DESCRIPTION
Title of Invention: RUST PREVENTIVE OIL COMPOSITION
5 Technical Field
[0001] The present invention relates to a rust preventive oil
composition.
Background Art
10 [0002] In many cases, metal members comprising iron as a main
component are manufactured through working such as cutting and
pressing. During manufacturing or when shipping as products, a rust
preventive oil is applied for the purpose of preventing discoloration
3
called rust or stain. The main purpose of the use yf the rust preventive
15 oil is to form a film on the metal surface to block oxygen, and thereby
preventing oxidation of metal, that is, rust.
[0003] However, if a chloride or water is attached to the metal surface,
it becomes difficult for the rust preventive oil to suficiently exert its
effect. For example, in the case where a metal working oil containing
20 a chlorine extreme-pressure agent is used for a preceding process of
working, in order to obtain a sufficient rust preventive property, the
chloride that is a rust generation factor needs to be removed in advance.
Thus, in many cases, after washing and removing the chloride with a
finger print remover type rust preventive oil called NP-0 specified by
25 JIS K 2246, a rust preventive oil is used.
[0004] Furthermore, when a water-soluble working oil is used, moisture
is considered to be attached. Also in this case, moisture needs to be
removed before using a rust preventive oil as is the case in chlorine.
An oil solution whose water displacement property is enhanced is
sometimes used to remove water. The water displacement property
5 herein means performance by which an additive agent in the oil solution
penetrates between water and metal, and water is removed from the
metal surface. Oil solutions corresponding to NP-3-1 and NP-3-2
classified by JIS K 2246 also have a water displacement property, but
this relates to a rust preventive property when moisture is mixed in a
10 rust preventive oil and does not specify performance capable of
removing water from a metal surface (see Non Patent Literature 1).
Hereinafter, in order to avoid confusion, performance to remove water
from a metal surface is called a "water removal property", and is
7
distinguished from the water displacement property specified by JIS.
15 [0005] As described above, in order to carry out rust preventive
treatment for metal to which moisture is attached, firstly, moisture is
removed by washing with an oil solution which excels in water removal
property, and furthermore, a rust preventive oil needs to be applied.
However, in many cases, the two processes, water removal and then rust
20 prevention, cannot be carried out due to causes such as productivity and
cost, and an oil solution capable of unifying treatment is required.
However, it is very much a situation that an oil solution having a water
removal property lacks a rust preventive property and a sufficient rust
preventive property cannot be obtained by applying a rust preventive oil
25 without a water removal process (for example, see Patent Literatures 1
and 2).
[0006] In order to unify processes, it is necessary to impart a suff~cient
rust preventive property (rust preventive performance) to an oil solution
(washing agent) having water removal performance. However, a
low-viscosity oil solution is advantageous for rapid water removal,
5 whereas an applied oil film needs to have high viscosity for a sufficient
rust preventive property. When viscosity is made to be intermediate so
as to achieve both of the two kids of performance, either performance
may be insufficient.
10 Citation List
Patent Literature
[0007] Patent Literature 1: Japanese Patent Application Laid-Open No.
2001-89795
Patent Literature 2: Japanese Patent Application Laid-Open No.
15 2001-89798
Non Patent Literature
[0008] Non Patent Literature 1: Junichi Shibata, ENEOS Technical
Review, vol. 50, No. 3, page 45
20 Summary of Invention
Technical Problem
[0009] The present invention has been made in view of these
circumstances, and it is an object of the present invention to provide a
rust preventive oil composition having performance to remove water
25 attached to various parts after metal working and metal parts, such as
steel sheets, bearings, steel balls, and guide rails, and capable of
obtaining a sufficient rust preventive property.
Solution to Problem
[0010] The present inventors made extensive research for the solution
5 of the above-described problem, and found that both a water removal
property and a rust preventive property can be achieved by combining a
specific base oil and a specific additive agent to complete the present
invention.
[0011] That is, a rust preventive oil composition of the present
10 invention contains:
a first mineral oil that is a mineral oil having a kinematic
viscosity at 40°C of 6 mm21s or less,
a second mineral oil that is a mineral oil having a kinematic
viscosity at 40°C of 250 mm2/s or more,
a fatty acid amine salt,
an ester, and
one or more rust preventive agents selected &om the group
consisting of a sarcosine-type compound, a nonionic surfactant, a
sulfonic acid salt, an amine, a carboxylic acid, a fatty acid amine salt, a
20 carboxylic acid salt, a paraffin wax, an oxidized wax salt, and a boron
compound.
[0012] The rust preventive oil composition of the present invention
further preferably contains a third mineral oil that is a mineral oil having
a kinematic viscosity at 40°C of 10 mm2/s or more and 120 mm21s or
25 less.
[0013] Moreover, an aromatic component content of the
above-described first mineral oil is preferably 3 mass% or less based on
a total amount of the fxst mineral oil.
[0014] Furthermore, the rust preventive oil composition of the present
invention preferably satisfies a requirement that time during which
5 Grade A of rust generation (rust generation of 0%) is maintained in a
neutral salt water spray test specified by JIS K 2246 "Rust preventive
oils" is 16 hours or more.
Advantageous Effects of Invention
10 [0015] As described above, according to the present invention, a rust
preventive oil composition capable of obtaining excellent water removal
performance, and furthermore, suppressing rust generation for long
periods of time is provided.
15 Description of Embodiments
[0016] Hereinafter, a preferred embodiment of the present invention
will be described in detail.
[0017] A rust preventive oil composition according to the embodiment
of the present invention contains:
20 (A-1) a mineral oil having a kinematic viscosity at 40°C of 6
mm2/s or less (first mineral oil),
(A-2) a mineral oil having a kinematic viscosity at 40°C of 250
mm2/s or more (second mineral oil),
(B) a fatty acid amine salt, - - -
25 (C) an ester, and
(D) one or more rust preventive agents selected &om the group
consisting of a sarcosine-type compound, a nonionic surfactant, a
sulfonic acid salt, an amine, a carboxylic acid, a fatty acid amine salt, a
carboxylic acid salt, a paraffin wax, an oxidized wax salt, and a boron
compound.
5 [0018] The (A-1) mineral oil having a kinematic viscosity at 40°C of 6
mm2/s or less (hereinafter, also referred to as low-viscosity base oil) and
the (A-2) mineral oil having a kinematic viscosity at 40°C of 250 mm2/s
or more (hereinafter, also referred to as high-viscosity base oil) are
constituents of a base oil. Hereinafter, an entire mixture of mineral oils
10 containing (A-1) and (A-2) components is referred to as an (A)
component or a mineral base oil.
[0019] The kinematic viscosity at 40°C of the low-viscosity base oil is
6.0 mm2/s or less, preferably 5.0 d s or less, more preferably 4.0
mm2/s or less, and hrther preferably 3.0 mm2/s or less. When the
15 kinematic viscosity exceeds the above-described upper limit, it becomes
difficult to obtain a sufficient rust preventive property. Moreover, the
kinematic viscosity at 40°C of the low-viscosity base oil is preferably
0.5 mm2/s or more, more preferably 1.0 mm2/s or more, and further
preferably 1.5 mm2/s or more. When the kinematic viscosity is less
20 than the above-described lower limit, handleability tends to deteriorate.
[0020] The kinematic viscosity at 40°C of the high-viscosity base oil is
250 mm2/s or more, preferably 300 mm2/s or more, more preferably 400
mm2/s or more, and further preferably 450 mm2/s or more. When the
kinematic viscosity-is less-than the above-described lower limit, a rust
25 preventive property deteriorates. Moreover, the kinematic viscosity at
40°C of the high-viscosity base oil is preferably 700 mm2/s or less,
more preferably 650 mm2/s or less, and further preferably 600 mm2/s or
less. When the kinematic viscosity exceeds the above-described upper
limit, stability of the rust preventive oil composition tends to become
insufficient.
5 [0021] Examples of each of the (A-1) component and the (A-2)
component include those having the above-described kinematic
viscosity at 40°C among paraffinic or naphthenic mineral oils and the
like, which are obtainable by arbitrarily combining and applying one or
two or more refining means such as solvent deasphalting, solvent
10 extraction, hydrocracking, solvent dewaxing, catalytic dewaxing,
hydrorefining, sulfuric acid washing, and clay treatment, with respect to
lubricant oil distillate obtained by atmospheric distillation and vacuum
distillation of crude oil. ' [0022] Moreover, the aromatic component contained '1 in the
15 low-viscosity base oil is preferably 3 mass% or less. When the
aromatic content in the low-viscosity base oil is 3 mass% or less, the
work environment may be improved, for example, a reduction in odor
and skin irritation, and furthermore, water separating performance when
a large amount of water is mixed in the rust preventive oil composition
20 may be improved, resulting in an effect of extending life of an oil
solution even in the case of removing a large amount of water. The
aromatic component means a value measured in conformity with
Fluorescent indicator adsorption method of JIS K 2536-1996 "Liquid
petroleum products-Testing method of components".
25 [0023] The content of the low-viscosity base oil is preferably 30 mass%
or more, more preferably 40 mass% or more, and further preferably 50
mass% or more, and preferably 90 mass% or less, more preferably 85
mass% or less, and further preferably 80 mass% or less, based on the
total amount of the composition. When the content of the
low-viscosity base oil is less than the above-described lower limit, a rust
5 preventive property tends to become insufficient, and even when it
exceeds the above-described upper limit, a rust preventive property
tends to become insufficient.
LO0241 The content of the high-viscosity base oil is preferably 1 mass%
or more, more preferably 2 mass% or more, and further preferably 3
10 mass% or more, and preferably 35 mass% or less, more preferably 25
mass% or less, and further preferably 20 mass% or less, based on the
total amount of the composition. When the content of the
high-viscosity base oil is less than the above-described lower limit, a
rust prever?$ve property tends to become insufficient, and when it
15 exceeds the above-described upper limit, a water removal property tends
to become insufficient.
[0025] The ratio of the high-viscosity base oil to the total of the
low-viscosity base oil and the high-viscosity base oil is preferably 1
mass% or more, more preferably 2 mass% or more, and further
20 preferably 3 mass% or more, and preferably 45 mass% or less, more
preferably 35 mass% or less, and further preferably 25 mass% or less.
When the ~atio of the high-viscosity base oil is less than the
above-described lower limit, a rust preventive property tends to
- decrease, and when it exceeds the above-described upper limit, a water
25 removal property tends to decrease.
[0026] In addition to the above-described low-viscosity base oil and
high-viscosity base oil, the (A) component can hrther contain (A-3) a
mineral oil having a kinematic viscosity at 40°C of 10 rnrn2/s or more
and 120 mm2/s or less (hereinafter, also referred to as medium-viscosity
base oil). By the combination of the (A-1) to (A-3) components, both
5 a water removal property and a rust preventive property can be achieved
at a higher level.
[0027] The kinematic viscosity at 40°C of the medium-viscosity base
oil is 10 rnm2/s or more, preferably 15 mm2/s or more, more preferably
18 mm2/s or more, and further preferably 20 mm2/s or more, and 120
10 mm2/s or less, preferably 100 mm2/s or less, more preferably 80 mm2/s
or less, and further preferably 70 mm2/s or less. When the kinematic
viscosity is less than the above-described lower limit, a rust preventive
property improving effect by the use of the medium-viscosity base oil
tends to become insu $ 4cient, and when it exceeds the above-described
15 upper limit, a water removal property improving effect by the use of the
medium-viscosity base oil tends to become insufficient.
[0028] The content of the medium-viscosity base oil is preferably 5
mass% or more, more preferably 8 mass% or more, and further
preferably 10 mass% or more, and preferably 30 mass% or less, more
20 preferably 25 mass% or less, and further preferably 20 mass% or less,
based on the total amount of the composition. When the content is
within the above-described range, a rust preventive property improving
effect and a water removal property improving effect by the addition of
. the medium-viscosity base oil may be-effectively obtainable.
