TECHNICAL FIELD
[0001] The present invention relates to a lubricating oil composition and a method for manufacturing
a lubricating oil composition; more specifically, it relates to a lubricating oil
composition having excellent initial antifoaming performance, capable of maintaining
its antifoaming performance in storage, due to the use of a specific antifoaming agent
dispersion system, and a method for manufacturing the lubricating oil composition.
BACKGROUND ART
[0002] In order to inhibit foaming during usage and maintain the various characteristics
of lubricating oil, antifoaming agent has always been added to the lubricant base
oil.
[0003] A method for diluting and dispersing polydimethylsiloxane having a specific molecular
weight, used as an antifoaming agent, in kerosene or gas oil, and mixing it into the
lubricating oil, is known, and polydimethylsiloxane is considered to be finely dispersed
in lubrication oil (
JP 2008-120889 A). A method of dissolving and dispersing perfluoroalkyl-modified organopolysiloxane,
as an antifoaming agent, in kerosene, and mixing it into the lubricating oil, is known
(
JP 2010-116493 A). A lubricating oil composition, comprising a base oil having high solubility for
additives and polyfluoroalkyl-modified organopolysiloxane as an antifoaming agent,
is known, and a mode whereby polyfluoroalkylsiloxane is mixed beforehand into a base
oil at approximately 1% by weight, finely dispersed to ≤10 µm, using a homomixer or
a homogenizer, to yield a concentrate, and then mixed, at a specific quantity, into
the base oil, was disclosed (
JP 2000-087069 A). The addition of an antifoaming agent solution, consisting of a combination of fluorinated
silicone, a specific fluorine-containing organic compound and a hydrocarbon-based
or alcohol-based organic solvent, to the lubricant base oil, is known (
JP 2010-132792 A). A method for diluting and dispersing perfluoropolyether polysiloxane block copolymer
as an antifoaming agent in kerosene, gas oil or another organic solvent, adjusting
the mean particle size of the block copolymer to ≤0.1µm and adding it to a base oil
is disclosed (
JP 2012-062350 A).
Prior Art Documents
Patent Documents
SUMMARY OF THE INVENTION
Problem(s) To Be Solved By the Invention
[0005] In recent years there has been progress in lowering the viscosity of lubricating
oil compositions, especially of lubricating oil compositions for automobiles, such
as lubricating oil compositions for internal combustion engines, lubricating oil compositions
for transmissions and lubricating oil composition for gears. The problem was, however,
that the antifoaming performance could not be maintained by using existing antifoaming
agents. This is because antifoaming agents are not moderately dispersed in the lubricant
base oil. In order to improve their dispersion, techniques of dispersing the antifoaming
agent in a solvent and then adding and dispersing it in the lubricant base oil have
been disclosed.
[0006] While dispersion is improved by conventional techniques in the case of lubricant
base oils having somewhat low viscosity, when the viscosity is decreased in order
to further improve the fuel efficiency, the dispersibility in the lubricant base oil
deteriorates. A new technique of further decreasing viscosity was therefore sought
after.
Means For Solving the Problem(s)
[0007] In light of this problem, the inventors discovered that antifoaming agents can be
well dispersed in lubricating oil compositions and their antifoaming performance can
be improved by using a specific dispersion medium mixture and mixing it with an antifoaming
agent to obtain an antifoaming agent dispersion system, which is then mixed with the
lubricating oil composition.
[0008] The first invention of the present invention is a lubricating oil composition comprising
a lubricant base oil and an antifoaming agent contained in the lubricant base oil,
wherein the lubricating oil composition comprises a lubricant base oil and drops of
an antifoaming agent dispersion system dispersed in the lubricant base oil; the antifoaming
agent dispersion system comprises a dispersion medium mixture and an antifoaming agent
dispersed in the dispersion medium mixture; and the dispersion medium mixture comprises
a dispersion medium and an additive for dispersion.
[0009] The second invention of the present invention is a method for manufacturing a lubricating
oil composition comprising a lubricant base oil and an antifoaming agent contained
in the lubricant base oil, comprising the steps of mixing a dispersion medium and
an additive for dispersion to prepare a dispersion medium mixture; mixing an antifoaming
agent with the dispersion medium mixture and dispersing the antifoaming agent in the
dispersion medium mixture to prepare an antifoaming agent dispersion system; and then
dispersing the antifoaming agent dispersion system in a lubricant base oil.
[0010] The third invention of the present invention is a method for preparing an antifoaming
agent dispersion system, comprising the steps of mixing a dispersion medium and an
additive for dispersion to prepare a dispersion medium mixture; and mixing an antifoaming
agent with the dispersion medium mixture to disperse the antifoaming agent in the
dispersion medium mixture.
Effect of the Invention
[0011] The lubricating oil composition containing an antifoaming agent has a high antifoaming
performance even when the lubricant base oil has low viscosity.
MODE FOR CARRYING OUT THE INVENTION
[0012] The present invention will now be described in detail.
[0013] The first invention of the present invention is a lubricating oil composition comprising
a lubricant base oil and an antifoaming agent contained in the lubricant base oil,
wherein the lubricating oil composition comprises a lubricant base oil and drops of
an antifoaming agent dispersion system dispersed in the lubricant base oil; the antifoaming
agent dispersion system comprises a dispersion medium mixture and an antifoaming agent
dispersed in the dispersion medium mixture; and the dispersion medium mixture comprises
a dispersion medium and an additive for dispersion.
[0014] Preferable embodiments of the first invention are as follows:
- (1) The above-mentioned antifoaming agent is fluoroalkylpolysiloxane.
- (2) The above-mentioned additive for dispersion is at least one selected from the
group consisting of an ashless dispersant, a metallic detergent, an antiwear agent,
a friction conditioner and an extreme pressure agent.
- (3) The ashless dispersant, mentioned in (2), is selected from a succinimide compound,
a succinamide compound and combinations thereof.
- (4) The above-mentioned dispersion medium mixture has a kinematic viscosity of 5-50,000
mm2/s at 40°C.
- (5) The above-mentioned dispersion medium is selected from a mineral oil, a synthetic
oil and combinations thereof.
