U.S. patent application number 13/716007 was filed with the patent office on 2016-07-21 for cold-proof grease composition for reducing noise.
The applicant listed for this patent is Hyundai Motor Company, Kia Motors Corporation, Klueber Lubrication Korea Ltd.. Invention is credited to Jin Young Lee, Sung Uk Lee.
Application Number | 20160208188 13/716007 |
Document ID | / |
Family ID | 50886390 |
Filed Date | 2016-07-21 |
United States Patent
Application |
20160208188 |
Kind Code |
A1 |
Lee; Sung Uk ; et
al. |
July 21, 2016 |
COLD-PROOF GREASE COMPOSITION FOR REDUCING NOISE
Abstract
The invention provides a cold-proof grease composition for
reducing noise. In certain embodiments, the invention provides a
grease composition having an improved noise-reduction effect
without sacrificing lubricant adhesiveness at high and low
temperatures. In one embodiment, the grease composition comprises a
synthetic hydrocarbon oil as a base oil, a lithium-based thickener,
and a poly(methyl acrylate) (PMA)-based copolymer.
Inventors: |
Lee; Sung Uk; (Boryeong,
KR) ; Lee; Jin Young; (Pohang, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hyundai Motor Company
Kia Motors Corporation
Klueber Lubrication Korea Ltd. |
Seoul
Seoul
Seoul |
|
KR
KR
KR |
|
|
Family ID: |
50886390 |
Appl. No.: |
13/716007 |
Filed: |
December 14, 2012 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2205/0285 20130101;
C10M 2209/084 20130101; C10M 105/02 20130101; C10N 2030/76
20200501; C10N 2050/10 20130101; C10M 145/14 20130101; C10M
2207/1265 20130101; C10N 2030/06 20130101; C10M 2207/1285 20130101;
C10M 169/06 20130101; C10N 2010/02 20130101; C10N 2030/02 20130101;
C10M 117/02 20130101 |
International
Class: |
C10M 145/14 20060101
C10M145/14; C10M 117/02 20060101 C10M117/02; C10M 169/06 20060101
C10M169/06; C10M 105/02 20060101 C10M105/02 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 29, 2012 |
KR |
10-2012-0120174 |
Claims
1. A cold-proof grease composition for reducing noise comprising:
50-75 wt % of a base oil comprising a synthetic hydrocarbon oil;
10-30 wt % of a poly(methyl acrylate) (PMA)-based copolymer; and
10-20 wt % of a lithium-based thickener.
2. The cold-proof grease composition for reducing noise according
to claim 1, wherein the synthetic hydrocarbon oil is an aliphatic
hydrocarbon oil with a viscosity of 4-6 cSt at 100.degree. C.
3. The cold-proof grease composition for reducing noise according
to claim 2, wherein the aliphatic hydrocarbon oil comprises
poly-.alpha.-olefin (PAO) or a copolymer of .alpha.-olefin and
olefin.
4. The cold-proof grease composition for reducing noise according
to claim 1, wherein the PMA-based copolymer is an asterisk type
having a radial or star-shaped structure and has a dynamic
viscosity of 500-800 cSt at 100.degree. C.
5. The cold-proof grease composition for reducing noise according
to claim 4, wherein the PMA-based copolymer comprises a
styrene-alkyl methacrylate copolymer or a styrene-alkyl
methacrylate copolymer.
6. The cold-proof grease composition for reducing noise according
to claim 1, wherein the lithium-based thickener is obtained by
reacting lithium hydroxide with 12-hydroxystearic acid or by
reacting lithium hydroxide with a hydrogenated castor oil.
7. The cold-proof grease composition for reducing noise according
to claim 1, further comprising 3 parts by weight of the grease
composition of one or more additive selected from a group
consisting of an extreme pressure additive, an antioxidant, a
corrosion inhibitor, a rust inhibitor, a metal deactivator and a
viscosity index improver.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. .sctn.119
to Korean Patent Application No. 10-2012-0120174, filed on Oct. 29,
2012, the disclosure of which is incorporated herein by reference
in its entirety.
