Technical Field
[0001] 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
[0002] 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.
[0003] GB 2157310 A relates to coating compositions which protect metal sheets against the formation
of rust and which act as lubricants which make easier the shaping of the sheets, for
example, by stamping, which composition comprises a blend of:
a) mixture A containing 65 to 95% by weight of a mineral oil having a viscosity in
the range of from 15x10-6 to 30x10-6 m2/sec at 40°C, and 5 to 35% by weight of a basic calcium salt of an alkylarylsulphonic
acid in admixture with another anti-corrosive compound selected from petrolatum oxidates,
calcium salts of petrolatum oxidates and calcium salts of mahogany sulphonic acids:
and
b) mixture B, in an amount of from 0.75 to 5%, by weight based on the weight of mixture
A, said mixture B containing a saturated higher fatty acid having from 12 to 18 carbon
atoms, a saturated non-ionic surface-active compound and a heat stable, anti-oxidizing
phenolic compound.
Disclosure of the Invention
[0004] 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.
[0005] 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.
[0006] 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.
[0007] 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.
[0008] 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.
[0009] 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.
[0010] Namely, a rust preventive oil composition, wherein a calcium 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 R
1 represents an alkyl group having 1 to 24 carbon atoms, R
2 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, and 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:
(D) at least one kind of salt of lanolin fatty acid selected from a group consisting
of an alkaline metal salt of lanolin fatty acid, an alkaline earth-metal salt of lanolin
fatty acid and an amine salt of lanolin fatty acid, with the exception of barium salt
of lanolin fatty acid.
[0011] 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.
[0012] 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.
[0013] 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.
[0014] 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.
[0015] 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.
[0016] 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.
[0017] Moreover, the rust preventive oil compositions according to the present invention
have a kinematic viscosity of preferably 7 to 400mm
2/s at 40° C.
[0018] 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.
[0019] 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.
[0020] 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.
[0021] 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):

(Wherein C
s represents a content [% by mass] of sulfonate, and TBN represents the total base
number [mgKOH/g].)
Brief Description of the Drawings
[0022] 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
[0023] The present invention will be described in more details below.
[0024] A rust preventive oil composition, wherein a calcium 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 R
1 represents an alkyl group having 1 to 24 carbon atoms, R
2 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, and
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:
(D) at least one kind of salt of lanolin fatty acid selected from a group consisting
of an alkaline metal salt of lanolin fatty acid, an alkaline earth-metal salt of lanolin
fatty acid and an amine salt of lanolin fatty acid, with the exception of barium salt
of lanolin fatty acid.
[0025] 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.
[0026] 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.
[0027] 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), dipentehylamine (includes all isomers), tripenteriylamine (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.
[0028] 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-alkyltetrapropylenepentamine,
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.
[0029] 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.
[0030] 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.
[0031] 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.
[0032] 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.
[0033] 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.
[0034] 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.
[0035] 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.
[0036] 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.
[0037] 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.
[0038] 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.
[0039] 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.
[0040] 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)sulfonateand borateperbasic(ultrabasic)sulfonate,
the content of sulfonate is that of neutral (normal salt) sulfonate excluding the
basic salt excessively contained.
[0041] 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).
[0042] 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.
[0043] 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 PROPOSED METHOD AK/81 Determination
of chlorine - Microcoulometery oxidative method". Detection limit of each element
by the above-mentioned measurement is generally 1ppm by mass.
[0044] 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 R
1 represents an alkyl group having 1 to 24 carbon atoms, R
2 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.
[0045] The compounds which have the group represented by the above-mentioned general formula
(1) include the following general formula (3) to (5):
A - H (3)
A - R
3 (4)