- (6) The antifoaming agent content in the above-mentioned lubricating oil composition
is 0.01-500 ppm in terms of elemental fluorine (F) and 0.05-400 ppm in terms of elemental
silicon (Si).
- (7) The above-mentioned lubricating oil composition is for a transmission, for a gear,
for gear oil, for a gear box, for an automotive gear box, for an industrial gear box,
or for a transmission fluid.
[0015] The second invention of the present invention is a method for manufacturing a lubricating
oil composition comprising a lubricant base oil and an antifoaming agent contained
in the lubricant base oil, comprising the steps of mixing a dispersion medium and
an additive for dispersion to prepare a dispersion medium mixture; mixing an antifoaming
agent with the dispersion medium mixture and dispersing the antifoaming agent in the
dispersion medium mixture to prepare an antifoaming agent dispersion system; and then
dispersing the antifoaming agent dispersion system in a lubricant base oil.
[0016] Preferable embodiments of the second invention are as follows:
- (1) The above-mentioned antifoaming agent is fluoroalkylpolysiloxane.
- (2) The above-mentioned additive for dispersion is at least one selected from the
group consisting of an ashless dispersant, a metallic detergent, an antiwear agent,
a friction conditioner and an extreme pressure agent.
- (3) The ashless dispersant, mentioned in (2), is selected from a succinimide compound,
a succinamide compound and combinations thereof.
- (4) The above-mentioned dispersion medium mixture has a kinematic viscosity of 5-50,000
mm2/s at 40°C.
- (5) The above-mentioned dispersion medium is selected from a mineral oil, a synthetic
oil and combinations thereof.
- (6) The antifoaming agent content in the above-mentioned lubricating oil composition
is 0.01-500 ppm in terms of elemental fluorine (F) and 0.05-400 ppm in terms of elemental
silicon (Si).
- (7) The above-mentioned lubricating oil composition is for a transmission, for a gear,
for gear oil, for a gear box, for an automotive gear box, for an industrial gear box,
or for a transmission fluid.
[0017] The third invention of the present invention is a method for preparing an antifoaming
agent dispersion system, comprising the steps of mixing a dispersion medium and an
additive for dispersion to prepare a dispersion medium mixture; and mixing an antifoaming
agent with the dispersion medium mixture to disperse the antifoaming agent in the
dispersion medium mixture.
[0018] Preferable embodiments of the third invention are as follows:
- (1) The above-mentioned antifoaming agent is fluoroalkylpolysiloxane.
- (2) The above-mentioned additive for dispersion is at least one selected from the
group consisting of an ashless dispersant, a metallic detergent, an antiwear agent,
a friction conditioner and an extreme pressure agent.
- (3) The ashless dispersant, mentioned in (2), is selected from a succinimide compound,
a succinamide compound and combinations thereof.
- (4) The above-mentioned dispersion medium mixture has a kinematic viscosity of 5-50,000
mm2/s at 40°C.
- (5) The above-mentioned dispersion medium is selected from a mineral oil, a synthetic
oil and combinations thereof.
(A) Antifoaming agent
[0019] An antifoaming agent used in the present invention is preferably, but not limited
to, fluoroalkylpolysiloxane.
[0020] Examples of an antifoaming agent include compounds having any one of the structures
of formulas (1) to (5), and especially a compound having the structure of formula
(5) is preferable.

where m+n = 8 to 45 and m/n = 20 to 100.

where o = 7 to 60.

where p+q = 40 to 180 and p/q = 0.5 to 2.

where r = 10 to 50. In the above formulas (1) to (4), X and X
1 are each independently selected from
- (i) a fluorine atom, and
- (ii) the group consisting of following (a) to (g):
- (a) -CH2OH
- (b) -CH2(OC2H4)tOH
- (c)

- (d)

- (e) -CH2COOH
- (f) -CF2COOH
- (g) -CF2COONH3-(CH2)5-CH3

where R is an organic group. An example of the organic group R in formula (5) is CxH2xCyF2y+1, where x is an integer of 1 to 6 and y is an integer of 1 to 14. For m and n, m:n
= 95:5 to 0:100. The organic group R may be linear or branched, but linear is preferable.
y is preferably an integer of 1 to 8, more preferably an integer of 1 to 6.
(B) Dispersion medium mixture
[0021] The dispersion medium mixture comprises an additive for dispersion and a dispersion
medium.
(B1) Dispersion medium
[0022] The dispersion medium in the dispersion medium mixture is preferably, but not limited
to, a dispersion medium usually used as a lubricant base oil, and is preferably selected
from a mineral oil, a synthetic oil and combinations thereof.
[0023] The mineral oil used as a dispersion medium includes, but is not limited to, paraffinic
mineral oils, naphthenic mineral oils, normal paraffins, isoparrafins, etc., obtained
by distilling a crude oil at a normal atmospheric pressure or under vacuum to prepare
a lubricating oil fraction and subjecting the lubricating oil fraction to one or more
of purification treatments such as solvent deasphalting, solvent extraction, hydrogenolysis,
solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid treatment and clay
treatment.
[0024] A method for manufacturing the mineral oil includes, but is not limited to, a method
comprising the steps of distilling a crude oil at a normal atmospheric pressure or
under vacuum to obtain a lubricating oil fraction and subjecting the lubricating oil
fraction to one or more of purification treatments such as solvent deasphalting, solvent
extraction, hydrogenolysis, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric
acid treatment and clay treatment.
[0025] Moreover, a single mineral oil may be used alone, or two or more mineral oils may
be used in combination at any ratio.
[0026] The synthetic oil used as a dispersion medium includes, but is not limited to, poly-α-olefins
or hydrogenated products thereof, isobutene oligomers or hydrogenated products thereof,
isoparaffin, alkylbenzene, alkylnaphthalene, diesters (such as ditridecyl glutarate,
di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate and di-2-ethylhexyl
sebacate), polyol esters (such as trimethylolpropane caprylate, trimethylolpropane
pelargonate, pentaerythritol 2-ethylhexanoate and pentaerythritol pelargonate), polyoxyalkylene
glycol, dialkyl diphenyl ether and polyphenyl ether.