25 [0029] Moreover, in the case of using the medium-viscosity base oil,
the ratio of the high-viscosity base oil to the total of the low-viscosity
base oil, the medium-viscosity base oil, and the high-viscosity base oil
is preferably 1 mass% or more, more preferably 2 mass% or more, and
further preferably 3 mass% or more, and preferably 45 mass% or less,
more preferably 35 mass% or less, and further preferably 25 mass% or
5 less. When the ratio of the high-viscosity base oil is less than the
above-described lower limit, a rust preventive property tends to
decrease, and when it exceeds the above-described upper limit, a water
removal property tends to decrease.
[0030] The content of the (A) component (the content of the entire base
10 oil containing the low-viscosity mineral oil, the high-viscosity mineral
oil, and the medium-viscosity base oil used as necessary) in the present
embodiment is preferably 60 mass% or more, more preferably 70
mass% or more, and further preferably 75 mass% or more, and
4 preferably 95 mass% or less, more prefeqably 90 mass% or less, and
15 further preferably 85 mass% or less, based on the total amount of the
composition.
[0031] Fatty acids which constitute the fatty acid amine salt as the (B)
component may be saturated fatty acids or unsaturated fatty acids, and
may be straight-chain fatty acids or branched fatty acids. Moreover,
20 the number of carbon atoms thereof is not particularly limited, but those
having 8 to 18 carbon atoms are preferable. Examples of the amine
include monoamines, polyamines, and akanolamines. Specifically,
examples of the above-described monoamines include alkyl amines,
- such as monomethylamine, dimethylamine, trimethylamine,
25 monoethylamine, diethylamine, triethylamine, monopropylamine (all
isomers), dipropylamine (all isomers), tripropylamine (all isomers),
monobutylamine (all isomers), dibutylamine (all isomers), tributylamine
(all isomers), monopentylamine (all isomers), dipentylamine (all
isomers), tripentylamine (all isomers), monohexylamine (all isomers),
dihexylamine (all isomers), monoheptylamine (all isomers),
5 diheptylamine (all isomers), monooctylamine (all isomers),
dioctylamine (all isomers), monononylamine (all isomers),
monodecylamine (all isomers), monoundecyl (all isomers),
monododecylamine (all isomers), monotridecylamine (all isomers),
monotetradecylamine (all isomers), monopentadecylamine (all isomers),
10 monohexadecylamine (all isomers), monoheptadecylamine (all isomers),
monooctadecylamine (all isomers), monononadecylamine (all isomers),
monoicosylamine (all isomers), monohenicosylamine (all isomers),
monodocosylamine (all isomers), monotricosylamine (all isomers),
dimethyl(ethyl)amine, dimethyl(propy1)amine (all isomers),
15 dimethyl(buty1)amine (all isomers), dimethyl(penty1)amine (all isomers),
dimethyl(hexy1)amine (all isomers), dimethyl(hepty1)amine (all
isomers), dimethyl(octy1)amine (all isomers), dimethyl(nony1)amine (all
isomers), dimethyl(decy1)amine (all isomers), dimethyl(undecy1)amine
(all isomers), dimethyl(dodecy1)amine (all isomers),
20 dimethyl(tridecy1)amine (all isomers), dimethyl(tetradecy1)amine (all
isomers), dimethyl(pentadecy1)amine (all isomers),
dimethyl(hexadecy1)amine (all isomers), dimethyl(heptadecy1)amine
(all isomers), dimethyl(octadecy1)amine (all isomers),
dimethyl(nonadecy1)amine (all isomers), dimeihyl(icosy1)amine (all
25 isomers), dimethyl(henicosy1)amine (all isomers), and
dimethyl(tricosy1)amine (all isomers); alkenyl amineq such as
monovinylamine, divinylamine, trivinylamine, monopropenylamine (all
isomers), dipropenylamine (all isomers), tripropenylamine (all isomers),
monobutenylamine (all isomers), dibutenylamine (all isomers),
tributenylamine (all isomers), monopentenylamine (all isomers),
5 dipentenylamine (all isomers), tripentenylamine (all isomers),
monohexenylamine (all isomers), dihexenylamine (all isomers),
monoheptenylamine (all isomers), diheptenylamine (all isomers),
monooctenylamine (all isomers), dioctenylamine (all isomers),
monononenylamine (all isomers), monodecenylamine (all isomers),
10 monoundecenyl (all isomers), monododecenylamine (all isomers),
monotridecenylamine (all isomers), monotetradecenylamine (all
isomers), monopentadecenylamine (all isomers),
monohexadecenylamine (all isomers), monoheptadecenylamine (all
isomers), monooctadecenylamine (all isomers), monononadecenylamine J
15 (all isomers), monoicosenylamine (all isomers), monohenicosenylamine
(all isomers), monodocosenylamine (all isomers), and
monotricosenylamine (all isomers); monoamines having an alkyl group
and an alkenyl group, such as dimethyl(vinyl)amine,
dimethyl(propeny1)amine (all isomers), dimethyl(buteny1)amine (all
20 isomers), dimethyl(penteny1)amine (all isomers),
dimethyl(hexeny1)amine (all isomers), dimethyl(hepteny1)amine (all
isomers), dimethyl(octeny1)amine (all isomers),
dimethyl(noneny1)amine (all isomers), dimethyl(deceny1)amine (all
isomers), dimethyl(undeceny1)amine (all isomers),
25 dimethyl(dodecenyl)amine (all isomers), dimethyl(trideceny1)amine (all
isomers), dimethyl(tetradeceny1)amine (all isomers),
dimethyl(pentadeceny 1)amine (all isomers),
dimethyl(hexadeceny1)amine (all isomers),
dimethyl(heptadeceny1)amine (all isomers),
dimethyl(octadeceny1)amine (all isomers), dimethyl(nonadecenyl)amine
5 (all isomers), dimethyl(icoseny1)amine (all isomers),
dimethyl(henicosenyl)amine (all isomers), and
dimethyl(tricoseny1)amine (all isomers); aromatic-substituted
alkylamines such as monobenzylamine, (1-phenylethyl)amine,
(2-phenylethy1)amine (another name: monophenethylamine),
10 dibenzylamine, bis(1-phenylethyl)amine, and
bis(2-phenylethy1ene)amine (another name: diphenethylamine);
cycloalkylamines having 5 to 16 carbon atoms, such as
monocyclopentylamine, dicyclopentylamine, tricyclopentylamine,
monocyclohexylamine, dicyclohexylamine, monocycloheptylamine,
15 and dicycloheptylamine; monoamines having an alkyl group and a
cycloalkyl group, such as dimethyl(cyclopentyl)amine,
dimethyl(cyclohexyl)amine, and dimethyl(cyclohepty1)amine; and
allcylcycloalkylamines such as (methyl cyclopenty1)amine (all
substituted isomers), bis(methy1 cyclopenty1)amine (all substituted
20 isomers), (dimethyl cyclopenty1)amine (all substituted isomers),
bis(dimethy1 cyclopenty1)amine (all substituted isomers), (ethyl
cyclopenty1)amine (all substituted isomers), bis(ethy1 cyclopenty1)amine
(all substituted isomers), (methyl ethyl cyclopenty1)amine (all
substituted isomers), bis(methy1 ethyl cyclopenty1)amine (all substituted
25 isomers), (diethyl cyclopenty1)amine (all substituted isomers), (methyl
cyc1ohexyl)amine (all substituted isomers), bis(methy1
cyclohexy1)amine (all substituted isomers), (dimethyl cyclohexy1)amine
(all substituted isomers), bis(dimethy1 cyclohexy1)amine (all substituted
isomers), (ethyl cyclohexy1)amine (all substituted isomers), bis(ethy1
cyclohexy1)amine (all substituted isomers), (methyl ethyl
5 cyclohexy1)amine (all substituted isomers), (diethyl cyc1ohexyl)amine
(all substituted isomers), (methyl cyclohepty1)amine (all substituted
isomers), bis(methy1 cyclohepty1)amine (all substituted isomers),
(dimethyl cyclohepty1)amine (all substituted isomers), (ethyl
cyclohepty1)amine (all substituted isomers), (methyl ethyl
10 cyclohepty1)amine (all substituted isomers), and (diethyl
cyclohepty1)amine (all substituted isomers). Moreover, the
monoamines include monoamines derived from oils and fats, which are
typified by beef tallow amine and the like. Specifically, examples of
the above-described polyamines include alkylene polyamines, such as
15 ethylene diamine, diethylene triamine, triethylene tetramine,
tetraethylene pentamine, pentaethylene hexamine, propylene diamine,
dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine,
pentapropylene hexamine, butylene diamine, dibutylene triamine,
tributylene tetramine, tetrabutylene pentamine, and pentabutylene
20 hexamine; N-alkylethylenediamines, such as N-methyl ethylene
diamine, N-ethyl ethylene diamine, N-propyl ethylene diamine (all
isomers), N-butyl ethylene diamine (all isomers), N-pentyl ethylene
diamine (all isomers), N-hexyl ethylene diamine (all isomers), N-heptyl
-.- C
ethylene diamine (all isomers), N-octyl ethylene diamine (all isomers),
25 N-nonyl ethylene diamine (all isomers), N-decyl ethylene diamine (all
isomers), N-undecyl ethylene diamine (all isomers), N-dodecyl ethylene
diamine (all isomers), N-tridecyl ethylene diamine (all isomers),
N-tetradecyl ethylene diamine (all isomers), N-pentadecyl ethylene
diamine (all isomers), N-hexadecyl ethylene diamine (all isomers),
N-heptadecyl ethylene diamine (all isomers), N-octadecyl ethylene
5 diamine (all isomers), N-nonadecyl ethylene diamine (all isomers),
N-icosyl ethylene diarnine (all isomers), N-henicosyl ethylene diamine
(all isomers), N-docosyl ethylene diamine (all isomers), and N-tricosyl
ethylene diamine (all isomers); N-alkenylethylenediamines such as
N-vinyl ethylene diamine, N-propenyl ethylene diarnine (all isomers),
10 N-butenyl ethylene diamine (all isomers), N-pentenyl ethylene diamine
(all isomers), N-hexenyl ethylene diamine (all isomers), N-heptenyl
ethylene diamine (all isomers), N-octenyl ethylene diamine (all isomers),
N-nonenyl ethylene diamine (all isomers), N-decenyl ethylene diamine
(all isomers), N-undecenyl ethylene diamine (all isomers), N-dodecenyl
15 ethylene diamine (all isomers), N-tridecenyl ethylene diamine (all
isomers), N-tetradecenyl ethylene diamine (all isomers),
N-pentadecenyl ethylene diamine (all isomers), N-hexadecenyl ethylene
diamine (all isomers), N-heptadecenyl ethylene diamine (all isomers),
N-octadecenyl ethylene diamine (all isomers), N-nonadecenyl ethylene
20 diamine (all isomers), N-icosenyl ethylene diamine (all isomers),
N-henicosenyl ethylene diamine (all isomers), N-docosenyl ethylene
diamine (all isomers), and N-tricosenyl ethylene diamine (all isomers);
and N-alkyl or N-alkenylalkylenepolyamines such as N-alkyl diethylene
triamine, N-alkenyl diethylene triamine,.N-alkyl triethylene tetramine, -
25 N-alkenyl triethylene tetramine, N-alkyl tetraethylene pentamine,
N-alkenyl tetraethylene pentamine, N-alkyl pentaethylene hexamine,
N-alkenyl pentaethylene hexamine, N-alkyl propylene diamine,
N-alkenyl propylene diamine, N-alkyl dipropylene triamine, N-alkenyl
dipropylene triamine, N-alkyl tripropylene tetramine, N-alkenyl
tripropylene tetramine, N-alkyl tetrapropylene pentamine, N-alkenyl
5 tetrapropylene pentarnine, N-alkyl pentapropylene hexamine, N-alkenyl
pentapropylene hexamine, N-alkyl butylene diamine, N-alkenyl
butylene diamine, N-alkyl dibutylene triamine, N-alkenyl dibutylene
triamine, N-alkyl tributylene tetramine, N-alkenyl tributylene tetramine,
N-alkyl tetrabutylene pentamine, N-alkenyl tetrabutylene pentamine,
10 N-alkyl pentabutylene hexamine, and N-alkenyl pentabutylene
hexamine. Moreover, the polyamines include polyamines derived
fiom oils and fats, which are typified by beef tallow polyamine and the
like. Specifically, examples of the above-described alkanolamines
include monomethanolamine, dimethanolamine, trimethanolamine,
15 monoethanolamine, diethanolamine, triethanolamine,
mono(n-propanol)amine, di(n-propanol)amine, tri(n-propanol)amine,
monoisopropanolamine, diisopropanolamine, triisopropanolamine,
monobutanolamine (all isomers), dibutanolamine (all isomers),
tributanolamine (all isomers), monopentanolamine (all isomers),
20 dipentanolamine (all isomers), tripentanolamine (all isomers),
monohexanolamine (all isomers), dihexanolamine (all isomers),
monoheptanolamine (all isomers), diheptanolamine (all isomers),
monooctanolamine (all isomers), monononanolamine (all isomers),
monodecanolamine (all isomers), monoundecanolamine (all isomers),
25 monododecanolamine (all isomers), monotridecanolamine (all isomers),
monotetradecanolamine (all isomers), monopentadecanolamine (all
isomers), monohexadecanolamine (all isomers), diethyl monoethanol
amine, diethyl monopropanol amine (all isomers), diethyl monobutanol
amine (all isomers), diethyl monopentanol amine (all isomers), dipropyl
monoethanol amine (all isomers), dipropyl monopropanol amine (all
isomers), dipropyl monobutanol amine (all isomers), dipropyl
monopentanol amine (all isomers), dibutyl monoethanol amine (all
isomers), dibutyl monopropanol amine (all isomers), dibutyl
monobutanol amine (all isomers), dibutyl monopentanol amine (all
isomers), monoethyl diethanol amine, monoethyl dipropanol amine (all
isomers), monoethyl dibutanol amine (all isomers), monoethyl
dipentanol amine (all isomers), monopropyl diethanol amine (all
isomers), monopropyl dipropanol amine (all isomers), monopropyl
dibutanol amine (all isomers), monopropyl dipentanol amine (all
isomers), monobutyl diethanol amine (all isomers), monobutyl
dipropanol amine (all isomers), monobutyl dibutanol amine (all
isomers), and monobutyl dipentanol amine (all isomers). Among the
above-described amines, monoamines are preferable because of little
impact on a refrigerated system, and among monoamines, in particular,
alkylamines, monoamines having an alkyl group and an alkenyl group,
monoamines having an alkyl group and a cycloalkyl group,
cycloalkylamines, and alkylcycloalkylamines are more preferable. In
terms of a stain resistance property, amines having 3 or more carbon
atoms in total in an amine molecule are preferable, and amines having 5
or more carbonatoms in total are more preferable.
