[Technical Field]
[0001] The present invention relates to a novel anti-flaking agent which can be contained
in a lubricant applicable to a metal surface of e.g. a rolling bearing. The present
invention also relates to a lubricant composition containing the anti-flaking agent.
[Background Art]
[0002] A peculiar early abnormal flaking involving formation of white etching area occurring
on the rolling surface of a rolling bearing has been a problem since the mid-1980s
because it reduces the fatigue life of the rolling bearing. Such flaking is called
white flaking, white band flaking, brittle flaking, hydrogen brittle flaking, or hydrogen
embrittlement flaking.
[0003] Although the mechanism of how such flaking takes place has not yet been elucidated,
Patent Literature 1 introduces a hydrogen hypothesis, for example. Specifically, the
hypothesis is as follows: when grease is used under a high load, the grease decomposes
to generate hydrogen; the hydrogen penetrates into the steel material of the rolling
bearing and reacts with carbide at the grain boundaries; and as a result, the steel
material becomes brittle. Patent Literature 1 reports that, when a grease composition
contains a specific compound containing at least one sulfur atom such as a thiazole
derivative, a sulfurized oil and/or fat, or a sulfurized olefin, it is possible to
deal with the problem of white band flaking, that is, the intrusion of hydrogen generated
by decomposition of the lubricant into the metal.
[0004] The mechanism of how flaking takes place is also explained from the viewpoint of
the formation of a new metal surface. Specifically, the mechanism is as follows: when
the metal transfer surface wears, a new surface is easily formed by the wear; the
newly formed surface brings about catalysis to chemically decompose the grease; and
as a result, a large amount of hydrogen is generated, and the generated hydrogen penetrates
into the steel to finally produce cracks on the metal surface. Patent Literature 2
reports an additive which is a passivating oxidizer such as a nitrite, where the additive
is added to the grease to oxidize the metal surface and suppress the catalytic activity
of the surface, thereby suppressing the generation of hydrogen due to the decomposition
of the lubricant. Patent Literature 3 reports a technique of combining a passivating
oxidizer with an organic sulfonate. Patent Literature 4 reports a technique of allowing
grease to contain a specific amount of an azo compound. Patent Literature 5 reports
a technique that suppresses the generation of hydrogen from grease by using a phenyl
ether-based synthetic oil as the base oil of the grease.
[Citation List]
[Patent Literature]
[0005]
[Patent Literature 1] International Publication No. WO2015/016376
[Patent Literature 2] Japanese Patent Application Publication No. Hei 3-210394
[Patent Literature 3] Japanese Patent Application Publication No. Hei 5-263091
[Patent Literature 4] Japanese Patent Application Publication No. 2002-130301
[Patent Literature 5] Japanese Patent Application Publication No. Hei 3-250094
[Summary of Invention]
[Technical Problems]
[0006] Meanwhile, it is known that plasma is generated in a minute range of several µm to
several mm on the friction surface (Nakayama, K., Yagasaki, F., Tribology Letters
(2018)). Such plasma is called "triboplasma." Discharge luminescence and electric
corrosion also take place on an elastohydrodynamic lubrication (EHL) thin film of
grease formed on rolling bearings. From these facts, there is a report suggesting
that discharge plasma is generated on an EHL thin film (Nakayama and Tanaka: Manuscript
Preparation for Tribology Conference, Tokyo (2016) A2).
[0007] The present inventors considered that the suppression of triboplasma generation could
prevent white band flaking of e.g. a rolling bearing.
[0008] In view of the above, an object of the present invention is to provide an anti-flaking
agent capable of suppressing white band flaking of e.g. a rolling bearing, and a lubricant
composition containing the anti-flaking agent.
[Solution to Problems]
[0009] The present inventors measured the amount of hydrogen generated using a candidate
compound for a base oil accounting for a large percentage of the lubricant composition
or the grease composition, and have found that a compound having a specific volume
resistivity of 1.0 × 10
10 Ω·cm or less can effectively suppress hydrogen generation. Based on this knowledge,
the present inventors have completed an invention which can effectively prevent white
band flaking of e.g. a rolling bearing.
[0010] Specifically, the present invention provides the following anti-flaking agent.
- [1] An anti-flaking agent comprising at least one selected from the group consisting
of
- (A) a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, and
- (B) a compound in which a percentage of the number of carbon atoms having an aromatic
ring structure is 40% or more among all carbon atoms constituting the compound,
each in an amount exceeding 0.1% by mass based on a total mass of the anti-flaking
agent, wherein
the compounds are none of dimethyl malonate, dimethyl succinate, dimethyl glutarate,
dimethyl adipate, dimethyl suberate, and dimethyl sebacate.
- [2] The anti-flaking agent according to 1 described above, wherein the compound (A)
is at least one selected from the group consisting of compounds having a dielectric
constant ε of 3.0 or more at 500 MHz and 1 GHz.
- [3] The anti-flaking agent according to 1 described above, wherein the compound (A)
is at least one selected from the group consisting of compounds having a Hansen solubility
parameter polar term δp of 3.5 or more.
- [4] The anti-flaking agent according to 1 to 3 described above, wherein the compound
(A) is at least one selected from the group consisting of polyvalent esters, glycols,
sulfur-containing compounds, phosphorus-containing compounds, nitrogen-containing
compounds, antistatic agents, ionic liquids, liquid crystals, SP compounds, NS compounds,
and fatty acid amine salts.
- [5] The anti-flaking agent according to any one of 1 to 4 described above, wherein
the compound (A) is a diester of an aliphatic monoalcohol having 6 or less carbon
atoms with an alicyclic fatty acid having 3 to 10 carbon atoms or aromatic dibasic
acid having 3 to 10 carbon atoms.
- [6] The anti-flaking agent according to any one of 1 to 5 described above, wherein
the compound (A) is a polyvalent ester selected from the group consisting of dimethyl
phthalate, dimethyl maleate, diethyl malonate, dibutyl malonate, and dihexyl malonate.
- [7] The anti-flaking agent according to any one of 1 to 4 described above, wherein
the compound (A) is an antistatic agent selected from the group consisting of poly(oxyethylene)alkylamines,
poly(oxyethylene)alkylamides, poly(oxyethylene)alkyl ethers, poly(oxyethylene)alkyl
phenyl ethers, glycerin aliphatic esters, sorbitan aliphatic esters, alkylsulfonates,
alkylbenzene sulfonates, alkyl phosphates, quaternary ammonium chlorides, quaternary
ammonium sulfates, quaternary ammonium nitrates, alkylbetaines, alkyl imidazolines,
alkylalanines, polyvinyl benzyl, polyacrylic, amine derivatives, succinic acid derivatives,
partial esters of poly(oxyalkylene)glycol and polyhydric alcohol, ammonium compounds
of alkyl naphthalene sulfonic acid, polyalkyl sulfones, and neutralized salts of alkyl
aryl sulfonic acid and alkyl amine.
- [8] The anti-flaking agent according to any one of 1 to 7 described above, wherein
the compound (B) is at least one selected from the group consisting of phenyl ethers,
alkylbenzenes, and alkylnaphthalenes.
The present invention also provides the following lubricant composition.
- [9] A lubricant composition comprising the compound according to any one of 1 to 8
described above.
- [10] The lubricant composition according to 9 described above, further comprising
at least one conventional base oil selected from the group consisting of mineral oils
and synthetic oils.
- [11] The lubricant composition according to 10 described above, wherein the base oil
is at least one selected from the group consisting of mineral oils, synthetic hydrocarbon
oils, and ether oils.
- [12] The lubricant composition according to any one of 9 to 11 described above, wherein
a content of the compound exceeds 0.1% by mass based on a total mass of the composition.
- [13] The lubricant composition according to any one of 9 to 11 described above, wherein
a content of the compound exceeds 1% by mass based on a total mass of the composition.
- [14] The lubricant composition according to any one of 9 to 11 described above, wherein
a content of the compound is 2% by mass or more based on a total mass of the composition.
- [15] The lubricant composition according to any one of 9 to 11 described above, wherein
a content of the compound is 3% by mass or more based on a total mass of the composition.
