefin are generally already hydrogenated in the double bonds thereof, and these commercial products can be also used as base oils according to the present invention.
An alkylbenzene suitably used as the base oil according to the present invention has preferably 1 to 4 alkyl groups in the molecule, and each group has 1 to 40 carbon atoms. To be more precise, the alkyl group having 1 to 40 carbon atoms described herein include methyl group, ethyl group, propyl group (includes all isomers), butyl group (includes all isomers), pentyl group (includes all isomers), hexyl group (includes all isomers'), heptyl group (includes all isomers), octyl group (includes all isomers), nonyl group (includes all isomers), decyl group (includes all isomers), undecyl group (includes all isomers), dodecyl group (includes all isomers), tridecyl group (includes all isomers), tetradecyl group (includes all isomers), pentadecyl group (includes all isomers), hexadecyl group (includes all isomers), heptadecyl group (includes all isomers), octadecyl group (includes all isomers), nonadecyl group (includes all isomers), eicosyl group (includes all isomers), heneicosyl group (includes all isomers), docosyl group (includes all isomers), tricosyl group (includes all isomers), tetracosyl group (includes all isomers), pentacosyl group (includes all isomers), hexacosyl group (includes all isomers), heptacosyl group (includes all isomers), octacosyl group (includes all isomers), nonacosyl group (includes all isomers), triacontyl group (includes all isomers), hentriacontyl group (includes all isomers), dotriacontyl group (includes all isomers), tritriacontyl group (includes all isomers), tetratriacontyl group (includes all isomers), pentatriacontyl group (includes all isomers), hexatriacontyl group (includes all isomers), heptatriacontyl group (includes all isomers), octatriacontyl group (includes all isomers), nonatriacontyl group (includes all isomers), tetracontyl group (includes all isomers), and the like. Furthermore, although the alkyl group of the alkylbenzene according to the present invention may be a straight or branched chain, the branched alkyl group is preferable in terms of the stability, the viscosity property, and the like. Particularly, a branched alkyl group derived from olefin oligomer such as propylene, butene and isobutylene is more preferable in terms of easy availability.
The number of alkyl groups in an alkylbenzene used in the present invention is preferably 1 to 4, and an alkylbenzene having one or two alkyl groups, i.e., monoalkylbenzene, dialkylbenzene or mixtures thereof is most preferable in terms of stability and availability. Furthermore, as an alkylbenzene, a mixture of alkylbenzenes having different structures as well as that having a single structure may be used.
The alkylbenzene according to the present invention is produced by using, for example, an aromatic compound as a raw material, an alkylating agent and an alkylation catalyst. Specific examples of the aromatic compound used as the raw material include benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene and mixtures thereof, and the like.
Specific examples of the alkylating agent include lower monoolefins such as ethylene, propylene, butene and isobutylene, preferably straight chain or branched olefins having 6 to 40 carbon atoms obtained by the polymerization of propylene; straight chain or branched olefins having 6 to 40 carbon atoms obtained by thermal cracking of a wax, a heavy oil a petroleum fraction, polyethylene, polypropylene, and the like; straight chain olefins having 9 to 40 carbon atoms obtained by separating n-paraffin from a petroleum fraction such as kerosene and diesel oil followed by an olefination of n-paraffin by catalysts; and mixtures thereof. Furthermore, examples of the alkylation catalyst used for the alkylation include well-known catalysts such as; a Friedel-Crafts catalyst such as aluminum chloride and zinc chloride; an acid catalyst such as sulfuric acid, phosphoric acid, tungstosilicic acid, hydrofluoric acid and activated clay.
According to the present invention, various types of the above-mentioned base oils may be used singly or in combination of two or more. Furthermore, no particular limitation is imposed on the contents of the above-mentioned base oils in the rust preventive compositions according to the present invention. However, the content is generally 3 to 98% by mass based on the total weight of the rust preventive oil composition, and preferably 10 to 97% by mass.
In addition, base oils of the rust preventive oil composition are suitably selected based on its application and usage. For example, multi-functional rust preventive oils such as a cleaning rust preventive oil which has a cleaning function, and a rust preventive process oil which has both functions of rust prevention for intermediate products and lubrication for processes thereafter, are known as rust preventive oils other than oils which are only used for preventing the rust generation. A relatively low viscosity base oil, or a base oil prepared by combining a low viscosity oil and a high viscosity oil is frequently used for these rust preventive oils for the purpose of an improvement in handling and an addition of a cleaning function.
The low viscosity oil referred to herein is the base oil (hereinafter, occasionally described as "solvent") having a kinematic viscosity of 0.5 to 6mm²/s at 40° C, on the other hand, the high viscosity oil denotes the base oil which has a kinematic viscosity exceeding 6mm²/s at 40° C. When the mixed base oil adjusted in combination of the low viscosity oil and the high viscosity oil is used, the handling of the rust preventive oil tends to be improved, and furthermore, the mixed base oil can be used as a cleaning rust preventive oil composition which has a property as a cleaning oil. The rust preventive oil in which the mixed base oils are used is occasionally called as a solvent diluted rust preventive oil.
By the way, the parts made of various organic materials besides metal parts are generally used for equipments on which metal parts such as a steel sheet, and a bearing are mounted, and furthermore, organic materials are occasionally used as packing materials upon shipment of the metal parts. Therefore, it is occasionally required to the rust preventive oils to have an excellent compatibility with organic materials.
When the rust preventive oil according to the present invention is used for an application such as a sealing material wherein compatibility with organic materials is required, it is preferable not to use a base oil having a kinematic viscosity of not more than 6mm²/s at 40° C as much as possible. To be more precise, the content of the base oil having a kinematic viscosity of not more than 6mm²/s at 40 ° C is preferably not more than 10% by mass based on the total weight of the composition, more preferably not more than 5% by mass and particularly preferably not more than 2% by mass. Then, increasingly preferable one is to use the only base oil having a kinematic viscosity exceeding 6mm²/s at 40° C without using the base oil having a kinematic viscosity of not more than 6mm²/s at 40° C, and the most preferable one is to use the only high viscosity base oil having a kinematic viscosity of not less than 7mm²/s at 40° C. When the content of the base oil having a kinematic viscosity of not more than 6mm²/s at 40° C exceeds 10% by mass based on the total weight of the rust preventive oil composition, compatibility with organic materials tends to become insufficient.
Furthermore, a kinematic viscosity of the high viscosity base oil at 40° C is not less than 6mm²/s as described above, preferably not less than 7mm²/s in terms of the compatibility with organic materials, more preferably not less than 10mm²/s, particularly preferably not less than 15mm²/s, more particularly preferably not less than 20mm²/s, increasingly preferably not less than 40mm²/s, especially preferably not less than 100mm²/s, and most preferably not less than 400mm²/s. Furthermore, said kinematic viscosity is preferably not less than 2000mm²/s in terms of handling, more preferably not more than 1500mm²/s, particularly preferably not more than 1000mm²/s, and more particularly preferably not more than 750mm²/s.
Furthermore, the content of the component having not more than 14 carbon atoms in the high viscosity base oil is preferably not more than 20% by mass, more preferably not more than 10% by mass, particularly preferably not more than 5% by mass, more particularly preferably not more than 1% by mass, and most preferably not more than 0.5% by mass. When the content of the component having not more than 14 carbon atoms exceeds 20% by mass, compatibility with organic materials tends to become insufficient.
Furthermore, the content of the component having not more than 20 carbon atoms in the high viscosity base oil is preferably not more than 20% by mass, more preferably not more than 10% by mass, particularly preferably not more than 5% by mass, and more particularly preferably not more than 1% by mass. When the content of the hydrocarbon having not more' than 20 carbon atoms satisfies the above-mentioned conditions, compatibility with organic materials tends to be improved.
Furthermore, the content of the hydrocarbon having not more than 25 carbon atoms in the high viscosity base oil is preferably not more than 20% by mass, more preferably not more than 10% by mass, particularly preferably not more than 5% by mass, and more particularly preferably not more than 1% by mass.
When the content of the hydrocarbon having not more than 25 carbon atoms satisfies the above-mentioned conditions, compatibility with organic materials tends to be moreover improved.
The contents of the hydrocarbons having not more than 14, 20, or 25 carbon atoms referred to herein is the value [% by mass] which is measured based on ASTM D2887.
Furthermore, the content of the aromatic component in the high viscosity base oil is preferably not more than 50% by mass, more preferably not more than 40% by mass, particularly preferably not more than 30% by mass. When the content of the aromatic component satisfies the above-mentioned conditions, compatibility with organic materials tends to be improved very much. The content of the aromatic component referred to herein is the value [% by mass] which is measured based on "Fluorescent indicator adsorption method (FIA)" in "Liquid petroleum products-Testing method of hydrocarbon type" described in JIS K 2536.
Furthermore, as described above, when the rust preventive oil composition is applied to a usage requiring compatibility with organic materials such as a sealing material, it is preferable not to use the low viscosity base oil having a kinematic viscosity of not more than 6mm²/s at 40° C as much as possible. However, when a sufficient drying process can be carried out after applying the rust preventive oil composition, a sufficient rust prevention ability can be obtained without deteriorating such organic materials, even though the solvent diluted rust preventive oil containing said low viscosity base oil is used as the rust preventive oil composition according to the prevent invention.