[0032] The content of the fatty acid amine salt is not particularly
limited, but is preferably 2 mass% or more, more preferably 2.5 mass%
or more, and further preferably 3 mass% or more, and preferably 10
mass% or less, more preferably 9 mass% or less, and further preferably
8 mass% or less, based on the total amount of the composition. When
the content of the fatty acid amine salt is less than the above-described
5 lower limit, a water removal property tends to decrease, and when it
exceeds the above-described upper limit, a rust preventive property
tends to decrease.
[0033] Examples of the ester that is the (C) component include (C-1) a
partial ester of a polyhydric alcohol, (C-2) an esterified oxidized wax,
10 (C-3) an esterified lanolin fatty acid, and (C-4) an alkyl or alkenyl
succinic acid ester.
The (C-1) partial ester of a polyhydric alcohol is an ester in
which at least one or more hydroxyl groups in a polyhydric alcohol are
not esterified an4 remain as hydroxyl groups. Any polyhydric alcohols
15 may be used as the polyhydric alcohol that is the raw materialof the
partial ester, but polyhydric alcohols having preferably 2 to 10, more
preferably 3 to 6 hydroxyl groups in the molecule and having 2 to 20,
more preferably 3 to 10 carbon atoms are suitably used. Among these
polyhydric alcohols, at least one polyhydric alcohol selected from the
20 group consisting of glycerin, trimethylolethane, trimethylolpropane,
pentaerythritol, and sorbitan is preferably used, and pentaerythritol is
more preferably used.
[0034] On the other hand, any carboxylic acids are used as the
carboxylic acid which constitutes the partial ester, but the number of
25 carbon atoms of carboxylic acids is preferably 2 to 30, more preferably
6 to 24, and further preferably 10 to 22. The carboxylic acids may be
saturated carboxylic acids or unsaturated carboxylic acids, and may be
straight-chain carboxylic acids or branched-chain carboxylic acids.
Examples of these fatty acids include saturated fatty acids such as acetic
acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid,
5 heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic
acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid,
pentadecanoic acid, hexadecanoic acid, heptadecanoic acid,
octadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid,
docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid,
10 hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic
acid, and triacontanoic acid; unsaturated fatty acids such as propenoic
acid, budenoic acid, pentenoic acid, hexenoic acid, heptenoic acid,
octenoic acid, nonenoic acid, decenoic acid, undecenoic acid,
7 dodecenoic acid, tridecenoic acidq tetradecenoic acid, pentadecenoic
15 acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid,
nonadecenoic acid, icosenoic acid, henicosenoic acid, docosenoic acid,
tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic
acid, heptacosenoic acid, octacosenoic acid, nonacosenoic acid, and
triacontenoic acid; and mixtures thereof, and also include all substituted
20 isomers of these fatty acids.
[0035] As the carboxylic acid which constitutes the partial ester,
hydroxycarboxylic acids may be used. The hydroxycarboxylic acids
may be saturated carboxylic acids or unsaturated carboxylic acids, and
in terms of-stability, saturated carboxylic acids are preferable. The
25 hydroxycarboxylic acids may be straight-chain carboxylic acids or
branched carboxylic acids; but straight-chain carboxylic acids, or
branched carboxylic acids which have 1 to 3, more preferably 1 to 2,
and particularly preferably one branched chain having 1 or 2 carbon
atoms, and more preferably one carbon atom, that is, methyl group, are
preferable.
5 [0036] In terms of achieving both a rust preventive property and storage
stability, the number of carbon atoms of the hydroxycarboxylic acids is
preferably 2 to 40, more preferably 6 to 30, and further preferably 8 to
24. The number of carboxylic acid groups in the hydroxycarboxylic
acids is not particularly limited; and the hydroxycarboxylic acids may
10 be monobasic acids or polybasic acids, monobasic acids being
preferable. The number of hydroxyl groups in the hydroxycarboxylic
acids is not particularly limited, but preferably 1 to 4, more preferably 1
to 3, further preferably 1 to 2, and particularly preferably 1, in terms of
stability.
15 [0037] Although the binding position of a hydroxyl group in the
hydroxycarboxylic acids is arbitrary, carboxylic acids in which a
hydroxyl group is bonded to a carbon atom to which a carboxylic acid
group is bonded (a-hydroxy acids), or carboxylic acids in which a
hydroxyl group is bonded to a carbon atom at the other end of a main
20 chain when viewed from a carbon atom to which a carboxylic acid
group is bonded (a-hydroxy acids) are preferable.
[0038] Preferred examples of the hydroxycarboxylic acids include
a-hydroxy acid represented by the formula (1) and o-hydroxy acid
represented by the formula (2): -
wherein, R' represents a hydrogen atom, an alkyl group having 1
to 38 carbon atoms, or an alkenyl group having 2 to 38 carbon atoms,
and R2 represents an akylene group having 1 to 38 carbon atoms or an
5 akenylene group having 2 to 38 carbon atoms.
[0039] Examples of the alkyl group and the alkenyl group represented
by R' include alkyl groups such as a methyl group, an ethyl group, a
propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl
group, an octyl group, a nonyl group, a decyl group, an undecyl group, a
10 dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, 4
a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl
group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl
group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a
heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl
15 group, a hentriacontyl group, a dotriacontyl group, a tritriacontyl group,
a tetratriacontyl group, a pentatriacontyl group, a hexatriacontyl group,
a heptatriacontyl group, and an octatriacontyl group; and alkenyl groups
such as an ethenyl group (a vinyl group), a propenyl group (an ally1
group), a butenyl group, a pentenyl group, a hexenyl group, a heptenyl
20 group, an octenyl group, a nonenyl group, a decenyl group, an
undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl
group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl
group, an octadecenyl group, a nonadecenyl group, an icosenyl group, a
henicosenyl group, a docosenyl group, a tricosenyl group, a tetracosenyl
group, a pentacosenyl group, a hexacosenyl group, a heptacosenyl group,
an octacosenyl group, a nonacosenyl group, a triacontenyl group, a
5 hentriacontenyl group, a dotriacontenyl group, a tritriacontenyl group, a
tetratriacontenyl group, a pentatriacontenyl group, a hexatriacontenyl
group, a heptatriacontenyl group, and an octatriacontenyl group, and
also include all isomers thereof.
[0040] Examples of the alkylene group and the alkenylene group
10 represented by R' include alkylene groups such as a methylene group,
an ethylene group, a propylene group, a butylene group, a pentylene
group, a hexylene group, a heptylene group, an octylene group, a
nonylene group, a decylene group, an undecylene group, a dodecylene
group, a tridecylene group, a tetradecylene group, a pentadecylene
15 group, a hexadecylene group, a heptadecylene group, an octadecylene
group, a nonadecylene group, an icosylene group, a henicosylene group,
a docosylene group, a tricosylene group, a tetracosylene group, a
pentacosylene group, a hexacosylene group, a heptacosylene group, an
octacosylene group, a nonacosylene group, a triacontylene group, a
20 hentriacontylene group, a dotriacontylene group, a tritriacontylene
group, a tetratriacontylene group, a pentatriacontylene group, a
hexatriacontylene group, a heptatriacontylene group, and an
octatriacontylene group; and alkenylene groups such as an ethenylene
group (a vinylene group), a propenyl group (an allylene group), a
25 butenylene group, a pentenylene group, a hexenylene group, a
heptenylene group, an octenylene group, a nonenylene group, a
decenylene group, an undecenylene group, a dodecenylene group, a
tridecenylene group, a tetradecenylene group, a pentadecenylene group,
a hexadecenylene group, a heptadecenylene group, an octadecenylene
group, a nonadecenylene group, an icosenylene group, a henicosenylene
5 group, a docosenylene group, a tricosenylene group, a tetracosenylene
group, a pentacosenylene group, a hexacosenylene group, a
heptacosenylene group, an octacosenylene group, a nonacosenylene
group, a triacontenylene group, a hentriacontenylene group, a
dotriacontenylene group, a tritriacontenylene group, a
10 tetratriacontenylene group, a pentatriacontenylene group, a
hexatriacontenylene group, a heptatriacontenylene group, and an
octatriacontenylene group, and also include all isomers thereof.
[0041] As a raw material containing the foregoing hydroxycarboxylic
acids, a lanolin fatty acid obtained by refining a waxy material that
15 adheres to sheep wool by hydrolysis or the like may be preferably used.
When the hydroxycarboxylic acids are used as a constituent carboxylic
acid of the partial ester, carboxylic acids having no hydroxyl group may
be used in combination. When the carboxylic acid which constitutes
the partial ester contains both hydroxycarboxylic acids and carboxylic
20 acids having no hydroxyl group, the ratio of the hydroxycarboxylic
acids to the total amount of the constituent carboxylic acid is preferably
5 to 80 mass%. When the ratio of the hydroxycarboxylic acids is less
than 5 mass%, a rust preventive property tends to become insufficient.
For the similar reason, theratio of the hydroxycarboxylic acids is
25 preferably 10 mass% or more, and hrther preferably 15 mass% or more.
Moreover, when the ratio of the hydroxycarboxylic acids exceeds 80
mass%, storage stability and solubility in a base oil tend to become
insufficient. For the similar reason, the ratio of the hydroxycarboxylic
acids is more preferably 60 mass% or less, further preferably 40 mass%
or less, even more preferably 30 mass% or less, and particularly
5 preferably 20 mass% or less.
[0042] The carboxylic acids having no hydroxyl group may be
saturated carboxylic acids or unsaturated carboxylic acids. Among the
carboxylic acids having no hydroxyl group, the saturated carboxylic
acids may be straight-chain carboxylic acids or branched carboxylic
10 acids; but straight-chain carboxylic acids, or branched carboxylic acids
which have 1 to 3, more preferably 1 to 2, and further preferably one
branched chain having 1 or 2 carbon atoms, and more preferably one
carbon atom, that is, methyl group, are preferable.