- [16] The lubricant composition according to any one of 9 to 11 described above, wherein
a content of the compound is 40% by mass or less based on a total mass of the composition.
- [17] The lubricant composition according to any one of 9 to 16 described above, further
comprising a thickener.
[0011] The anti-flaking agent and lubricant composition of the present invention can prevent
white band flaking effectively (20% or less as compared with
n-hexadecane).
[Brief Description of Drawings]
[0012] [Fig. 1] Fig. 1 is a schematic view of an apparatus, used in Examples, for generating
hydrogen gas by triboplasma.
[Description of Embodiments]
[Definitions]
[0013] In the present specification, the specific volume resistivity represents a ratio
between a DC electric field (V/m) applied to the sample at 25°C and a current per
unit cross-sectional area applied to the sample at that time, and is equal to the
resistance between opposing faces of a cubic sample with one side being 1 cm. The
specific volume resistivity can be measured based on the testing methods of electrical
insulating oils specified in JIS C2101.
[0014] In the present specification, the dielectric constant ε is a coefficient representing
the relationship between the electric charge in the substance and the force given
thereby. The dielectric constant ε was measured at 25°C with E4991B Impedance Analyzer
(Keysight Technologies).
[0015] In the present specification, the "Hansen solubility parameters" are each an index
indicating the solubility of a certain solute in a certain solvent, and include three
components: the dispersion term (δD), the polar term (δP), and the hydrogen bond term
(δH). The dispersion term (δD) represents the effect due to the dispersion force,
the polar term (δP) represents the effect due to the force between dipoles, and the
hydrogen bond term (δH) represents the effect due to the hydrogen bond force. Details
of the definitions and calculation methods for the Hansen solubility parameters are
described in the following literature:
Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook," CRC Press, 2007.
[0016] In the present specification, "white band flaking" refers to a peculiar early abnormal
flaking involving formation of white etching area. In the present specification, the
term "white band flaking" is synonymous with a term called e.g. white flaking, white
band flaking, brittle flaking, hydrogen brittle flaking, or hydrogen embrittlement
flaking in the art. Normally, for rolling fatigue, the life can be estimated based
on the life calculation formula defined in the standards (ISO281, JIS B-1518). However,
in the case where white band flaking takes place, the lifetime is reached in a shorter
time than the calculated lifetime. In the actual market, it has been reported that
the life is reached at about 1/10 to 1/20 of the calculated life. White band flaking
is one type of internal origin damage, and shows a specific phenomenon in which a
white band is observed when the metal structure after the occurrence is etched with
a nital solution.
[Compound Used as Anti-Flaking Agent]
[0017] The compound used in the present invention is a compound having a specific volume
resistivity of 1.0 × 10
10 Ω·cm or less. The present inventors have found that a compound having such a physical
property can suppress hydrogen generation by plasma. Although the experimental methods
and results are described in detail in the Examples section, the present inventors
systematically examined the influence of the carbon chain length of ester on the amount
of hydrogen generated. Then, as regards the length of the carbon chain derived from
the dibasic fatty acid constituting the ester with methanol (R
2OOC-R
1-COOR
2) (that is, R
1), no hydrogen was generated when the number of carbon atoms was 6 or less. Conversely,
when the number of carbon atoms was 8 (that is, when the dibasic acid was sebacic
acid), hydrogen was generated. However, the amount generated was only 17% compared
with
n-hexadecane used as a standard substance. It was considered that triboplasma was generated
in the case of using dimethyl sebacate. Thus, the specific volume resistivity was
measured and found to be 9.0 × 10
9 Ω·cm. Moreover, when the specific volume resistivity was measured while changing
the number of carbon atoms of R
1, it was found that the specific volume resistivity increased as the number of carbon
atoms of R
1 increased.
Table 1
|
Number of Carbon Atoms of R1 |
Amount of Hydrogen Generated, %* |
Specific Volume Resistivity, Ω·cm |
Dimethyl Malonate |
1 |
0 |
6.6 × 107 |
Dimethyl Adipate |
4 |
0 |
4.0 × 109 |
Dimethyl Sebacate |
8 |
17 |
9.0 × 109 |
* The amount of hydrogen generated for n-hexadecane is set to 100. |
[0018] On the other hand, the present inventors examined the influence of the length of
the carbon chain derived from the alcohol constituting the ester with sebacic acid
(that is, R
2) on the amount of hydrogen generated. Then, it was found that the specific volume
resistivity increased as the number of carbon atoms of R
2 increased. This tendency was also observed in the case of monoesters.
Table 2
|
Number of Carbon Atoms of R2 |
Amount of Hydrogen Generated, %* |
Specific Volume Resistivity, Ω·cm |
Dimethyl Sebacate |
1 |
17 |
9.0 × 109 |
Dihexyl Sebacate |
6 |
95 |
9.0 × 1011 |
Di(2-Ethylhexyl)Sebacate |
8 |
100 |
2.4 × 1012 |
* The amount of hydrogen generated for n-hexadecane is set to 100. |
[0019] The present inventors have also found that a specific aromatic compound can effectively
suppress hydrogen generation even when the compound has a specific volume resistivity
exceeding 1.0 × 10
10 Ω·cm.
[0020] Therefore, the compound of the present invention is at least one selected from the
group consisting of
- (A) a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, and
- (B) a compound in which a percentage of the number of carbon atoms having an aromatic
ring structure is 40% or more among all carbon atoms constituting the compound, wherein
the compounds are none of dimethyl malonate, dimethyl succinate, dimethyl glutarate,
dimethyl adipate, dimethyl suberate, and dimethyl sebacate.
(Compound (A))
[0021] The compound (A) preferably has a specific volume resistivity of 5.0 × 10
9 Ω·cm or less.
[0022] In addition, the compound (A) is preferably liquid at 25°C.
[0023] In addition, the compound (A) preferably has a dielectric constant ε of 3.0 or more
at 500 MHz (25°C) and 1 GHz (25°C).
[0024] In addition, the compound (A) preferably has a Hansen solubility parameter polar
term δp of 3.5 or more.
[0025] The term δp is expressed by the following formula, and δp increases as the dielectric
constant ε increases. Generally, it is said that the dielectric constant ε of oil
affects electron wave absorption, and it is said that the larger the dielectric constant
ε and the larger the dielectric loss tangent, the more effectively electron waves
can be absorbed, which can be a countermeasure against electron wave noise.
[0026] It has been found that a compound having a specific volume resistivity of 1.0 × 10
10 Ω·cm has a δp of 3.5 or more. Therefore, it is considered that, when δp is 3.5 or
more, hydrogen generation can be prevented and white band flaking can be prevented.
The term δp is preferably 4.0 or more. The Hansen solubility parameter polar term
δp is preferably 20 or less.
[0027] The term δp is preferably 3.5 or more, and the reason is as follows. Such a value
makes it possible to achieve a conductivity to an extent sufficient to prevent charging
and a high dielectric constant, and it is therefore considered that white band flaking
can be suppressed through suppression of triboplasma generation.
[0028] Specific examples of the compound (A) include polyvalent esters, glycols, sulfur-containing
compounds, phosphorus-containing compounds, nitrogen-containing compounds, antistatic
agents, ionic liquids, liquid crystals, SP compounds, NS compounds, and fatty acid
amine salts.
[0029] The polyvalent ester is selected from diesters, triesters, and tetraesters. A polyvalent
ester having 15 or less carbon atoms is preferable. A diester having 15 or less carbon
atoms is more preferable. Among others, preferable is a diester of a linear or branched
aliphatic monoalcohol having 6 or less and preferably 4 or less carbon atoms with
a linear or branched saturated or unsaturated aliphatic dibasic acid having 3 to 10
carbon atoms, a saturated or unsaturated alicyclic dibasic acid having 3 to 10 carbon
atoms, or an aromatic dibasic acid having 3 to 10 carbon atoms. Particularly preferable
is a diester of a linear or branched aliphatic monoalcohol having 6 or less carbon
atoms with a saturated or unsaturated dibasic acid having 3 to 10 carbon atoms. Most
preferable is a diester of a linear or branched aliphatic monoalcohol having 4 or
less carbon atoms with a saturated or unsaturated dibasic acid having 3 to 10 carbon
atoms.