[0027] A preferable synthetic oil includes poly-α-olefin. Typical examples of poly-α-olefin
include oligomers or co-oligomers of α-olefin having 2 to 32 carbon atoms, preferably
2 to 16 carbon atoms (such as 1-octene oligomer, 1-decene oligomer and ethylene-propylene
oligomer) and hydrogenated products thereof.
[0028] The method for manufacturing poly-α-olefin includes, but is not limited to, α-olefin
polymerization in the presence of a polymerization catalyst such as a Friedel-Crafts
catalyst including aluminum trichloride, boron trifluoride or a complex of boron trifluoride
with water, an alcohol (such as ethanol, propanol or butanol), a carboxylic acid or
an ester (such as ethyl or ethyl acetate propionate).
[0029] The kinematic viscosity of the dispersion medium at 100°C is preferably, but not
limited to, 2 to 1,000 mm
2/s, more preferably 5 to 500 mm
2/s, still more preferably 10 to 500 mm
2/s and most preferably 20 to 300 mm
2/s.
(B2) Additive for dispersion
[0030] The additive for dispersion is an agent having a function of raising the viscosity
of a mixture of the dispersion medium and the agent above the viscosity of the dispersion
medium alone when it is mixed with the dispersion medium. The additive for dispersion
is preferably at least one selected from the group consisting of an ashless dispersant,
metallic detergent, friction conditioner, antiwear agent and extreme pressure agent
among additives usually added to lubricating oil, but is not limited to these.
[0031] Of the above-mentioned additives for dispersion, an ashless dispersant is preferable.
A conventional publicly-known ashless dispersant may be used. The ashless dispersant
includes, but are not limited to, products obtained by modifying a nitrogen-containing
compound having at least one linear or branched C
40-400 alkyl or alkenyl group in one molecule or derivatives thereof or alkenylsuccinimide
with boron, etc. The ashless dispersant also includes products modified with carboxylic
acid, alcohol, aldehyde, ketone or alkylphenol, but a boron-modified product (hereinafter
referred to as a "boronated ashless dispersant") is preferable. One ashless dispersant
may be used alone, or two or more ashless dispersants may be used in combination.
The boronated ashless dispersant is a product obtained by boronating any ashless dispersant
used in lubricating oil. Boronation is generally conducted by reacting a nitrogen-containing
compound with boric acid to neutralize some or all of the remaining amino groups and/or
imino groups.
[0032] The carbon number of the above alkyl group or alkenyl group is preferably from 40
to 400, more preferably from 60 to 350. If the carbon number of the alkyl group or
alkenyl group is below the above lower limit, the solubility of the compound in the
lubricant base oil tends to decrease. If, on the other hand, the carbon number of
the alkyl group or alkenyl group exceeds the above upper limits, the low-temperature
fluidity of the lubricating oil composition tends to deteriorate. The above alkyl
group and alkenyl group may have a straight chain structure or a branched chain structure.
Preferable examples thereof include branched alkyl groups or branched alkenyl groups,
derived from oligomers of olefin, such as propylene, 1-butene and isobutylene, and
co-oligomers of ethylene and propylene.
[0033] Examples of succinimide include a so-called monotype succinimide, which is a reaction
product of one end of a polyamine and succinic anhydride, and a so-called bis-type
succinimide, which is a reaction product of both ends of polyamine and succinic anhydride.
The lubricating oil composition of the present invention may contain either the monotype
or the bis-type, or it may contain both.
[0034] The above modified alkenylsuccinimide may be, for example, a product obtained by
modifying a succinimide compound containing an alkenyl group with a boron compound
(hereinafter referred to as "boronated succinimide"). One boronated succinimide may
be used alone, or two or more boronated succinimides may be used in combination. A
boronated succinimide and an unboronated succinimide may be used in combination, and
a combination of two or more types of boronated succinimide may be used. Furthermore,
combined use of a monotype and a bis-type, combined use of two monotypes or combined
use of two bis-types is possible.
[0035] Examples of a method for manufacturing a boronated succinimide include methods disclosed
in Japanese Examined Patent Publication Nos.
S42-8013 and
S42-8014, Japanese Unexamined Patent Publication Nos.
S51-52381 and
S51-130408, etc. Specifically, it can be obtained, for example, by mixing polyamine, polyalkenylsuccinic
acid or anhydride, and a boron compound such as boric acid, borate ester or borate
salt with an organic solvent such as alcohols, hexane or xylene, a light lubricant
base oil, etc., and heat-treating them. The boron content of the boronated succinimide,
obtained in this way, can usually be from 0.1 to 4% by weight. A boron-modified alkenylsuccinimide
compound, i.e., boronated succinimide, is especially preferable, since the heat resistance,
oxidation resistance and wear prevention thereof are superior.
[0036] The boron content of the boronated ashless dispersant is usually, but not limited
to, 0.1 to 3% by weight based on the weight of the ashless dispersant. The boron content
of the ashless dispersant is preferably not less than 0.2% by weight, more preferably
not less than 0.4% by weight, and is preferably not more than 2.5% by weight, more
preferably not more than 2.0% by weight and still more preferably not more than 1.5%
by weight. The boronated ashless dispersant is preferably boronated succinimide, and
especially preferably boronated bis-succinimide.
[0037] The boronated ashless dispersant has a boron/nitrogen weight ratio (B/N ratio) of
preferably not less than 0.1, more preferably not less than 0.2, and preferably less
than 1.0, more preferably not more than 0.8.
[0038] A metallic detergent may also be used as the additive for dispersion in the dispersion
medium mixture. An example of a metallic detergent is a detergent containing an alkali
metal or an alkaline earth metal.
[0039] Examples of alkali metals and alkaline earth metals include, but are not limited
to, magnesium, barium, sodium and calcium.
[0040] Examples of the metallic detergent include, but are not limited to, sulfonates containing
an alkali metal or an alkaline earth metal, salicylates containing an alkali metal
or an alkaline earth metal, and phenates containing an alkali metal or an alkaline
earth metal.
