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(11) | EP 0 535 990 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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| (54) |
A lubricating oil composition Schmierölzusammensetzung Composition d'huile lubrifiante |
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| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
(a) polyvalent branched aliphatic alcohols with 2-4 primary hydroxy groups and 4-10 carbon atoms and
(b) di- and/or trimeric fatty acids produced by polymerisation of unsaturated fatty acids with 16-18 carbon atoms, and
(c) saturated straight or branched chain aliphatic monocarboxylic acids with 6-16 carbon atoms, with the amount of hydroxy group esterified by monocarboxylic acids amounting to 50 to 90%. These complex esters are highly viscous and usable as engine oils for two-stroke engines, inter alia.
1. biodegradability and thermal stability
(1) biodegradability
BOD: Biological Oxygen Demand of a test substance (Value found, mg)
B: Oxygen consumption by a culture medium into which activated sludge has been inoculated (Value found, mg)
TOD: Theoretical Oxygen Demand required for complete oxidation of the test substance (Value calculated, mg). The value for TOD was determined by calculating the molecular formula obtained from the elemental analysis of the test substance (oil).
(2) Thermal stability
(1) Comparative Example 1 uses a TMP ester which consists mainly of a fatty acid (oleic acid) having 18 carbon atoms. This ester exhibited good biodegradability, but, however, showed poor thermal stability as compared with the composition of the present invention.
(2) Comparative Example 2 uses a PET ester which consists of a branched-chain fatty acid having 8 carbon atoms. This PET ester exhibited low biodegradability although it exhibited good thermal stability.
(3) Comparative Examples 3 and 4 used therein, alone, oils which were the same as components (A-1) and (A-2) of this invention, respectively. Each of these oils exhibited good biodegradability and thermal stability. However, when either of said oils is used alone as a lubricating oil, it shows a kinematic viscosity of less than 6 mm2/s at 100°C. This viscosity is too low as a base oil for a two-stroke engine oil, and therefore, these oils are likely to exhibit insufficient lubricity and insufficient antiseizure performance. In addition, Comparative Example 5 used therein, alone, an oil which was the same as the component (B) of this invention. Unlike the oils in Comparative Examples 3 and 4, the oil used alone in Comparative Example 5 exhibited a kinematic viscosity of higher than 30 mm2/s at 100°C, and raised problems as to its detergency and fluidity.
(4) Comparative Example 6 used therein an oil prepared by mixing the components (A) and (B) of this invention. The oil so prepared exhibited inferior biodegradability since the mixing ratio was outside that specified for the composition of this invention.
(5) Comparative Examples 7 and 8 show commercially-available biodegradable two-stroke engine oils respectively. These oils use therein the same ester as used in Comparative Example 1 as a main component of the base oil. In contrast to these Comparative Examples, it is apparent that the compositions of this invention set out in Examples 1 to 6 were remarkably improved in thermal stability. In addition, Comparative Example 9 shows a polybutene base oil for a commercially-available low-smoke exhaust gas type two-stroke engine oil. This polybutene base oil exhibits good thermal stability in the HTT, but it has low biodegradability. Comparative Example 10 shows a mineral base oil for two-stroke engine oil, and Comparative Example 11 shows an oil for a commercially-available low-smoke exhaust gas type two-stroke engine oil, in which the base oil has partly been replaced by a polybutene base oil. Such a mineral base oil possesses poor thermal stability and biodegradability.
(6) As shown in the Examples, the composition of this invention comprises the components (A) and (B) in the specified mixing ratio thereby enabling the composition to have a suitable range of viscosity values for use in two-stroke engine oils, and also to exhibit excellent lubricity as well as excellent biodegradability and thermal stability which are important properties of the composition of this invention.
2. Engine test results
(1) High-temperature cleanliness test on motorcycle engines
| Test oils | Ex. 3 | Comp. Ex. 7 | Comp. Ex. 8 | |
| ring sticking, | top ring | 10 | 0 | 6 |
| second ring | 10 | 0 | 6 | |
| ring land | top | 4.1 | 1.5 | 3.8 |
| second | 5.6 | 0.3 | 4.1 | |
| piston skirt | 9.4 | 5.3 | 9.2 | |
| undercrown | 2.9 | 0.6 | 2.0 | |
| Total: 60 points (full marks) | 42.0 | 7.7 | 33.1 | |
| Note: Since the piston seizure took place within 2.5 hours in Comparative Example 7, Comparative Example 7 shows the piston cleanliness at that time | ||||
(2) Cleanliness test on engine for electric generator
| Test oils | Ex. 4 | Comp. Ex. 7 | Comp. Ex. 10 | |
| ring sticking, | top ring | 10 | 8 | 10 |
| second ring | 10 | 10 | 10 | |
| ring land | top | 6.7 | 1.0 | 1.6 |
| second | 8.2 | 5.3 | 4.4 | |
| piston skirt | 10 | 9.3 | 9.2 | |
| undercrown | 10 | 2.2 | 1.6 | |
| cylinder head | 10 | 8.9 | 5.7 | |
| Total: 70 points (full marks) | 64.9 | 44.7 | 42.5 | |
(3) Engine cleanliness test on chain saw engine
| Test oils | Ex. 4 | Comp. Ex. 11 | |
| ring sticking, | top ring | 7.0 | 5.0 |
| second ring | 10 | 10 | |
| ring land | top | 8.4 | 3.9 |
| second | 9.5 | 5.2 | |
| piston skirt | 10 | 9.0 | |
| undercrown | 2.4 | 0.9 | |
| Total: 60 points (full marks) | 47.3 | 34.0 | |
(A) 60 - 95 % by weight of an ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms, and
(B) 5 - 40 % by weight of a complex ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms and also with an aliphatic dibasic acid having 2 - 50 carbon atoms.