However, even though the drying process is carried out, from a viewpoint of compatibility with organic materials, the content of the base oil having a kinematic viscosity exceeding 6mm²/s and less than 15mm²/s at 40° C is preferably not more than 40% by mass, more preferably not more than 20% by mass, particularly preferably not more than 10% by mass, especially preferably not more than 5% by mass, and the most preferable one is not to contain the base oil having a kinematic viscosity exceeding 6mm²/s and less than 15mm²/s at 40° C.
Similarly, even though the drying process is carried out, from a viewpoint of compatibility with organic materials, the content of the base oil having a kinematic viscosity exceeding 6mm²/s and less than 20mm²/s at 40° C is preferably not more than 40% by mass, more preferably not more than 20% by mass, particularly preferably not more than 10% by mass, especially preferably not more than 5% by mass, and the most preferable one is not to contain the base oil having a kinematic viscosity exceeding 6mm²/s and less than 20mm²/s at 40° C.
Furthermore, when the low viscosity base oil and the high viscosity base oil are mixed to use, the mixing ratio (weight ratio) of the low viscosity base oil to the high viscosity base oil is preferably in the range of 15:1 to 1:20, and more preferably 10:1 to 1:15.
When the rust preventive oil composition according to the present invention is the solvent diluted rust preventive oil, the used solvents are the following oils having a kinematic viscosity of 0.5 to 6mm²/s at 40° C; to be more precise, a paraffinic or a naphthenic mineral oil obtained by one or not less than two refining processes selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydro-refining, sulfuric acid washing, and clay treatment, which are applied to a lubricant fraction obtained by atmospheric distillation or vacuum distillation of a crude oil with a suitable combination thereof; and a synthetic oil such as polyolefin and alkylbenzene.
The kinematic viscosity at 40° C of said solvent is not less than 0.5mm²/s as described above in terms of work environment, preferably not less than 0.7mm²/s, and more preferably not less than 1mm²/s. Furthermore, said kinematic viscosity is not more than 6mm²/s as described above in terms of drying characteristics, preferably not more than 4mm²/s, and more preferably not more than 2.5mm²/s.
Furthermore, the content of the hydrocarbon having hot more than 16 carbon atoms in said solvent is preferably not more than 20% by mass in terms of compatibility with organic materials, more preferably not more than 10% by mass, particularly preferably not more than 5% by mass, and especially preferably not more than 1% by mass.
Furthermore, the content of the hydrocarbon having not more than 8 carbon atoms in said solvent is preferably not more than 10% by mass from the perspective that work environment is improved, more preferably not more than 5% by mass, and particularly preferably not more than 1% by mass.
Furthermore, the content of the hydrocarbon having not more than 10 carbon atoms in said solvent is preferably not more than 10% by mass from the perspective that work environment is moreover improved, more preferably not more than 5% by mass, and particularly preferably not more than 1% by mass.
Even furthermore, the content of the aromatic component in said solvent is preferably not more than 90% by mass in terms of compatibility with organic compounds, more preferably not more than 80% by mass, particularly preferably not more than 50% by mass, more particularly preferably not more than 30% by mass, increasingly preferably not more than 10% by mass, especially preferably not more than 5% by mass, and it is most preferable not to contain aromatic compounds.
Furthermore, when a mineral oil is used as the solvent, said mineral oil generally contains a naphthene component, a paraffin component, or furthermore an aromatic component. A ratio of the naphthene component to the paraffin component in a mineral oil is preferably in the range of 0:1 to 5:1.
As described above, in the present invention, the base oils which are the mixture of the low viscosity base oil and the high viscosity base oil are occasionally used for the rust preventive oil composition, and also the only high viscosity base oil is occasionally used. When the rust preventive oil composition according to the present invention is applied to a usage requiring compatibility with organic materials, the content of the component having not more than 14 carbon atoms in a base oil is preferably not more than 20% by mass, more preferably not more than 10% by mass, particularly preferably not more than 5% by mass, more particularly preferably not more than 1% by mass, and especially preferably not more than 0.5% by mass.
Furthermore, the content of the base oil which contains not less than 20% by mass of the components having not more than 20 carbon atoms is preferably not more than 40% by mass based on the total weight of the composition, in terms of compatibility with organic materials. Furthermore, the content of the component having not more than 10 carbon atoms in a base oil are preferably not more than 20% by mass based on the total weight of the composition, in terms of work environment (odor and the like), more preferably not more than 10% by mass, particularly preferably not more than 5% by mass, more particularly preferably not more than 1% by mass, and especially preferably not more than 0.5% by mass.
Furthermore, when the rust preventive oil composition according to the present invention is applied to a usage requiring compatibility with organic materials, the content of the aromatic component in a base oil is preferably not more than 50% by mass, more preferably not more than 40% by mass, and particularly preferably not more than 30% by mass. Furthermore, according as the base oil viscosity becomes lower, the possibility of a malign influence on organic materials by aromatic components is increased. Therefore, when a base oil having a kinematic viscosity of 0.5 to 6mm²/s at 40° C is used, the content of the aromatic component is preferably not more than 10% by mass, more preferably not more than 5% by mass, and particularly preferably not more than 3% by mass.
Furthermore, the content of the aromatic component having not more than 12 carbon atoms is preferably not more than 5% by mass, in terms of work environment (odor and the like), more preferably not more than 1% by mass, particularly preferably not more than 0.5% by mass, and most preferably not more than 0.1% by mass. In addition, the measurement of the content of the aromatic component having not more than 12 carbon atoms is carried out by analyzing the result of gas chromatography measured based on ASTM D2887 using mass spectrometry (mass spectrum).
In the rust preventive oil composition according to the present invention, at least one kind of compound selected from the following group (A) to (F) is preferably formulated:
(A) a partial ester of polyhydric alcohol
(B) at least one kind of oxidized wax selected from the group consisting of an alkaline metal salt of a oxidized wax, an alkaline earth metal salt of a oxidized wax (with the exception of barium salt of a oxidized wax) and an amine salt of a oxidized wax;
(C) an esterified oxidized wax;
(D) at least one kind of lanoline fatty acid salt selected from the group consisting of an alkaline metal salt of a lanoline fatty acid, an alkaline earth metal salt of a lanoline fatty acid (with the exception of barium salt of a lanoline fatty acid) and an amine salt of a lanoline fatty acid;
(E) an esterified lanoline fatty acid; and
(F) at least one kind of fatty acid salt selected from alkaline metal salt of a fatty acid, alkaline earth metal salt of a fatty acid (with the exception of barium salt of fatty acid) and amine salt of a fatty acid.
The partial ester of polyhydric alcohol as the above-mentioned compound (A) is the ester, wherein at least one or more hydroxyl groups in a polyhydric alcohol are not esterified but remains as a hydroxyl group. Any of polyhydric alcohols may be used as the raw materials of the ester, however, a polyhydric alcohol is suitably used wherein the number of hydroxyl group in the molecule is preferably 2 to 10 (more preferably 3 to 6), and the number of total carbon atoms thereof is preferably 2 to 20 (more preferably 3 to 10). Among the polyhydric alcohol, at least one kind of polyhydric alcohol selected from the group consisting of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitan is preferably used.
On the other hand, any of acids may be used as a constituent of the partial ester, however, a fatty acid having 6 to 24 carbon atoms (more preferably 10 to 22) is preferable. The fatty acid used in the present invention may be a saturated fatty acid and an unsaturated fatty acid, and also may be a straight chain fatty acid and a branched fatty acid. Specific examples of the fatty acid include saturated fatty acids such as hexanoic acid (includes all isomers), heptanoic acid (includes all isomers), octanoic acid (includes all isomers), nonanoic acid (includes all isomers), decanoic acid (includes all isomers), undecanoic acid (includes all isomers), dodecanoic acid (includes all isomers), tridecanoic acid (includes all isomers), tetradecanoic acid (includes all isomers), pentadecanoic acid (includes all isomers), hexadecanoic acid (includes all isomers), heptadecanoic acid (includes all isomers), octadecanoic acid (includes all isomers),nonadecanoic acid (includes all isomers), eicosanoic acid (includes all isomers), heneicosanoic acid (includes all isomers),docosanoic acid (includes all isomers), tricosanoic acid (includes all isomers) and tetracosanoic acid (includes all isomers); unsaturated acids such as hexenoic acid (includes all isomers), heptenoic acid (includes all isomers), octenoic acid (includes all isomers), nonenoic acid (includes all isomers), decenoic acid (includes all isomers), undecenoic acid (includes all isomers), dodecenoic acid (includes all isomers), tridecenoic acid (includes all isomers), tetradecenoic acid (includes all isomers), pentadecenoic acid (includes all isomers), hexadecenoic acid (includes all isomers), heptadecenoic acid (includes all isomers), octadecenoic acid (includes all isomers),nonadecenoic acid (includes all isomers), eicosenoic acid (includes all isomers), heneicosenoic acid (includes all isomers), docosenoic acid (includes all isomers), tricosenoic acid (includes all isomers) and tetracosenoic acid (includes all isomers); and mixtures thereof. Among these fatty acids, oleic acid, isostearic acid, stearic acid, and erucic acid are especially preferable.
Specific examples of the partial ester of the polyhydric alcohol obtained by the above-mentioned polyhydric alcohol and the above-mentioned acid include partial esters of glycerin such as glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, glycerin didodecanoate (glycerin dilaurate), glycerin diisolaurate, glycerin monotetradecanoate (glycerin monomyristate), glycerin monoisomyristate, glycerin ditetradecanoate (glycerin dimyristate), glycerin diisomyristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, glycerin dihexadecanoate (glycerin dipalmitate), glycerin diisopalmitate, glycerin monooctadecanoate (glycerin monostearate), glycerin monoisostearate, glycerin dioctadecanoate (glycerin distearate), glycerin diisostearate, glycerin monooctadecenoate (glycerin monooleate), glycerin monoisooleate, glycerin dioctadecenoate (glycerin dioleate) and glycerin diisooleate;