BACKGROUND
[0002] (a) Technical Field
[0003] The invention provides a cold-proof grease composition. In
certain embodiments, the grease composition of the invention is
useful for reducing noise. In particular, the grease composition of
the invention comprises a synthetic hydrocarbon oil as a base oil,
a lithium-based thickener, and a poly(methyl acrylate) (PMA)-based
copolymer. The grease composition of the invention offers an
improved noise-reduction effect without sacrificing lubricant
adhesiveness at high and low temperatures.
[0004] (b) Background Art
[0005] Grease is generally used as a lubricant for automotive
components. Although a grease material having high viscosity helps
to reduce noise, operation of the components is impaired due to an
increased load. Consequently, an operation failure may occur. In
general, the viscosity of grease decreases at high temperatures and
increases at low temperatures. Generally, a grease material with a
high viscosity at high temperatures also has a high viscosity at
low temperatures. As for the grease used in an automobile which is
exposed to various temperature environments ranging from low to
high temperatures, if a grease material having a high viscosity is
used to reduce noise, an operation load may be induced at low
temperatures. And, if a grease material having a low viscosity is
used to ensure operability at low temperatures, operation noise may
increase. As the result, the basic performance and durability of
the related components may be compromised at high temperatures.
[0006] Accordingly, development of a grease material with a
viscosity having a decreased dependency on temperatures is
necessary for achieving an improvement of the performance and
durability.
[0007] To minimize the change in viscosity as the temperature
varies, costly ester base oils, silicone base oils or fluoroether
base oils are often used as the base oil of grease. However, due to
limitations placed by electric parts and a high cost associated
with the above base oils, a poly-.alpha.-olefin (PAO) synthetic
base oil, which exhibits good cost effectiveness, is commonly used.
Further, a method of increasing viscosity at high temperatures
using polymer materials (such as, polyisobutylene, polybutylene
(PB), etc.) has also been developed. U.S. Pat. No. 5,116,522 and
U.S. Pat. No. 5,108,635 disclose a grease composition including PMA
or a lithium-based thickener in a base oil. However, the grease
composition has limited effects in maintaining durability of the
components used in the latest high-power, high-efficiency
automobiles, and in reducing noise.
[0008] Korean Patent No. 513,625 discloses the use of PAO as a base
oil, PMA as a polymer additive, and a lithium-based soap as a
thickener for a grease material. Nevertheless, the resulting grease
material is highly temperature-dependent compared with that of the
invention and offers limited effects in improving durability of
automotive parts under various temperature environments,
maintaining operability of the automotive parts, and reducing
noise. The details are described in examples infra. Korean Patent
No. 135,414 discloses a grease composition for a ball joint. The
grease composition includes a synthetic base oil comprising a
mixture of poly-.alpha.-olefin with a high viscosity index and
poly-.alpha.-olefin with a low viscosity index, a lithium-based
soap as a thickener, a PMA-based copolymer, and other supplementary
additives. The durability at high temperatures and noise reduction
effects are unsatisfactory despite that a relatively high weight
percentage (25-50%) of the PMA-based copolymer is used.
Satisfactory result has not been obtained even after an
antioxidant, an extreme pressure additive, etc. are added to
improve the durability at high temperatures.
SUMMARY
[0009] The invention is based on the finding that use of a
synthetic hydrocarbon oil, instead of an ester oil, as a base oil
and a lithium-based thickener results in an improved service life
of grease at high temperatures while degradation is minimized at
high temperatures. In particular, the invention is based on the
finding that use of a PMA-based copolymer results in an improved
operability at low temperatures and an improved durability at high
temperatures, thereby providing effects of reducing noise
independent of a change in temperature.
[0010] In one embodiment of the invention, a PMA polymer material,
instead of a PIB/PB polymer material, is added to a PAO-based
synthetic base oil. When PAO with a viscosity of 4-6 cSt at
100.degree. C. is used and when an asterisk type of PMA, instead of
a linear type PMA, is used as the PMA-based copolymer, the
dependency of the viscosity on temperature can be minimized.