[0030] A specific example of the diester is a diester in which the alcohol is methanol,
ethanol, propalol, butanol, or hexanol, and the dibasic acid is malonic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic
acid, phthalic acid, fumaric acid, maleic acid, dihydromuconic acid, 1,4-phenylenediacetic
acid, or
cis-4-cyclohexene-1,2-dicarboxylic acid. Particularly preferable among these is a diester
in which the alcohol is methanol, ethanol,
n-propalol, or
n-butanol, and the dibasic acid is malonic acid, succinic acid, glutaric acid, adipic
acid, suberic acid, sebacic acid, phthalic acid, or maleic acid. In particular, diethyl
malonate, dibutyl malonate, and dihexyl malonate are preferable.
[0031] Specific examples of triesters include tributyl trimellitate.
[0032] Specific examples of tetraesters include full esters of pentaerythritol with carboxylic
acid. Preferable is a tetraester with pentaerythritol, mainly containing 2-ethylhexanoic
acid,
n-heptanoic acid, or
n-octanoic acid as the carboxylic acid.
[0033] Examples of glycols which can be used in the present invention include alkylene glycols,
polyalkylene glycols, and alkyl ethers thereof. Examples of the alkylene glycols include
tetraethylene glycol and tripropylene glycol. Examples of the polyalkylene glycols
include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(oxyethylene)glycol,
poly(oxypropylene)glycol, poly(oxybutylene)glycol, and poly(oxypropylene, oxybutylene)glycol.
Examples of the alkyl ethers of alkylene glycols include tetraethylene glycol dimethyl
ether. Examples of the alkyl ethers of polyalkylene glycols include polyethylene glycol
alkyl ethers, polypropylene glycol alkyl ethers (for example, polypropylene glycol
monobutyl ether), polybutylene glycol alkyl ethers, and poly(oxypropylene, oxybutylene)glycol
alkyl ethers. The alkyl ether has 1 to 18 carbon atoms in the alkyl, and may be monoether
or diether.
[0034] The sulfur-containing compound which can be used in the present invention is a compound
containing a sulfur atom in one molecule, which is usually used as a building block
in a solvent or organic synthesis. Specific examples include dimethyl sulfoxide, 2,2'-thiodiethanol,
diethyl sulfoxide, dibutyl sulfoxide, butyl sulfide, butyl disulfide, propyl sulfide,
propyl disulfide, phenyl sulfide, and bis(2-hydromethoxy)disulfide. Among these, dimethyl
sulfoxide and 2,2'-thiodiethanol are preferable.
[0035] The phosphorus-containing compound which can be used in the present invention is
a compound containing a phosphorus atom in one molecule, which is usually used as
an extreme pressure agent or antiwear agent for lubricating oil. Specific examples
include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphine,
triethyl phosphine, tributyl phosphine, and 2-ethylhexyl diphenyl phosphate. Among
these, trimethyl phosphate is preferable.
[0036] The nitrogen-containing compound which can be used in the present invention is a
compound containing a nitrogen atom in one molecule, which is usually used as a building
block in a solvent or organic synthesis. Specific examples include formamide,
N-methylformamide,
N-ethylformamide,
N-
tert-butylformamide, tetramethylurea, tetraethylurea, and tetrabutylurea. Among these,
formamide,
N-methylformamide,
N-
tert-butylformamide, tetramethylurea, and tetraethylurea are preferable.
[0037] The antistatic agent can be anionic, cationic, amphoteric, or nonionic, and examples
thereof include poly(oxyethylene)alkylamines, poly(oxyethyl ene)alkylamides, poly(oxyethylene)alkyl
ethers, poly(oxyethylene)alkyl phenyl ethers, glycerin aliphatic esters, sorbitan
aliphatic esters, alkylsulfonates, alkylbenzene sulfonates, alkyl phosphates, quaternary
ammonium chlorides, quaternary ammonium sulfates, quaternary ammonium nitrates, alkylbetaines,
alkyl imidazolines, alkylalanines, polyvinyl benzyl, and polyacrylic, which are described
in
page 1238 of "16918 Chemical Products, Year 2018 Edition," published by The Chemical
Daily Co., Ltd. Other examples include amine derivatives, succinic acid derivatives, partial esters
of poly(oxyalkylene)glycol and polyhydric alcohol, ammonium compounds of alkyl naphthalene
sulfonic acid, polyalkyl sulfones, and neutralized salts of alkyl aryl sulfonic acid
and alkyl amine.
[0038] The ionic liquid is a molten salt which is liquid at room temperature, also called
a room temperature molten salt. Examples of the ionic liquid which can be used in
the present invention include ones in which the anion of the ionic liquid is selected
from the group consisting of hexafluorophosphate, trifluoromethanesulfonic acid, bis(perfluoroalkylsulfonyl)imide,
(trifluoromethylsulfonyl)(heptafluoropropylsulfonyl)imide, bis[fluorosulfonyl]imide,
bis(pentafluoroethanesulfonic acid)imide, nitrogen trioxide,
p-toluenesulfonic acid, diethylene glycol monomethyl ether sulfonic acid, acetic acid,
trifluoromethanecarboxylic acid, biscyanoimide, tris(trifluoromethanesulfonic acid)methide,
tris(perfluoroalkyl)trifluorophosphate, and bis(perfluoroalkyl) (trifluoromethyl)trifluorophosphate.
[0039] For example, it is also possible to suitably use an ionic liquid in which the anion
is represented by any one of the following formulas 1 and 2.
(Rf1-SO
2)(Rf2-SO
2)N
- formula 1
(Rf3)(Rf3)(Rf3)PF
3- formula 2
(In formula 1, Rf1 and Rf2 may be the same as or different from each other, and represent
F, CF
3, C
2F
5, C
3F
7, or C
4F
9. In formula 2, Rf3 may be the same as or different from each other, and represents
CF
3, C
2F
5, C
3F
7, or C
4F
9.)
[0040] Examples of the anion represented by formula 1 include bis(perfluoroalkylsulfonyl)imide,
(trifluoromethylsulfonyl) (heptafluoropropylsulfonyl)imide, and bis[fluorosulfonyl]imide.
Examples of the anion represented by formula 2 include tris(perfluoroalkyl)trifluorophosphate
and bis(perfluoroalkyl) (trifluoromethyl)trifluorophosphate.
[0041] Examples of the cation constituting the ionic liquid include imidazoliums, pyridiniums,
pyrazoliums, piperidiniums, pyrrolidiniums, morpholines, piperazines, pyrroles, phosphoniums,
quaternary ammonium salts, and isoxazoliums, and examples thereof include imidazoliums
such as ethylmethylimidazolium, hexylmethylimidazolium, methyloctylimidazolium, and
butyldimethylimidazolium; pyridiniums such as butyl-4-methylpyridinium; piperidiniums
such as methoxyethyl-methyl piperidinium; pyrrolidiniums such as methoxyethyl-methyl
pyrrolidinium; phosphoniums such as octyltriethylphosphonium and triethyloctylphosphonium;
and isoxazoliums such as propyldimethylisoxazolium. In addition, some are classified
as aliphatic amine-based, alicyclic amine-based, and pyridine-based (aromatic).
[0042] The ionic liquid which can be used in the present invention is preferably an ionic
liquid in which the anion is bis(trifluoromethylsulfonyl)imide and the cation is 1-butyl-2,3-dimethylimidazolium,
an ionic liquid in which the anion is bis(trifluoromethylsulfonyl)imide and the cation
is 1-(2-methoxyethyl)-1-methylpyrrolidinium, an ionic liquid in which the anion is
bis(trifluoromethylsulfonyl)imide and the cation is triethyloctylphosphonium, and
an ionic liquid in which the anion is (trifluoromethylsulfonyl) (heptafluoropropylsulfonyl)imide
and the cation is 1-ethyl-3-methylimidazolium.