partial esters of trimethylolethane such as trimethylolethane monododecanoate (trimethylolethane monolaurate), trimethylolethane monoisolaurate, trimethylolethane didodecanoate (trimethylolethane dilaurate), trimethylolethane diisolaurate, trimethylolethane monotetradecanoate (trimethylolethane monomyristate), trimethylolethane monoisomyristate, trimethylolethane ditetradecanoate (trimethylolethane dimyristate), trimethylolethane diisomyristate, trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylolethane dihexadecanoate (trimethylolethane dipalmitate), trimethylolethane diisopalmitate, trimethylolethane monooctadecanoate (trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylolethane dioctadecanoate (trimethylolethane distearate), trimethylolethane diisostearate, trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate, trimethylolethane dioctadecenoate (trimethylolethane dioleate) and trimethylolethane diisooleate;
partial esters of trimethylolpropane such as trimethylolpropane monododecanoate (trimethylolpropane monolaurate), trimethylolpropane monoisolaurate, trimethylolpropane didodecanoate (trimethylolpropane dilaurate), trimethylolpropane diisolaurate, trimethylolpropane monotetradecanoate (trimethylolpropane monomyristate), trimethylolpropane monoisomyristate, trimethylolpropane ditetradecanoate (trimethylolpropane dimyristate), trimethylolpropane diisomyristate, trimethylolpropane monohexadecanoate (trimethylolpropane monopalmitate), trimethylolpropane monoisopalmitate, trimethylolpropane dihexadecanoate (trimethylolpropane dipalmitate), trimethylolpropane diisopalmitate, trimethylolpropane monooctadecanoate (trimethylolpropane monostearate), trimethylolpropane monoisostearate, trimethylolpropane dioctadecanoate (trimethylolpropane distearate), trimethylolpropane diisostearate, trimethylolpropane monooctadecenoate (trimethylolpropane monooleate), trimethylolpropane monoisooleate, trimethylolpropane dioctadecenoate (trimethylolpropane dioleate) and trimethylolpropane diisooleate;
partial esters of pentaerythritol such as pentaerythritol monododecanoate (pentaerythritol monolaurate), pentaerythritol monoisolaurate, pentaerythritol didodecanoate (pentaerythritol dilaurate), pentaerythritol diisolaurate, pentaerythritol tridodecanoate (pentaerythritol trilaurate), pentaerythritol triisolaurate, pentaerythritol monotetradecanoate (pentaerythritol monomyristate), pentaerythritol monoisomyristate, pentaerythritol ditetradecanoate (pentaerythritol dimyristate), pentaerythritol diisomyristate, pentaerythritol tritetradecanoate (pentaerythritol trimyristate), pentaerythritol triisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol dihexadecanoate (pentaerythritol dipalmitate), pentaerythritol diisopalmitate, 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 dioctadecenoate (pentaerythritol dioleate), pentaerythritol diisooleate, pentaerythritol trioctadecenoate (pentaerythritol trioleate) and pentaerythritol triisooleate;
partial esters of sorbitan such as 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 trioleate) and sorbitan triisooleate; and mixtures thereof. Monoesters are particularly preferable among them. Specific examples of the monoesters are glycerin monododecanoate (glycerin monolaurate), glycerin monoisolaurate, glycerin monotetradecanoate (glycerin monomyristate), glycerin monoisomyristate, glycerin monohexadecanoate (glycerin monopalmitate), glycerin monoisopalmitate, glycerin monooctadecanoate (glycerin monostearate), glycerin monoisostearate, glycerin monooctadecenoate (glycerin monooleate), glycerin monoisooleate; trimethylolethane monododecanoate (trimethylolethane monolaurate), trimethylolethane monoisolaurate, trimethylolethane monotetradecanoate (trimethylolethane myristate), trimethylolethane monoisomyristate, trimethylolethane monohexadecanoate (trimethylolethane monopalmitate), trimethylolethane monoisopalmitate, trimethylolethane monooctadecanoate (trimethylolethane monostearate), trimethylolethane monoisostearate, trimethylolethane monooctadecenoate (trimethylolethane monooleate), trimethylolethane monoisooleate; trimethylolpropane monododecanoate (trimethylolpropane 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 monoisomyristate, pentaerythritol monohexadecanoate (pentaerythritol monopalmitate), pentaerythritol monoisopalmitate, pentaerythritol monooctadecanoate (pentaerythritol monostearate), pentaerythritol monoisostearate, pentaerythritol monooctadecenoate (pentaerythritol monooleate), pentaerythritol monoisooleate; sorbitan monododecanoate (sorbitan monolaurate), sorbitan monoisolaurate, sorbitan monotetradecanoate (sorbitan monomyristate), sorbitan monoisomyristate, sorbitan monohexadecanoate (sorbitan monopalmitate), sorbitan monoisopalmitate, sorbitan monooctadecanoate (sorbitan monostearate), sorbitan monoisostearate, sorbitan monooctadecenoate (sorbitan monooleate), sorbitan monoisooleate; and mixtures thereof.
The oxidized wax salt of the above-mentioned compound (B) denotes the salt which is prepared by reacting a oxidized wax with at least one kind of compound selected from an alkaline metal, an alkaline earth metal (with the exception of barium) and an amine to neutralize some or all of acidic groups which the oxidized wax has. No particular limitation is imposed on the oxidized wax used as the raw material of the above-mentioned oxidized wax salt, however, specific examples of the oxidized wax include the compounds obtained by the oxidation of waxes such as paraffin wax, microcrystalline wax or petrolatum which are obtained in the purification of petroleum fractions, synthetic polyolefin wax and slack wax. Furthermore, no particular limitation is imposed on the alkaline metal, the alkaline earth metal and the amine used as the raw material, however, the alkaline metal, the alkaline earth metal and the amine exemplified in the explanation of the sulfonate according to the present invention are preferable. In addition, if the barium salt of the oxidized wax is used, safety to a human body and ecosystem becomes insufficient. When the oxidized wax salt of the compound (B) is a sodium salt, the sulfonate according to the present invention is preferably the sodium salt in terms of the storage stability.
The esterified oxidized wax of the above-mentioned compound (C) denotes a compound which is prepared by reacting a oxidized wax with alcohols to esterify some or all of acidic groups which the oxidized wax has. The oxidized wax used as the raw material of the above-mentioned esterified oxidized wax denotes the oxidized wax exemplified in the explanation of the above-mentioned compound (B); and the alcohols denote straight chain or branched saturated monohydric alcohols having 1 to 20 carbon atoms, straight chain or branched unsaturated monohydric alcohols having 1 to 20 carbon atoms, the polyhydric alcohols exemplified in the explanation of the above-mentioned compounds (A), alcohols obtained by hydrolysis of lanolin, and the like.
The lanolin fatty acid salt of the above-mentioned compound (D) denotes a salt which is prepared by reacting a lanolin fatty acid obtained by purifying (hydrolysis, and the like) a waxy substance attached to wool with at least one kind of component selected from an alkaline metal, an alkaline earth metal (with the exception of barium) and an amine to neutralize some or all of acidic groups which the lanolin fatty acid has.
The alkaline metal, the alkaline earth metal, and the amine used as the raw materials of the lanoline fatty acid salt denote the alkaline earth metal, and the amine exemplified in the explanation of the sulfonate according to the present invention. In addition, when the barium salt of the lanolin fatty acid is used, safety to a human body or ecosystem becomes insufficient. Furthermore, when the lanoline fatty acid salt according to the present invention is the sodium salt, it is preferable because the storage stability of the rust.preventive compound tends to be improved.
The esterified lanolin fatty acid of the above-mentioned compound (E) denotes an acid which is obtained by reacting a lanolin fatty acid obtained by purifying (hydrolysis, and the like) a waxy substance attached to wool with an alcohol. The alcohol used as the raw material of the above-mentioned compound (E) denotes the alcohol exemplified in the explanation of the above-mentioned esterified oxidized wax, preferably a polyhydric alcohol among the alcohols, and more preferably trimethylolpropane, trimethylolethane, sorbitan, pentaerythritol, and glycerin.
The fatty acid salt of the above-mentioned compound (F) denotes a fatty acid which is obtained by reacting at least one kind of component selected from an alkaline metal, an alkaline earth metal (with the exception of barium) and an amine with a fatty acid. The alkaline metal, the alkaline earth metal and the amine used as the raw materials of the above-mentioned fatty acid salt denote the alkaline metal, the alkaline earth metal and the amine exemplified in the explanation of the sulfonate according to the present invention; and the fatty acid denotes the fatty acid exemplified in the explanation of the above-mentioned compound (A).
In addition, when the above-mentioned compounds (A) to (F) are manufactured, a chlorine bleach is occasionally used for the purpose of decoloration. However, in the present invention, it is preferable either to use a non-chlorine type compound such as hydrogen peroxide as a bleaching agent or not to carry out a decoloration process. Furthermore, although chlorine type compounds such as hydrochloric acid are occasionally used for hydrolysis of waxes and the like, it is also preferable to use either a non-chlorine type acid or a basic compound. Furthermore, it is preferable to carry out a sufficient washing process such as water washing for the obtained compounds (A) to (F) .
No particular limitation is imposed on the chlorine concentration of the above-mentioned compounds (A) to (F) as long as the property of rust preventive oil composition is not deteriorated, however, the concentration is preferably not more than 200ppm by mass, more preferably not more than 100ppm by mass, particularly preferably not more than 50ppm by mass, and especially preferably not more than 25ppm by mass.
In the rust preventive oil compositions according to the present invention, the above-mentioned compounds (A) to (F) may be used singly or in combination of two or more. When the compositions are used for an application requiring a degreasing ability, the compound (B) and/or (F) are preferable among the compounds (A) to (F). Furthermore, since a higher rust prevention improvement effect is obtained, it is preferable to use a combination of at least one kind of compound selected from the group consisting of the compounds (A), (C) and (E) and at least one kind of compound selected from the group consisting of the compounds (B), (D) and (F).
