Technical Field
[0001] The present invention relates to a grease composition particularly excellent in anti-flaking
performance and anti-seizure performance in a wide temperature range of from a low
temperature to a high temperature and having a low torque performance. Moreover, the
invention relates to a rolling device such as a rolling bearing, a ball screw device,
or a linear guide device into which such a grease composition is charged.
Background Art
[0002] In rolling bearings for use in motors and the like and ball screw devices and linear
guide devices for use in machine tools and the like, a small torque, a maintenance-free
property (durability for a long period of time), and the like characteristics are
required for enhancing working efficiency. In these rolling devices, grease compositions
have been generally used for lubrication. In order to satisfy such requirements, a
lithium soap grease (e.g., "Multemp SRL" manufactured by Kyodo Yushi Co., Ltd.) containing
a low viscosity ester oil-based synthetic oil has been used. However, such a grease
composition achieves a low torque but ester-based synthetic oil are generally insufficient
in heat resistance and are problematic in seizure life.
[0003] Moreover, rolling bearings have widely been used in engine auxiliaries of automobiles,
such as an alternator, but they have many chances to come into contact with water.
Among the machine tools, some of them come into contact with water. Therefore, these
rolling devices should be excellent in antirust properties. Thus, a sulfonate salt
excellent in antirust properties is frequently added to a grease composition (e.g.,
see
Japanese Patent Unexamined Publication JP-A-7-179879). However, the sulfonate salt has a problem that it promotes generation of hydrogen
owing to degradation of a grease composition and is apt to induce flaking involving
white texture change caused by the hydrogen (hereinafter referred to as "white texture
flaking").
[0004] The invention is conducted in consideration of the above circumstances and an object
of the invention is to provide a grease composition particularly maintaining a low
torque over a wide temperature range of from a low temperature to a high temperature
and further suppressing generation of white texture flaking as well as a rolling device
into which the above grease composition is charged and which works with a low torque,
hardly induces white texture flaking, and is excellent in durability.
Disclosure of the Invention
[0005] In order to achieve the above object, the present invention provides a grease composition
comprising a base oil having a dynamic viscosity at 40°C of 20 to 50 mm
2/s; a urea compound as a thickening agent in an amount of 8 to 30% by weight with
respect to total weight of the grease; at least one antirust additive selected from
carboxylic acids, carboxylate salts, and ester-based antirust additives in an amount
of 0.1 to 10% by weight per single additive with respect to total weight of the grease
and in an amount of 0.1 to 15% by weight in total of the additive with respect to
total weight of the grease, and a rolling device into which the above grease composition
is charged.
Brief Description of the Drawings
[0006]
FIG. 1 is a sectional view illustrating one embodiment of a rolling bearing which
is one of the rolling devices of the invention,
FIG. 2 is a graph illustrating the relationship between dynamic viscosity of a base
oil and an flaking life ratio obtained in Examples,
FIG. 3 is a graph illustrating the relationship between dynamic viscosity of a base
oil and dynamic torque obtained in Examples,
FIG 4 is a graph illustrating the relationship between dynamic viscosity of a base
oil and a seizure life ratio obtained in Examples,
FIG. 5 is a schematic block diagram illustrating a test apparatus for use in measurement
of flaking generation probability,
FIG. 6 is a graph illustrating the relationship between an amount of zinc naphthenate
added and flaking generation probability or a rust evaluation score obtained in Examples,
and
FIG. 7 is a graph illustrating the relationship between an amount of an organometallic
salt (ZnDTC) and flaking generation probability or seizure life time obtained in Examples.
[0007] Numeral 1 represents an inner ring, 2 represents an outer ring, 3 represents a ball,
4 represents a holder, and 5 represents a sealing member in the figures.
Best Mode for Carrying Out the Invention
[0008] The following will explain the present invention in detail.
[Grease Composition]
(Base Oil)
[0009] In the invention, the base oil for use in the grease composition is not particularly
limited except that the dynamic viscosity at 40°C is from 20 to 50 mm
2/s. In order to secure torque performance at a low temperature and more surely avoid
seizure which occurs since an oil film is hardly formed at a high temperature, the
dynamic viscosity of the base oil at 40°C is preferably from 25 to 50 mm
2/s.