[0043] The liquid crystal compound is a compound which, in a certain temperature range,
is liquid in appearance and simultaneously exhibits birefringence characteristic of
an optically anisotropic crystal. The liquid crystal compound is classified into a
smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal, and
a discotic liquid crystal depending on its molten state, and any of these liquid crystal
compounds can be used in the present invention.
[0044] Specific examples of the liquid crystal compound used in the present invention include
(1) Schiff base liquid crystals, (2) azo-based and azoxy-based liquid crystals, (3)
benzoate-based liquid crystals, (4) biphenyl-based and terphenyl-based liquid crystals,
(5) cyclohexyl carboxylic acid ester-based liquid crystals, (6) phenylcyclohexane-based
and biphenylcyclohexane-based liquid crystals, (7) pyrimidine-based and dioxane-based
liquid crystals, (8) cyclohexyl cyclohexane ester-based liquid crystals, (9) cyclohexyl
ethane-based liquid crystals, (10) cyclohexane-based liquid crystals, (11) tolan-based
liquid crystals, (12) cholesteric liquid crystals, (13) triazine-based liquid crystals,
(14) COS-based liquid crystals, (15) CCN-based liquid crystals, and (16) discotic
liquid crystals, which are as described later.
[0045] A cyanobiphenyl-based liquid crystal compound categorized as (4) is excellent in
chemical stability but has a slightly narrow temperature range of liquid crystal phase,
and is desirably mixed with other liquid crystal compounds. The compound is a nematic
liquid crystal having a high dielectric anisotropy and is often used for a liquid
crystal display. Examples of the cyanobiphenyl-based liquid crystal include 4-cyano-4'-pentylbiphenyl,
4-cyano-4'-butylbiphenyl, 4-cyano-4'-hexylbiphenyl, 4-cyano-4'-heptylbiphenyl, 4-cyano-4'-octylbiphenyl,
4-cyano-4'-nonylbiphenyl, 4-cyano-4'-undecylbiphenyl, 4-cyano-4'-dodecylbiphenyl,
4-butoxy-4'-cyanobiphenyl, 4-ethoxy-4'-cyanobiphenyl, 4-propoxy-4'-cyanobiphenyl,
4-pentoxy-4'-cyanobiphenyl, 4-hexoxy-4'-cyanobiphenyl, 4-heptoxy-4'-cyanobiphenyl,
4-octoxy-4'-cyanobiphenyl, 4-nonaloxy-4'-cyanobiphenyl, 4-decyloxy-4'-cyanobiphenyl,
4-dodecyloxy-4'-cyanobiphenyl, (
S)-4-cyano-4'-(2-methylbutyl)biphenyl, 4-(
trans-4-propylcyclohexyl)benzonitrile, 4-(
trans-4-butylcyclohexyl)benzonitrile, 1-(
trans-4-amylcyclohexyl )-4-cyanobenzene, 4-[
trans-4-[(
E)-1-propenyl]cyclohexyl]benzonitrile, 4-cyano-4"-pentyl-
p-terphenyl, 4-cyano-4"-propyl-p-terphenyl, and
trans-4'-(4-amylcyclohexyl)biphenyl-4-carbonitrile.
[0046] The SP compound which can be used in the present invention is a compound containing
a sulfur atom and a phosphorus atom in one molecule, which is usually used as an extreme
pressure agent or an antiwear agent for lubricating oil. Specific examples include
alkylated triphenyl phosphorothioates and ZnDTP. Among these, alkylated triphenyl
phosphorothioates are preferable.
[0047] The NS compound which can be used in the present invention is a compound containing
a nitrogen atom and a sulfur atom in one molecule, which is usually used as a metal
corrosion prevention agent for lubricating oil. Specific examples include dimercaptothiadiazole
derivatives, molybdenum dithiocarbamate, and ZnDTC. Among these, dimercaptothiadiazole
derivatives and molybdenum dithiocarbamate are preferable.
[0048] The fatty acid amine salt which can be used in the present invention is a compound
which is usually used as a corrosion inhibitor for lubricating oil. Specific examples
include oleic acid dicycloamine salt, lauric acid amine salt, myristic acid amine
salt, palmitic acid amine salt, stearic acid amine salt, linoleic acid amine salt,
arachidonic acid amine salt, and linolenic acid amine salt. Among these, oleic acid
dicycloamine salt is preferable.
(Compound (B))
[0049] The compound (B) is a compound in which the percentage of the number of carbon atoms
having an aromatic ring structure is 40% or more, preferably 50% or more, and more
preferably 60% or more among all the carbon atoms constituting the compound.
[0050] Here, the percentage of the number of carbon atoms having an aromatic ring structure
among all the carbon atoms constituting the molecule can be obtained by calculation.
For example, in the case of diphenylamine, the total number of carbon atoms is 13,
and the number of carbon atoms having an aromatic ring structure is 12. Therefore,
the value obtained by dividing 12 by 13 is the percentage.
[0051] As the compound (B), an alkyl compound or an alkenyl compound having two or more
aromatic rings is preferable. Specific examples include diphenylmethane, diphenylpropane,
and diphenylethylene. Phenyl ethers having three or more aromatic rings are also preferable,
and phenyl ethers such as pentaphenyl ether, tetraphenyl ether, and alkyl tetraphenyl
ethers, alkyl benzenes, and alkyl naphthalenes are preferable.
[0052] The anti-flaking agent of the present invention may contain any substance as long
as it does not negatively affect the anti-flaking effect of the compound (A) or (B)
described above. However, the content of the compound is preferably 1% by mass or
more, more preferably 2% by mass or more, and further preferably 3% by mass or more
relative to the total mass of the anti-flaking agent of the present invention. When
any one of the compound (A) and the compound (B) is used as the compound, the content
thereof is more than 0.1% by mass, preferably more than 1% by mass, more preferably
2% by mass or more, and further preferably 4% by mass or more as in the case of the
compound. When the compound (A) and the compound (B) are used in combination, the
total amount thereof is preferably 2% or more and more preferably 4% or more. The
upper limit of the percentage of the compound in the anti-flaking agent of the present
invention is not particularly limited. In the case of polyvalent esters and glycols,
from the viewpoints of heat resistance and resin resistance, the upper limit is preferably
less than 40% by mass and more preferably 10% by mass or less based on the total mass
of the anti-flaking agent. In the case of a compound other than polyvalent esters
and glycols, the upper limit is preferably 10% by mass or less and more preferably
3% by mass or less from an economical viewpoint.
[0053] The flash point of the compound of the present invention is preferably 70°C or lower
because there is a risk of ignition by plasma generated due to friction of the lubrication
portion. The flash point can be measured based on JIS K2265.
[Lubricant Composition]
[0054] Since being liquid at room temperature, the compound can be used alone as a lubricant
composition, can also be used as a lubricant or a base oil of a grease, or can be
mixed with a conventional base oil as a lubricant or a base oil of a grease to form
a lubricant composition.
(Conventional Base Oil)
[0055] As the conventional base oil, one having a specific volume resistivity exceeding
1.0 × 10
10 Ω·cm can be used. One containing a saturated or unsaturated hydrocarbon group having
12 or more carbon atoms in total is preferable, and specific examples thereof include
mineral oils and synthetic oils. As the mineral oil, it is possible to use a paraffinic
mineral oil, a naphthenic mineral oil, or a mixture thereof. It is preferable to contain
a highly refined mineral oil (that is, a mineral oil which has been subjected to dewaxing
treatment to reduce wax component precipitation at low temperature, thereby lowering
its pour point as compared with the pour point of unrefined mineral oils (-5°C to
-20°C, measured according to JIS K 2269)). Examples of synthetic oils include synthetic
hydrocarbons, ester oils, ether oils, glycol oils, silicone oils, and fluorinated
oils. Examples of synthetic hydrocarbon oils include poly alpha olefins ("PAOs") and
polybutene. Among these, poly alpha olefins are preferable. Examples of ester oils
include diesters, trimellitate esters, and polyol esters. Examples of ether oils include
alkyl diphenyl ethers ("ADEs"), dialkyl diphenyl ethers, and polypropylene glycol.
Examples of glycol oils include polypropylene glycol and polypropylene alkyl ethers.