Furthermore the above-mentioned compounds (A) to (F) may be used in any content, however, the total content of the above-mentioned compounds (A) to (F) is preferably 1 to 20 % by mass based on the total weight of the composition. When the total content of 'the above-mentioned compounds (A) to (F) is less than 1% by mass, the rust prevention improvement effect by adding these components tends to become unattainable. In addition, due to a similar reason, the total content of the above-mentioned compounds (A) to (F) is more preferably more than 1.5% by mass, particularly preferably more than 2% by mass, and especially preferably more than 4% by mass. On the other hand, when the total content of the above-mentioned compounds (A) to (F) exceeds 20% by mass, the improvement effect of rust prevention ability tends to become unproportional to the contents of the compounds. Moreover, due to a similar reason, the total content of the above-mentioned compounds (A) to (F) is more preferably not more than 10% by mass, particularly preferably not more than 9% by mass, and especially preferably not more than 8% by mass.
When the composition is used for an application wherein the degreasing ability is required, the total content of the above-mentioned compounds (A), (C), (D), and (E) is preferably not more than 10% by mass based on the total weight of the composition, more preferably not more than 5% by mass, particularly preferably not more than 3% by mass, and especially preferably not more than 1% by mass.
Furthermore, when the rust preventive oil composition of the present invention contains one or not less than two compounds selected from' the above-mentioned compounds (A) to (F), the sulfonate and the compounds (A) to (F) may be mixed in any ratio, however, the total content of the above-mentioned compounds (A) to (F) is preferably not more than 500 parts by mass per 100 parts by mass of sulfonate, more preferably not more than 400 parts by mass, particularly preferably not more than 300 parts by mass, and especially preferably not more than 200 parts by mass, in terms of storage stability. In addition, the total content of the above-mentioned compounds (A) to (F) is preferably more than 20 parts by mass per 100 parts by mass of sulfonate, more preferably more than 25 parts by mass, particularly preferably more than 30 parts by mass, and especially preferably more than 50 parts by mass, in terms of the rust prevention ability.
The rust preventive oil composition according to the present invention may contain other additives, if required. Herein, other additives used in the present invention are specifically paraffin wax which has a significantly improved exposed rust prevention effect in an acid atmosphere; oils and sulfurized fats which have a significantly improved press formability effect or lubricity, sulfurized ester, long-chain alkyl zinc dithiophosphate, phosphate such as tricresyldiphosphate, oils and fats such as lard, fatty acid, higher alcohol, calcium carbonate, potassium borate; phenol series or amine series antioxidants for improving an oxidation inhibiting performance; corrosion inhibitor for improving corrosion inhibiting performance (benzotriazole or its derivatives, thiadiazole, benzothiazole and the like); wetting agents such as diethyleneglycolmonoalkylether; film forming agents such as acryl polymer, paraffin wax, micro wax, slack wax, polyolefin wax and petrolatum; antifoaming agents such as methyl silicone, fluoro silicone and polyacrylate; water and surfactant for removing a water-soluble putrefaction factor, and mixtures thereof. In addition, as for anticorrosive additives other than sulfonates according to the present invention, concretely, the compounds that can be also blended are monocarboxylic acid represented by stearic acid, palm oil fatty acid and the like, alkyl or alkenyl succinic acid (includes anhydride) and its derivatives, dicarboxylic acid represented by dimer and the like of unsaturated fatty acid of oleic acid and the like, carboxylic acid containing other polar groups represented by hydroxyfatty acid, mercaptofatty acid, sarcosine derivatives and the like, carboxylic acids of oxidized wax and the like; carboxylic acid salts represented by metal carboxylates (sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, zinc salts, lead salts and the like) of fatty acid, naphtenic acid, resin acids, alkenylsuccinic acid, amino acid derivatives and the like, and by amine salts (monoamine salts, beef tallow amine salts, polyamine salts, alkanolamine salts and the like); esters represented by esters prepared by polyhydric alcohols such as glycerin, pentaerythritol, sorbitol and saccharose and carboxylic acids such as lauric acid and oleic acid; alcohols represented by higher aliphatic alcohol and the like; amines represented by amines and the like exemplified in the descriptions of the aforementioned sulfonates; phosphomonoester, phosphodiester, phosphite ester, phosphate(phosphite) derivatives represented by these amine salts; boric compounds and the like. In addition, although the contents of the aforementioned other additives are arbitrary, it is preferred that the total content of these additives is 10% by mass or less based on the total weight of rust preventive oil composition.
In the rust preventive oil composition according to the present invention, an arbitrary basic compound can be used besides the basic compounds such as the sulfonates, the compound (B) and the compound (F) according to the present invention. Concretely taken up as basic compounds are Ca sulfonates where calcium carbonate is dispersed (the so-called perbasicsulfonates), Mg sulfonate where magnesium carbonate is dispersed, Ca salts additives of paraffin oxide where calcium carbonate is dispersed, lanolin additives where calcium carbonate is dispersed, amines (for example, the aforementioned amines), Ca salts of paraffin oxide or Ca calboxylates contained in Ca salts of lanolin fatty acid, an additive which is made by calcium-carboxylation of an almost pure carboxylic acid synthesized for an industrial usage, a non-ash dispersant derived from alkenylsuccinic acid and ethylenediamine, and the like.
It is preferred that the total base number of the rust preventive oil composition according to the present invention is 1 to 20mgKOH/g. The total base number is preferably 1mgKOH/g or more from the viewpoint of rust prevention property, more preferable is 1.5mgKOH/g or more, further preferable is 2mgKOH/g or more and mostly preferable is 3mgKOH/g or more. In addition, from the viewpoint of storage stability, the total base number is preferably 20mgKOH/g or less, 'more preferable is 15mgKOH/g or less, further preferable is 10mgKOH/g or less and mostly preferable is 8mgKOH/g. Besides, the total base number referred to here denotes the total base number [mgKOH/g] measured by the hydrochloric acid method in accordance with item 6 in JIS K 2501 [Petroleum products and lubricating oil-neutralization value test method].
In addition in the rust preventive oil according to the present invention, it is preferred that the content and total base number of a sulfonate satisfy the condition expressed by the following formula (5): TBN/Cs≦3 (wherein C_s represents the content of a sulfonate (% by mass), and TBN represents the total base number [mgKOH/g])
If TBN/C_s exceeds 3, storage stability is liable to be insufficient. Due to a similar reason, more preferable is TBN/C_s is 2 or less, and further preferable is 1.5 or less. In addition, although the lower limit of TBN/C_s is not particularly limited, preferable is 0.2 or more, and more preferable is 0.3 or more. If TBN/C_s is less than the aforementioned lower limit, rust prevention property is insufficient or the cost is liable to increase. Although the kinematic viscosity at 40 ° C of the rust preventive oil composition according to the present invention is not particularly limited, preferred is 1.5 to 1000mm²/s. If the kinematic viscosity of the rust preventive oil composition at 40° C is less than 1.5mm²/s, there is a tendency that a sufficient rust prevention property can not be obtained. Thus, due to a similar reason, it is more preferred that the kinematic viscosity of the rust preventive oil composition at 40° C is 2mm²/s or more, further preferred is 2.5mm²/s or more, and particularly preferred is 3mm²/s or more. Particularly, when the rust preventive oil composition according to the present invention is applied to a usage where a compatibility with an organic material is required, it is preferred that the kinematic viscosity at 40° C is 7mm²/s or more, more preferred is 10mm²/s and further preferred is 15mm²/s. On the other hand, if the kinematic viscosity at 40 ° C exceeds 1000mm²/s, performance in handling of the rust preventive oil composition is liable to deteriorate. Then, due to a similar reason, it is more preferred that the kinematic viscosity at 40° C according to the present invention is 500mm²/s or less, further preferred is 100mm²/s or less, particularly preferred is 40mm²/s or less, and mostly preferred is 20mm²/s or less.
In addition, when the rust preventive oil composition according to the present invention is applied to a usage where a cleaning ability is required; namely, when the oil is used as a cleaning rust preventive oil, it is preferred that the kinematic viscosity at 40° C is 10mm²/s or less, more preferred is 6mm²/s or less, further preferred is 4mm²/s or less, and particularly preferred is 3mm²/s or less.
The rust preventive oil composition of such a constitution according to the present invention has a sufficiently high rust prevention performance and a sufficiently high safety to a human body and ecosystem, and can be also used for various steel sheets such as an automobile vehicle body and for metal parts such as precision parts of bearings. In addition, since the composition can acquire the more excellent performance in compatibility with an organic material, degreasing property, cleaning ability and the like, the composition is preferably used for these various applications.
The rust preventive oil composition according to the present invention can be coated on a metal part with the methods such as spray, shower, dropping, transcription by a felt material and electrostatic oil coating. Further, in a coating process, it is preferred that a drain separation process using a centrifugal separator or a drain separation process by a long time leaving is provided after an excessive rust preventive oil composition is coated. When a rust preventive oil is used for metal plate materials such as steel sheets utilized for automobile vehicle bodies or appliance bodies (however, the case of cleaning rust preventive oil is excluded), preferred is spray, shower and electrostatic oil coating, and more preferred is electrostatic oil coating among these coating methods.
In addition, when the rust preventive oil composition according to the present invention has a relatively high kinematic viscosity (for example; 400mm²/s or more at 40° C), the coating performance is liable to deteriorate. However, even in such a case, coating can be preferably performed by a method of atomizing the rust preventive oil composition, and by a method of heating an object to be coated at a predetermined temperature (preferably at 30°C to 80°C) and the like. Here, when the rust preventive oil composition is atomized, if an airless spray is used, good mists can be formed compared with a method using an air spray.