[0041] Preferable examples of a sulfonate containing an alkali metal or an alkaline earth
metal include, but are not limited to, calcium sulfonate and magnesium sulfonate.
[0042] Preferable examples of a salicylate containing an alkali metal or an alkaline earth
metal include, but are not limited to, calcium salicylate and magnesium salicylate.
[0043] Preferable examples of a phenate containing an alkali metal or an alkaline earth
metal include, but are not limited to, calcium phenate and magnesium phenate.
[0044] The content of the alkali metal or an alkaline earth metal in the metallic detergent
is preferably, but is not limited to, from 0.1 to 20% by weight, more preferably from
0.5 to 15% by weight and still more preferably from 1.0 to 15% by weight. The metallic
detergent has a total base number of preferably, but not limited to, from 10 to 500
mgKOH/g, more preferably from 50 to 400 mgKOH/g and still more preferably from 150
to 400 mgKOH/g.
[0045] An antiwear agent may also be used as the additive for dispersion in the dispersion
medium mixture. A conventional publicly-known antiwear agent may be used.
[0046] Among them, a phosphorus-containing antiwear agent is preferable. For example, zinc
dithiophosphate (ZnDTP, also referred to as "ZDDP"), represented by following formula
(6), may be used.

In formula (6), R
1 and R
2 may be different or the same, and are a hydrogen atom or a C
1-26 monovalent hydrocarbon group. Examples of a monovalent hydrocarbon group include
a C
1-26 primary or secondary alkyl group; a C
2-26 alkyenyl group; a C
6-26 cycloalkyl group; a C
6-26 aryl group, alkylaryl group or arylalkyl group; or a hydrocarbon group containing
an ester bond, ether bond, alcohol group or a carboxyl group. R
1 and R
2 are preferably a C
2-12 primary or secondary alkyl group, C
8-18 cycloalkyl group or C
8-18 alkylaryl group, and they may be different or the same. Zinc dialkyldithiophosphate
is especially preferable, and the primary alkyl group has preferably 3 to 12 carbon
atoms, more preferably 4 to 10 carbon atoms. The secondary alkyl group has preferably
3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. In order to increase the
torque reduction rate, zinc dialkyldithiophosphate having a secondary alkyl group
is preferable. One of the above-mentioned zinc thiophosphates may be used alone or
two or more thereof may be used in mixture. Moreover, zinc dithiocarbamate (ZnDTC)
may be used in combination therewith.
[0047] Moreover, at least one compound selected from phosphate- and phosphite-based phosphorus
compounds represented by formulas (7) and (8) below and metal salts and amine salts
thereof may be used.

In formula (7), R
3 is a C
1-30 monovalent hydrocarbon group, R
4 and R
5 are each independently a hydrogen atom or a C
1-30 monovalent hydrocarbon group, and m is 0 or 1.

In formula (8), R
6 is a C
1-30 monovalent hydrocarbon group, R
7 and R
8 are each independently a hydrogen atom or a C
1-30 monovalent hydrocarbon group, and n is 0 or 1.
[0048] Examples of the C
1-30 monovalent hydrocarbon group represented by R
3 to R
8 in formulas (7) and (8) include an alkyl group, cycloalkyl group, alkenyl group,
alkylsubstituted cycloalkyl group, aryl group, alkylsubstituted aryl group and arylalkyl
group. In particular, it is preferably a C
1-30 alkyl group or a C
6-24 aryl group, more preferably a C
3-18 alkyl group, and most preferably a C
4-15 alkyl group.
[0049] Examples of the phosphorus compound represented by formula (7) include monoesters
of phosphorous acid and hydrocarbylphosphonous acids having one of the above C
1-30 hydrocarbon groups; diesters of phosphorous acid, diesters of monothiophosphorous
acid and monoesters of hydrocarbylphosphonous acid having two of the above C
1-30 hydrocarbon groups; triesters of phosphorous acid and diesters of hydrocarbylphosphonous
acid having three of the above C
1-30 hydrocarbon groups; and mixtures thereof.
[0050] Metal salts or amine salts of the phosphorus compounds represented by formulas (7)
or (8) can be obtained by reacting the phosphorus compounds represented by formulas
(7) and (8) with a metallic base, such as a metal oxide, metal hydroxide, metal carbonate,
and metal chloride, a nitrogen compound, such as ammonia, and an amine compound having,
in its molecule, only a C
1-30 hydrocarbon group or a hydroxyl group-containing hydrocarbon group, or the like,
and neutralizing part or all of the remaining acidic hydrogen. Examples of a metal
in the above-mentioned metallic base include an alkali metal such as lithium, sodium,
potassium, and cesium; an alkaline earth metal such as calcium, magnesium, and barium;
a heavy metal such as zinc, copper, iron, lead, nickel, silver, and manganese (except
for molybdenum). Of these, an alkaline earth metal, such as calcium and magnesium,
and zinc are preferable, and zinc is especially preferable.
[0051] A friction conditioner may also be used as the additive for dispersion in the dispersion
medium mixture. Examples of the friction conditioner include, but are not limited
to, a molybdenum-based friction conditioner. Moreover, friction conditioners other
than a molybdenum-based friction conditioner may also be used, and examples thereof
include ester-based friction conditioners, amine-based friction conditioners and ether-based
friction conditioners.
[0052] Conventional publicly-known molybdenum-based friction conditioners can be used. Examples
of a molybdenum-based friction conditioner include, but are not limited to, sulfur-containing
organomolybdenum compounds such as molybdenum dithiophosphate (MoDTP) and molybdenum
dithiocarbamate (MoDTC); complexes of a molybdenum compound with a sulfur-containing
organic compound or another organic compound; complexes of sulfur-containing molybdenum
compounds, such as molybdenum sulfide and sulfurized molybdenum acid, with alkenylsuccinimide;
etc. Examples of the above molybdenum compounds include molybdenum oxides such as
molybdenum dioxide and molybdenum trioxide; molybdic acids such as orthomolybdic acid,
paramolybdic acid, and molybdic acid (poly)sulfide; salts of molybdic acid such as
metal salts and ammonium salts of the above molybdic acids; molybdenum sulfides such
as molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, and molybdenum
polysulfide; molybdic sulfide acid; metal salts or amine salts of sulfurized molybdic
acid; molybdenum halides such as molybdenum chloride; etc. Examples of the above sulfur-containing
organic compounds include alkyl(thio)xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate,
tetrahydrocarbylthiuram disulfide, bis(di(thio)hydrocarbyl dithiophosphonate) disulfide,
organo(poly)sulfide, sulfurized esters, etc. Organomolybdenum compounds such as molybdenum
dithiophosphate (MoDTP) and molybdenum dithiocarbamate (MoDTC) are especially preferable.