[0056] In the case of use in combination with a mineral oil or synthetic hydrocarbon (especially
poly alpha olefin), hydrogen generation can be effectively suppressed even when the
compound is in a small amount, for example more than 0.1% by mass, preferably more
than 1% by mass, more preferably 2% by mass or more, and further preferably 3% by
mass or more based on the total mass of the lubricant composition. The content of
the compound in the lubricant composition of the present invention can be, for example,
40% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less,
or 3% by mass or less. Considering the compatibility with the compounds described
above, preferable conventional oils are ester oils such as diesters and polyol esters,
ether oils such as alkyl phenyl ether oils, glycol oils such as water-insoluble polyalkylene
glycols, silicone oils, fluorinated oils, and the like. From the viewpoints of resin
resistance and heat resistance, mineral oils, synthetic oils, hydrocarbon oils, phenyl
ether oils, and alkyl phenyl ether oils are preferable.
[0057] The kinematic viscosity at 40°C of the base oil in the lubricant composition of the
present invention (that is, the compound (A) and/or (B) alone, or a mixture oil with
the conventional oil) is preferably 10 to 500 mm
2/s. When the kinematic viscosity at 40°C of the base oil is less than 10 mm
2/s, it may be impossible to achieve a sufficient oil film at low speed or high temperature.
Meanwhile, when the kinematic viscosity at 40°C of the base oil exceeds 500 mm
2/s, there is a risk that the torque may rise at high speed or low temperature. For
the same reasons, the range is more preferably 50 to 200 mm
2/s and further preferably 60 to 130 mm
2/s. Note that the kinematic viscosity of the base oil can be measured based on JIS
K2283.
[0058] The content of the base oil in the lubricant composition of the present invention
is preferably 60 to 99.9 parts by mass, more preferably 90 to 99.9 parts by mass,
and further preferably 97 to 99.9 parts by mass relative to 100 parts by mass in total
of the base oil and the anti-flaking agent. The content of the base oil is preferably
in such ranges because of excellence in lubricity and low volatility.
(Optional Additive)
[0059] The lubricant composition of the present invention may further contain a general-purpose
additive as necessary. For example, a rust inhibitor, a load-bearing additive, an
antioxidant, and the like can be contained as necessary. The content of these optional
additives is usually 0.5 to 5% by mass based on the total mass of the lubricant composition
of the present invention.
[0060] Examples of the rust inhibitor include inorganic rust inhibitors and organic rust
inhibitors. Examples of the inorganic rust inhibitors include inorganic metal salts
such as sodium silicate, lithium carbonate, potassium carbonate, and zinc oxide. Examples
of the organic rust inhibitors include benzoates such as sodium benzoate and lithium
benzoate, sulfonates such as calcium sulfonate and zinc sulfonate, carboxylates such
as zinc naphthenate and sodium sebacate, succinic acid derivatives such as succinic
acid, succinic anhydride, and succinic acid half ester, sorbitan esters such as sorbitan
monooleate and sorbitan trioleate, and fatty acid amine salts.
[0061] Examples of the load-bearing additive include phosphorus-containing ones such as
phosphate esters, sulfur-based ones such as polysulfide and sulfurized oils and/or
fats, phosphorus-sulfur-based ones such as phosphorothioates, thiocarbamates, thiophosphates,
and organic phosphate esters.
[0062] The antioxidant is known to suppress oxidative degradation of grease, and examples
thereof include phenol-based antioxidants and amine-based antioxidants.
[0063] Examples of the phenol-based antioxidants include 2,6-di-
tert-butyl-p-cresol (BHT), 2,2'-methylenebis(4-methyl-6-
tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-
tert-butylphenol), 2,6-di-
tert-butyl-phenol, 2,4-dimethyl-6-
tert-butylphenol,
tert-butylhydroxyanisole (BHA), 4,4'-butylidenebis(3-methyl-6-
tert-butylphenol), 4,4'-methylenebis(2,3-di-
tert-butylphenol), 4,4'-thiobis(3-methyl-6-
tert-butylphenol), and octadecyl-3-(3,5-di-
tert-butyl-4-hydroxyphenyl)propionate. Among these, octadecyl-3-(3,5-di-
tert-butyl-4-hydroxyphenyl)propionate is preferable.
[0064] Examples of the amine-based antioxidants include
N-
n-butyl-
p-aminophenol, 4,4'-tetramethyl-di-aminodiphenylmethane, α-naphthylamine,
N-phenyl-α-naphthylamine, phenothiazine, and alkyl diphenylamines. Among these, alkyl
diphenylamines are preferable.
[0065] The lubricant composition of the present invention can be used as lubricating oil,
conductive oil, dynamic pressure oil, and the like. The lubricant composition of the
present invention is effective in preventing flaking wear.
[Grease Composition]
[0066] The lubricant composition of the present invention may further contain a thickener
to form a grease composition.
[0067] For the same reasons as described for the lubricant composition, the content of the
compound (A) and/or (B) is preferably more than 0.1% by mass, more preferably more
than 1% by mass, further preferably 2% by mass or more, and particularly preferably
3% by mass or more based on the total mass of the grease composition of the present
invention, and the upper limit can be, for example, 40% by mass or less, 20% by mass
or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less.
[0068] Examples of the thickener which can be used in the grease composition of the present
invention include urea-based thickeners typified by diurea, lithium soap-based thickeners
typified by lithium soap and lithium complex soap, and solid thickeners such as bentonite
and silica gel. Urea-based thickeners and lithium soap-based thickeners are preferable.
[0069] The grease composition of the present invention may further contain a general-purpose
additive as necessary. Examples of additives which can be used include ones described
for the lubricant composition. The content of the optional additive is usually 0.1
to 5% by mass based on the total mass of the grease composition of the present invention.
(Penetration)
[0070] The worked penetration of the grease composition of the present invention is preferably
200 to 300 and more preferably 220 to 280. When the worked penetration exceeds 300,
leakage due to high-speed rotation increases, which may result in failure to satisfy
a sufficient lubrication life. Meanwhile, when the worked penetration is less than
200, the fluidity of the grease is deteriorated, which may result in failure to satisfy
a sufficient lubrication life. Note that, in the present specification, the term "penetration"
refers to a 60-stroke worked penetration. The penetration can be measured according
to JIS K2220-7.
(Content of Thickener)
[0071] The content of the thickener is preferably 5 to 25% by mass and more preferably 10
to 20% by mass based on the total mass of the grease composition of the present invention.
When the content is less than 5% by mass, the grease is soft and may leak, which could
result in failure to satisfy a sufficient lubrication life. Meanwhile, when the content
is more than 25% by mass, the fluidity is inferior and thus it becomes difficult for
the grease to enter the lubrication portion, which could result in failure to satisfy
a sufficient lubrication life.
(Content of Base Oil)
[0072] The content of the base oil is preferably 60 to 90% by mass and more preferably 70
to 90% by mass based on the total mass of the grease composition of the present invention.
The content of the base oil is preferably in such ranges because of excellence in
lubricity and low volatility.
[Bearing]
[0073] The grease composition of the present invention is used in various rolling bearings
for industrial machines and automobiles. Examples for industrial machines include
rolling bearings in various motors for industrial machines, reducers and hydraulic
equipment of industrial robots, main shafts and reducers of wind power generators,
and peripherals of elevator hoists. The use for automobiles is preferably a rolling
bearing for automobile electrical equipment and auxiliaries. Examples of the automobile
electrical equipment and auxiliaries include alternators, electromagnetic clutches
for automobile air conditioners, intermediate pulleys, idler pulleys, and tension
pulleys.