In the present invention, although the quantity of the rust preventive oil composition to be coated on a metal part is not particularly limited, preferred is 0.1 to 20g/m², more preferred is 0.2 to 10g/m², further preferred is 0.3 to 5g/m² and particularly preferred is 0.3 to 3g/m². When the coated quantity of the rust preventive oil composition is less than the aforementioned lower limit value, the rust prevention performance is liable to be insufficient, and on the other hand, when the coated quantity exceeds the aforementioned upper limit value, an organic material is liable to deteriorate.
In addition, when the rust preventive oil composition according to the present invention is used as a cleaning rust preventive oil composition, a good cleaning followed by an rust prevention operation can be performed by supplying a large excess quantity of the rust preventive oil composition of the present invention to the surface of the metal part by a spray, a shower, a dip coating and the like. Further, when a surface cleaning is simultaneously performed with a roll brush and the like after the aforementioned metal processing is performed if required, a foreign matter removal efficiency can be increased. Moreover, when a cleaning is performed by using the rust preventive oil composition according to the present invention, it is preferred that the surface treatment is simultaneously performed on the metal part with a linger roll and the like to control the quantity of the oil attached to the surface of the metal part.
Even though the coating method of the rust preventive oil composition according to the present invention is any of the aforementioned methods, it is preferred that the rust preventive oil composition which is excessively coated on the metal part is recovered, circulated and reused. In addition, when the rust preventive oil composition is circulated, it is preferred that a foreign matter mixed in the circulation system is simultaneously removed. Concretely, for example, the foreign matter can be removed by providing a filter halfway in the circulation path of the rust preventive oil composition according to the present invention, preferably just before the rust preventive oil composition is ejected to the metal part. In addition, a magnet is provided at the bottom of a tank where the rust preventive oil composition according to the present invention is stored, thus the foreign matter such as wear-out can be also removed by adsorption by a magnetic force. However, there is a concern that the performance of the rust preventive oil composition according to the present invention which is reused in such a process may deteriorate due to the incorporation of a pre-treated oil into the process. Therefore, when the rust preventive oil composition according to the present invention is reused, it is preferred that the physical properties of the oil are controlled by regularly measuring the kinematic viscosity or density of the oil reused, and by performing copper plate corrosion test, rust prevention test and the like. If required, an action is preferably conducted such as oil regeneration, drain disposal, tank cleaning and oil purification. Further, with respect to the disposed oil solution, the total quantity of the used oil can be reduced by using the oil solution as it is, or by diluting the oil solution with a solvent or a low viscosity base oil for a line requiring a lower performance of the rust preventive oil composition than that for the line used before disposing the oil. Moreover, when the rust preventive oil composition according to the present invention is stored in the tank, it is preferred that the oil composition is replenished in accordance with a reduced quantity thereof in the tank. In this case, the composition is not necessary to be the same one as the rust preventive oil composition initially filled, and a replenishment may be carried out by a composition having an increased quantity of an additive to exert the performance which is required to enhance in accordance with case by case. On the contrary, a low viscosity composition obtained by a method to reduce the content of the base oil having kinematic viscosity of 6mm²/s or more at 40 ° C may be replenished to maintain the cleaning performance of the rust preventive oil composition.
The rust preventive oil composition according to the present invention can be used for metal plate materials such as hot-rolled steel sheet which is prepared for an automobile vehicle body or an appliance body, cold-rolled steel sheet, high tension steel sheet, surface treated steel sheet such as zinc-plated steel sheet, aluminum alloy sheet and magnesium alloy sheet.
In this case, the rust preventive oil composition according to the present invention can be used for any of the processes for oils including a rust preventive oil used for intermediate rust prevention agent of metal plate materials, a rust preventive oil used for rust prevention at the time of the product shipment (shipping rust preventive oil) and an rust preventive oil used in a cleaning process for removing a foreign matter before press working is performed (cleaning rust preventive oil).
In addition, the rust preventive oil composition according to the present invention may be used in a cleaning process for removing a foreign matter prior to the product shipment in a metal sheet manufacturer. In this case, metal sheets can be wound in coils just after the cleaning process or they can be shipped by stacking the products as sheet materials. Namely, the rust preventive oil composition according to the present invention can be used as a cleaning rust preventive oil and a shipping rust preventive oil. This method has an advantage that the adhered quantity of a foreign matter is small, and cleaning can be easily and definitely performed if a cleaning process is performed with a cleaning rust preventive oil just before a press work is performed in the press working process. In addition, although it is quite natural, a process where a rust preventive oil is coated again may be provided to perform an rust prevention treatment in two steps following a cleaning process with a cleaning rust preventive oil in a steel sheet manufacturing factory.
In addition, in a metal part obtained through metal machining processes such as grinding, polishing and press working, although a rust is likely to take place because an extreme pressure additive remains on the surface of the part which is contained in a lubricating oil (a metal processing oil agent) used in the metal machining process, the generation of such a rust can be preferably prevented when the rust preventive oil composition according to the present invention contains the compounds (A) to (F) besides the aforementioned sulfonates. In addition, the generation of rust can be preferably prevented while sufficiently lowering the added quantities of sulfonates or the compounds (A) to (F) by completely removing the residue such as extreme pressure additives from the part after the metal machining process is performed.
With respect to the method of removing the residue of the extreme pressure additives and the like, the solvent dilution type rust preventive oil composition according to the present invention may be used as a cleaning rust preventive oil, however, it is preferred that the following methods are used to more effectively remove the residue. Namely, when a non water metal machining oil is used, it is preferable to provide a method by which a cleaning is performed with a cleaning oil composition where water is dissolved in the base oil using a surfactant. In addition, when a water soluble metal machining oil is used, it is preferred that cleaning is performed by a method using a cleaning oil composition where water exchangeability is given by adding amine salts of fatty acid, alkylsuccinic acid derivatives or alkenylsuccinic acid derivatives, phosphates, phosphites and the like to the base oil.
In addition, upon performing the packing, when polyethylene resin, polypropylene resin or paper on which these resins are coated, or a vapor phase rust prevention packing material are used, the generation of a rust can be sufficiently prevented although the aforementioned additives are not added to the rust preventive oil composition according to the present invention, as a result, in most cases, there is no problem in practical use.
In addition, with respect to the rust preventive oil composition according to the present invention, by selecting a proper base oil, an excellent effect is exerted in terms of compatibility with organic materials such as polyethylene, polystyrene, acrylic resin, polycarbonate resin, ABS resin, denatured PPO resin, and the generation of rust can be sufficiently prevented. Therefore, the generation of rust can be sufficiently prevented on a metal part without deteriorating the packaging materials comprising the aforementioned materials (cover and the like), structural material (frame materials and the like), window materials, sealants, buffer materials, axis materials, gears, bearing cages, a paper feeder and the arm section of a robot by applying the rust preventive oil composition according to the present invention to the metal parts such as various steel sheets for automobile vehicle bodies and precision parts such as bearings.
Further, when the rust preventive oil composition according to the present invention is a solvent dilution type rust preventive oil, it is preferable to provide a drying process for vaporizing a solvent after coating the rust preventive oil composition because the deterioration of organic materials can be more definitely prevented. With respect to a method for vaporizing the solvent, concretely taken up are heating, ventilation, decompression, a long time leaving and the like. When the solvent is vaporized by ventilation, air at a room temperature may be blown, and heated air may be also blown.
After the relevant drying process, although an oil film is formed on the surface of the metal part, this oil film quantity is preferably 0.1 to 20g/m², more preferably is 0.2 to 10g/m² and further preferably is 0.3 to 5g/m². When the oil film quantity is less than the aforementioned lower limit value, an rust prevention is liable to be insufficient, on the other hand, when the quantity exceeds the upper limit value, the organic material is liable to deteriorate.
In addition, after the aforementioned drying process, although there is a case where the non volatile component of a solvent is contained in an oil film formed on the surface of the metal part, it is preferred that the content of the solvent in the oil film is 10% by mass or less, preferable is 5% by mass or less and further preferable is 1% by mass or less, more preferable is 0.5% by mass or less, and particularly preferable is 0.1% by mass or less. When the content of the solvent in the oil film exceeds' the upper limit value, compatibility with an organic material is liable to deteriorate.
In addition, when the coated quantity or the oil film quantity is controlled, an rust preventive oil composition may be coated so as to be a desired coated quantity or oil film quantity, and the coated quantity or the oil film quantity may be also controlled by removing its excessive component with a linger roll and the like after the excessive quantity of the rust preventive oil composition is coated.