[0043] In terms of achieving both a rust preventive property and storage
15 stability, the number of carbon atoms of the saturated carboxylic acids
having no hydroxyl group is preferably 2 to 40, more preferably 6 to 30,
and further preferably 8 to 24. The number of carboxylic acid groups
in the saturated carboxylic acids having no hydroxyl group is not
particularly limited; and the saturated carboxylic acids having no
20 hydroxyl group may be monobasic acids or polybasic acids, monobasic
acids being preferable. Among the saturated carboxylic acids having
no hydroxyl group, in terms of oxidation stability and a stain resistance
property, straight-chain saturated carboxylic acids having 10 to 16
carbon atoms, such as lauric acid and stearic acid, are particularly
25 preferable.
[0044] Among the carboxylic acids having no hydroxyl group, the
unsaturated carboxylic acids may be straight-chain carboxylic acids or
branched carboxylic acids; but straight-chain carboxylic acids, or
branched carboxylic acids which have 1 to 3, more preferably 1 to 2,
and further preferably one branched chain having 1 or 2 carbon atoms,
5 and more preferably one carbon atom are preferable. Among the
carboxylic acids having no hydroxyl group, in terms of achieving both a
rust preventive property and storage stability, the number of carbon
atoms of the unsaturated carboxylic acids is preferably 2 to 40, more
preferably 6 to 30, hrther preferably 8 to 24, and particularly preferably
10 12 to22.
LO0451 The number of carboxylic acid groups in the unsaturated
carboxylic acids having no hydroxyl group is not particularly limited;
and the unsaturated carboxylic acids having no hydroxyl group may be
4
-1 monobasic acids or polybasic acids, monobasic acids being preferable.
15 Although the number of unsaturated bonds in the unsaturated carboxylic
acids having no hydroxyl group is not particularly limited, it is
preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and
particularly preferably 1, in terms of stability. Among the unsaturated
carboxylic acids having no hydroxyl group, in terms of a rust preventive
20 property and solubility in a base oil, straight-chain unsaturated
carboxylic acids having 18 to 22 carbon atoms, such as oleic acid, are
preferable, and furthermore, in terms of oxidation stability, solubility in
a base oil, and a stain resistance property, branched unsaturated
carboxylic acids having 18 to 22 carbon atoms, such as isostearic acid,
25 are preferable, oleic acid being particularly preferable.
[0046] In the partial ester of a polyhydric alcohol and a carboxylic acid,
the ratio of the unsaturated carboxylic acids to the constituent
carboxylic acid is preferably 5 to 95 mass%. By makimg the ratio of
the unsaturated carboxylic acids be 5 mass% or more, a rust preventive
property and storage stability may be further improved. For the similar
5 reason, the ratio of the unsaturated carboxylic acids is more preferably
10 mass% or more, further preferably 20 mass% or more, even more
preferably 30 mass% or more, and particularly preferably 35 mass% or
more. On the other hand, when the ratio of the unsaturated carboxylic
acids exceeds 95 mass%, an atmospheric exposure property and
10 solubility in a base oil tend to become insufficient. For the similar
reason, the ratio of the unsaturated carboxylic acids is more preferably
80 mass% or less, further preferably 60 mass% or less, and particularly
preferably 50 mass% or less.
[0047] The unsaturated carboxylic acids include both unsaturated
15 carboxylic acids having a hydroxyl group and unsaturated carboxylic
acids having no hydroxyl group, and the ratio of the unsaturated
carboxylic acids having no hydroxyl group to the total amount of the
unsaturated carboxylic acids is preferably 80 mass% or more, more
preferably 90 mass% or more, and hrther preferably 95 mass% or
20 more.
[0048] When the above-described partial ester is a partial ester in which
the ratio of the unsaturated carboxylic acids to the constituent
carboxylic acid is 5 to 95 mass%, the iodine value of the partial ester is
. preferably 5 to 75, more preferably 10 to 60, and further preferably 20
25 to 45. When the iodine value of the partial ester is less than 5, a rust
preventive property and storage stability tend to decrease. Moreover,
when the iodine value of the partial ester exceeds 75, an atmospheric
exposure property and solubility in a base oil tend to decrease. The
"iodine value" in the present invention means an iodine value measured
by Indicator titration method of JIS K 0070 "Acid value, saponification
5 value, iodine value, hydroxyl value, and unsaponifiable matter value of
chemical products".
[0049] Examples of a manufacturing method of the above-described
partial ester include the following manufacturing methods (i), (ii), and
(iii).
10 (i) A method in which a partial ester of a polyhydric alcohol and
a hydroxycarboxylic acid, or a mixture of a hydroxycarboxylic acid and
a saturated carboxylic acid having no hydroxyl group, and a partial ester
of a polyhydric alcohol and an unsaturated carboxylic acid having no
7
hydroxyl group, or B mixture of an unsaturated carboxylic acid having
15 no hydroxyl group and a saturated carboxylic acid having no hydroxyl
group, are mixed such that the carboxylic acid composition in a mixture
of the two satisfies the above-described conditions.
(ii) A method in which a carboxylic acid having a hydroxyl
group and an unsaturated carboxylic acid having no hydroxyl group are
20 mixed, or a saturated carboxylic acid having no hydroxyl group is
further mixed, and a partial esterification reaction of the carboxylic acid
mixture and a polyhydric alcohol is carried out such that the carboxylic
acid composition of a partial ester to be obtainable satisfies the
above-described conditions. -
25 (iii) A method in which a partial ester of a polyhydric alcohol
and a hydroxycarboxylic acid, or a mixture of a hydroxycarboxylic acid
and a saturated carboxylic acid having no hydroxyl group, or a partial
ester of a polyhydric alcohol and an unsaturated carboxylic acid having
no hydroxyl group, or a mixture of an unsaturated carboxylic acid
having no hydroxyl group and a saturated carboxylic acid having no
5 hydroxyl group, is mixed into a partial ester with a mixture of a
hydroxycarboxylic acid and an unsaturated carboxylic acid having no
hydroxyl group, or a mixture of these carboxylic acids and a saturated
carboxylic acid having no hydroxyl group such that the carboxylic acid
composition satisfies the above-described conditions.
10 [0050] In the case of the above-described manufacturing method (i), for
example, as the mixture of a hydroxycarboxylic acid and a saturated
carboxylic acid having no hydroxyl group, a lanolin fatty acid may be
preferably used, and as the unsaturated carboxylic acid having no
hydroxyl group, an unsaturated carbox7- ~lica cid having 2 to 40 carbon
15 atoms such as oleic acid may be preferably used. In this case, the
content ratio of the partial ester (first partial ester) composed of a
polyhydric alcohol and the mixture of a hydroxycarboxylic acid and a
saturated carboxylic acid having no hydroxyl group, preferably a lanolin
fatty acid, to the partial ester (second partial ester) composed of a
20 polyhydric alcohol and the unsaturated carboxylic acid having no
hydroxyl group, preferably oleic acid, is not particularly limited as long
as the carboxylic acid composition ratio in the mixture of the two
satisfies the above-described conditions, but the ratio of the first partial
ester to the total amount of the first and second partial esters is
25 preferably 20 to 95 mass%, more preferably 40 to 80 mass%, and
particularly preferably 55 to 65 mass%. When the ratio of the frst
partial ester is less than 20 mass% or exceeds 95 mass%, a rust
preventive property such as an atmospheric exposure property tends to
become insufficient. Furthermore, when the ratio of the first partial
ester exceeds 95 mass%, solubility of the entire partial ester in a base oil
5 decreases, and storage stability tends to become insufficient.
[0051] The (C-2) esterified oxidized wax refers to one obtained by
reacting an oxidized wax with alcohols and esterifying a part or all of
acidic groups in the oxidized wax. Examples of the oxidized wax used
as a raw material for the esterified oxidized wax include oxidized
10 waxes; and examples of the alcohols used as a raw material for the
esterified oxidized wax include 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 explzp7 ation of the
15 above-described esters, and an alcohol obtained by hydrolysis of
lanolin.
[0052] The (C-3) esterified lanolin fatty acid indicates one obtained by
reacting a lanolin fatty acid obtained by refming, such as hydrolysis, of
a waxy material that adheres to sheep wool, with alcohols. Examples
20 of the alcohols used as a raw material for the esterified lanolin fatty acid
include the alcohols exemplified in the explanation of the
above-described esterified oxidized wax, and among them, polyhydric
alcohols are preferable, and trimethylolpropane, trimethylolethane,
sorbitan, pentaerythritol, and glycerin are more preferable. Examples
25 of the above-described alkyl or alkenyl succinic acid ester include esters
of the above-described alkyl or alkenyl succinic acid and a monohydric
alcohol or a dihydric or higher polyhydric alcohol. Among them,
esters of a monohydric alcohol or a dihydric alcohol are preferable.
[0053] The monohydric alcohol may be straight-chain or
branched-chain, and may be saturated alcohols or unsaturated alcohols.
5 The number of carbon atoms of the monohydric alcohol is not
particularly limited, but aliphatic alcohols having 8 to 18 carbon atoms
are preferable. As the dihydric alcohol, alkylene glycols and
polyoxyalkylene glycols are preferably used. Examples of the
alkylene glycols include ethylene glycol, propylene glycol, butylene
10 glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene
glycol, nonylene glycol, and decylene glycol.
[0054] Examples of the polyoxyalkylene glycols include one obtained
g by homopolymerization or copolymerization of ethylene oxide,
7
propylene oxide, and butylene oxide. When alkylene oxides having
15 different structures are copolymerized in a polyoxyalkylene glycol, the
form of polymerization of oxyalkylene groups is not particularly limited,
and it may be a random copolymerization or a block copolymerization.
The polymerization degree of the polyoxyalkylene glycol is not
particularly limited, but is preferably 2 to 10, more preferably 2 to 8,
20 and further preferably 2 to 6.
[0055] The (C-4) alkyl or alkenyl succinic acid ester may be diesters
(complete esters) in which both of two carboxyl groups in alkyl or
alkenyl succinic acid are esterified, or monoesters (partial esters) in
which only one of carboxyl groups is esterified, and in terms of a better
25 rust preventive property, the monoesters are preferable. Among these
esters, in terms of exhibiting a better rust preventive property, the use of
partial esters of polyhydric alcohols is particularly preferable, and
specifically, examples thereof include pentaerythritol ester of lanolin,
sorbitan monooleate, and sorbitan isostearate.
[0056] The amount of esters added is preferably 4 mass% or more,
5 more preferably 5 mass% or more, and further preferably 6 mass% or
more, and preferably 20 mass% or less, more preferably 15 mass% or
less, and further preferably 10 mass% or less, based on the total amount
of the composition. When it is too little, a sufficient rust preventive
property is not obtainable, and when it is too much, life of an oil
10 solution when a large amount of water is mixed is shortened.
[0057] The (D) component is at least one rust preventive agent selected
from the group consisting of (D-1) a sarcosine-type compound, (D-2) a
sulfonic acid salt, (D-3) an amine, (D-4) a carboxylic acid, (D-5) a
carboxylic acid salt, (D-6) a paraffin wax, @-7) an oxidized wax salt,
15 and (D-8) a boron compound.
[0058] The 0-1) sarcosine-type compound used in the present
embodiment has a structure represented by the following formula (3),
(4), or (5):
R~-CO-NR~-(CH~),-CO~X(3 )
20 wherein, R3 represents an akyl group having 6 to 30 carbon
atoms or an alkenyl group having 6 to 30 carbon atoms, R4 represents an
alkyl group having 1 to 4 carbon atoms, X represents a hydrogen atom,
an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having
1 to 30 carbon atoms, and n represents an integer of 1 to 4;
25 [R~-co-NR~-(cH~)~-coo],Y (4)
wherein, R3 represents an alkyl group having 6 to 30 carbon
atoms or an alkenyl group having 6 to 30 carbon atoms, R4 represents an
alkyl group having 1 to 4 carbon atoms, Y represents an alkali metal or
an alkali earth metal, n represents an integer of 1 to 4, and m represents
1 when Y is an alkali metal, and represents 2 when Y is an alkali earth
5 metal;
[R~-C~-NR~-(CH~),-COO]~-Z-(5() OH)~
wherein, R3 represents an alkyl group having 6 to 30 carbon
atoms or an alkenyl group having 6 to 30 carbon atoms, R4 represents an
alkyl group having 1 to 4 carbon atoms, Z represents a residue other
10 than hydroxyl groups of a dihydric or higher polyhydric alcohol, m
represents an integer of 1 or more, m' represents an integer of 0 or more,
m + m' represents a valence of Z, and n represents an integer of 1 to 4.