wherein A represents a group represented by general formula (1), R
3 represents a hydrocarbon group having 1 to 24 carbon atoms or an acyl group having
1 to 24 carbon atoms.
[0046] 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.
[0047] 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.
[0048] 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.
[0049] 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.
[0050] Furthermore, among α -olefin having 5 to 12 carbon atoms, 1-octene, 1-decene, 1-dodecen
and mixtures thereof are more preferable.
[0051] The above-mentioned polyolefin can be obtained by conventionally well-known processes.
[0052] 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.
[0053] 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.
[0054] 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.
[0055] 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.
[0056] 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.
[0057] 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.
[0058] 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.
[0059] 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.
[0060] The low viscosity oil referred to herein is the base oil (hereinafter, occasionally
described as "solvent") having a kinematic viscosity of 0.5 to 6mm
2/s at 40° C, on the other hand, the high viscosity oil denotes the base oil which
has a kinematic viscosity exceeding 6mm
2/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.
[0061] 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.
[0062] 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
6mm
2/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 6mm
2/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 6mm
2/s at 40°C without using the base oil having a kinematic viscosity of not more than
6mm
2/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 7mm
2/s at 40°C. When the content of the base oil having a kinematic viscosity of not more
than 6mm
2/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.
[0063] Furthermore, a kinematic viscosity of the high viscosity base oil at 40°C is not
less than 6mm
2/s as described above, preferably not less than 7mm
2/s in terms of the compatibility with organic materials, more preferably not less
than 10mm
2/s, particularly preferably not less than 15mm
2/s, more particularly preferably not less than 20mm
2/s, increasingly preferably not less than 40mm
2/s, especially preferably not less than 100mm
2/s, and most preferably not less than 400mm
2/s. Furthermore, said kinematic viscosity is preferably not less than 2000mm
2/s in terms of handling, more preferably not more than 1500mm
2/s, particularly preferably not more than 1000mm
2/s, and more particularly preferably not more than 750mm
2/s.
[0064] 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.
[0065] 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.
[0066] 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.
[0067] 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.
[0068] 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.
[0069] 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.
[0070] 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 6mm
2/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.
[0071] 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
6mm
2/s and less than 15mm
2/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 6mm
2/s and less than 15mm
2/s at 40° C.
[0072] 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
6mm
2/s and less than 20mm
2/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 6mm
2/s and less than 20mm
2/s at 40°C.
[0073] 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.
[0074] 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 6mm
2/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.
[0075] The kinematic viscosity at 40°C of said solvent is not less than 0.5mm
2/s as described above in terms of work environment, preferably not less than 0.7mm
2/s, and more preferably not less than 1mm
2/s. Furthermore, said kinematic viscosity is not more than 6mm
2/s as described above in terms of drying characteristics, preferably not more than
4mm
2/s, and more preferably not more than 2.5mm
2/s.
[0076] 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
[0077] 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.
[0078] 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.
[0079] 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.
[0080] 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.
[0081] 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.
[0082] 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.
[0083] 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 6mm
2/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.
[0084] 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).
[0085] 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.
[0086] 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.
[0087] 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
[0088] 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, trimethylolpropanemonotetradecanoate
(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.
[0089] 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.
[0090] 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.
[0091] 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.
[0092] 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.
[0093] 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.
[0094] 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).
[0095] 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).
[0096] 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.
[0097] 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).
[0098] 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.
[0099] 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.
[0100] 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.
[0101] 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.
[0102] 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.
[0103] 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].
[0104] 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):