(I) 100 parts by weight of an ester mixture consisting of
(A) 60 - 95 % by weight of an ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms, and
(B) 5 - 40 % by weight of a complex ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms and also with an aliphatic dibasic acid having 2 - 50 carbon atoms,
(II) not more than 30 parts by weight of a hydrocarbon based solvent and/or a lubricating base oil.
(A) 60 - 95 % by weight of an ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms, and
(B) 5 - 40 % by weight of a complex ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms and also with an aliphatic dibasic acid having 2 - 50 carbon atoms.
(I) 100 parts by weight of an ester mixture consisting of
(A) 60 - 95 % by weight of an ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms and
(B) 5 - 40 % by weight of a complex ester of a hindered alcohol with a straight-chain saturated fatty acid having 8 - 12 carbon atoms and also with an aliphatic dibasic acid having 2 - 50 carbon atoms, and
(II) not more than 30 parts by weight of a hydrocarbon based solvent and/or a lubricating base oil.
(A) 60 bis 95 Gew.% Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen und
(B) 5 bis 40 Gew.% komplexer Ester eines gehinderten Alkohols mit einer geradkettigen ungesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen sowie mit einer aliphatischen dibasischen Säure mit 2 bis 50 Kohlenstoffatomen.
(I) 100 Gewichtsteile Estermischung, bestehend aus
(A) 60 bis 95 Gew.% Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen und
(B) 5 bis 40 Gew.% komplexer Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen sowie mit einer aliphatischen dibasischen Säure mit 2 bis 50 Kohlenstoffatomen,
(II) nicht mehr als 30 Gewichtsteile eines Lösungsmittels auf Kohlenwasserstoffbasis und/oder eines Schmierrohöls.
(A) 60 bis 95 Gew.% Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen und
(B) 5 bis 40 Gew.% komplexer Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen sowie einer aliphatischen dibasischen Säure mit 2 bis 50 Kohlenstoffatomen.
(I) 100 Gewichtsteile Estermischung, bestehend aus
(A) 60 bis 95 Gew.% Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen und
(B) 5 bis 40 Gew.% komplexer Ester eines gehinderten Alkohols mit einer geradkettigen gesättigten Fettsäure mit 8 bis 12 Kohlenstoffatomen sowie mit einer aliphatischen dibasischen Säure mit 2 bis 50 Kohlenstoffatomen,
(II) nicht mehr als 30 Gewichtsteile eines Lösungsmittels auf Kohlenwasserstoffbasis und/oder eines Schmierrohöls.
A) 60 à 95 % en poids d'un ester d'un alcool stériquement encombré et d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone, et de
B) 5 à 40 % en poids d'un ester complexe d'un alcool stériquement encombré, d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone et d'un diacide aliphatique comportant de 2 à 50 atomes de carbone.
I) 100 parties en poids d'un mélange d'esters constitué de
A) 60 à 95 % en poids d'un ester d'un alcool stériquement encombré et d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone, et de
B) 5 à 40 % en poids d'un ester complexe d'un alcool stériquement encombré, d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone et d'un diacide aliphatique comportant de 2 à 50 atomes de carbone, et
II) au plus 30 parties en poids d'un solvant à base d'hydrocarbures et/ou d'une huile de base lubrifiante.
A) 60 à 95 % en poids d'un ester d'un alcool stériquement encombré et d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone, et de
B) 5 à 40 % en poids d'un ester complexe d'un alcool stériquement encombré, d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone et d'un diacide aliphatique comportant de 2 à 50 atomes de carbone.
I) 100 parties en poids d'un mélange d'esters constitué de
A) 60 à 95 % en poids d'un ester d'un alcool stériquement encombré et d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone, et de
B) 5 à 40 % en poids d'un ester complexe d'un alcool stériquement encombré, d'un acide gras saturé à chaîne linéaire comportant de 8 à 12 atomes de carbone et d'un diacide aliphatique comportant de 2 à 50 atomes de carbone, et
II) au plus 30 parties en poids d'un solvant à base d'hydrocarbures et/ou d'une huile de base lubrifiante.