[0011] Accordingly, the invention provides a less
temperature-dependent cold-proof grease composition for reducing
noise. In certain embodiments, the grease composition of the
invention includes a synthetic hydrocarbon oil as a base oil, a
PMA-based copolymer, and a lithium-based thickener.
[0012] In an aspect, the present invention provides a cold-proof
grease composition for reducing noise comprising:
[0013] 50-75 wt % of a base oil including a synthetic hydrocarbon
oil;
[0014] 10-30 wt % of a poly(methyl acrylate) (PMA)-based copolymer;
and
[0015] 10-20 wt % of a lithium-based thickener.
DETAILED DESCRIPTION
[0016] Reference will now be made in detail hereinafter to various
embodiments and examples of the invention. Further, the invention
is illustrated in the accompanying drawings and described below.
While the invention is described in conjunction with exemplary
embodiments, it will be understood that the present description is
not intended to limit the invention to those exemplary embodiments.
On the contrary, the invention is intended to cover not only the
exemplary embodiments, but also various alternatives,
modifications, equivalents and other embodiments, which may be
included within the spirit and scope of the invention as defined by
the appended claims.
[0017] The invention provides a grease composition comprising a
synthetic hydrocarbon oil, instead of an ester oil, as a base oil,
a PMA-based copolymer, and a lithium-based thickener. The grease
composition of the invention improves compatibility and adhesivity
among various materials including plastics, improves the service
life of components to which the composition is applied under high
temperatures and low temperatures, and ensures a low-noise
operation and an improved durability.
[0018] The base oil used in the invention can be any base oil
commonly used in grease. In certain embodiments, base oils having
no effects on metals, plastics or rubbers may be used. Such base
oils including, for example, a synthetic hydrocarbon oil, a mineral
oil and a mixture thereof. In one embodiment, a base oil consisting
essentially of a synthetic hydrocarbon oil is used. The synthetic
hydrocarbon oil may comprise poly-.alpha.-olefin (PAO) or a
copolymer of .alpha.-olefin and olefin.
[0019] In one embodiment, the synthetic base oil of the invention
has a dynamic viscosity of 4-6 cSt at 100.degree. C. and a pour
point of -50.degree. C. or lower at low temperatures. If the
dynamic viscosity is lower than 4 cSt, the composition may
evaporate easily, rendering the heat resistance insufficient. On
the other hand, if the dynamic viscosity exceeds 6 cSt, torque and
heat generation may increase.
[0020] According to the invention, the base oil may be used in an
amount of 50-75 wt %, or 58-72 wt %. If the content of the base oil
is less than 50 wt %, the grease composition may be solidified
easily. And, if it exceeds 75 wt %, the composition may be
liquefied at high temperatures.
[0021] In certain embodiments of the invention, a PMA-based
copolymer is used to improve the viscosity index and adhesivity of
the base oil. In certain embodiments, the PMA-based copolymer is
added in an amount of 10-30 wt %, or 13-24 wt %, of the entire
grease composition. If the content of the PMA-based copolymer is
less than 10 wt %, there would be an insufficient improvement of
the viscosity index and adhesivity resulted from the addition of
the PMA-based copolymer. And, if the content of the PMA-based
copolymer exceeds 30 wt %, operability and noise problems may occur
at low temperatures due to an increased viscosity.
[0022] In one embodiment, the PMA-based copolymer used in the
invention is a copolymer containing a vinyl (--C.dbd.C--) group or
a carbonyl (--COO--) group. The copolymer is represented by the
following chemical formulas 1-4:
R.sub.1COOR.sub.2 (1)
R.sub.3COOR.sub.4COOR.sub.5 (2)
R.sub.6CH.dbd.CHR.sub.7 (3)
R.sub.8CH.dbd.CHR.sub.9COOR.sub.10 (4)
[0023] In the chemical formulas 1-4, R.sub.1-R.sub.10 is a
hydrocarbon group, including, such as, a saturated aliphatic group,
an unsaturated aliphatic group, an aromatic group or a substituent
group. In a separate embodiment, the PMA-based copolymer of the
invention is an asterisk type, not a linear type. The asterisk type
copolymer has a radial or star-shaped structure and, because of its
structural characteristics, exhibits an increased viscosity, an
increased viscosity index and superior low-temperature properties
when dissolved in oil. The improvement of the viscosity index and
adhesivity of the base oil resulted from the addition of the
PMA-based copolymer means that the viscosity index of the base oil
comprising 20 wt % of the PMA-based copolymer is 200 or greater at
40.degree. C. and 100.degree. C. The viscosity index is calculated
by measuring the viscosity of the base oil using a viscometer. The
dynamic viscosity is measured according to KS M 2014.