[Examples]
[Hydrogen Generation Test and Measurement of Amount of Hydrogen Generated]
[0075] Specifically, a triboplasma generator (Fig. 1) was used capable of generating triboplasma
between the needle and the flat plate electrode. The needle was the cathode and the
flat plate was the anode. The material of the needle was SCM435 steel and the apex
angle of the needle was 120°. The needle was arranged perpendicular to the anode flat
plate, and was fixed at a position where the distance between the tip of the needle
and the upper surface of the anode was 50 µm. The distance between the needle and
the flat plate electrode was controlled by a micrometer. The material of the anode
flat plate was SPCC steel. The anode flat plate constituted the bottom portion inside
the container. The container was charged with the anti-flaking agent and the like
of Examples or Comparative Examples, and the needle was in contact with the anti-flaking
agent and the like inside the container. The anode flat plate and the cathode needle
were connected by a high voltage power source. The voltage and current when a voltage
was applied was measurable by an oscilloscope. The container and the needle were surrounded
by a larger casing (hereinafter referred to as the "atmosphere control chamber") so
as to cover both. The top portion of the atmosphere control chamber had an opening
provided therein, and the gas inside the atmosphere control chamber was collectable
through a microsyringe. The upper side portion of the atmosphere control chamber also
had an opening provided therein so as to introduce dry air therethrough. The gas inside
the atmosphere control chamber was detectable by a semiconductor sensor.
[0076] Dry air was introduced for 30 seconds to replace the gas inside the atmosphere control
chamber. After the gas inside the atmosphere control chamber was replaced with dry
air, the atmosphere control chamber was subjected to discharging for 30 seconds while
monitoring the current value and the voltage value with an oscilloscope, and then
left for 20 seconds to collect the generated gas through a microsyringe. The collected
gas was introduced into gas chromatography to measure the amount of hydrogen gas.
Note that the gas chromatography was measured using a gas chromatograph GC-2010 (manufactured
by Shimadzu Corporation), a column RT-Msieve ϕ0.43 mm × 30 m, and a detector TCD.
The amount of hydrogen generated for each compound was calculated with the amount
of hydrogen generated for
n-hexadecane set to 100%.
[0077] Tables 3 to 10 present the results. Examples 1 to 38 are examples of the anti-flaking
agent, and Examples 39 to 71 are examples of the lubricating oil composition containing
the anti-flaking agent. Example 42 is a mixture of 3.0% by mass of dimethyl malonate
of Example 3 and 97.0% by mass of poly alpha olefin of Comparative Example 8, and
indicates that, even when the specific volume resistivity of the mixture exceeds 1.0
× 10
10 Ω·cm, the amount of hydrogen generated can be suppressed to 0% if a predetermined
amount of the anti-flaking agent of the present application having a specific volume
resistivity of 1.0 × 10
10 Ω·cm or less is contained.
Table 3
|
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ref. Ex. |
Ref. Ex. |
Ref. Ex. |
Ref. Ex. |
Ref. Ex. |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
9 |
10 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
100 |
|
|
|
|
|
|
|
|
|
Dipheny lpropane |
|
100 |
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
100 |
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
100 |
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
100 |
|
|
|
|
|
Dimethyl Malonate |
|
|
|
|
|
100 |
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
100 |
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
100 |
|
|
Dimethy 1 Adipate |
|
|
|
|
|
|
|
|
100 |
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
100 |
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Trie ster |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
|
2,2'-Thiodiethanol |
|
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
|
|
|
|
|
|
|
|
|
|
N-Methy lformamide |
|
|
|
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly (Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
|
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
|
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
|
|
|
|
|
|
|
|
|
Ether |
ADE |
|
|
|
|
|
|
|
|
|
|
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
92 |
80 |
86 |
60 |
0 |
0 |
0 |
0 |
0 |
0 |
Specific Volume Resistivity Ω·cm |
3.6E+12 |
1.3E+ 13 |
7.5E+ 12 |
3.0E+08 |
9.4E+06 |
2.2E+07 |
2.7E+07 |
6.0E+07 |
1.1E+09 |
5.8E+08 |
Dielectric Constant 500 MHz |
3.2 |
- |
- |
8.8 |
10.2 |
11.2 |
8.5 |
9.1 |
7.9 |
- |
Dielectric Constant 1 GHz |
3.3 |
- |
- |
8.0 |
10.1 |
11.3 |
8.5 |
9.1 |
8.0 |
- |
Hansen Parameter Polar Force δP |
1.0 |
2.1 |
1.9 |
7.8 |
10.4 |
7.0 |
6.6 |
6.4 |
5.6 |
5.1 |
Amount of Hydrogen Generated % |
2 |
3 |
2 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Table 4
|
Ref. Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
11 |
12 |
13 |
14 |
15 |
16 |
17 |
18 |
19 |
20 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
|
|
|
|
|
|
|
|
|
|
Diphenylpropane |
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
100 |
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
100 |
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
100 |
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
100 |
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Triester |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
100 |
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
100 |
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
100 |
|
|
|
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
100 |
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
100 |
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
100 |
2,2'-Thiodiethanol |
|
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
|
|
|
|
|
|
|
|
|
|
N-Methylformamide |
|
|
|
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly(Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
|
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrrolidiniu m Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
|
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
|
|
|
|
|
|
|
|
|
Ether |
ADE |
|
|
|
|
|
|
|
|
|
|
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Specific Volume Resistivity Ω·cm |
3.5E+09 |
4.1E+06 |
4.1E+08 |
4.4E+09 |
6.8E+06 |
2.0E+07 |
3.5E+07 |
3.1E+06 |
9.3E+09 |
3.1E+06 |
Dielectric Constant 500 MHz |
6.4 |
9.0 |
- |
- |
15.6 |
7.8 |
9.0 |
18.1 |
4.6 |
47.6 |
Dielectric Constant 1 GHz |
6.4 |
9.0 |
- |
- |
12.3 |
6.3 |
9.0 |
13.9 |
4.3 |
47.3 |
Hansen Parameter Polar Force δP |
4.5 |
6.0 |
4.4 |
3.8 |
9.4 |
7.8 |
6.0 |
9.4 |
7.8 |
16.4 |
Amount of Hydrogen Generated % |
17 |
0 |
0 |
1 |
0 |
0 |
0 |
0 |
6 |
0 |
Table 5
|
Ex. 21 |
Ex.22 |
Ex.23 |
Ex.24 |
Ex.25 |
Ex.26 |
Ex.27 |
Ex.28 |
Ex.29 |
Ex.30 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
|
|
|
|
|
|
|
|
|
|
Diphenylpropane |
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Triester |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
|
2,2'-Thiodiethanol |
100 |
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
100 |
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
|
|
100 |
|
|
|
|
|
|
|
N-Methylformamide |
|
|
|
100 |
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
100 |
|
|
|
|
|
Tetramethy lurea |
|
|
|
|
|
100 |
|
|
|
|
Tetraethy lurea |
|
|
|
|
|
|
100 |
|
|
|
General Antistatic Agent |
Poly(Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
100 |
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
100 |
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrroli dinium Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
100 |
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
|
|
|
|
|
|
|
|
|
Ether |
ADE |
|
|
|
|
|
|
|
|
|
|
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Specific Volume Resistivity Ω·cm |
<1.6E+06 |
4.4E+06 |
<1.6E+06 |
<1.6E+06 |
<1.6E+06 |
1.9E+06 |
1.7E+06 |
<1.6E+06 |
2.8E+08 |
<1.6E+06 |
Dielectric Constant 500 MHz |
23.0 |
28.7 |
107.7 |
158.4 |
- |
24.5 |
- |
7.5 |
7.2 |
- |
Dielectric Constant 1 GHz |
15.5 |
27.5 |
104.2 |
117.3 |
- |
24.1 |
- |
6.5 |
6.0 |
- |
Hansen Parameter Polar Force δP |
8.8 |
10.5 |
26.2 |
18.8 |
11.8 |
8.2 |
7.9 |
7.2 |
6.8 |
18.0 |
Amount of Hydrogen Generated % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Table 6
|
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
31 |
32 |
33 |
34 |
35 |
36 |
37 |
38 |
39 |
40 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
|
|
|
|
|
|
|
|
|
|
Diphenylpropane |
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
3.0 |
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
3.0 |
Dimethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Triester |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
|
2,2'-Thiodiethanol |
|
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
|
|
|
|
|
|
|
|
|
|
N-Methylformamide |
|
|
|
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly(Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
|
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrrolidiniu m Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
|
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
100 |
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
|
|
|
|
|
|
|
97.0 |
97.0 |
Ether |
ADE |
|
|
|
|
|
|
|
|
|
|
Alkyl Tetraphenyl Ether |
|
100 |