[0053] Molybdenum dithiocarbamate (MoDTC) is a compound represented by following formula
[I] and molybdenum dithiophosphate (MoDTP) is a compound represented by following
formula [II].

[0054] In formulas [I] and [II], R
1 to R
8 may be different or the same, and are a C
1-30 monovalent hydrocarbon group. The hydrocarbon group may be linear or branched. Examples
of the monovalent hydrocarbon group include a C
1-30 linear or branched alkyl group; a C
2-30 alkyenyl group; a C
4-30 cycloalkyl group; a C
6-30 aryl group, alkylaryl group or arylalkyl group; etc. In the arylalkyl group, the
aryl may bond to any position of the alkyl group. In the alkylaryl group, the alkyl
may bond to any position of the aryl group. More specifically, examples of the alkyl
group include a methyl group, ethyl group, propyl group, butyl group, pentyl group,
hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl
group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl
group, octadecyl group, etc., and branched alkyl groups thereof, and a C
3-8 alkyl group is especially preferable. Moreover, X
1 and X
2 are oxygen atoms or sulfur atoms, and Y
1 and Y
2 are oxygen atoms or sulfur atoms.
[0055] In addition, organomolybdenum compounds not containing sulfur may also be used. Examples
of such compounds include molybdenum-amine complexes, molybdenum-succinimide complexes,
molybdenum salts of organic acids, molybdenum salts of alcohols, etc.
[0056] An extreme pressure agent may also be used as the additive for dispersion in the
dispersion medium mixture. An extreme pressure agent is preferably, but not limited
to, at least one extreme pressure agent selected from the group consisting of phosphorus-based
extreme pressure agent, sulfur-based extreme pressure agent and phosphorus-sulfur-based
extreme pressure agent.
[0057] Examples of phosphorus-based extreme pressure agents include phosphoric acid, phosphorous
acid, and phosphates and phosphites having a C
2-30, preferably C
3-20 hydrocarbon group, and salts thereof.
[0058] Examples of sulfur-based extreme pressure agents include sulfurized oils and fats,
sulfurized olefins, dihydrocarbyl polysulfides, dithiocarbamates, thiadiazoles and
benzothiazoles.
[0059] Moreover, examples of phosphorus-sulfur-based extreme pressure agents include thiophosphoric
acid, thiophosphorous acid, thiophosphates and thiophosphites having a C
2-30, preferably C
3-20 hydrocarbon group, and salts thereof, and zinc dithiophosphate.
[0060] Examples of suitably used extreme pressure agentsinclude at least one phosphorus-based
extreme pressure agent selected from phosphorous acid, monoesters of phosphorous acid,
diesters of phosphorous acid, triesters of phosphorous acid and salts thereof; at
least one sulfur-based extreme pressure agent selected from sulfurized fats and oils,
olefin sulfides, dihydrocarbyl polysulfides, dithiocarbamates, thiadiazoles and benzothiazoles;
and/or at least one phosphorus-sulfur-based extreme pressure agent selected from thiophosphorous
acid, monoesters of thiophosphorous acid, diesters of thiophosphorous acid, triesters
of thiophosphorous acid, dithiophosphorous acid, monoesters of dithiophosphorous acid,
diesters of dithiophosphorous acid, triesters of dithiophosphorous acid, trithiophosphorous
acid, monoesters of trithiophosphorous acid, diesters of trithiophosphorous acid,
triesters of trithiophosphorous acid, and salts thereof.
[0061] Examples of the above-mentioned C
2-30 hydrocarbon group include an alkyl group, cycloalkyl group, alkylcycloalkyl group,
alkenyl group, aryl group, alkylaryl group and arylalkyl group.
[0062] Examples of the alkyl group include ethyl group, propyl group, butyl group, pentyl
group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group,
heptadecyl group, octadecyl group, etc. These alkyl groups may be linear or branched.
[0063] Examples of the cycloalkyl group include a C
5-7 cycloalkyl group such as a cyclopentyl group, cyclohexyl group, and cycloheptyl group.
[0064] Examples of the alkylcycloalkyl group include a C
6-11 alkylcycloalkyl group such as methylcyclopentyl group, dimethylcyclopentyl group,
methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl
group, methylethylcyclohexyl group, diethylcyclohexyl group, methylcycloheptyl group,
dimethylcycloheptyl group, methylethylcycloheptyl group and diethylcycloheptyl group.
The alkyl group(s) may bond to any position on the cycloalkyl group.
[0065] Examples of the alkenyl group include a butenyl group, pentenyl group, hexenyl group,
heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl
group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group,
heptadecenyl group and octadecenyl group. These alkenyl groups may be linear or branched,
and the double bond may exist at any position of the group.
[0066] Examples of the aryl group include a phenyl group, naphthyl group, etc.
[0067] Examples of the alkylaryl group include a C
7-18 alkylaryl group such as a tolyl group, xylyl group, ethylphenyl group, propylphenyl
group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group,
octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group and dodecylphenyl
group. The alkyl group may be linear or branched, and may bond to any position of
the aryl group.
[0068] Examples of the arylalkyl group include a C
7-12 arylalkyl group such as a benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl
group, phenylpentyl group, and phenylhexyl group. The alkyl group may be linear or
branched.