[0059] In the formulas (3) to (5), R3 represents an alkyl group having 6
to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms.
15 In terms of solubility in a base oil and the like, it is necessary that R3 be
an alkyl group or an alkenyl group having 6 or more carbon atoms, and
the number of carbon atoms is preferably 7 or more, and more
preferably 8 or more. Moreover, in terms of storage stability and the
like, it is necessary that R~ be an alkyl group or an alkenyl group having
20 30 or less carbon atoms, and the number of carbon atoms is preferably
24 or less, and more preferably 20 or less. Specifically, examples of
these alkyl groups and alkenyl groups include alkyl groups such as a
hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl
group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl
25 group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an
octadecyl group, a nonadecyl group, and an icosyl group (these alkyl
groups may be straight-chain or branched); and alkenyl groups such as a
hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a
decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl
group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group,
5 a heptadecenyl group, an octadecenyl group, a nonadecenyl group, and
an icosenyl group (these alkenyl groups may be straight-chain or
branched, and the position of a double bond is also arbitrary).
[0060] In the formulas (3) to (S), R4 represents an alkyl group having 1
to 4 carbon atoms. In terms of storage stability and the like, it is
10 necessary that R4 be an alkyl group having 4 or less carbon atoms, and
the number of carbon atoms is preferably 3 or less, and more preferably
2 or less.
[0061] In the formulas (3) to (9, n represents an integer of 1 to 4. In
terms of storage stability and the like, it is necessary that n be an integer
15 of 4 or less, n is preferably 3 or less, and n is more preferably 2 or less.
[0062] In the formula (3), X represents a hydrogen atom, an alkyl group
having 1 to 30 carbon atoms, or an alkenyl group having 1 to 30 carbon
atoms. In terms of storage stability and the like, it is necessary that an
alkyl group or an alkenyl group represented by X have 30 or less carbon
20 atoms, and the number of carbon atoms is preferably 20 or less, and
more preferably 10 or less. Specifically, examples of these alkyl
groups and alkenyl groups include alkyl groups such as a methyl group,
an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, and a decyl group
25 (these alkyl groups may be straight-chain or branched); and alkenyl
groups such as an ethenyl group, a propenyl group, a butenyl group, a
pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a
nonenyl group, and a decenyl group (these alkenyl groups may be
straight-chain or branched, and the position of a double bond is also
arbitrary). Moreover, in terms of a better rust preventive property and
5 the like, alkyl groups are preferable. In terms of a better rust
preventive property and the like, X is preferably a hydrogen atom, an
alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1
to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group
having 1 to 20 carbon atoms, and hrther more preferably a hydrogen
10 atom or an alkyl group having 1 to 10 carbon atoms.
[0063] In the formula (4), Y represents an alkali metal or an alkali earth
metal, and specifically, examples thereof include sodium, potassium,
magnesium, calcium, and barium. Among them, in terms of a better
rust preventive property, alkali earth metals are preferable. It is to be
15 noted that, in the case of barium, safety for human bodies and
ecosystems may become insuficient. In the formula (4), m represents
1 when Y is an alkali metal, and represents 2 when Y is an alkali earth
metal.
[0064] In the formula (5), Z represents a residue other than hydroxyl
20 groups of a dihydric or higher polyhydric alcohol. Specifically,
examples of the foregoing polyhydric alcohol include dihydric alcohols
such as ethylene glycol, propylene glycol, l,4-butanediol,
1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol,
1,s-octanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite,
25 catechol, resorcin, hydroquinone, bisphenol A, bisphenol F,
hydrogenated bisphenol A, hydrogenated bisphenol F, and dimerdiol;
trihydric alcohols such as glycerin, 2-(hydroxymethy1)-l,3-propanediol,
1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-l,2,3-propanetriol,
2-methyl-2,3,4-butanetriol, 2-ethyl-l,2,3-butanetriol,2 ,3,4-pentanetriol,
2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol,
5 2,4-dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol,
trimethylolethane, and trimethylolpropane; tetrahydric alcohols such as
pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol,
1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, and sorbitan;
pentahydric alcohols such as adonitol, arabitol, xylitol, and triglycerin;
10 hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol, iditol,
inositol, dulcitol, talose, and allose; polyglycerin, and dehydration
condensation products thereof.
[0065] In the formula (5), m represents an integer of 1 or more, m'
rJq presents an integer of 0 or more, and m+m' is the same as the valence
15 of Z. That is, all of hydroxyl groups in a polyhydric alcohol of Z may
be substituted or only a part thereof may be substituted.
[0066] Among the sarcosines represented by the above formulas (3) to
(5), in terms of a better rust preventive property, at least one compound
selected fiom the formulas (3) and (4) is preferable. Moreover, only
20 one compound selected from the formulas (3) to (5) may be used alone,
or a mixture of two or more compounds may be used.
[0067] The content of the sarcosines represented by the formulas (3) to
(5) is not particularly limited, but is preferably 0.05 to 10 mass%, more
preferably 0.1 to 7 mass%, and further preferably 0.3 to 5 mass%, based
25 on the total amount of the composition. When the content of the
sarcosines is less than the above-described lower limit, a rust preventive
I
property and long-term sustainability thereof tend to become
insufficient. Even when the content of the sarcosines exceeds the
above-described upper limit, an improving effect of a rust preventive
property and long-term sustainability thereof, which meets the content,
5 does not tend to be obtainable.
[0068] Preferred examples of the (D-2) sulfonic acid salt include
sulfonic acid alkali metal salts, sulfonic acid alkali earth metal salts, and
sulfonic acid amine salts. Every sulfonic acid salt has sufficiently-high
safety for human bodies and ecosystems, and can be obtained by
10 reacting an alkali metal, an alkali earth metal, or an amine with sulfonic
acid.
Examples of the alkali metal which constitutes the sulfonic acid
salt include sodium and potassium. Moreover, examples of the alkali
7 earth metal incl~de~magnesiumca, lcium, and barium. Among them,
15 as the alkali metal and the alkali earth metal, sodium, potassium,
calcium, and barium are preferable, and calcium is particularly
preferable.
[0069] In the case where the sulfonic acid salt is amine salts, examples
of the amines include monoamines, polyamines, and alkanolamines.
20 [0070] Examples of the monoamines include alkylamines such as
monomethylamine, dimethylamine, trimethylamine, monoethylamine,
diethylamine, triethylamine, monopropylamine, dipropylamine,
tripropylamine, monobutylamine, dibutylamine, tributylamine,
monopentylamine, dipentylamine, tripentylamine, monohexylamine,
25 dihexylamine, monoheptylamine, diheptylamine, monooctylamine,
dioctylamine, monononylamine, monodecylamine, monoundecylamine,
I
monododecylamine, monotridecylamine, monotetradecylamine,
monopentadecylamine, monohexadecylamine, monoheptadecylamine,
monooctadecylamine, monononadecylamine, monoicosylamine,
monohenicosylamine, monodocosylamine, monotricosylamine,
5 dimethyl(ethyl)amine, dimethyl(propyl)amine, dimethyl(butyl)amine,
dimethyl(pentyl)amine, dimethyl(hexyl)amine, dimethyl(heptyl)amine,
dimethyl(octyl)amine, dimethyl(nonyl)amine, dimethyl(decyl)amine,
dimethyl(undecyl)amine, dimethyl(dodecyl)amine,
dimethyl(tridecyl)amine, dimethyl(tetradecyl)amine,
10 dimethyl(pentadecyl)amine, dimethyl(hexadecyl)amine,
dimethyl(heptadecyl)amine, dimethyl(octadecyl)amine,
dimethyl(nonadecyl)amine, dimethyl(icosyl)amine,
dimethyl(henicosyl)amine, and dimethyl(tricosy1)amine;
. -1 akenylamines such as novinylam~pe, divinylamine, trivinylamine,
15 monopropenylamine, dipropenylamine, tripropenylamine,
monobutenylamine, dibutenylamine, tributenylamine,
monopentenylamine, dipentenylamine, tripentenylamine,
monohexenylamine, dihexenylamine, monoheptenylamine,
diheptenylamine, monoocteny lamine, dioctenylamine,
20 monononenylamine, monodecenylamine, monoundecenylamine,
monododecenylamine, monotridecenylamine, monotetradecenylamine,
monopentadecenylamine, monohexadecenylamine,
monoheptadecenylamine, monooctadecenylamine,
monononadecenylamine, monoicosenylamine, monohenicosenylamine,
25 monodocosenylamine, and monotricosenylamine;
monoamines having an akyl group and an alkenyl group, such as
dimethyl(vinyl)amine, dimethyl(propenyl)amine,
dimethyl(butenyl)amine, dimethyl(pentenyl)amine,
dimethyl(hexenyl)amine, dimethyl(heptenyl)amine,
dimethyl(octenyl)amine, dimethyl(nonenyl)amine,
5 dimethyl(decenyl)amine, dimethyl(undecenyl)amine,
dimethyl(dodecenyl)amine, dimethyl(tridecenyl)amine,
dimethyl(tetradecenyl)amine, dimethyl(pentadecenyl)amine,
dimethyl(hexadecenyl)amine, dimethyl(heptadecenyl)amine,
dimethyl(octadecenyl)amine, dimethyl(nonadecenyl)amine,
10 dimethyl(icosenyl)amine, dimethyl(henicosenyl)amine, and
dimethyl(tricoseny1)amine;
aromatic-substituted alkylamines such as monobenzylamine,
(1-phenethyl)amine, (2-phenethy1)amine (another name:
7
monophenethylamine), dibenzylamine, bis(1-pheneth;;l)amine, and
15 bis(2-phenethy1)amine (another name: diphenethylamine);
cycloalkylamines having 5 to 16 carbon atoms, such as
monocyclopentylamine, dicyclopentylamine, tricyclopentylamine,
monocyclohexylamine, dicyclohexylamine, monocycloheptylamine,
and dicycloheptylamine; monoamines having an alkyl group and a
20 cycloalkyl group, such as dimethyl(cyclopentyl)amine,
dimethyl(cyclohexyl)amine, and dimethyl(cycloheptyl)amine; and
alkylcycloalkylamines such as (methyl cyclopentyl)amiae, bis(methy1
cyclopentyl)amine, (dimethyl cyclopentyl)amine, bis(dimethy1
cyclopentyl)amine, (ethyl cyclopentyl)amine, bis(ethy1
25 cyclopentyl)amine, (methyl ethyl cyclopentyl)amine, bis(methy1 ethyl
cyclopentyl)amine, (diethyl cyclopentyl)amine, (methyl
cyclohexyl)amine, bis(methy1 cyclohexyl)amine, (dimethyl
cyclohexyl)amine, bis(dimethy1 cyclohexyl)amine, (ethyl
cyclohexyl)amine, bis(ethy1 cyclohexyl)amine, (methyl ethyl
cyclohexyl)amine, (diethyl cyclohexyl)amine, (methyl
5 cycloheptyl)amine, bis(methy1 cycloheptyl)amine, (dimethyl
cycloheptyl)amine, (ethyl cycloheptyl)amine, (methyl ethyl
cycloheptyl)amine, and (diethyl cycloheptyl)amine, and also include all
substituted isomers of these monoamines. The monoamines described
herein include monoamines such as beef tallow amine, which are
10 derived from oils and fats.
[0071] Examples of the polyamines include alkylenepolyamines such as
ethylene diamine, diethylene triamine, triethylene tetramine,
tetraethylene pentamine, pentaethylene hexamine, propylene diamine,
7
dipropylene triamine, tripropylene tetramine, tetrapropylene pentamhe,?