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
100 |
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
100 |
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
100 |
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
100 |
|
|
|
|
MoDTC |
|
|
|
|
|
|
100 |
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
100 |
|
|
Number of Aromatic Carbon Atoms % |
35 |
60 |
100 |
100 |
40 |
11 |
0 |
0 |
- |
- |
Specific Volume Resistivity Ω·cm |
2.4E+08 |
2.4E+ 14 |
7.9E+ 12 |
3.1E+13 |
3.5E+12 |
<1.6E+06 |
2.8E+08 |
1.3E+07 |
- |
- |
Dielectric Constant 500 MHz |
- |
- |
- |
- |
- |
5.0 |
2.3 |
4.0 |
- |
- |
Dielectric Constant 1 GHz |
- |
- |
- |
- |
- |
4.5 |
2.4 |
4.0 |
- |
- |
Hansen Parameter Polar Force δP |
4.4 |
29.1 |
4.9 |
3.5 |
3.6 |
6.8 |
- |
- |
- |
- |
Amount of Hydrogen Generated % |
12 |
16 |
1 |
1 |
1 |
0 |
0 |
0 |
0 |
0 |
Table 7
|
Ex.41 |
Ex.42 |
Ex.43 |
Ex.44 |
Ex.45 |
Ex.46 |
Ex.47 |
Ex.48 |
Ex.49 |
Ex.50 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
|
|
|
|
|
|
|
|
|
|
Diphenylpropane |
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Malonate |
3.0 |
3.0 |
40.0 |
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
5.0 |
10.0 |
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
5.0 |
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
10.0 |
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
|
|
60.0 |
|
|
|
|
|
|
|
Triester |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
1.0 |
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
10.0 |
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
10.0 |
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
|
2,2'-Thiodiethanol |
|
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
|
|
|
|
|
|
|
|
|
|
N-Methylformamide |
|
|
|
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly (Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
|
|
|
Glycerin Aliphatic Ester Monocapry lin |
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
|
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
97.0 |
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
97.0 |
|
95.0 |
|
95.0 |
90.0 |
99.0 |
90.0 |
90.0 |
Ether |
ADE |
|
|
|
|
90.0 |
|
|
|
|
|
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Specific Volume Resistivity Ω·cm |
5.7E+14 |
2.3E+13 |
- |
- |
- |
- |
- |
- |
- |
- |
Dielectric Constant 500 MHz |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Dielectric Constant 1 GHz |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Hansen Parameter Polar Force δP |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Amount of Hydrogen Generated % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Table 8
|
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
51 |
52 |
53 |
54 |
55 |
56 |
57 |
58 |
59 |
60 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
|
|
|
|
|
|
|
|
|
|
Diphenylpropane |
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
99.0 |
|
|
97.0 |
|
|
|
90.0 |
|
|
Triester |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxyethylene)Glycol |
1.0 |
0.5 |
1.0 |
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
3.0 |
3.0 |
3.0 |
|
|
|
|
2,2'-Thiodiethanol |
|
|
|
|
|
|
3.0 |
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
10.0 |
10.0 |
10.0 |
N-cont. cmd. |
Formamide |
|
|
|
|
|
|
|
|
|
|
N-Methylformamide |
|
|
|
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly(Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
|
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methy lpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
|
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
99.5 |
|
|
97.0 |
|
97.0 |
|
90.0 |
|
Ether |
ADE |
|
|
99.0 |
|
|
97.0 |
|
|
|
90.0 |
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Specific Volume Resistivity Ω·cm |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Dielectric Constant 500 MHz |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Dielectric Constant 1 GHz |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Hansen Parameter Polar Force δP |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Amount of Hydrogen Generated % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Table 9
|
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
Ex. |
61 |
62 |
63 |
64 |
65 |
66 |
67 |
68 |
69 |
70 |
71 |
Aromatic Hydrocarbon Compound |
Dipheny lmethane |
|
|
|
|
|
|
|
|
|
|
|
Dipheny lpropane |
|
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
|
|
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Malonate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
|
|
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
99.0 |
|
|
|
|
|
|
|
99.0 |
|
|
Trie ster |
Tributyl Trimellitate |
|
|
|
|
|
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
|
|
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
|
|
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
|
Poly (Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
|
|
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
|
|
2,2'-Thiodiethanol |
|
|
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
1.0 |
0.1 |
1.0 |
|
|
|
|
|
|
|
|
N-Methylformamide |
|
|
|
0.1 |
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
3.0 |
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
3.0 |
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly (Oxyethylene)Alkylamine |
|
|
|
|
|
|
3.0 |
3.0 |
|
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrrolidiniu m Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
1.0 |
0.5 |
1.0 |
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
|
|
|
|
|
Synthetic Hydrocarbon |
PAO |
|
99.9 |
|
99.9 |
97.0 |
97.0 |
97.0 |
|
|
99.5 |
|
Ether |
ADE |
|
|
99.0 |
|
|
|
|
97.0 |
|
|
99.0 |
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Specific Volume Resistivity Ω·cm |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Dielectric Constant 500 MHz |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Dielectric Constant 1 GHz |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Hansen Parameter Polar Force δP |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
- |
Amount of Hydrogen Generated % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
Table 10
|
Comp. Ex. 1 |
Comp. Ex.2 |
Comp. Ex.3 |
Comp. Ex.4 |
Comp. Ex.5 |
Comp. Ex.6 |
Comp. Ex.7 |
Comp. Ex.8 |
Comp. Ex.9 |
Comp. Ex.10 |
Aromatic Hydrocarbon Compound |
Diphenylmethane |
|
|
|
|
|
|
|
|
|
|
Diphenylpropane |
|
|
|
|
|
|
|
|
|
|
Cis-1,2-Diphenylethylene |
|
|
|
|
|
|
|
|
|
|
Monoester |
Methyl Myristate |
100 |
|
|
|
|
|
|
|
|
|
Diester |
Dimethyl Phthalate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Maleate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Succinate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Glutarate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Adipate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Suberate |
|
|
|
|
|
|
|
|
|
|
Dimethyl Sebacate |
|
|
|
|
|
|
|
|
|
|
Diethyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dibutyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Malonate |
|
|
|
|
|
|
|
|
|
|
Dihexyl Sebacate |
|
100 |
|
|
|
|
|
|
|
|
Di-2-Ethylhexyl Sebacate |
|
|
100 |
|
|
|
|
|
|
|
Triester |
Tributyl Trimellitate |
|
|
|
100 |
|
|
|
|
|
|
Tetraester |
Pentaerythritol |
|
|
|
|
100 |
|
|
|
|
|
Glycol |
Tetraethylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tripropylene Glycol |
|
|
|
|
|
|
|
|
|
|
Tetraethylene Glycol Dimethyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxyethylene)Glycol |
|
|
|
|
|
|
|
|
|
|
Polypropylene Glycol Monobutyl Ether |
|
|
|
|
|
|
|
|
|
|
Poly(Oxypropylene, Oxybutylene)Glycol |
|
|
|
|
|
100 |
|
|
|
|
S-cont. cmd. |
Dibutyl Sulfoxide |
|
|
|
|
|
|
|
|
|
|
2,2'-Thiodiethanol |
|
|
|
|
|
|
|
|
|
|
P-cont. cmd. |
Trimethyl Phosphate |
|
|
|
|
|
|
|
|
|
|
N-cont. cmd. |
Formamide |
|
|
|
|
|
|
|
|
|
0.05 |
N-Methylformamide |
|
|
|
|
|
|
|
|
|
|
N-tert-Butylformamide |
|
|
|
|
|
|
|
|
|
|
Tetramethylurea |
|
|
|
|
|
|
|
|
|
|
Tetraethylurea |
|
|
|
|
|
|
|
|
|
|
General Antistatic Agent |
Poly(Oxyethylene)Alkylamine |
|
|
|
|
|
|
|
|
|
|
Glycerin Aliphatic Ester Monocaprylin |
|
|
|
|
|
|
|
|
|
|
Ionic Liquid |
(N-(Methoxyethyl)-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide) |
|
|
|
|
|
|
|
|
|
|
Liquid Crystal |
4-Cyano-4'-Pentylbiphenyl |
|
|
|
|
|
|
|
|
|
|
Mineral Oil |
P-Based Mineral Oil |
|
|
|
|
|
|
100 |
|
|
|
Synthetic Hydrocarbon |
PAO |
|
|
|
|
|
|
|
100 |
|
99.95 |
Ether |
ADE |
|
|
|
|
|
|
|
|
100 |
|
Alkyl Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Pentaphenyl Ether |
|
|
|
|
|
|
|
|
|
|
Tetraphenyl Ether |
|
|
|
|
|
|
|
|
|
|
SP-cont. cmd. |
Alkylated Triphenyl Phosphorothioate |
|
|
|
|
|
|
|
|
|
|
NS-Based Compound |
Dimercaptothiadiazole Derivative |
|
|
|
|
|
|
|
|
|
|
MoDTC |
|
|
|
|
|
|
|
|
|
|
Fatty Acid Amine Salt |
Oleic Acid Dicycloamine Salt |
|
|
|
|
|
|
|
|
|
|
Number of Aromatic Carbon Atoms % |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
0 |
35 |
- |
Specific Volume Resistivity Ω·cm |
7.9E+10 |
2.2E+11 |
2.4E+12 |
2.7E+10 |
2.8E+13 |
2.1E+11 |
5.7E+14 |
4.3E+13 |
7.7E+14 |
- |
Dielectric Constant 500 MHz |
4.0 |
- |
4.2 |
- |
3.5 |
3.5 |
2.7 |
2.7 |
2.8 |
- |
Dielectric Constant 1 GHz |
4.1 |
- |
3.9 |
- |
3.5 |
3.5 |
2.8 |
2.8 |
2.9 |
- |
Hansen Parameter Polar Force δP |
2.7 |
3.0 |
2.1 |
6.8 |
2.1 |
8.1 |
- |
1.0 |
25.0 |
- |
Amount of Hydrogen Generated % |
105 |
95 |
100 |
77 |
88 |
101 |
106 |
100 |
93 |
100 |
[0078] The suppliers and trade names of the compounds used in Examples and Comparative Examples
are presented below.