[0010] As specific examples usable as the base oil, there may be mentioned mineral oil-,
synthetic oil-, or natural oil-based lubricating oil and the like. As the mineral
oil-based lubricating oil, use can be made of those obtained by purifying mineral
oil by suitably combining distillation under reduced pressure, oil-deasphalting, solvent
extraction, hydrogenolysis, solvent dewaxing, sulfuric acid washing, clay purification,
hydrogenative purification, and the like. As the synthetic oil-based lubricating oil,
there may be mentioned hydrocarbon oil, aromatic oil, ester-based oil, ether-based
oil, and the like. As the hydrocarbon oil, there may be mentioned normal paraffins,
isoparaffins, poly-α-olefins such as polybutene, polyisobutyrene, 1-decene oligomers,
and cooligomers of 1-decene with ethylene, hydrogenated products thereof, and the
like. As the aromatic oil, there may be mentioned alkylbenzenes such as monoalkylbenzenes
and dialkylbenzenes, alkylnaphthalenes such as monoalkylnaphthalenes, dialkylnaphthalenes,
and polyalkylnaphthalene, and the like. As the ester-based oil, there may be mentioned
diester oil such as dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl
adipate, ditridecyl adipate, ditridecyl glutamate, and methyl acetylcinolate, aromatic
ester oil such as trioctyl trimellitate, tridecyl trimellitate, and tetraoctyl pyromellitate,
further, polyol ester oil such as trimethylolpropane caprilate, trimethylolpropane
pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, furthermore,
complex ester oil which are oligoesters of polyhydric alcohols with mixed fatty acids
of dibasic acids and monobasic acids, and the like. As the ether-based oil, there
may be mentioned polyglycols such as polyethylene glycol, polypropylene glycol, polyethylene
glycol monoethers, and polypropylene glycol monoethers, phenyl ether oil such as monoalkyl
triphenyl ether, alkyl diphenyl ether, dialkyl diphenyl ether, pentaphenyl ether,
tetraphenyl ether, monoalkyltetraphenyl ether, and dialkyltetraphenyl ether, and the
like. As the other synthetic lubricating base oil, there may be mentioned tricresyl
phosphate, silicone oil, perfluoroalkyl ethers, and the like. As the natural oil-based
lubricating base oil, there may be mentioned oil-and-fat-based oil such as beef tallow,
lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel
oil and hydrogenation products thereof. Among these lubricating oil, in view of the
use in a wide temperature range of from a low temperature to a high temperature, ester-based
synthetic oil, synthetic hydrocarbon oil, ether-based synthetic oil, and the like
are preferred.
[0011] The lubricating oil mentioned above can be used singly or as a mixture obtained by
suitably combining them and they are adjusted to a preferred dynamic viscosity as
mentioned above.
(Thickening agent)
[0013] Wherein R
1 is a cyclohexyl group or an alkylcyclohexyl group having 7 to 12 carbon atoms, R
2 is a divalent aromatic ring-containing hydrocarbon group having 6 to 15 carbon atoms,
and R
3 is an alkyl group having 8 to 20 carbon atoms.
[0014] Moreover, at the mixing, the above diurea compounds are mixed so that a ratio of
[number of moles of R
1/(number of moles of R
1 + number of moles of R
3)] becomes from 0.1 to 1.0. When the value is less than 0.1, grease leakage increases
and there is a possibility that the seizure life may be shortened. The ratio is preferably
from 0.2 to 0.9.
(Antirust additive)
[0015] In order to impart antirust performance without generating white texture flaking,
at least one antirust additive selected from carboxylic acids, carboxylate salts,
and ester-based antirust additives is blended into the grease composition. These antirust
additives do not promote generation of hydrogen involved in grease degenerative decomposition
unlike sulfonate salts and can suppress the generation of white texture flaking. The
amount of the antirust additive to be added is from 0.1 to 10% by weight per single
additive with respect to total weight of the grease. When the amount is less than
0.1% by weight, impartment of the antirust performance is insufficient and when the
amount exceeds 10% by weight, grease is softened and grease leakage tends to occur.