[0024] In other embodiments of the invention, a lithium-based
thickener is used as the thickener of grease. The lithium-based
thickener is used in an amount of 10-20 wt %, or 12-17 wt %, of the
entire grease composition. If the content of the lithium-based
thickener is less than 10 wt %, viscosity decreases at both high
and low temperatures. And, if the content of the lithium-based
thickener exceeds 20 wt %, viscosity becomes excessively high at
both high and low temperatures, resulting in solidification of the
composition.
[0025] The lithium-based thickener that may be used in the
invention are represented by the following chemical formula 5:
(R.sub.11--COOLi).sub.n (5)
[0026] In the chemical formula 5, R.sub.11 is a C.sub.6-C.sub.20
aliphatic hydrocarbon group and n is an integer. If the number of
carbons in R.sub.11 is less than 6, the grease composition may not
be thickened sufficiently. And, if the number of carbons in
R.sub.11 exceeds 20, the heat resistance of the grease composition
may be poor.
[0027] The lithium-based thickener can be obtained by reacting
lithium hydroxide with a fatty acid compound. To ensure that no
reactive fatty acid groups remain in the final product, lithium
hydroxide and the fatty acid compound containing fatty acid groups
in a mole almost equivalent to the lithium hydroxide are mixed. The
lithium hydroxide and the fatty acid compound may be reacted in the
base oil. Alternatively, a previously synthesized fatty acid
lithium-based soap thickener may be mixed with the base oil. In a
specific embodiment, the former method is used to achieve a better
grease stability.
[0028] The grease composition according to the invention may
further comprise additives commonly added to grease. Such additives
including, such as, an extreme pressure additive, an antioxidant, a
corrosion inhibitor, etc.
[0029] Further, if so desired, supplementary additives, such as, a
rust inhibitor, a metal deactivator, and a viscosity index
improver, may also be added.
[0030] An extreme pressure additive that is commonly used may be
added to improve the load resistance or extreme pressure
properties. For example, the following compounds may be used as
extreme pressure additives. In one embodiment, the extreme pressure
additives are organometals including an organomolybdenum compound,
such as, molybdenum dithiocarbamate, molybdenum dithiophosphate,
etc.; an organozinc compound such as, zinc dithiocarbamate, zinc
dithiophosphate, zinc phenate, etc.; an organoantimony compound,
such as, antimony dithiocarbamate, antimony dithiophosphate, etc.;
an organoselenium compound, such as, selenium dithiocarbamate,
etc.; an organobismuth compound, such as, bismuth naphthenate,
bismuth dithiocarbamate, etc.; an organoiron compound, such as,
iron dithiocarbamate, iron octylate, etc.; an organocopper
compound, such as, copper dithiocarbamate, copper naphthenate,
etc.; an organotin compound, such as, tin maleate, dibutyltin
sulfide, etc.; an organic sulfonate, phenate or phosphate of an
alkali metal or an alkaline earth metal; an organometal compound of
gold, silver, titanium, cadmium, etc. In another embodiment, the
extreme pressure additives are sulfur compounds including a sulfide
or polysulfide compound, such as, dibenzyl disulfide, etc.; a
sulfurized oil; an ashless carbamate compound; a thiourea compound;
and a thiocarbonate compound, or the like.