Tetraester |
: Ester of pentaerythritol with carboxylic acid (manufactured by Kao Corporation under
the trade name of "KAOLUBE 279") |
Glycol |
: Poly(oxyethylene)glycol (manufactured by NOF Corporation under the trade name of
"PEG #200") |
|
Polypropylene glycol monobutyl ether (manufactured by NOF Corporation under the trade
name of "UNILUBE MB-19") |
|
: Poly(oxypropylene, oxybutylene)glycol monodecyl ether (manufactured by Dow Chemical
Company under the trade name of "OSP-68") |
Antistatic Agent |
: Poly(oxyethylene)laurylamine (manufactured by Nippon Nyukazai Co., Ltd. under the
trade name of "Newcol LA-407") |
|
: Glycerin aliphatic ester monocaprylin (manufactured by Riken Vitamin Co., Ltd. under
the trade name of "Poem M-100") |
Ionic Liquid |
: N-(Methoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (manufactured
by Merck) |
Liquid Crystal |
: 4-Cyano-4'-pentylbiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd. under
the trade name of "5CB") |
Mineral Oil |
: P-based mineral oil (manufactured by JX Energy under the trade name of "Super Oil
K-100") |
Synthetic Hydrocarbon |
: PAO8 (kinematic viscosity at 40°C is 45 mm2/s) |
Ether Oil |
: ADE (manufactured by MORESCO under the trade name of "LB-100") |
|
: Alkyl tetraphenyl ether (manufactured by MORESCO under the trade name of "s-3101") |
|
: Pentaphenyl ether (manufactured by MORESCO under the trade name of "s-3105") |
|
: Tetraphenyl ether (manufactured by MORESCO under the trade name of "s-3103") |
SP-Based Compound |
: Alkylated triphenyl phosphorothionate (manufactured by BASF Japan under the trade
name of "IRGALUBE 211") |
NS-Based Compound |
: Dimercaptothiadiazole derivative (manufactured by The Elco Corporation under the
trade name of "Elco 461") |
|
: MoDTC (manufactured by ADEKA Corporation under the trade name of "SAKURA-LUBE 525") |
Fatty Acid Amine Salt |
: Oleic acid dicycloamine salt (manufactured by Albess Co., Ltd. under the trade name
of "NONRUST Z-1000") |
1. An anti-flaking agent comprising at least one selected from the group consisting of
(A) a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, and
(B) a compound in which a percentage of the number of carbon atoms having an aromatic
ring structure is 40% or more among all carbon atoms constituting the compound,
each in an amount exceeding 0.1% by mass based on a total mass of the anti-flaking
agent, wherein
the compounds are none of dimethyl malonate, dimethyl succinate, dimethyl glutarate,
dimethyl adipate, dimethyl suberate, and dimethyl sebacate.
2. The anti-flaking agent according to claim 1, wherein the compound (A) is at least
one selected from the group consisting of compounds having a dielectric constant ε
of 3.0 or more at 500 MHz and 1 GHz.
3. The anti-flaking agent according to claim 1 or 2, wherein the compound (A) is at least
one selected from the group consisting of compounds having a Hansen solubility parameter
polar term δp of 3.5 or more.
4. The anti-flaking agent according to any one of claims 1 to 3, wherein the compound
(A) is at least one selected from the group consisting of polyvalent esters, glycols,
sulfur-containing compounds, phosphorus-containing compounds, nitrogen-containing
compounds, antistatic agents, ionic liquids, liquid crystals, SP compounds, NS compounds,
and fatty acid amine salts.
5. The anti-flaking agent according to any one of claims 1 to 4, wherein the compound
(A) is a diester of an aliphatic monoalcohol having 6 or less carbon atoms with an
alicyclic fatty acid having 3 to 10 carbon atoms or aromatic dibasic acid having 3
to 10 carbon atoms.
6. The anti-flaking agent according to any one of claims 1 to 5, wherein the compound
(A) is a diester selected from the group consisting of dimethyl phthalate, dimethyl
maleate, diethyl malonate, dibutyl malonate, and dihexyl malonate.
7. The anti-flaking agent according to any one of claims 1 to 4, wherein the compound
(A) is an antistatic agent selected from the group consisting of poly(oxyethylene)alkylamines,
poly(oxyethylene)alkylamides, poly(oxyethylene)alkyl ethers, poly(oxyethylene)alkyl
phenyl ethers, glycerin aliphatic esters, sorbitan aliphatic esters, alkylsulfonates,
alkylbenzene sulfonates, alkyl phosphates, quaternary ammonium chlorides, quaternary
ammonium sulfates, quaternary ammonium nitrates, alkylbetaines, alkyl imidazolines,
alkylalanines, polyvinyl benzyl, polyacrylic, amine derivatives, succinic acid derivatives,
partial esters of poly(oxyalkylene)glycol and polyhydric alcohol, ammonium compounds
of alkyl naphthalene sulfonic acid, polyalkyl sulfones, and neutralized salts of alkyl
aryl sulfonic acid and alkyl amine.
8. The anti-flaking agent according to any one of claims 1 to 7, wherein the compound
(B) is at least one selected from the group consisting of phenyl ethers, alkylbenzenes,
and alkylnaphthalenes.
9. A lubricant composition comprising the compound according to any one of claims 1 to
8.
10. The lubricant composition according to claim 9, further comprising at least one conventional
base oil selected from the group consisting of mineral oils and synthetic oils.
11. The lubricant composition according to claim 9 or 10, wherein the base oil is at least
one selected from the group consisting of mineral oils, synthetic hydrocarbon oils,
and ether oils.
12. The lubricant composition according to any one of claims 9 to 11, wherein a content
of the compound exceeds 0.1% by mass based on a total mass of the composition.
13. The lubricant composition according to any one of claims 9 to 12, further comprising
a thickener.