In view of sufficient impartment of the antirust performance and grease leakage, the
amount to be added is preferably from 0.25 to 5% by weight. Furthermore, total amount
of the antirust additives is from 0.1 to 15% by weight.
[0016] Among the carboxylate salts, naphthenate salts are preferred. The naphthenate salts
are not particularly limited as far as they are saturated carboxylate salts having
a naphthene base. For example, there may be mentioned saturated monocyclic carboxylate
salts (C
nH
2n-1COOM), saturated polycyclic carboxylate salts (C
nH
2n-3COOM), aliphatic carboxylate salts (C
nH
2n+1COOM), and derivatives thereof. Moreover, as the monocyclic carboxylate salts, compounds
represented by the following general formulae (4) and (5) can be exemplified:

[0017] Wherein R
4 represents a hydrocarbon group and specifically, an alkyl group, an alkenyl group,
an aryl group, an alkaryl group, or an aralkyl group, or the like may be mentioned;
and M represents a metal element and specifically Co, Mn, Zn, Al, Ca, Ba, Li, Mg,
Cu, or the like. These naphthenate salts may be used singly or as a suitable combination
thereof.
[0018] Further, as a carboxylic acid salt, sccinic acid derivate is also preferable. As
this succinic acid derivate, succinic acid, alkylsccinic acid, alkylsuccinic half
ester, alkenylsuccinic acid, alkenylsuccinic half ester, succinic acid imido can be
raised. These succinic acid derivates can be used singly or as a mixture obtained
by suitably combining them.
(Other additives)
[0019] To the grease composition, if necessary, various additives hitherto known can be
added. Among them, organometallic salts are additives effective for improving flaking
performance. Among the organometallic salts, dialkyl dithiocarbamic acid(DTC)-based
compounds shown in the following general formula (6) and dialkyl dithiophosphoric
acid(DTP)-based compounds shown in the following general formula (7) can be suitably
used:

[0020] Wherein M represents a metal species and specifically Sb, Bi, Sn, Ni, Te, Se, Fe,
Cu, Mo, or Zn is used; R
5 and R
6 may be the same or different from each other and each represents an alkyl group,
a cycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group, or an arylalkyl
group. Particularly preferred groups include a 1,1,3,3-tetramethylbutyl group, a 1,1,3,3-tetramethylhexyl
group, a 1,1,3-trimethylhexyl group, a 1,3-dimethylbutyl group, 1-methylundecane group,
a 1-methylhexyl group, a 1-methylpentyl group, a 2-ethylbutyl group, a 2-ethylhexyl
group, a 2-methylcyclohexyl group, a 3-heptyl group, a 4-methylcyclohexyl group, an
n-butyl group, an isobutyl group, an isopropyl group, an isoheptyl group, an isopentyl
group, an undecyl group, an eicosyl group, an ethyl group, an octadecyl group, an
octyl group, a cyclooctyl group, a cyclododecyl group, a cyclopentyl group, a dimethylcyclohexyl
group, a decyl group, a tetradecyl group, a docosyl group, a dodecyl group, a tridecyl
group, a trimethylcyclohexyl group, a nonyl group, a propyl group, a hexadecyl group,
a hexyl group, a henicosyl group, a heptadecyl group, a heptyl group, a pentadecyl
group, a pentyl group, a methyl group, a tert-butylcyclohexyl group, a tert-butyl
group, a 2-hexenyl group, a 2-methallyl group, an allyl group (changed from "an aryl
group" since it is overlapped with the above aryl group), an undecenyl group, an oleyl
group, a decenyl group, a vinyl group, a butenyl group, a hexenyl group, a heptadecenyl
group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a tert-butylphenyl
group, a sec-pentylphenyl group, an n-hexylphenyl group, a tert-octylphenyl group,
an isononylphenyl group, an n-dodecylphenyl group, a phenyl group, a benzyl group,
a 1-phenylmethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 1,1-dimethylbenzyl
group, a 2-phenylisopropyl group, a 3-phenylhexyl group, a benzhydryl group, a biphenyl
group, and the like and also these groups may have an ether bond.