[0031] Further, the extreme pressure additive can also be
phosphate-based, which includes a phosphate compound, such as,
trioctyl phosphate, tricresyl phosphate, etc.; or a phosphate ester
compound, such as, phosphoric acid ester, phosphorus ester,
phosphorus acid ester, etc. Also, a halogen-based extreme pressure
additive can be used in the invention. The halogen-based extreme
pressure additives include, such as, chlorinated paraffin, etc. In
addition, a solid lubricant, such as, molybdenum disulfide,
tungsten disulfide, graphite, PTFE, antimony sulfide, boron
nitride, boron, etc., may be used. In a specific embodiment, the
invention uses a dithiocarbamate compound or a dithiophosphate
compound as the extreme pressure additive.
[0032] The antioxidant of the invention may be selected from the
group of an aging resister, an antiozonant, and an antioxidant that
can be added to rubber, plastics, lubricating oil, etc. For
example, the antioxidant of the invention can be an amine compound,
such as, phenyl-1-naphthylamine, phenyl-2-naphthylamine,
diphenyl-p-phenylenediamine, dipyridylamine, phenothiazine,
N-methylphenothiazine, N-ethylphenothiazine,
3,7-dioctylphenothiazine, p,p'-dioctyldiphenylamine,
N,N'-diisopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine, etc., or a phenol compound,
such as, 2,6-di-tert-dibutylphenol, etc., or the like.
[0033] The corrosion inhibitor of the invention can be, for
example, an ammonium salt of a sulfonic acid, an organic sulfonate,
carbonate, phenate or phosphate of an alkali or alkaline earth
metal (such as, barium, zinc, calcium, magnesium, etc.), an alkyl
or alkenyl succinic acid derivative (such as, alkyl or alkenyl
succinic acid ester), a partial ester of a polyol (such as,
sorbitan monooleate), a hydroxy fatty acid (such as,
oleoylsarcosine), a mercapto fatty acid (such as, 1-mercaptostearic
acid) or a metal salt thereof, a higher fatty acid (such as,
stearic acid), an ester of a higher alcohol (such as, isostearyl
alcohol) with a higher fatty acid, a thiazole compound (such as,
2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptothiadiazole, etc.), an
imidazole compound (such as, 2-(decyldithio)-benzimidazole,
benzimidazole, etc.), a disulfide compound (such as,
2,5-bis(dodecyldithio)benzimidazole), a phosphate ester compound
(such as, trisnonylphenyl phosphite), a thiocarbonate ester
compound (such as, dilauryl thiopropionate), or the like. Also, a
nitrite compound may be used.
EXAMPLES
[0034] The invention is described in more detail through examples.
The following examples are for illustrative purposes only. It will
be apparent to those skilled in the art not that the scope of this
invention is not limited by the examples.
Examples 1-5 and Comparative Examples 1-7
[0035] A cold-proof grease composition for reducing noise was
prepared by mixing a base oil, a lithium-based thickener and a
PMA-based copolymer as described in Table 1. Poly-.alpha.-olefin
oil (ExxonMobil, viscosity: 4-6 cSt at 100.degree. C.), which is a
synthetic hydrocarbon oil, was used as the base oil. The
lithium-based thickener was obtained by reacting lithium hydroxide
with 12-hydroxystearic acid. And, asterisk type PMA (Lubrizol,
viscosity: 500-800 cSt at 100.degree. C.) was used as the PMA-based
copolymer.
TABLE-US-00001 TABLE 1 Examples Comparative Examples (wt %) 1 2 3 4
5 1 2 3 4 5 6 7 Synthetic hydrocarbon oil 63.3 71 59 62.2 64.9 73
55.5 66.3 60.3 54.3 56.3 62.1 Methacrylate polymer A 22.2 14.5 26.5
21.8 22.8 9.2 32 22.2 22.2 -- -- -- Methacrylate polymer B -- -- --
-- -- -- -- -- -- 24.6 -- Methacrylate polymer C -- -- -- -- -- --
-- -- -- 25.5 -- Methacrylate polymer D -- -- -- -- -- -- -- -- --
-- -- 23.4 Li-soap 14.5 14.5 14.5 16 12.5 14.5 14.5 9 21.5 14.5
14.5 14.5
Test Example
[0036] Penetration of the base oil was measured according to ASTM
D217.