[0069] Concrete preferable examples of the phosphorus-based extreme pressure agent include
monobutyl phosphate, monooctyl phosphate, monolauryl phosphate, dibutyl phosphate,
dioctyl phosphate, dilauryl phosphate, tributyl phosphate, trioctyl phosphate, trilauryl
phosphate, triphenyl phosphate;, monobutyl phosphite, monooctyl phosphite, monolauryl
phosphite, dibutyl phosphite, dioctyl phosphite, dilauryl phosphite, tributyl phosphite,
trioctyl phosphite, trilauryl phosphite, triphenyl phosphite; and salts thereof. Of
these, phosphite-based extreme pressure agents are preferable, and extreme pressure
agents based on diester of phosphorous acid are especially preferable.
[0070] Concrete preferable examples of the phosphorus-sulfur-based extreme pressure agent
include monobutyl thiophosphate, monooctyl thiophosphate, monolauryl thiophosphate,
dibutyl thiophosphate, dioctyl thiophosphate, dilauryl thiophosphate, tributyl thiophosphate,
trioctyl thiophosphate, triphenyl thiophosphate, trilauryl thiophosphate; monobutyl
thiophosphite, monooctyl thiophosphite, monolauryl thiophosphite, dibutyl thiophosphite,
dioctyl thiophosphite, dilauryl thiophosphite, tributyl thiophosphite, trioctyl thiophosphite,
triphenyl thiophosphite, trilauryl thiophosphite having one to three, preferably two
or three, more preferably three sulfur atoms per molecule; and salts thereof. Of these,
thiophosphite-based extreme pressure agents are preferable, and trithiophosphite-based
extreme pressure agents are especially preferable.
[0071] Moreover, examples of salts of (thio)phosphates and (thio)phosphites include salts
obtained by reacting a (thio)phosphate monoester, (thio)phosphate dister, (thio)phosphite
monoester, (thio)phosphite diester, etc., with a nitrogen compound such as ammonia
and an amine compound containing only a C
1-8 hydrocarbon group or hydroxyl-containing hydrocarbon group in its molecule, or a
metallic base such as zinc oxide and zinc chloride to neutralize part or all of the
remaining acidic hydrogen.
[0072] Specific examples of the above nitrogen compound include ammonia; alkylamines, in
which the alkyl group may be linear or branched, such as monomethylamine, monoethylamine,
monopropylamine, monobutylamine, monopentylamine, monohexylamine , monoheptylamine,
monooctylamine, dimethylamine, methylethylamine, diethylamine, methylpropylamine,
ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine,
dibutylamine, dipentylamine, dihexylamine, diheptylamine, and dioctylamine; alkanolamines,
in which the alkanol group may be linear or branched, such as monomethanolamine, monoethanolamine,
monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, monoheptanolamine,
monooctanolamine, monononanolamine, dimethanolamine, methanolethanolamine, diethanolamine,
methanolpropanolamine, ethanolpropanolamine, dipropanolamine, methanolbutanolamine,
ethanolbutanolamine, propanolbutanolamine, dibutanolamine, dipentanolamine, dihexanolamine,
diheptanolamine, and dioctanolamine; and mixtures thereof.
[0073] Examples of sulfurized fats and oils include oils such as sulfurized lard, sulfurized
rapeseed oil, sulfurized castor oil, sulfurized soybean oil, and sulfurized rice bran
oil; fatty acid disulfide such as oleic acid sulfide; and sulfurized esters such as
sulfurized methyl oleate.
[0074] Examples of olefin sulfides include compounds represented by following formula (9).
R
11-S
x-R
12 (9)
In formula (9), R
11 is a C
2-15 alkenyl group, R
12 is a C
2-15 alkyl group or alkenyl group, and x is an integer of 1 to 8.
[0075] This compound can be obtained by reacting a C
2-15 olefin or a dimer, trimer or tetramer thereof with a sulfurizing agent such as sulfur
and sulfur chloride. Preferable examples of the olefin include propylene, isobutene
and diisobutene.
[0076] Dihydrocarbyl polysulfide is a compound represented by following formula (10).
R
13-S
y-R
14 (10)
In formula (10), R
13 and R
14 represent each independently a C
1-20 alkyl group (including cycloalkyl group), a C
6-20 aryl group and a C
7-20 arylalkyl group, and they may be different or the same, and y is an integer of 2
to 8.
[0077] Specific examples of R
13 and R
14 include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various
hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various
decyl groups, various dodecyl groups, cyclohexyl group, phenyl group, naphthyl group,
tolyl group, xylyl group, benzyl group, phenethyl group, etc.
[0078] Specific preferable examples of dihydrocarbyl polysulfide include dibenzyl polysulfide,
di-tert-nonyl polysulfide, didodecyl polysulfide, di-tert-butyl polysulfide, dioctyl
polysulfide, diphenyl polysulfide, dicyclohexyl polysulfide, etc.
[0079] Regarding the weight ratio of the additive for dispersion to the dispersion medium
in the dispersion medium mixture, the dispersion medium mixture comprises preferably,
but not limited to, 5 to 95% by weight of the additive for dispersion and 95 to 5%
by weight of the dispersion medium, more preferably 10 to 90% by weight of the additive
for dispersion and 90 to 10% by weight of the dispersion medium, and most preferably
20 to 80% by weight of the additive for dispersion and 80 to 20% by weight of the
dispersion medium.
[0080] The dispersion medium mixture can be obtained by mixing and stirring the dispersion
medium with the additive for dispersion at a temperature within the range of 30 to
80°C. Into the dispersion medium mixture obtained in this way, an antifoaming agent
is added at a quantity of 0.1 to 10% by weight, preferably 0.3 to 2% by weight, and
dispersed using a homogenizer or a nozzle injector. Since the kinematic viscosity
of the dispersion medium mixture has increased, the antifoaming agent disperses better
than when an antifoaming agent is dispersed in a solvent such as kerosene.
[0081] When a homogenizer is used, they are stirred preferably at a high-speed rotation
of 8,000 to 24,000 rpm for 1 to 15 minutes, and more preferably at 15,000 to 20,000
rpm for 5 to 10 minutes, but the rotating speed and stirring duration are not limited
to these.