[0021] Moreover, as the other organometallic salts, use can be made of ashless dithiocarbamates
such as methylene-bis-alkyl dithicarbamate represented by the following general formula
(8):

[0022] Wherein R
7 and R
8 each represents a hydrocarbon group having 1 to 18 carbon atoms and R
7 and R
8 may be the same or different from each other.
[0023] The above organometallic salts may be used singly or as a combination of two or more
thereof. In this connection, no limitation exists for the combination. Moreover, the
organometallic salt is added in an amount of 0.1 to 10% by weight with respect to
total weight of the grease in the case that it is used singly. The organometallic
salt has an action of forming a reaction film in minute spaces to suppress the white
texture flaking but this action is not sufficiently exhibited when the amount added
is less than 0.1% by weight. On the other hand, when the amount added exceeds 10%
by weight, there is a possibility of deteriorating seizure performance through induction
of excessive reaction between the organometallic salts. Furthermore, the organometallic
salt is expensive and hence the case is not preferred also economically. Moreover,
in the case that the organometallic salts are used in combination, the amount of each
organometallic salt is from 0.1 to 10% by weight as in the case of single use but
the total amount is preferably 15% by weight or less. When the amount added is more
than 15% by weight, blending ratios of the base oil, the thickening agent, and the
antirust additive relatively decrease and thus respective effects become insufficient.
(Production process)
[0024] The process for producing the grease composition is not particularly limited. An
antirust additive and furthermore, if necessary, various additives such as organometallic
salts and ashless dithiocarbamate may be added to a grease composition obtained by
reacting a thickening agent in the base oil and the whole may be thoroughly mixed
and homogeneously dispersed. At the time when the treatment is conducted, heating
is also effective.
[0025] Moreover, consistency of the above grease composition is preferably NLGI (National
Lubricating Grease Institute) No. 1 to 3.
(Rolling device)
[0026] The invention relates to a rolling device into which the above grease composition
is charged. The rolling device is not limited and a rolling bearing, a ball screw
device, a linear guide device, and the like can be exemplified. With regard to any
rolling devices, the constitution is not limited and it may be known one. For example,
as a rolling bearing, a ball bearing shown in FIG. 1 can be exemplified. The rolling
bearing shown in the figure has a constitution wherein there are provided an outer
ring 2 having an outer ring raceway 2a on its inside surface, an inner ring 1 having
an inner ring raceway 1a on its outside surface, a plurality of rolling elements,
balls 3 provided between the outer ring raceway 2a and the inner ring raceway 1a in
a freely rollable manner, and a holder 4 which holds a plurality of the balls 3 in
a freely rollable manner, the above grease composition G is charged into a space 6
between the outer ring raceway 2a and the inner ring raceway 1a, and a space between
the inner ring 1 and the outer ring 2 is sealed by a sealing member 5 fixed to a seal
groove 2b of the outer ring 2.
[0027] In this connection, the amount of the grease composition to be charged is suitably
selected according to the kind of rolling devices.
Examples
[0028] The following will specifically describe the invention with reference to Examples
and Comparative Examples but the invention is not limited thereto. Examples 1 and
2, Comparative Examples 1 to 6
[0029] Test greases were prepared with formulations shown in Table 1. With regard to Examples
1 and 2 and Comparative Examples 2 to 6, a base oil mixed with a diisocyanate was
reacted with the same base oil mixed with an amine and the whole was stirred under
heating to obtain a semi-solid material, an antirust additive (zinc naphthenate, a
succinate ester, barium sulfonate) and/or an organometallic salt (zinc dialkyldithiocarbamate:
ZnDTC, zinc dialkyldithiophosphate: ZnDTP), which were already solved in the base
oil, were added to the semi-solid material, and the whole was thoroughly stirred and,
after gradual cooling, was passed through a roll mill to obtain a grease. With regard
to Comparative Example 1, stearic acid and lithium hydroxide were reacted in a base
oil to form a lithium soap, barium sulfonate was added after cooling to room temperature,
and the whole was thoroughly stirred and then was passed through a roll mill to obtain
a grease. Thereafter, test greases were subjected to (1) white flaking life test,
(2) dynamic torque test, and (3) seizure life test.