[Examples]

Although the present invention is described in details based on the examples and comparative examples hereafter, the present invention is not limited to the following examples. In addition, in the following examples, "%" denotes "% by mass" unless otherwise specially specified.

Examples 1 to 8

In the Examples 1 to 8, the rust preventive oil composition was prepared by using each component as shown below. Shown in Table 1 are the compounding ratios of each component, the concentrations of compounds containing barium (Ba), zinc (Zn), chlorine (Cl), lead (Pb) and a group represented by the aforementioned general formula (1), and the kinematic viscosity at 40 ° C in the rust preventive oil composition in each example.

Base oil

Base oil 1: mineral oil (kinematic viscosity at 40° C: 6.5mm²/s, initial boiling point: 235° C, final boiling point: 425 ° C, naphthene component: 29%, paraffin component: 58%, aromatic component: 13%, (naphthene/paraffin) ratio: 0.50, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 20: about 50%, content of hydrocarbons having a carbon atom number of not more than 25: 97%)
Base oil 2: mineral oil (kinematic viscosity at 40° C: 22mm²/s, initial boiling point: 300° C, final boiling point: 485 ° C, naphthene component: 22%, paraffin component: 56%, aromatic component: 22%, (naphthene/paraffin) ratio: 0.39, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 20: about 1%, content of hydrocarbons having a carbon atom number of not more than 25: 33%)
Base oil 3: mineral oil (kinematic viscosity at 40° C: 100mm²/s, initial boiling point: 335° C, final boiling point: 595 ° C, naphthene component: 25%, paraffin component: 41%, aromatic component: 32%, (naphthene/paraffin) ratio: 0.61, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 20: less than 1%, content of hydrocarbons having a carbon atom number of not more than 25: 3%)
Base oil 4: mineral oil (kinematic viscosity at 40° C: 400mm²/s, initial boiling point: 440° C, final boiling point: 700 ° C, naphthene component: 15%, paraffin component: 35%, aromatic component: 43%, (naphthene/paraffin) ratio: 0.43, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 20: less than 1%, content of hydrocarbons having a carbon atom number of not more than 25: less than 1%)
Base oil 5: mineral oil (kinematic viscosity at 40 ° C: 2mm²/s, initial boiling point: 200° C, final boiling point: 255 ° C, naphthene component: 31%, paraffin component: 68%, aromatic component: 0.5%, (naphthene/paraffin) ratio: 0.46, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.50%, content of hydrocarbons having a carbon atom number of not more than 14: 98%, content of hydrocarbons having a carbon atom number of not more than 20: 100%, content of hydrocarbons having a carbon atom number of not more than 25: 100%)

Sulfonate

S1: dinonylnaphtalenecalciumsulfonate solution (content of net sulfonate: 50%, carrier oil: 50%)
S2: dialkylbenzenecalciumsulfonate solution (content of net sulfonate: 60%, carrier oil: 40%)(dialkylbenzenecalciumsulfonate having two alkyl groups derived from ethylene oligomer, and the main component is such that the total number of carbon atoms of two alkyl groups is 20.)
S3: dialkylbenzenesodiumsulfonate solution (content of net sulfonate: 60%, carrier oil: 40%)(dialkylbenzenesodiumsulfonate having two alkyl groups derived from ethylene oligomer, and the main component is such that the total number of carbon atoms of two alkyl groups is 20.)
S4: dinonylnaphthalene decylaminesulfonate solution (content of net sulfonate: 50%, carrier oil: 50%)
In addition, the carrier oils in the aforementioned S1 to S4 are mineral oils with kinematic viscosity of about 20mm²/s. Moreover, the compounding ratios of S1 to S4 in Table 1 are the values of the solution comprising a sulfonate and a carrier oil, and the compounding ratio of the sulfonate in each composition can be calculated by multiplying the compounding ratio of each solution by the rate of the content of the aforementioned net sulfonate.

Compound (A)

A1: trimethylolpropanemonooleate
A2: sorbitanmonooleate
A3: sorbitanmonoisostearate

Compound (B)

B1: calcium salt of paraffin oxide (total acid value: 5mgKOH/g, total base number: 16mgKOH/g, saponification value: 80mgKOH/g)
B2: sodium salt of paraffin oxide (total acid value: 14mgKOH/g, total base number: 1mgKOH/g, saponification value: 35mgKOH/g)

Compound (C)

C1: ester of paraffin oxide (total acid value: 30mgKOH/g, total base number: 0.2mgKOH/g, saponification value: 135mgKOH/g)

Compound (D)

D1: calcium salt of lanolin fatty acid (total acid value: 2.5mgKOH/g, total base number: 11mgKOH/g, saponification value: 120mgKOH/g)

Compound (E)

E1: partial ester of lanolin fatty acid and trimethylolpropane (total acid value: 8mgKOH/g, total base number: 0.5mgKOH/g, saponification value: 170mgKOH/g, hydroxyl value: 100mgKOH/g)

Other components

H1: di-tert-butyl-p-cresol
H2: benzotriazole
H3: benzotriazole derivative represented by the following general formula (6):
H4: paraffin wax (melting point: 51.7° C)
H5: inactive type lard sulfide (content of sulfur: 12% by mass, saponification value: 250mgKOH/g, total acid value: 1mgKOH/g)
H6: succinic acid derivative (partial ester of alkenylsuccinic acid derived from propylene oligomer having a carbon atom number of 9 to 15 and a dimer to tetramer of propyleneglycol)
Next, the following test was performed on each rust preventive oil composition in the Examples 1 to 6 and the reference example 1. In addition, in the Examples, a similar test was performed by using a commercially available barium series rust preventive oil composition as the comparative example 1.

(Rust prevention test)

A test piece was prepared by cutting a piece of 60 x 80mm size out of a commercially available cold-rolled steel sheet equivalent to SPCE-SD. Next; each rust preventive oil composition was 'coated on the test piece with an air spray so as to allow the coated quantity to be 3g/m². The test piece after coating was stored in an instrument shelter installed outdoors, and it was observed whether or not rust was generated on the test piece after a predetermined time lapsed, then the rust prevention properties of each rust preventive oil composition were evaluated in accordance with the following standards:
A: the generation of rust was not observed in 20 days after the test piece was coated,
B: the generation of rust was observed in 10 to 19 days after the test piece was coated,
C: the generation of rust was observed in 4 to 9 days after the test piece was coated, and
D: the generation of rust was observed within 3 days after the test piece was coated.

(Cylindrical deep drawing test)

A test piece was prepared by cutting a disc of 110mm diameter out of a commercially available cold-rolled steel sheet of 0.75mm thickness equivalent to SPCE-SD. Each rust preventive oil composition was manually coated on the test piece so as to allow the coated quantity to be about 3g/m², and the formability was evaluated by a cylinder formation testing machine with punch diameter of 50mm (shoulder R: 5mm) and die diameter of 52mm (shoulder R: 5mm). Shown in Table 1 is the limit BHF[tf](the maximum blank holder force where formation is possible without breakage) obtained on each test piece.

(Compatibility test 1 between rust preventive oil composition and resin material)

A compatibility test was performed between the rust preventive oil composition and the resin material by using a device shown in Fig. 1. Namely, a polycarbonate test piece 1 (64 x 13 x 3mm) was fixed in place on a jig 3 with a fixing bolt 2, and each rust preventive oil composition was coated on the test piece while a stress (bending) was applied to the test piece 1. It was observed whether or not cracking or split was generated on the test piece 1 after a predetermined time lapsed, and the compatibility between the rust preventive oil composition and the resin material was evaluated in accordance with the following standards:
A: the generation of rust was not observed in 15 days after the test piece was coated,
B: the generation of rust was observed in 3 to 14 days after the test piece was coated, and
C: the generation of rust was observed within 2 days after the test piece was coated.

(Compatibility test 2 between rust preventive oil composition and resin material)

The test oil of 5g was poured into a stainless steel pad of bottom area 200 x 300mm, height 30mm, and the test oil was hot air-dried with a general household hair dryer (output: 1200W) for 5 minutes while the distance between a wind-blow outlet and the test oil was kept at 300mm. After that, the test oil was cooled down to a room temperature for 30 minutes, the test was performed on the obtained test oil by the same procedure as that in the compatibility test 1 between the rust preventive oil composition and the resin material. The results are shown in Table 1.

(Storage stability test)

A test oil of 30g was sampled in a glass bottle of 50ml volume. After the test oil was kept at 20° C and RH 50% for 12 hours, the test oil was further kept at 50° C and RH 95% for 2 hours. This treatment was defined as one cycle. This cycle was continuously repeated until cloudiness or precipitation was caused. The storage stability of each test oil was evaluated in accordance with the following standards from the required number of days until the cloudiness or precipitation was caused (number of cycles):
A: 10 days or more,
B: 7 to 9 days,
C: 4 to 6 days,
D: 2 to 3 days, and
E: within one day

It is confirmed that the rust preventive oil compositions in the Examples 1 to 8 have the rust preventive oil property equivalent to or sufficiently higher than that of a conventional barium series rust preventive oil composition (Comparative Example 1) as shown in Table 1.