15 pentapropylene hexamine, butylene diamine, dibutylene triamine,
tributylene tetramine, tetrabutylene pentamine, and pentabutylene
hexamine;
N-alkylethylenediamines such as N-methyl ethylene diamine, N-ethyl
ethylene diamine, N-propyl ethylene diamine, N-butyl ethylene diamine,
20 N-pentyl ethylene diamine, N-hexyl ethylene diamine, N-heptyl
ethylene diamine, N-octyl ethylene diamine, N-nonyl ethylene diamine,
N-decyl ethylene diamine, N-undecyl ethylene diamine, N-dodecyl
ethylene diamine, N-tridecyl ethylene diamine, N-tetradecyl ethylene
diamine, N-pentadecyl ethylene diamine, N-hexadecyl ethylene diamine,
25 N-heptadecyl ethylene diamine, N-octadecyl ethylene diamine,
N-nonadecyl ethylene diamine, N-icosyl ethylene diamine, N-henicosyl
ethylene diamine, N-docosyl ethylene diamine, and N-tricosyl ethylene
diamine;
N-alkenylethylenediamines such as N-vinyl ethylene diamine,
N-propenyl ethylene diamine, N-butenyl ethylene diamine, N-pentenyl
5 ethylene diamine, N-hexenyl ethylene diamine, N-heptenyl ethylene
diamine, N-octenyl ethylene diamine, N-nonenyl ethylene diamine,
N-decenyl ethylene diamine, N-undecenyl ethylene diamine,
N-dodecenyl ethylene diamine, N-tridecenyl ethylene diamine,
N-tetradecenyl ethylene diamine, N-pentadecenyl ethylene diamine,
10 N-hexadecenyl ethylene diamine, N-heptadecenyl ethylene diamine,
N-octadecenyl ethylene diamine, N-nonadecenyl ethylene diamine,
N-icosenyl ethylene diamine, N-henicosenyl ethylene diamine,
N-docosenyl ethylene diamine, and N-tricosenyl ethylene diamine; and
N-alkyl or N-alkenylalkylenepolyamines such as N-alkyl diethylene
15 triamine, N-alkenyl diethylene triamine, N-alkyl triethylene tetramine,
N-alkenyl hiethylene tetramine, N-alkyl tetraethylene pentamine,
N-alkenyl tetraethylene pentamine, N-alkyl pentaethylene hexamine,
N-alkenyl pentaethylene hexamine, N-alkyl propylene diamine,
N-alkenyl propylene diamine, N-alkyl dipropylene triamine, N-alkenyl
20 dipropylene triamine, N-alkyl tripropylene tetramine, N-alkenyl
tripropylene tetramine, N-alkyl tetrapropylene pentamine, N-alkenyl
tetrapropylene pentamine, N-alkyl pentapropylene hexamine, N-alkenyl
pentapropylene hexamine, N-alkyl butylene diamine, N-alkenyl
butylene diamine, N-alkyl dibutylene triamine, N-alkenyl dibutylene
25 triamine, N-alkyl tributylene tetramine, N-alkenyl tributylene tetramine,
N-alkyl tetrabutylene pentamine, N-alkenyl tetrabutylene pentamine,
N-alkyl pentabutylene hexamine, and N-alkenyl pentabutylene
hexamine, and also include all substituted isomers of these polyamines.
Moreover, the polyamines described herein include polyamines (beef
tallow polyamine and the like) which are derived from oils and fats.
5 Examples of the alkanolamines include monomethanolamine,
dimethanolamine, trimethanolamine, monoethanolamine,
diethanolamine, triethanolamine, mono(n-propanol)amine,
di(n-propanol)amine, tri(n-propanol)amine, monoisopropanolamine,
diisopropanolamine, triisopropanolamine, monobutanolamine,
10 dibutanolamine, tributanolamine, monopentanolamine, dipentanolamine,
tripentanolamine, monohexanolamine, dihexanolamine,
monoheptanolamine, diheptanolamine, monooctanolamine,
monononanolamine, monodecanolamine, monoundecanolamine,
monododecanolamine, monotridecanolamine, monotetradecanolamine,
15 monopentadecanolamine, monohexadecanolamine, diethyl monoethanol
amine, diethyl monopropanol amine, diethyl monobutanol amine,
diethyl monopentanol amine, dipropyl monoethanol amine, dipropyl
monopropanol amine, dipropyl monobutanol amine, dipropyl
monopentanol amine, dibutyl monoethanol amine, dibutyl
20 monopropanol amine, dibutyl monobutanol amine, dibutyl
monopentanol amine, monoethyl diethanol amine, monoethyl
dipropanol amine, monoethyl dibutanol amine, monoethyl dipentanol
amine, monopropyl diethanol amine, monopropyl dipropanol amine,
monopropyl dibutanol amine, monopropyl dipentanol amine, monobutyl
25 diethanol amine, monobutyl dipropanol amine, monobutyl dibutanol
amine, monobutyl dipentanol amine, monocyclohexyl monoethanol
amine, monocyclohexyl diethanol amine, monocyclohexyl
monopropanol amine, and monocyclohexyl dipropanol amine, and also
include all substituted isomers of these alkanolamines.
[0072] As the above-described sulfonic acid, those which are
5 manufactured by a conventional method and well-known may be used.
Specifically, general examples thereof include synthetic sulfonic acids
such as one obtained by sulfonating an alkyl aromatic compound of
lubricant oil distillate of a mineral oil; a petroleum sulfonic acid such as
a so-called mahogany acid by-produced when manufacturing white oil;
10 or one obtained by sulfonating an alkylbenzene having a straight-chain
or branched-chain alkyl group, which is obtainable by alkylating
benzene with a polyolefin by-produced from a manufacturing plant of
an alkylbenzene which is to be a raw material for a detergent and the
like, and one obtained by sulfonating an alkylnaphthalene such as
15 dinonylnaphthalene.
[0073] Among the above-described sulfonic acids, at least one selected
from the group consisting of: dialkylnaphthalene sulfonic acids in which
the number of carbon atoms in total of two alkyl groups bonded to a
naphthalene ring is 14 to 30; dialkylbenzene sulfonic acids in which
20 each of two alkyl groups bonded to a benzene ring is a straight-chain
alkyl group or a branched-chain alkyl group having one side-chain
methyl group, and the number of carbon atoms in total of the two alkyl
groups is 14 to 30; and monoalkylbenzene sulfonic acids in which an
alkyl bonded to a benzene ring has 15. or more carbon atoms, is
25 preferably used.
[0074] In those in which the number of carbon atoms in total of two
alkyl groups bonded to a naphthalene ring is 14 to 30 as the preferred
dialkylnaphthalene sulfonic acids, when the number of carbon atoms in
total of the two alkyl groups is less than 14, a demulsification property
tends to become insufficient, and on the other hand, when it exceeds 30,
5 storage stability of the rust preventive oil composition to be obtained
tends to decrease. The two alkyl groups may be straight-chain or
branched-chain, respectively. Moreover, although the number of
carbon atoms of each of the alkyl groups is not particularly limited as
long as the number of carbon atoms in total of the two alkyl groups is
10 14 to 30, the number of carbon atoms of each of the alkyl groups is
preferably 6 to 18.
[0075] The preferred dialkylbenzene sulfonic acids are those in which
each of two alkyl groups bonded to a benzene ring is a straight-chain
4
3 alkyl group or a branched-chain alkyl group having one side-chain
15 methyl group, and the number of carbon atoms in total of the two alkyl
groups is 14 to 30. Although monoalkylbenzene sulfonic acids having
an alkyl group having 15 or more carbon atoms may be suitably used as
described below, when using monoalkylbenzene sulfonic acids having
an alkyl group having less than 15 carbon atoms, storage stability of the
20 composition tends to decrease. Moreover, also in the case of using
alkylbenzene sulfonic acids having three or more alkyl groups, storage
stability of the composition tends to decrease.
[0076] When the alkyl group bonded to a benzene ring of a
- dialkylbenzene sulfonic acid is a branched-chain alkyl group having a
25 branched structure other than a side-chain methyl group, for example, a
branched-chain alkyl group having a side-chain ethyl group, or the like,
or a branched-chain alkyl group having two or more branched structures,
for example, a branched-chain alkyl group derived om an oligomer of
propylene, or the like, human bodies and ecosystems may be adversely
impacted, and furthermore, a rust preventive property tends to become
5 insufficient. Moreover, when the number of carbon atoms in total of
the two alkyl groups bonded to a benzene ring of a dialkylbenzene
sulfonic acid is less than 14, a demulsification property tends to
decrease, and on the other hand, when it exceeds 30, storage stability of
the composition tends to decrease. In addition, although the number of
10 carbon atoms of each of the alkyl groups is not particularly limited as
long as the number of carbon atoms in total of the two alkyl groups
bonded to a benzene ring is 14 to 30, the number of carbon atoms of
each of the alkyl groups is preferably 6 to 18.
$00771 The preferred monoalkylbenzene sulfonic acids are, as described
15 above, those in which the number of carbon atoms of one alkyl group
bonded to a benzene ring is 15 or more. When the number of carbon
atoms of the alkyl group bonded to a benzene ring is less than 15,
storage stability of the composition to be obtainable tends to decrease.
Moreover, the alkyl group bonded to a benzene ring may be
20 straight-chain or branched-chain as long as the number of carbon atoms
thereof is 15 or more.
LO0781 Examples of the sulfonic acid salts obtained by using the
above-described raw materials include the following: alkali metal bases
such as alkali metal oxides or hydroxides; neutral (normal salt)
25 sulfonates obtained by reacting alkali earth metal bases such as alkali
earth metal oxides or hydroxides, or amines such as ammonia,
alkylamines, and alkanolamines with sulfonic acid; basic sulfonates
obtained by heating the above-described neutral (normal salt) sulfonates
and excess alkali metal bases, alkali earth metal bases, or amines in the
presence of water; carbonate overbasic (ultrabasic) sulfonates obtained
5 by reacting the above-described neutral (normal salt) sulfonates with
alkali metal bases, alkali earth metal bases, or amines in the presence of
carbon dioxide gas; borate overbasic (ultrabasic) sulfonates obtained by
reacting the above-described neutral (normal salt) sulfonates with alkali
metal bases, alkali earth metal bases, or amines and boric acid
10 compounds such as boric acid and anhydrous boric acid, or by reacting
the above-described carbonate overbasic (ultrabasic) sulfonates with
boric acid compounds such as boric acid and anhydrous boric acid, and
mixtures thereof.
[0079] In the c7y e where the above-described neutral (normal salt)
15 sulfonates are manufactured, desired sulfonic acid salts may be
obtainable by adding, as a reaction accelerator, chlorides of the same
alkali metal, alkali earth metal, or amines as the desired sulfonic acid
salts, or by adding chlorides of the same alkali metal, alkali earth metal,
or amines as the desired sulfonic acid salts after preparing neutral
20 (normal salt) sulfonates of different alkali metal, alkali earth metal, or
amines om the desired sulfonates to carry out an exchange reaction.
However, since chloride ions are likely to remain in the sulfonic acid
salts obtained by these methods, it is preferable that, in the present
invention, the sulfonic acid salts obtained by these methods be not used,
25 or sufficient washing treatment such as water washing be carried out for
the obtained sulfonic acid salts. Specifically, the chloride
concentration in the sulfonic acid salts is preferably made to be 200
mass ppm or less, more preferably 100 mass ppm or less, hrther
preferably 50 mass ppm or less, and particularly preferably 25 mass
ppm or less.
5 [0080] As the sulfonic acid salts, at least one selected fiom the group
consisting of dialkylnaphthalene sulfonic acid salts in which the number
of carbon atoms in total of two alkyl groups bonded to a naphthalene
ring is 14 to 30; dialkylbenzene sulfonic acid salts in which each of two
alkyl groups bonded to a benzene ring is a straight-chain alkyl group or
10 a branched-chain alkyl group having one side-chain methyl group, and
the number of carbon atoms in total of the two alkyl groups is 14 to 30;
and monoalkylbenzene sulfonic acid salts in which the an alkyl bonded
to a benzene ring has 15 or more carbon atoms, is preferably used.