Table 1
| |
Example 1 |
Example 2 |
Comparative Example 1 |
Comparative Example 2 |
Comparative Example 3 |
Comparative Example 4 |
Comparative Example 5 |
Comparative Example 6 |
| Thickening agent |
diurea compound |
Li soap |
diurea compound |
| Amount of thickening agent |
13% by weight |
20% by weight |
11% by weight |
13% by weight |
20% by weight |
| R1/(R1+R3) |
0.3 |
1.0 |
- |
0.3 |
1.0 |
| Base oil |
PAO |
PAO+ether oil |
ester oil |
PAO |
PAO+ether oil |
| Dynamic viscosity of base oil |
20 to 50 |
20 to 50 |
26 |
30 |
15 |
60 |
15 |
60 |
| Zinc naphthenate |
1% by weight |
2% by weight |
- |
- |
1% by weight |
1% by weight |
2% by weight |
2% by weight |
| Succinate ester |
1% by weight |
2% by weight |
- |
- |
1% by weight |
1% by weight |
2% by weight |
2% by weight |
| ZnDTC |
1% by weight |
― |
- |
- |
1% by weight |
1% by weight |
- |
- |
| ZnDTP |
- |
1% by weight |
- |
- |
- |
- |
1% by weight |
1% by weight |
| Barium sulfonate |
- |
- |
1% by weight |
2% by weight |
- |
- |
- |
- |
| Mixed consistency |
240 to 250 |
260 to 270 |
260 |
235 |
251 |
240 |
280 |
271 |
| Note 1) Unit of dynamic viscosity of base oil: mm2/s (40°C) |
(1) White flaking life test
[0030] Each of the above test greases was charged in an amount of 2.3 g into a single row
deep groove ball bearing fitted with a contact rubber seal having an inner diameter
of 17 mm, an outer diameter of 47 mm, and a width of 14 mm to prepare a test bearing.
Then, the test bearing was continuously rotated under conditions of an inner ring
rotation speed of 10500 min
-1, room temperature atmosphere, and a radial load of 1320 N. When flaking was induced
on the running surface of the outer ring to generate vibration, the rotation was stopped
and time passed until that time was measured. The test was repeated five times per
each of the test greases and an average value was regarded as white flaking life.
The results are shown in FIG. 2, the results being shown as relative values to the
white flaking life of the test grease of Comparative Example 2.
[0031] From FIG. 2, among the test greases wherein a diurea compound is used as a thickening
agent and zinc naphthenate and a succinate ester were blended, there is a tendency
that white flaking life increases as the dynamic viscosity of the base oil increases
and it is found that the life is almost saturated in the range exceeding 50 mm
2/s (40°C). Moreover, when the dynamic viscosity of the base oil is less than 20 mm
2/s (40°C), an improving effect on the white flaking life is hardly observed.
(2) Dynamic torque test
[0032] Each of the above test greases was charged in an amount of 3.4 g into a single row
deep groove ball bearing fitted with a non-contact rubber seal having an inner diameter
of 25 mm, an outer diameter of 62 mm, and a width of 17 mm (see FIG. 1) to prepare
a test bearing. Then, dynamic torque was measured when the test bearing was continuously
rotated for 30 minutes under conditions of an inner ring rotation speed of 3600 min
-1, a bearing temperature of 30°C, a radial load of 30 N, and an axial load of 60 N.
[0033] The results were shown in FIG. 3 and it is found that an acceptance criterion of
0.1 N·m or less is satisfied when the dynamic viscosity of the base oil falls within
the range of 50 mm
2/s (40°C) or less
(3) Seizure life test
[0034] Each of the above test greases was charged in an amount of 2.0 g into a single row
deep groove ball bearing fitted with a non-contact rubber seal having an inner diameter
of 25 mm, an outer diameter of 62 mm, and a width of 17 mm (see FIG. 1) to prepare
a test bearing. Then, the test bearing was continuously rotated under conditions of
an inner ring rotation speed of 10000 min
-1, a bearing temperature of 120°C, and a radial load of 98 N. When the outer ring temperature
reached 150°C due to seizure, the rotation was stopped and time passed until that
time was measured. The test was repeated four times per each of the test greases and
an average value was regarded as seizure life. The results are shown in FIG. 4, the
results being shown as relative values to the seizure life of the test grease of Comparative
Example 1.