Examples 9 to 16

In the Examples 9 to 16, the rust preventive oils were prepared by using each component shown below. Shown in Table 2 are the compounding ratios of each component in the rust preventive oils obtained in each example, the concentrations of the compounds having barium (Ba), zinc (Zn), chlorine (Cl), lead (Pb) and the compound having a group represented by the aforementioned general formula (1), the content of a sulfonate, the total base number, the total weight of the compounds (A) to (F), the ratio of the sum of the contents of the compounds (A) to (E) and the content of the sulfonate, the total base number (TBN), TBN/C_s and the kinematic viscosity at 40° C.

Base oil

Base oil 6: mineral oil (kinematic viscosity at 40° C: 6.5mm²/s, initial boiling point: 235° C, final boiling point: 425 ° C, naphthene component: 29%, paraffin component: 58%, aromatic component: 13%, (naphthene/paraffin) ratio: . 0.50, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 20: about 50%, content of hydrocarbons having a carbon atom number of not more than 25: 97%)
Base oil 7: mineral oil (kinematic viscosity at 40° C: 22mm²/s, initial boiling point: 300° C, final boiling point: 485 ° C, naphthene component: 22%, paraffin component: 56%, aromatic component: 22%, (naphthene/paraffin) ratio: 0.39, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 1%, content of hydrocarbons having a carbon atom number of not more than 20: about 1%, content of hydrocarbons having a carbon atom number of not more than 25: 33%)
Base oil 8: mineral oil (kinematic viscosity at 40° C: 100mm²/s, initial boiling point: 335° C, final boiling point: 595 ° C, naphthene component: 25%, paraffin component: 41%, aromatic component: 32%, (naphthene/paraffin) ratio: 0.61, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 20: less than 1%, content of hydrocarbons having a carbon atom number of not more than 25: 3%)
Base oil 9: mineral oil (kinematic viscosity at 40° C: 400mm²/s, initial boiling point: 440° C, final boiling point: 700 ° C, naphthene component: 15%, paraffin component: 35%, aromatic component: 43%, (naphthene/paraffin) ratio: 0.43, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.5%, content of hydrocarbons having a carbon atom number of not more than 20: less than 1%, content of hydrocarbons having a carbon atom number of not more than 25: less than 1%)
Base oil 10: mineral oil (kinematic viscosity at 40° C: 2mm²/s, initial boiling point: 200° C, final boiling point: 255 ° C, naphthene component: 31%, paraffin component: 68%, aromatic component: 0.5%, (naphthene/paraffin) ratio: 0.46, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: 0.5%, content of hydrocarbons having a carbon atom number of not more than 14: 98%, content of hydrocarbons having a carbon atom number of not more than 20: 100%, content of hydrocarbons having a carbon atom number of not more than 25: 100%)
Base oil 11: mineral oil (kinematic viscosity at 40° C: 2mm²/s, initial boiling point: 200° C, final boiling point: 245 ° C, naphthene component: 77%, paraffin component: 23%, aromatic component: less than 0.1%, (naphthene/paraffin) ratio: 3.35, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: 98%, content of hydrocarbons having a carbon atom number of not more than 20: 100%, content of hydrocarbons having a carbon atom number of not more than 25: 100%)
Base oil 12: oligomer of 1-decene (kinematic viscosity at 40° C: 100mm²/s, naphthene component: 0%, paraffin component: 100%, aromatic component: 0%, (naphthene/paraffin) ratio: 0, content of hydrocarbons having a carbon atom number of not more than 6: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 8: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 10: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 14: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 20: less than 0.1%, content of hydrocarbons having a carbon atom number of not more than 25: 1% or less)

Sulfonate

S5: dinonylnaphtalenecalciumsulfonate solution (content of sulfonate: 50%, carrier oil 50%, total base number: 1mgKOH/g)
S6: dialkylbenzenecalciumsulfonate solution (content of sulfonate: 60%, total base number: 5mgKOH/g) (dialkylbenzenecalciumsulfonate having two alkyl groups derived from ethylene oligomer, and the main component is such that the total number of carbon atoms of two alkyl groups is 20.)
S7: dialkylbenzenesodiumsulfonate solution (content of sulfonate: 60%, total base number: 1mgKOH/g) (dialkylbenzenesodiumsulfonate having two alkyl groups derived from ethylene oligomer, and the main component is such that the total number of carbon atoms of two alkyl groups is 20.)
S8: dinonylnaphthalenedecylaminesulfonate solution (content of sulfonate: 50%, total base number: 1mgKOH/g)
S9: dinonylnaphtalenecalciumsulfonate solution (content of sulfonate: 40%, total base number: 50mgKOH/g)
S10: dialkylbenzenecalciumsulfonate solution (content of sulfonate: 30%, total base number: 300mgKOH/g) (dialkylbenzenecalciumsulfonate having two alkyl groups derived from ethylene oligomer, and the main component is such that the total number of carbon atoms of two alkyl groups is 20.)
In addition, the carrier oils in the aforementioned S5 to S10 are mineral oils with kinematic viscosity of about 20mm²/s. Moreover, the compounding ratios in Table 2 are the values of the aforementioned solutions, and the compounding ratio of the sulfonates in each preventive oil can be calculated by multiplying the compounding ratio of the solution by the rate of the content of the aforementioned net sulfonate.

Compound (A)

A4: trimethylolpropanemonooleate
A5: sorbitanmonooleate
A6: sorbitanmonoisostearate
A7: glycerinmonooleate

Compound (B)

B3: calcium salts of paraffin oxide (total acid value: 5mgKOH/g, total base number: 16mgKOH/g, saponification value: 80mgKOH/g)
B4: sodium salts of paraffin oxide (total acid value: 14mgKOH/g, total base number: 1mgKOH/g, saponification value: 35mgKOH/g)

Compound (C)

C2: ester of paraffin oxide (total acid value: 30mgKOH/g, total base number: 0.2mgKOH/g, saponification value: 135mgKOH/g)

Compound (D)

D2: calcium salt of lanolin fatty acid (total acid value: 2.5mgKOH/g, total base number: 11mgKOH/g, saponification value: 120mgKOH/g)

Compound (E)

E2: partial ester of lanolin fatty acid with trimethylolpropane (total acid value: 8mgKOH/g, total base number: 0.5mgKOH/g, saponification value: 170mgKOH/g, hydroxyl value: 100mgKOH/g)

Other components

H7: di-tert-butyl-p-cresol
H8: benzotriazole
H9: benzotriazole derivative represented by the aforementioned general formula (6)
H10: paraffin wax (melting point: 51.7° C)
H11: inactive type lard sulfide (content of sulfur: 12% by mass, saponification value: 25mgKOH/g, total acid value: 1mgKOH/g)
H12: active type lard sulfide (content of sulfur: 19% by mass, saponification value: 200mgKOH/g, total acid value: 1mgKOH/g)
Next, the following test was performed on each preventive oil composition in the Examples 9 to 16. In addition, in the following tests, a similar test was performed by using a commercially available barium series rust preventive oil composition as the comparative example 2.

(Rust prevention test)

A test piece was prepared by cutting a piece of 60 x 80mm size out of a commercially available cold-rolled steel sheet equivalent to SPCE-SD. Next, each rust preventive oil composition was coated on the test piece with an air spray so as to allow the coated quantity to be 3g/m². The test piece after coating was stored in an instrument shelter installed outdoors, and it was observed whether or not rust was generated on the test piece after a predetermined time lapsed, then the rust prevention properties of each rust preventive oil composition were evaluated in accordance with the following standards:
A: the generation of rust was not observed in 20 days after the test piece was coated,
B: the generation of rust was observed in 10 to 19 days after the test piece was coated,
C: the generation of rust was observed in 4 to 9 days after the test piece was coated, and
D: the generation of rust was observed within 3 days after the test piece was coated.

(Degreasing property test)

A test piece was prepared by cutting a piece of 60 x 80mm size out of a commercially available cold-rolled steel sheet equivalent to SPCE-SD. Next, each rust preventive oil composition was coated on the test piece with an air spray so as to allow the coated quantity to be 3g/m². The test piece after coating was stored in an instrument shelter installed outdoors for 24 hours, and the test piece was used for the following degreasing property test.
After the test piece was dipped in an alkaline degreasing agent where a nonionic surfactant was blended to sodium phosphate and a sodium silicate series alkaline builder for 2 minutes, and the test piece was washed in running water for 30 seconds. After that, the test piece was vertically held for 20 seconds, and the degreasing property was evaluated in accordance with the following standards in the water-wet area rate:
A: 90% or more
B: 90 to 60%
C: 60% or less

(Detergency test)

A piece of 60 x 80mm size was cut out of a commercially available cold-rolled steel sheet equivalent to SPCE-SD, and a test piece was prepared by attaching a dust of JIS11 class. Each of the aforementioned rust preventive oil compositions was sprayed on the test piece in a certain injected quantity for 10 seconds. After the washing was completed, the dust quantity left on the test piece was measured, and the detergency of each rust preventive oil composition was evaluated in accordance with the detergency rate of the test piece calculated by the following formula: Detergency rate (%)= (1- (attached dust quantity before test - attached dust quantity after test)/attached dust quantity before test)) x 100 and the following standards:
A: 95% or more
B: 95 to 80%
C: 80% or less

(Cylindrical deep drawing test).