7 [0081] In the present embodimentq among the above, one or two or
15 more selected fkom neutral, basic, and overbasic alkali metal sulfonates
and alkali earth metal sulfonates are more preferably used; and neutral
or nearly neutral alkali metal sulfonates or alkali earth metal sulfonates
having a base value of 0 to 50 mgKOWg, and preferably 10 to 30
mgKOWg, and/or (over)basic alkali metal sulfonates or alkali earth
20 metal sulfonates having a base value of 50 to 500 mgKOWg, and
preferably 200 to 400 mgKOWg are particularly preferably used.
Moreover, the mass ratio of the above-described alkali metal sulfonates
or alkali earth metal sulfonates having a base value of 0 to 50 mgKOWg
to the alkali-metal sulfonates or alkali earth metal sulfonates having a - - -
25 base value of 50 to 500 mgKOWg (alkali metal sulfonates or alkali
earth metal sulfonates having base value of 0 to 50 mgKOWg1alkali
metal sulfonates or alkali earth metal sulfonates having base value of 50
to 500 mgKOH/g) is preferably 0.1 to 30, more preferably 1 to 20, and
particularly preferably 1.5 to 15, based on the total amount of the
composition.
5 [0082] The base value herein means a base value measured by
Hydrochloric acid method in conformity with JIS K 2501 "Petroleum
products and lubricants-Determination of neutralization number",
Section 6, in the state where generally 30 to 70 mass% of a diluent such
as a lubricant base oil is contained.
10 [0083] Among the above-described sulfonic acid salts, amine sulfonates,
calcium sulfonate, and barium sulfonate are preferable, and
alkylenediamine sulfonates and calcium sulfonate are particularly
preferable.
[0084] Examples of the (D-3) amine as a rust prevy1ti.ve component
15 include the amines exemplified in the explanation of the
above-described sulfonic acid salts. Among the above-described
amines, monoamines are preferable because a stain resistance property
is good, and among monoamines, alkylamines, monoamines having an
alkyl group and an alkenyl group, monoamines having an alkyl group
20 and a cycloalkyl group, cycloalkylamines, and alkylcycloalkylamines
are more preferable. Moreover, in terms of a good stain resistance
property, amines having 3 or more carbon atoms in total in an amine
molecule are preferable, and amines having 5 or more carbon atoms in
total in an amine molecule are more preferable. - -
25 [0085] Any carboxylic acids can be used as the (D-4) carboxylic acid as
a rust preventive component, but preferable examples thereof include
fatty acids, dicarboxylic acids, hydroxyfatty acids, naphthenic acids,
resin acids, oxidized waxes, and lanolin fatty acid. The number of
carbon atoms of the above-described fatty acids is not particularly
limited, but is preferably 6 to 24, and more preferably 10 to 22.
5 Moreover, the fatty acids may be saturated fatty acids or unsaturated
fatty acids, and may be straight-chain fatty acids or branched-chain fatty
acids.
(00861 Examples of these fatty acids include saturated fatty acids such
as hexane acid, heptane acid, octane acid, nonane acid, decane acid,
10 undecane acid, dodecane acid, tridecane acid, tetradecane acid,
pentadecane acid, hexadecane acid, heptadecane acid, octadecane acid,
nonadecane acid, icosane acid, henicosane acid, docosane acid,
tricosane acid, and tetracosane acid; unsaturated fatty acids such as
hexene acid, heptene acid, octene acid, nonene acid, decene acid1!
15 undecene acid, dodecene acid, tridecene acid, tetradecene acid,
pentadecene acid, hexadecene acid, heptadecene acid, octadecene acid,
nonadecene acid, icosene acid, henicosene acid, docosene acid,
tricosene acid, and tetracosene acid; and mixtures thereof, and also
include all substituted isomers of these fatty acids.
20 [0087] As the dicarboxylic acids, preferably, dicarboxylic acids having
2 to 40 carbon atoms, and more preferably, dicarboxylic acids having 5
to 36 carbon atoms are used. Among them, dimer acids obtained by
dimerizing unsaturated fatty acids having 6 to 18 carbon atoms, and
alkyl or alkenyl succinic acids are preferably used. Examples of the
25 dimer acids include a dimer acid of oleic acid. Moreover, among the
alkyl or alkenyl succinic acids, alkenyl succinic acids are preferable,
and alkenyl succinic acids having an alkenyl group having 8 to 18
carbon atoms are more preferable.
[0088] As the hydroxyfatty acids, hydroxyfatty acids having 6 to 24
carbon atoms are preferably used. Although the number of hydroxy
5 groups in the hydroxyfatty acids may be one or may be more than one,
those having 1 to 3 hydroxy groups are preferably used. Examples of
these hydroxyfatty acids include recinoleic acid.
[0089] The naphthenic acids indicate carboxylic acids in petroleum, in
which a -COOH group is bonded to a naphthene ring. The resin acids
10 indicate organic acids present in a free state or as esters in a natural resin.
The oxidized waxes are those obtained by oxidizing waxes. Although
the waxes used as a raw material are not particularly limited,
specifically, examples thereof include paraffm waxes, microcrystalline
waxes, and petrolaturns obtained when refining petroleum distillate, and
15 polyolefin waxes obtained by synthesis.
[0090] The lanolin fatty acid is a carboxylic acid obtained by refining,
such as hydrolysis, of a waxy material that adheres to sheep wool.
[0091] Among these carboxylic acids, in terms of a rust preventive
property, a degreasing property, and storage stability, dicarboxylic acids
20 are preferable, dimer acids are more preferable, and a dimer acid of
oleic acid is more preferable.
[0092] Examples of the (D-5) carboxylic acid salt as a rust preventive
component include alkali metal salts, alkali earth metal salts, and amine
salts of the above-described carboxylic acids. Examples of the alkali
25 metal which constitutes the carboxylic acid salt include sodium and
potassium, and examples of the alkali earth metal include barium,
calcium, and magnesium. Among them, a calcium salt is preferably
used. Moreover, examples of the amine include the amines
exemplified in the explanation of the amines. In the case of a barium
salt, safety for human bodies and ecosystems may become insufficient.
5 [0093] Examples of the @-6) paraffin wax as a rust preventive
component include parafin waxes, microcrystalline waxes, and
petrolatums obtained when refining petroleum distillate, and polyolefin
waxes obtained by synthesis.
[0094] Although not particularly limited, examples of the oxidized wax
10 used as a raw material for the (D-7) oxidized wax salt include oxidized
paraffin waxes produced by oxidizing waxes such as the
above-described paraffin waxes.
[0095] When the oxidized wax salt is an alkali metal salt, examples of
the alkali metal used as a raw material include sodium and potassium.
15 When the oxidized wax salt is an alkali earth metal salt, examples of the
alkali earth metal used as a raw material include magnesium, calcium,
and barium. When the oxidized wax salt is a heavy metal salt,
examples of the heavy metal used as a raw material include zinc and
lead. Among them, a calcium salt is preferable. It is to be noted that,
20 in terms of safety for human bodies and ecosystems, the oxidized wax
salt is preferably not a barium salt and a heavy metal salt.
[0096] Examples of the (D-8) boron compound as a rust preventive
component include potassium borate and calcium borate.
400971 In the present embodiment, one of the rust preventive agents of
25 the above-described @) component may be used alone, or a mixture of
two or more of the same type of the rust preventive agents may be used,
and furthermore, a mixture of two or more of the different types of the
rust preventive agents may be used.
[0098] In terms of exhibiting a better rust preventive property, as the
rust preventive agents of the (D) component, a sarcosine, a sulfonic acid
5 salt, and a paraffin wax are preferable, and these three types are
preferably used in combination.
[0099] In addition to the above-described rust preventive agents,
alcohols typified by higher aliphatic alcohols; and phosphoric acid
derivatives and phosphorous acid derivatives typified by amine salts of
10 phosphoric acid monoesters, phosphoric acid diesters, phosphorous acid
esters, phosphoric acid, and phosphorous acid can be contained as a rust
preventive agent.
[0100] Although not particularly limited, in the case where the rust
preventive agent other than the carboxylic acid of the (D) component is
15 used, in terms of a rust preventive property, the content is preferably 0.1
mass% or more, more preferably 0.5 mass% or more, and further
preferably 1.0 mass% or more, based on the total amount of the
composition. Moreover, in terms of storage stability, the content of the
rust preventive agent other than the carboxylic acid of the (D)
20 component is preferably 20 mass% or less, more preferably 15 mass%
or less, and further preferably 10 mass% or less, based on the total
amount of the composition.
[0101] Furthermore, although not particularly limited, in the case where
the carboxylic acid of the (D) component is used as a rust preventive
25 agent, in terms of a rust preventive property, the content is preferably
0.01 mass% or more, more preferably 0.03 mass% or more, and further
preferably 0.05 mass% or more, based on the total amount of the
composition.
When the content of the carboxylic acid is less than the
above-described lower limit, a rust preventive property improving effect
5 by the addition may become insufficient. Moreover, the content of the
carboxylic acid is preferably 2 mass% or less, more preferably 1.5
mass% or less, and further preferably 1 mass% or less, based on the
total amount of the composition. When the content of the carboxylic
acid exceeds the above-described upper limit, solubility in a base oil
10 becomes insufficient, and storage stability may decrease.
[0102] The kinematic viscosity at 40°C of the rust preventive oil
composition according to the present embodiment is preferably 2 mm2/s
or more, more preferably 2.5 mm2/s or more, and further preferably 3
I
mm2/s or more, and preferably 13 mm2/s or less, more preferably 8
15 mm2/s or less, and hrther preferably 7 mm2/s or less. When the
kinematic viscosity is less than the above-described lower limit, an oil
film cannot be maintained, and thus, problems with a rust preventive
property may arise, and when it exceeds the above-described upper limit,
a water removal property may decrease.
20 [0103] Although a chlorine bleaching agent is sometimes used for the
purpose of decoloration when manufacturing the rust preventive agent
that is the @) component, it is preferable that, in the present
embodiment, non-chlorine compounds such as hydrogen peroxide be
used as a bleaching agent, or no decoloration treatment be carried out.
25 Moreover, chlorine compounds such as hydrochloric acid are sometimes
used in hydrolysis or the like of oils and fats, and in this case, it is
preferable that non-chlorine acids or basic compounds be used.
Furthermore, the compound to be obtained is preferably subjected to
sufficient washing treatment such as water washing.
[0104] The chlorine concentration of the rust preventive agent that is
the (D) component is not particularly limited as long as properties of the
rust preventive oil composition according to the present embodiment are
not impaired, but it is preferably 200 mass ppm or less, more preferably
100 mass ppm or less, further preferably 50 mass ppm or less, and
particularly preferably 25 mass ppm or less.
[0105] The rust preventive oil composition according to the present
embodiment may further contain other additive agents as necessary.
Specifically, examples thereof include paraffin waxes which have a
significant rust preventive property improving effect under exposure to
an acidic atmosphere; sulfurized oils and fats, sulfurized esters,
long-chain alkylzinc dithiophosphates, phosphoric acid esters such as
tricresyl phosphate, oils and fats such as lard, fatty acids, higher
alcohols, calcium carbonate, and potassium borate which have
significant press moldability improving effect and lubricating property
improving effect; phenol-based or amine-based antioxidants for
improving antioxidation performance; corrosion inhibitors for
improving corrosion preventive performance, such as benzotriazole or a
derivative thereof, thiadiazole, and benzothiazole; wetting agents such
as diethylene glycol monoalkylether; film-forming agents such as
acrylic polymers and slack waxes; antifoaming agents such as
methylsilicone, fluorosilicone, and polyacrylate, surfactants, and
mixtures thereof. It is to be noted that the content of the
above-described other additive agents is arbitrary, but the total content
of these additive agents is preferably 10 mass% or less based on the
total amount of the rust preventive oil composition according to the
present embodiment.
5 [0106] The rust preventive oil composition according to the present
embodiment does not substantially contain water, is made not to contain
water other than moisture that is naturally absorbed, and is used without
being diluted with water intentionally.