[0035] From FIG. 4, it is found that seizure life increases as the dynamic viscosity of
the base oil increases and the life is almost saturated in the range exceeding 50
mm
2/s (40°C). Moreover, when the dynamic viscosity of the base oil is less than 20 mm
2/s (40°C), an improving effect on the seizure life is hardly observed.
[0036] From the above test results, it is found that the grease compositions obtained by
adding an urea compound as a thickening agent and zinc naphthenate or a succinate
ester as an antirust additive to a base oil having a dynamic viscosity of 20 to 50
mm
2/s (40°C) according to the invention hardly induces white texture flaking and seizure
at a high temperature and exhibits a low torque.
(4) Verification of blending amount of antirust additive
[0037] A base grease containing 13% by weight of a diurea compound (R
1/(R
1+R
3) = 0.3) and 1% by weight of ZnDTC in a poly-α-olefin having a dynamic viscosity of
40 mm
2/s (40°C) was prepared and zinc naphthenate was added to the base grease with changing
the amount of the salt to be added, whereby test greases were obtained. Then, each
of the test greases was charged in an amount of 2.3 g into a single row deep groove
ball bearing with a contact rubber seal having an inner diameter of 17 mm, an outer
diameter of 47 mm, and a width of 14 mm to prepare a test bearing and flaking generation
probability was determined using a test apparatus shown in FIG. 5. In this connection,
the test apparatus shown in the figure has a constitution that the inner ring of a
test bearing 75 was fitted to an edge of a shaft 70 supported by one pair of supporting
bearings 71, 71, furthermore its outer ring is fixed to a holder 72, and rotation
from a motor (not shown in the figure) is transmitted to the test bearing 75. The
test was conducted under the same conditions as in the above (1) white flaking life
test.
[0038] Moreover, the same test grease was charged in an amount of 2.3 g into a single row
deep groove ball bearing with a contact rubber seal having an inner diameter of 17
mm, an outer diameter of 47 mm, and a width of 14 mm to prepare a test bearing. After
it was rotated at 1800 min
-1 for 1 minute, 0.5 mL of 0.5% by weight of saline was introduced into the bearing
and then the bearing was rotated at 1800 min
-1 for another 1 minute. After the test bearing was allowed to stand under conditions
of 52°C and 100% RH for 48 hours, the test bearing was dismantled and a rusting state
of each track surface of the inner and outer rings was observed. Evaluation was conducted
according to the following standards and a score of 2 or less was regarded to be acceptable.
<Rust evaluation score>
[0039]
1: no rust
2: three small rust points or less
3: four small rust points or more
[0040] Results of the flaking generation probability and rust evaluation score are shown
in FIG. 6. It is found that the generation of the white texture flaking and the rust
generation are both suppressed when the amount of zinc naphthenate added falls within
the range of 0.1 to 10% by weight.
(5) Verification of blending amount of organometallic salt
[0041] A base grease containing 13% by weight of a diurea compound (R
1/ (R
1+R
3) = 0.3), 1% by weight of zinc naphthenate, and 1% by weight of a succinate ester
in a poly-α-olefin having a dynamic viscosity of 40 mm
2/s (40°C) was prepared and ZnDTC was added to the base grease with changing the amount
thereof to be added, whereby test greases were obtained. Then, the flaking generation
probability was determined in the same manner as above. Furthermore, the above (3)
seizure life test was conducted.
[0042] Results of the flaking generation probability and rust evaluation score are shown
in FIG. 7 and it is found that the white texture flaking generation is suppressed
when the amount of zinc naphthenate added falls within the range of 0.1 to 10% by
weight and the seizure life is also improved at the same time.
Industrial Applicability
[0043] As described in the above, according to the invention, there is obtained a grease
composition and rolling device having a good antirust property, suppressing generation
of white texture flaking, and further having excellent anti-seizure performance.