[0082] When a nozzle injector is used, the liquid pressure and the liquid flow rate are
not limited. The liquid pressure is preferably from 30 MPa to 200 MPa, more preferably
from 100 MPa to 200 MPa.
[0083] In other words, provided is a method for producing an antifoaming agent dispersion
system, comprising the steps of mixing an antifoaming agent with a dispersion medium
mixture comprising an additive for dispersion and a dispersion medium, and dispersing
the antifoaming agent in the dispersion medium mixture using a homogenizer or a nozzle
injector.
[0084] Thus, the initial dispersion performance and the dispersion performance after storage
of the antifoaming agent in the dispersion medium mixture are increased.
[0085] Moreover, when a lubricating oil composition is made using the antifoaming agent
dispersion system, the dispersion performance of the antifoaming agent in the lubricating
oil composition is good not only initially but also after long-term storage.
[0086] The lubricating oil composition of the present invention can be suitably used as
lubricating oil compositions for an automobile, such as lubricating oil compositions
for internal combustion engines, lubricating oil compositions for transmissions and
lubricating oil composition for gears. The lubricating oil composition for transmissions
can be used for any of non-stage transmission oil, stage transmission oil and motor
speed changer oil.
(C) Lubricant base oil
[0087] The lubricant base oil used in a lubricating oil composition is preferably selected
from, but not limited to, mineral oils, synthetic oils and combinations thereof.
[0088] The mineral oil used as a lubricant base oil include, but not limited to, paraffinic,
naphthenic and other mineral oils and normal paraffin, isoparrafin, etc., obtained
by distilling crude oil at a normal atmospheric pressure or under vaccum to obtain
a lubricating oil distillate fraction and purifying the lubricating oil distillate
fraction by use of one or a combination of two or more of purification treatments
such as solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing,
catalytic dewaxing, hydrorefining, sulfuric acid treatment and clay treatment.
[0089] An example of a method for manufacturing the mineral oil includes, but is not limited
to, a method comprising the steps of distilling crude oil at a nornal atmospheric
pressure or under vacuum to obtain a lubricating oil fraction; and purifying the lubricating
oil fraction by use of one or a combination of two or more of purification treatments
such as solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing,
catalytic dewaxing, hydrorefining, sulfuric acid treatment and clay treatment.
[0090] Moreover, one of these mineral oils may be used alone, or two or more thereof may
be used in combination at any ratio.
[0091] The synthetic oil used as a lubricant base oil includes, but not limited to, poly-α-olefins
or hydrogenated products thereof, isobutene oligomers or hydrogenated products thereof,
isoparaffin, alkylbenzene, alkylnaphthalene, diesters (such as ditridecyl glutarate,
di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate and di-2-ethylhexyl
sebacate), polyol esters (such as trimethylolpropane caprylate, trimethylolpropane
pelargonate, pentaerythritol 2-ethylhexanoate and pentaerythritol pelargonate), polyoxyalkylene
glycol, dialkyl diphenyl ether, polyphenyl ether, etc.
[0092] A preferable synthetic oil includes poly-α-olefin. Typical examples of poly-α-olefin
include oligomers or co-oligomers of α-olefins having 2 to 32 carbon atoms, preferably
2 to 16 carbon atoms (such as 1-octene oligomer, 1-decene oligomer and ethylene-propylene
oligomer) and hydrogenated products thereof.
[0093] An example of a method of manufacturing poly-α-olefin include, but are not limited
to, a method comprising the step of polymerizing α-olefin in the presence of a polymerization
catalyst such as a Friedel-Crafts catalyst including aluminum trichloride, boron trifluoride
or a complex of boron trifluoride with water, an alcohol (such as ethanol, propanol
or butanol), a carboxylic acid or an ester (such as ethyl acetate or ethyl propionate).
[0094] One of these synthetic oils may be used alone, or two or more synthetic oils may
be used in combination at any ratio.
[0095] Moreover, the above mineral oil(s) and synthetic oil(s) may be used in combination
at any ratio, wherein one mineral or synthetic oil may be used, or two or more mineral
or synthetic oils may be used.
[0096] The kinematic viscosity of the lubricant base oil at 100°C is, but not limited to,
preferably 1 to 300 mm
2/s, more preferably 1 to 100 mm
2/s, still more preferably 1 to 50 mm
2/s and most preferably 1 to 30 mm
2/s.
(D) Additives to the lubricant base oil
[0097] In addition to the antifoaming agent, any publicly-known additives may be added to
the lubricant base oil.
[0098] Examples of the additive include, but are not limited to, an ashless dispersant,
metallic detergent, antiwear agent, friction conditioner, extreme pressure agent,
viscosity index improver, metal deactivator, pour point depressant, antioxidant, etc.
[0099] Conventional publicly-known ashless dispersants, metallic detergents, antiwear agents,
friction conditioners and extreme pressure agents may be used, and no particular restrictions
are placed on it. Specifically, the additives for dispersion described above may be
suitably used.
[0100] Examples of a viscosity index improver include polymethacrylate, dispersed polymethacrylate,
olefin copolymer (polyisobutylene, ethylene-propylene copolymer), dispersed olefin
copolymer, polyalkylstyrene, hydrogenated styrene-butadiene copolymer, styrene-maleic
anhydride ester copolymer, star isoprene, etc. In addition, a comb polymer, whose
backbone comprises at least a repeating unit based on polyolefin macromer and a repeating
unit based on alkyl (meth)acrylate having a C
1-30 alkyl group, can be also used.
[0101] Examples of the metal deactivator include imidazoline, pyrimidine derivatives, alkylthiadiazole,
mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide,
1,3,4-thiadiazolyl-2,5-bis-dialkyl dithiocarbamate, 2-(alkyldithio)benzimidazole,
β-(o-carboxybenzylthio)propiononitrile, etc.
[0102] As a pour point depressant, for example, a polymethacrylate-based polymer that suits
a used lubricant base oil, etc. can be used.
[0103] Examples of an antioxidant include phenol-based or amine-based ashless antioxidants,
and metal-based antioxidants such as copper-based and molybdenum-based antioxidants.