[0107] In the rust preventive oil composition according to the present
10 embodiment, the content of each of barium, zinc, chlorine, and lead is,
in terms of element, preferably 1000 mass pprn or less, more preferably
500 mass pprn or less, further preferably 100 mass pprn or less, further
more preferably 50 mass ppm or less, even more preferably 10 mass
pprn or V7 ss, particularly preferably 5 mass pprn or less, and further
15 preferably 1 mass ppm or less, based on the total amount of the
composition. When either one of these elements has a content
exceeding 1000 mass ppm, safety for environments such as human
bodies and ecosystems may become insuficient.
It is to be noted that the content of the element in the present
20 invention indicates a value measured by the following methods. That
is, the content means a content (mass ppm) based on the total amount of
the composition, measured in conformity with ASTM D 51 85-95 in the
case of barium, zinc, and lead, and IP "PROPOSED METHOD AW81
Determination of-chlorine Microcoulometry oxidative method" in the
25 case of chlorine. The detection limit of each element in the
above-described measuring methods is usually 1 mass ppm.
[0108] The rust preventive oil composition according to the present
embodiment may achieve all of a rust preventive property, a water
removal property, a degreasing property, storage stability, and a washing
property in a high level and a balanced manner, and may be suitably
5 used as a rust preventive oil for various metal members. In particular,
regarding a rust preventive property, time during which Grade A of rust
generation (rust generation of 0%) is maintained in a salt water spray
test specified by JIS K 2246 "Rust preventive oils" is 16 hours or more,
and non-conventional excellent performance is maintained.
10 The metal member that is a body to be treated is not particularly
limited, and specifically, examples thereof include surface-treated steel
sheets such as a cold-rolled steel sheet, a hot-rolled steel sheet, a
high-tensile steel sheet, and a zinc-coated steel sheet, which are to be an
1 automobile body or electriqal product body, metal sheet materials such
15 as a primitive sheet for tinning, an aluminum alloy sheet, and a
magnesium alloy sheet, and furthermore, bearing parts such as a rolling
bearing, a tapered rolling bearing, and a needle bearing, construction
steel, and precision parts.
Conventional rust preventive oils for the foregoing metal
20 members include intermediate rust preventive oils used during processes
such as a working process of metal members, shipping rust preventive
oils used to prevent rust during shipping, and washing rust preventive
oils used during a washing process for removing foreign bodies before
being subjected to press working or for removing foreign bodies before -
25 shipment in manufacturers of metal sheets, and the washing and rust
preventive oil composition of the present invention can be used for all
of these intended purposes.
[0109] A method of applying the rust preventive oil composition
according to the present embodiment to a body to be treated is not
particularly limited, and for example, it may be applied to a metal
5 member by spraying, dropping, transfer with a felt material or the like,
electrostatic oiling and the like. Among these applying methods, the
spraying method is preferable because an oil film thickness can be made
uniform by application with fine mist. A coating applicator when
using the spraying method is not particularly limited as long as the rust
10 preventive oil composition according to the present embodiment may be
atomized, and for example, any of an air spray type, an airless spray
type, and a hot-melt type may be used. In the application process, after
applying the excess washing and rust preventive oil composition, a step
of draining using a centrifugal separator, or a 93 tep of draining by being
15 left for long periods of time is preferably provided.
[0110] In the case where the rust preventive oil composition according
to the present embodiment is used as a wash oil, a large excessive
amount of the rust preventive oil composition according to the present
embodiment is supplied to the surface of the metal member by spraying,
20 showering, immersion application or the like so that good water
removal and subsequent rust prevention may be carried out.
Furthermore, by also carrying out surface cleaning using a roll brush or
the like after the above-described metal working process as necessary,
efficiency of removing foreign bodies can be increased.
25 [Olll] When carrying out washing using the mst preventive oil
composition according to the present embodiment, the amount of the oil
attached to the surface of the metal member is preferably adjusted by
also carrying out surface treatment of the metal member using a ringer
roll or the like.
[0112] In every case of the above-described applying methods of the
5 rust preventive oil composition according to the present embodiment, an
excessive amount of the washing and rust preventive oil composition
that has been applied to the metal member is preferably recovered,
circulated, and reused. In addition, it is preferable that, when
circulating the rust preventive oil coniposition according to the present
10 embodiment, removal of foreign bodies mixed in a circulating system
be also carried out. For example, the removal of foreign bodies may
be carried out by providing a filter in a circulation pathway of the rust
preventive oil composition according to the present embodiment, and
1
preferably shortly before spraying the rust preventive ~ $c1om position
15 according to the present embodiment toward the metal member.
Moreover, by providing a magnet at the bottom of a tank that stores the
rust preventive oil composition according to the present embodiment,
foreign bodies such as abrasion powder can be absorbed by magnetic
force to be removed.
20 [0113] Performance of the rust preventive oil composition reused in
such a process may be decreased due to mixing of a preceding process
oil or the like. Therefore, it is preferable that, when reusing the rust
preventive oil composition according to the present embodiment,
periodic measurement of the kinematic viscosity and the density of an
25 oil to be used, a copper corrosion test, a rust preventive property test and
the like be carried out to manage the properties, and oil change, drain
disposal, tank cleaning, an oil purifying operation and the like be carried
out as necessary.
[0114] Regarding a disposed oil solution, the oil solution is used
directly, or with being diluted with a solvent or a low-viscosity base oil,
in a line whose required performance for the washing and rust
preventive oil composition is lower than a line used before disposal so
that the total amount of the oil used may be decreased. When the rust
preventive oil composition according to the present embodiment is
stored in a tank, it is preferably supplied depending on the amount of the
composition reduced in the tank. In this case, not always the same
composition as the composition that is filled initially, but a composition
in which an additive agent for eliciting performance to be enhanced is
increased or the like may be supplied on a moment-to-moment basis.
7
Alternatively, a composition whose viscosity is decreased by a method
of reducing the content of a high-viscosity base oil or the like may be
supplied to maintain washing capacity of the washing and rust
preventive oil composition.
[0115] When the rust preventive oil composition according to the
present embodiment is used in a washing process for removing foreign
bodies before shipment in a manufacturer of metal sheets, metal sheets
may be shipped by being wound in a coil immediately after the washing
process or being stacked as sheet materials. This method has the
advantage in that the amount of foreign bodies attached is small and
washing may be easily and surely carried out even when carrying out
the washing process with the washing rust preventive oil shortly before
a press process in press working. It should be understood that rust
preventive treatment may be carried out in two stages by providing a
process of applying a rust preventive oil again after a washing process
with a washimg rust preventive oil at a steel sheet manufacturing place.
5 Examples
[0116] Hereinafter, the present invention will be described in further
detail with reference to examples and comparative examples, but the
present invention is not limited to the following examples.
[0117] [Examples 1 to 42, Comparative Examples 1 to 151
10 In Examples 1 to 42 and Comparative Examples 1 to 15, rust
preventive oil compositions having compositions shown in Tables 1 to 6
were prepared, respectively, using components shown below.
(A) component
Al: a mineral oil having a kinematic viscosity at 40°C of 0.9 mm2/s
15 (aromatic component: 0.1 mass% or less)
A2: a mineral oil having a kinematic viscosity at 40°C of 1.6 mm2/s
(aromatic component: 0.1 mass% or less)
A3: a mineral oil having a kinematic viscosity at 40°C of 1.9 d s
(aromatic component: 4.8 mass% or less)
20 A4: a mineral oil having a kinematic viscosity at 40°C of 8.4 rnm2/s
AS: a mineral oil having a kinematic viscosity at 40°C of 23 mm2/s
A6: a mineral oil having a kinematic viscosity at 40°C of 68 mm2/s
A7: a mineral oil having a kinematic viscosity at 40°C of 195 mm2/s
A8: a mineraloil having a kinematic viscosity at 40°C of 461 mm2/s
25 A9: a mineral oil having a kinematic viscosity at 40°C of 586 mm2/s
(B) component
B1: C8 alkylamine salt of C8 fatty acid
B2: C18 alkylamine salt of C8 fatty acid
B3: C8 alkylamine salt of C18 fatty acid
B4: C18 alkylamine salt of C18 fatty acid
5 (C) component
C1: lanolin fatty acid partial ester of pentaerythritol
C2: sorbitan monoisostearate
C3: sorbitan monooleate
C4: trimethylolpropane monooleate
10 (D) component
Dl : oleoyl sarcosine (N-Methyloleamidoacetic acid)
D2: ethylenediamine sulfonate
D3: basic Ca sulfonate (base value: 95 mgKOWg)
D4: paraffin wax
15 [0118] Next, for the respective rust preventive oil compositions of
Examples 1 to 42 and Comparative Examples 1 to 15, the following
evaluation tests were carried out.
[0119]
20 The evaluation was carried out in conformity with a neutral salt
water spray test of JIS K 2246 "Rust preventive oils". It is to be noted
that polishing of a test piece was carried out in conformity with a water
displacement test method of JIS K 2246 "Rust preventive oils1', using A,
PlOO abrasive. Before carrying out the test, the test piece was
25 immersed in tap water for 5 minutes in advance with being kept in a
horizontal position, immediately after that, was immersed in a rust
preventive oil for 5 seconds with being kept in a horizontal position, and
then, was taken out with being kept in a horizontal position and was left
to stand for 3 hours in a constant temperature and humidity bath at 50°C
and 95%. After that, the neutral salt water spray test was carried out in
5 conformity with the test method. Time (h) until rust was generated
was measured and evaluated, and the evaluation was carried out each
predetermined time (16, 24, 36, 48 hours). The evaluation was carried
out with the test number of 3, based on JIS Act. The obtained results
are shown in Tables 1 to 6.
10 It is to be noted that one in which stability of an oil solution was
poor and separation was observed was subjected to the test after being
sufficiently stirred.
If water removal performance is insufficient, rust due to water is
generated, and thus, in the present evaluation, a water removal property
15 can be evaluated in addition to a rust preventive property of the oil
solution itself.
[0120]
1 L of ion-exchange water was added to 1 L of an oil solution to
be stirred for 10 hours in a 5 L beaker with intensity for suspending the
20 whole (fxst day). After that, it was left to stand, and the following day,
the same operation was carried out. This was repeated 10 times. On
the first day, third day, fifth day, and tenth day, after the stirring, an oil
layer was separated to be used as a test oil, and a neutral salt water spray
test of JIS K 2246 was carried out and a degree of a decrease in rust
25 preventive performance was compared. The evaluation of a rust
preventive property was evaluated by observing a state of a test piece
after 24 hours. The obtained results are shown in Tables 1 to 6.
[0121]
After preparing a rust preventive oil composition, it was held in
a constant temperature bath adjusted to 45OC for 240 hours, and the
5 presence or absence of separation of an oil solution was visually
evaluated. Lack of separation was indicated by "Absence", and
separation was indicated by "Presence". The obtained results are
shown in Tables 1 to 6.
[0122]
10 The kinematic viscosity at 40°C of the rust preventive oil
composition was measured in conformity with JIS K 2283. The
obtained results are shown in Tables 1 to 6.
CLAIMS
[Claim 1]
A rust preventive oil composition containing:
a first mineral oil that is a mineral oil having a kinematic
5 viscosity at 40°C of 6 mm2/s or less;
a second mineral oil that is a mineral oil having a kinematic
viscosity at 40°C of 250 d s or more;
a fatty acid amine salt;
an ester; and
10 one or more rust preventive agents selected ffom the group
consisting of a sarcosine-type compound, a nonionic surfactant, a
sulfonic acid salt, an amine, a carboxylic acid, a fatty acid amine salt, a
carboxylic acid salt, a paraffin wax, an oxidized wax salt, and a boron
compound.
15 [Claim 2]
The rust preventive oil composition according to claim 1, further
containing a third mineral oil that is a mineral oil having a kinematic
viscosity at 40°C of 10 mm2/s or more and 120 rnm2/s or less.
[Claim 3]
20 The rust preventive oil composition according to claim 1 or 2,
wherein an aromatic component content of the first mineral oil is 3
mass% or less based on a total amount of the first mineral oil.
[Claim 4]
The rust preventive oil composition according to any one of
25 claims 1 to 3, wherein time during which Grade A of rust generation
(rust generation of 0%) is maintained in a neutral salt water spray test
FP12-0665-00
specified by JIS K 2246 "Rust preventive oils" is 16 hours or more.