[0037] Apparent viscosity of grease was tested according to DIN
51810.
[0038] Low-temperature torque of grease was tested according to KS
M 2130.
[0039] Operation noise was tested by applying the grease
composition of the invention or samples prepared according to the
existing art to a door latch. Noise is compared.
TABLE-US-00002 TABLE 2 Examples Comparative Examples (wt %) 1 2 3 4
5 1 2 3 4 5 6 7 Penetration 290 280 285 267 310 295 290 325 245 294
289 295 Apparent viscosity (25.degree. C.) 2.6 2.3 2.8 2.8 2.4 1.9
3.2 1.7 2.9 2.3 2.5 2.1 Apparent viscosity (-40.degree. C.) 14.9
13.2 17.2 18.6 13.0 12.4 22.3 11.7 22.0 35.0 40.0 37.0 Low- startup
2379 2156 2689 2415 2015 1956 3318 1828 3508 5527 6082 5723
temperature revolution 856 795 902 895 752 698 1084 611 1052 1858
2130 2017 torque (-40.degree. C.)
[0040] Table 2 shows the result of penetration measurement, change
in viscosity at room temperature and low temperature, and
low-temperature torque of the grease compositions of Examples 1-5
and Comparative Examples 1-7. It can be seen that the compositions
of Examples 1-5 do not show significant viscosity increase at low
temperatures, compared to the prior art samples at low
temperatures.
TABLE-US-00003 TABLE 3 Existing The present art invention
Improvement Viscosity (Pa s) room 2.02 2.6 0.58 (29%) temperature
low 5.96 14.9 8.94 (150%) temperature Operation Latch closed 72.1
67.1 5.0 (6.9%) noise locking open 78.0 75.1 2.9 (3.7%) Ac- closed
71.0 65.2 5.8 (8.1%) tuator open 64.5 60.6 3.9 (6.0%)
[0041] The grease composition according to the existing art
contains poly-.alpha.-olefin oil as the synthetic hydrocarbon oil
and a lithium-based thickener obtained by reacting lithium
hydroxide with 12-hydroxystearic acid. A low-viscosity
poly-.alpha.-olefin oil was used to ensure good low-temperature
properties. Although the grease composition according to the
existing art showed good low-temperature properties, operation
noise occurred because of the low viscosity. In contrast, the
grease composition according to the invention showed an improvement
in reducing operation noise, as its viscosity was higher than that
of the prior art composition both at the room temperature and low
temperatures. Table 3 compares the results of the measured
viscosity and operation noise of the prior art grease compositions
and the grease compositions of the invention at the room
temperature and low temperatures. It was expected that the grease
composition of the invention is effective in reducing noise as it
has an increased viscosity compared to that of the prior art
composition. This noise-reduction effect of the grease composition
of the invention was confirmed in latch locking and actuator
operation, when the operation noise was tested for a door
latch.
[0042] The grease composition according to the invention comprises
a synthetic hydrocarbon oil, instead of ester oil, as a base oil.
The synthetic hydrocarbon oil is effective in preventing
brittleness (cracking) and enhancing durability without incurring
adverse effects on plastics and rubbers. Further, the addition of a
lithium-based thickener improves mechanical stability and
durability. The addition of a PMA-based copolymer, which improves
viscosity index and adhesivity of the base oil, helps to prevent
degradation of grease, and greatly improves the service life of
grease at high temperatures and the lubricating performance at very
low temperatures. Furthermore, the grease composition ensures low
noise and vibration under all temperature and humidity conditions
to which high-power, high-efficiency automobiles may be
exposed.
[0043] The invention has been described in detail with reference to
specific embodiments thereof. However, it will be appreciated by
those skilled in the art that various changes and modifications may
be made in these embodiments without departing from the principles
and spirit of the invention, the scope of which is defined in the
appended claims and their equivalents.
* * * * *