Examples of phenol-based ashless antioxidants include 4,4'-methylene-bis(2,6-di-tertbutylphenol),
4,4'-bis(2,6-di-tert-butylphenol), isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)proprionate,
and the like. Examples of amine-based ashless antioxidants include phenyl-α-naphthylamine,
alkylphenyl-α-napthylamine, dialkyldiphenylamine, etc.
[0104] These additives may be suitably added according to the intended usage. The quantity
added depends on the usage, but is from 0 to 20% by weight of the lubricating oil
composition.
[0105] A lubricating oil composition is provided by mixing an antifoaming agent with a dispersion
medium mixture consisting of an additive for dispersion and a dispersion medium, and
dispersing the antifoaming agent in the dispersion medium mixture using a homogenizer
or a nozzle injector to form an antifoaming agent dispersion system, and mixing the
antifoaming agent dispersion system with a lubricant base oil.
[0106] Moreover, a method of manufacturing a lubricating oil composition, comprising mixing
an antifoaming agent with a dispersion medium mixture consisting of an additive for
dispersion and a dispersion medium, and dispersing the antifoaming agent in the dispersion
medium mixture using a homogenizer or a nozzle injector to form an antifoaming agent
dispersion system, and mixing the antifoaming agent dispersion system with a lubricant
base oil, is provided.
EXAMPLES
[0107] The present invention will now be explained by means of examples and comparative
examples.
[0108] Lubricating oil compositions for transmissions are illustrated in the following examples,
but the present invention is not limited to or by these examples.
(Example 1)
[0109] FA-630® (Shin-Etsu Chemical Co., Ltd.), which is one of fluoroalkylpolysiloxanes,
was used as an antifoaming agent. Its structure is as follows:

where R is C
xH
2xC
yF
2y+1.
[0110] 49.5 parts by weight of poly-α-olefin oil having a kinematic viscosity at 100°C of
100 mm
2/s used as a dispersion medium, and 49.5 parts by weight of polybutenylsuccinimide
having a molecular weight of the polybutenyl group of 3000, a nitrogen content of
2.0% by weight, and a boron content of 1.0% by weight, which is an ashless dispersant
used as an additive for dispersion, were mixed to prepare a dispersion medium mixture.
One part by weight of the above-mentioned fluoroalkylpolysiloxane was added to the
dispersion medium mixture, and the mixture was jetted at a liquid pressure of 100
MPa, using a nozzle injector (Nanomizer, Nanofuel Co., Ltd.), to obtain an antifoaming
agent dispersion system, in which the antifoaming agent was dispersed in the dispersion
medium mixture.
[0111] When the antifoaming agent dispersion system was put into a beaker and left to stand
for one week, no precipitation of the antifoaming agent was observed.
[0112] To a mineral oil having a kinematic viscosity of 15 mm
2/s at 40°C used as a lubricant base oil, an additive package for ATF (T4278 of Infineum
Co.) was added at a quantity of 10% by weight based on the total weight of the lubricating
oil composition, and the above-mentioned antifoaming agent dispersion system was added
at a quantity of 0.4% by weight, and the mixture was heated to 60°C and mixed by stirring,
using a propeller, to prepare a lubricating oil composition.
[0113] 3.3 kg thereof were moved to a 4L can and the static stability was evaluated; in
the early phase, the whippability was 10 mm, and after 84 days (12 weeks) the whippability
remained at 13 mm. In other words, the antifoaming performance was maintained.
[0114] The whippability after 84 days was measured by putting 200 cm
3 of sample into a 500 cm
3 tall beaker, raising the temperature to 140°C on a hot plate, stirring it for 5 minutes
at 11,600 rpm by use of a homogenizer (manufactured by IKA) while blowing air at 200
mL/min, and measuring the increase in the height of the liquid level.
[0115] The lubricating oil composition thus obtained is useful as a lubricating oil composition
for transmissions.
(Example 2)
[0116] An antifoaming agent dispersion system was obtained using the same method as in Example
1, except that a homogenizer was used for dispersion instead of the nozzle injector.
[0117] When the antifoaming agent dispersion system was put into a beaker and left to stand
for one week, no precipitation of the antifoaming agent was observed. Using the obtained
antifoaming agent dispersion system with the same lubricant base oil and additive
as used in Example 1, a lubricating oil composition was obtained in the same way as
in Example 1. 3.3 kg thereof were moved to a 4L can and the static stability was evaluated;
in the early phase, the whippability was 13 mm, and after 84 days (12 weeks) it remained
at 15 mm. In other words, the antifoaming performance was maintained. The lubricating
oil composition thus obtained is useful as a lubricating oil composition for transmissions.
(Comparative Example 1)
[0118] Forty (40) parts by weight of fluoroalkylpolysiloxane used in the above Example 1
was added to 60 parts by weight of kerosene, and an antifoaming agent dispersion system
was obtained in the same way as in Example 1.
[0119] When put into a beaker and left to stand, precipitation of the antifoaming agent
was observed after 30 minutes, and after one hour all the antifoaming agent precipitated.
For this reason, it was unsuitable for use as a lubricating oil composition.
[0120] The above results showed that the antifoaming agent dispersion system used in the
present invention enables dispersion of an antifoaming agent without precipitation
over a long time. As the result, it is not necessary to produce a lubricating oil
composition immediately after the production of an antifoaming agent dispersion system,
thus improving the production efficiency of an lubricating oil composition.
[0121] Moreover, it was found that in the lubricating oil composition of the present invention,
the antifoaming performance of the antifoaming agent is maintained over a long time.
INDUSTRIAL APPLICABILITY
[0122] The lubricating oil composition of the present invention can be used in a wide variety
of fields, in which a lubricating oil is needed. While the above examples relate to
lubricating oil compositions for transmissions, the invention is not limited to or
by them; it is applicable to all lubricating oil compositions, and can be suitably
used especially to lubricating oil compositions for automobiles, more especially to
lubricating oil compositions for internal combustion engines, lubricating oil compositions
for transmissions, and lubricating oil composition for gears. The lubricating oil
composition for transmissions includes non-stage transmission oil, stage transmission
oil and motor speed changer oil.