(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 1000mm
2/s. If the kinematic viscosity of the rust preventive oil composition at 40° C is
less than 1.5mm
2/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 2mm
2/s or more, further preferred is 2.5mm
2/s or more, and particularly preferred is 3mm
2/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 7mm
2/s or more, more preferred is 10mm
2/s and further preferred is 15mm
2/s. On the other hand, if the kinematic viscosity at 40 ° C exceeds 1000mm
2/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 500mm
2/s or less, further preferred is 100mm
2/s or less, particularly preferred is 40mm
2/s or less, and mostly preferred is 20mm
2/s or less.
[0105] 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 10mm
2/s or less, more preferred is 6mm
2/s or less, further preferred is 4mm
2/s or less, and particularly preferred is 3mm
2/s or less.
[0106] 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.
[0107] 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.
[0108] In addition, when the rust preventive oil composition according to the present invention
has a relatively high kinematic viscosity (for example, 400mm
2/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.
[0109] 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/m
2, more preferred is 0.2 to 10g/m
2, further preferred is 0.3 to 5g/m
2 and particularly preferred is 0.3 to 3g/m
2. 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.
[0110] 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.
[0111] 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 6mm
2/s or more at 40 ° C may be replenished to maintain the cleaning performance of the
rust preventive oil composition.
[0112] 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.
[0113] 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).
[0114] 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.
[0115] 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.
[0116] 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.
[0117] 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.
[0118] 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.
[0119] 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.
[0120] 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/m
2, more preferably is 0.2 to 10g/m
2 and further preferably is 0.3 to 5g/m
2. 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.
[0121] 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.
[0122] 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]
[0123] 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
[0124] 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
[0125] Base oil 1: mineral oil (kinematic viscosity at 40° C: 6.5mm
2/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%)
[0126] Base oil 2: mineral oil (kinematic viscosity at 40°C: 22mm
2/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%)
[0127] Base oil 3: mineral oil (kinematic viscosity at 40° C: 100mm
2/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%)
[0128] Base oil 4: mineral oil (kinematic viscosity at 40° C: 400mm
2/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%)
[0129] Base oil 5: mineral oil (kinematic viscosity at 40 ° C: 2mm
2/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
[0130]
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%)
[0131] In addition, the carrier oils in the aforementioned S1 to S4 are mineral oils with
kinematic viscosity of about 20mm
2/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)
[0132]
A1: trimethylolpropanemonooleate
A2: sorbitanmonooleate
A3: sorbitanmonoisostearate
Compound (B)
[0133]
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)
[0134]
C1: ester of paraffin oxide (total acid value: 30mgKOH/g, total base number: 0.2mgKOH/g,
saponification value: 135mgKOH/g)
Compound (D)
[0135]
D1: calcium salt of lanolin fatty acid (total acid value: 2.5mgKOH/g, total base number:
11mgKOH/g, saponification value: 120mgKOH/g)
Compound (E)
[0136]
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
[0137]
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)
[0138] 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)
[0139] 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/m
2. 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.
The results are shown in Table 1.
(Cylindrical deep drawing test)
[0140] 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/m
2, 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)
[0141] 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.
The results are shown in Table 1.
(Compatibility test 2 between rust preventive oil composition and resin material)
[0142] 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)
[0143] 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
The obtained results are shown in Table 1.

[0144] 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
[0145] 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
[0146] Base oil 6: mineral oil (kinematic viscosity at 40° C: 6.5mm
2/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%)
[0147] Base oil 7: mineral oil (kinematic viscosity at 40° C: 22mm
2/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%)
[0148] Base oil 8: mineral oil (kinematic viscosity at 40° C: 100mm
2/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%)
[0149] Base oil 9: mineral oil (kinematic viscosity at 40° C: 400mm
2/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%)
[0150] Base oil 10: mineral oil (kinematic viscosity at 40° C: 2mm
2/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%)
[0151] Base oil 11: mineral oil (kinematic viscosity at 40° C: 2mm
2/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%)
[0152] Base oil 12: oligomer of 1-decene (kinematic viscosity at 40° C: 100mm
2/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
[0153]
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.)
[0154] In addition, the carrier oils in the aforementioned S5 to S10 are mineral oils with
kinematic viscosity of about 20mm
2/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)
[0155]
A4: trimethylolpropanemonooleate
A5: sorbitanmonooleate
A6: sorbitanmonoisostearate
A7: glycerinmonooleate
Compound (B)
[0156]
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)
[0157]
C2: ester of paraffin oxide (total acid value: 30mgKOH/g, total base number: 0.2mgKOH/g,
saponification value: 135mgKOH/g)
Compound (D)
[0158]
D2: calcium salt of lanolin fatty acid (total acid value: 2.5mgKOH/g, total base number:
11mgKOH/g, saponification value: 120mgKOH/g)
Compound (E)
[0159]
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
[0160]
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)

[0161] 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)
[0162] 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/m
2. 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.
The results are shown in Table 3.
(Degreasing property test)
[0163] 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/m
2. 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.
[0164] 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
The obtained results are shown in Table 3.
(Detergency test)
[0165] 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:

and the following standards:
A: 95% or more
B: 95 to 80%
C: 80% or less
The obtained results are shown in Table 3.
(Cylindrical deep drawing test).
[0166] 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/m
2, 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
The obtained results are shown in Table 3.
(Storage stability test)
[0167] 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
The obtained results are shown in Table 3.
Table 3
|
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 |
* not according to the invention |
[0168] 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
[0169] 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
4-5 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.
[0170] 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.
[0171] 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.
[0172] Further, compatibility test 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.
Table 4
|
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 [mqKOH/g] |
3.80 |
3.80 |
3.26 |
3.31. |
3.31 |
3.58 |
TBN/Cs |
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 |
5 |
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 not according to the invention |
A |
A |
A |
A |
A |
A |
* not according to the invention |

[0173] 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
[0174] 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.