A test piece was prepared by cutting a disc of 110 mm diameter out of a commercially available cold-rolled steel sheet of 0.75mm thickness equivalent to SPCE-SD. Each rust preventive oil composition was manually coated on the test piece so as to allow the coated quantity to be about 3g/m², and the formability was evaluated by a cylinder formation testing machine with punch diameter of 50mm (shoulder R: 5mm) and die diameter of 52mm (shoulder R: 5mm). The limit BHF[tf](the maximum blank holder force where formation is possible without breakage) obtained on each test piece was evaluated in accordance with the following standards:
A: 3tf or more
B: exceeding 2tf and less than 3tf
C: 2tf or less

(Storage stability test)

	Ex. 9	Ex. 10	Ex. 11	Ex. 12	Ex. 13	Ex. 14	Ex. 15	Ex. 16	Ref. Ex. 2
Rust prevention property	A	A	A	B	B	A	A	A	C
Degreasing property	A	A	B	A	A	A	A	A	C
Detergency	C	A	C	C	B	C	C	C	C
Cylindrical deep drawing property	A	B	A	C	B	A	A	B	C
Storage stability	A	A	A	A	A	B	B	B	A

It is confirmed that the rust preventive oil compositions in the Examples 9 to 16 have the rust preventive oil property equivalent to or sufficiently higher than that of a conventional barium series rust preventive oil composition (Comparative Example 2), and also have excellent degreasing property as shown in Table 3. In addition, it is confirmed that the rust preventive oil compositions in the Examples 10 and 13 further show a better detergency.

Examples 17 to 26, Comparative Examples 3 to 5

In the Examples 17 to 26 and Comparative Examples 3 to 4, the rust preventive oil compositions were prepared by using each component described above. Shown in Table 1 are the compounding ratios of each component in the rust preventive oil compositions obtained in each example, the concentrations of the compounds having barium (Ba), zinc (Zn), chlorine (Cl), lead (Pb) and the compounds having a group represented by the aforementioned general formula (1), the content of a sulfonate, the total base number, TBN/C_s, the ratio of the sum of the contents of the compounds (A) to (E) and the content of the sulfonate, and the kinematic viscosity at 40° C.
In addition, for these rust preventive oil compositions, rust prevention property test, Cylindrical deep drawing, compatibility tests 1 and 2 between the rust preventive oil compositions and the resin materials, and storage stability test were performed in the same manner as in Example 1. The obtained results are shown in Tables 4 and 5. In addition, in the following tests, a commercially available barium series rust preventive oil composition was used as Comparative Example 5.
Moreover, rust prevention property test was evaluated in accordance with the following standards:
S: the generation of rust was not observed in 30 days after the test piece was coated,
A: the generation of rust observed in 20 to 29 after the test piece was coated,
B: the generation of rust observed in 10 to 19 after the test piece was coated,
C: the generation of rust observed in 4 to 9 after the test piece was coated, or
D: the generation of rust was not observed within 3 days after the test piece was coated.
Further, compatibility test 1 between the rust preventive oil composition and the resin material was evaluated in accordance with the following standards:
S: the generation of split or cracking was not observed in 30 days after the test piece was coated,
A: the generation of split or cracking was observed in 15 to 29 after the test piece was coated,
B: the generation of split or cracking was observed in 3 to 14 after the test piece was coated, or

C: the generation of split or cracking was within 2 days after the test piece was coated.

	Ex. 17	Ex. 18	Ex. 19	Ex. 20	Ex. 21	Ex. 22
Compounding ratio [% by mass]	Base oil 1	-	-	-	16.39	16.39	-
Base oil 2	24	24	24	-	-	-
Base oil 3	10.5	10.5	10.5	40	40	-
Base oil 4	-	-	-	-	-	45
Base oil 5	50	48	50	20	20	-
Base oil 11	-	-	-	-	-	38
Base oil 12	-	-	-	-	-	-
S1	7	7	3	-	-	7
S2	-	-	-	5	5	-
S3	-	-	-	-	-	-
S4	-	-	-	-	-	-
S5	-	-	5	5	5	-
S6	1	1	-	-	-	1
A2	3	3	3	-	-	-
B1	4	4	4	3	3	3
C1	-	-	-	-	-	-
D1	-	-	-	-	-	-
E1	-	-	-	5	5	6
F1	-	-	-	-	-	-
H1	0.5	0.5	0.5	0.5	0.5	-
H2	-	-	-	0.01	0.01	-
H3	-	-	-	0.1	0.1	-
H4	-	2	-	-	-	-
H5	-	-	-	5	-	-
H6	-	-	-	-	5	-
Ba conc. [ppm by mass]	4	4	4	4	4	<1
Zn conc. [ppm by mass]	1	1	1	<1	<1	<1
Cl conc. [ppm by mass]	<1	<1	<1	3	3	2
Pb conc. [ppm by mass]	<1	<1	<1	<1	<1	<1
Conc. of a compound having a group represented by general formula (1) [ppm by mass]	<1	<1	<1	<1	<1	<1
Sulfonate content [% by mass]	3.8	3.8	3.5	5.0	5.0	3.8
Total base number [mgKOH/g]	3.80	3.80	3.26	3.31	3.31	3.58
TBN/C_s	1.00	1.00	0.93	0.66	0.66	0.94
[Total weight of (A) to (F)]/sulfonate content	1.84	1. 84	2.00	1.60	1.60	2.37
Kinematic viscosity (40°C) [mm²/s]	15.2	15.2	27.3	16.9	16.9	5.9
Rust prevention property	A	S	A	S	S	S
Limit BHF[ tf ]	2	2	1.5	4	4	4
Compatibility 1 with resin material	C	C	C	C	C	C
Compatibility
2 with resin material	A	A	A	B	B	S
Storage stability	A	A	A	A	A	A

It is confirmed that the rust preventive oil compositions in the Examples 17 to 26 have the rust preventive oil property equivalent to or sufficiently higher than that of a conventional barium series rust preventive oil composition (Comparative Example 3) as shown in Tables 4 and 5.

Industrial Applicability

As described above, in accordance with the present invention, it is possible to obtain a rust preventive oil composition having a sufficiently high rust prevention property and a sufficiently high safety to a human body and the ecosystem without using a barium or zinc series rust prevention agent or a 'film forming agent containing an alkylene oxide additive of alkylphenol.

Claims

A rust preventive oil composition, wherein at least one kind of sulfonate selected from a group consisting of an alkaline metal sulfonate, an alkaline earth-metal sulfonate (with the exception of barium sulfonate) and an amine sulfonate is contained by 1 to 10% by mass based on the total weight of the composition in at least one kind of base oil selected from a group consisting of a mineral oil and a synthetic oil,
contents of barium, zinc, chlorine and lead are each 1000ppm by mass or less based on the total weight by element conversion of the composition, and the content of a compound having a group represented by the following general formula (1):
[wherein R¹ represents an alkyl group having 1 to 24 carbon atoms , R² represents an alkylene group having 2 to 4 carbon 'atoms, m represents an integer of 1 to 5 and n represents an integer of 1 to 6] is 1000ppm by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein said sulfonate is at least one kind selected from a group consisting of:

dialkylnaphthalenesulfonate where the total number of carbon atoms in two alkyl groups bonding to a naphthalene ring is 14 to 30;

dialkylbenzenesulfonate where two alkyl groups bonding to a benzene ring are each a straight chain alkyl group or a branched chain alkyl group having one side chain methyl group, and where the total number of carbon atoms in the two alkyl groups is 14 to 30; and

monoalkylbenzenesufonate where the number of carbon atoms of alkyl groups bonding to a benzene ring is 15 or more.
The rust preventive oil composition according to claim 1, wherein the content of monoalkylbenzenesulfonate having one alkyl group of a carbon atom number of 13 or less is 1% by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein the content of alkylbenzenesulfonate having an alkyl group derived from a propylene oligomer is 1% by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein at least one kind of compounds are contained by 1 to 20% by mass based on the total weight of the composition and the compounds are selected from a group consisting of:

(A) a partial ester of polyhydric alcohol;

(B) at least one kind of oxidized wax salt selected from a group consisting of an alkaline metal salt of oxidized wax, an alkaline earth-metal salt of oxidized wax (with the exception of barium salt of oxidized wax) and an amine salt of oxidized wax;

(C) esterified oxidized wax;

(D) at least one kind of lanolin fatty acid ester selected from a group consisting of an alkaline metal salt of lanolin fatty acid, an alkaline earth-metal salt (with the exception of barium salt of lanolin fatty acid) and an amine salt of lanolin fatty acid;

(E) esterified lanolin fatty acid; and

(F) at least one kind of fatty acid ester selected from a group consisting of an alkaline metal salt of fatty acid, an alkaline earth-metal salt of fatty acid (with the exception of barium salt of fatty acid) and an amine salt of fatty acid.
The rust preventive oil composition according to claim 5, wherein the sum of the contents of said compounds (A) to (F) is 20 to 500 parts by mass per 100 parts by mass of said sulfonate.
The rust preventive oil composition according to claim 5, wherein the sum of the contents of said compounds (A), (C), (D) and (E) is 10% by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein the kinematic viscosity at 40° C is 7 to 400mm²/s.
The rust preventive oil composition according to claim 1, wherein the content of the compound having a carbon atom number of 14 or less in said base oil is 20% by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein the content of the aromatic component in said base oil is 50% by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein the content of the compound having a carbon atom number of 10 or less in said base oil is 20% by mass or less based on the total weight of the composition.
The rust preventive oil composition according to claim 1, wherein the total base number is 1 to 20mgKOH/g, and the content of said sulfonate and said total base number satisfy the condition represented by the following formula (2): TBN/Cs ≦3 (wherein C_s is the content [% by mass] of the sulfonate and TBN is the total base number [mgKOH/g]).