JP5092517B2 - Lubricating oil composition - Google Patents
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- JP5092517B2 JP5092517B2 JP2007107748A JP2007107748A JP5092517B2 JP 5092517 B2 JP5092517 B2 JP 5092517B2 JP 2007107748 A JP2007107748 A JP 2007107748A JP 2007107748 A JP2007107748 A JP 2007107748A JP 5092517 B2 JP5092517 B2 JP 5092517B2
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- 239000000203 mixture Substances 0.000 title claims description 50
- 239000010687 lubricating oil Substances 0.000 title claims description 37
- 239000002199 base oil Substances 0.000 claims description 47
- 239000003921 oil Substances 0.000 claims description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- 229920005862 polyol Polymers 0.000 claims description 21
- 239000010696 ester oil Substances 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 17
- -1 polyol ester Chemical class 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Lubricants (AREA)
Description
本発明は、潤滑油組成物に関する。さらに詳しくは、常用回転数が3000rpm未満の軸受に好適に用いられる潤滑油組成物に関する。 The present invention relates to a lubricating oil composition. More specifically, the present invention relates to a lubricating oil composition suitably used for a bearing having a normal rotational speed of less than 3000 rpm.
自動車電装機器で使用される焼結含油軸受としては、世界中のいかなる使用環境条件下でも使用可能であることが要求される。かかる焼結軸受中に含油される潤滑油についても、例えば熱帯地域での動作環境を想定し、150℃にも至る高温条件下においても、潤滑油が軸受内に長期間安定して維持され、潤滑性を維持できること、一方極寒冷地の-40℃にも至る低温度領域でも流動性を維持し、回転トルクを異常に上昇させるなどの軸受にとって動作不良のないことなど、非常に広範囲な温度領域で安定した性能を発揮し得ることが重要である。 Sintered oil-impregnated bearings used in automobile electrical equipment are required to be usable under any use environment conditions around the world. As for the lubricating oil contained in the sintered bearing, for example, assuming an operating environment in a tropical region, the lubricating oil is stably maintained in the bearing for a long time even under a high temperature condition as high as 150 ° C. A very wide range of temperatures, such as being able to maintain lubricity, while maintaining fluidity even in the low temperature range up to -40 ° C in extremely cold regions, and that there is no malfunction in bearings such as abnormally increasing rotational torque. It is important that stable performance can be exhibited in the region.
このような広範囲の温度範囲において使用可能な潤滑油としては、合成炭化水素油、エステル油等の合成油が使用可能であるが、かかる合成油にあっても潤滑油の粘度が非常に重要な因子の一つとなる。一般には、粘度が高い潤滑油程揮発性が低く、高温においても油膜を保持し易い。しかしながら、あまり高粘度な潤滑油は、低温度領域においてはさらに高粘度となり、低温時の軸受作動性に悪影響を及ぼすので、あまり高粘度の潤滑油は使用できない。そこで、耐熱性を維持できる程度に低粘度な基油をベースとし、これに粘度指数向上剤を配合して、高温における油膜を保持するということが実際に行われている。 Synthetic oils such as synthetic hydrocarbon oils and ester oils can be used as lubricating oils that can be used in such a wide temperature range. Even in such synthetic oils, the viscosity of the lubricating oil is very important. One of the factors. In general, the higher the viscosity of a lubricating oil, the lower the volatility and the easier it is to hold an oil film even at high temperatures. However, a lubricating oil having a very high viscosity has a higher viscosity in a low temperature range and adversely affects the bearing operability at a low temperature, so that a lubricating oil having a very high viscosity cannot be used. Therefore, it is actually practiced to use a base oil having a low viscosity to the extent that heat resistance can be maintained, and to add a viscosity index improver thereto to maintain an oil film at a high temperature.
さらに、近年は低温性への考慮がより必要とされてきており、すなわち高粘度指数でかつ低温での粘度が小さく、省電力化に寄与できるものが求められている。 Furthermore, in recent years, consideration for the low temperature property has been more required, that is, a material having a high viscosity index and a low viscosity at a low temperature, which can contribute to power saving.
かかる観点から、ベースオイルとしての潤滑油基油自体についての検討も行われており、特許文献1には基油としてポリオレフィンおよびポリオールエステルを使用したものが示されているが、これら両者の混合比率によっては、十分な耐熱性と低温特性とを両立させることができず、また特許文献2〜3には特定のエステル油を使用することが、特許文献4には合成炭化水素油について特徴付けしたものがそれぞれ提案されている。
例えば、特許文献3にあっては、耐久性、耐トルク性にすぐれた軸受用潤滑油として、炭素数6〜10の1価飽和脂肪族アルコールと炭素数10の2価飽和脂肪族カルボン酸ジエステルを基油とし、40℃動粘度が11mm2／秒未満の低粘度潤滑油を3〜20重量％含む潤滑油組成物が提案され、これは流体動圧軸受ユニット、多孔質含油軸受ユニットまたはこの軸受ユニットを備えたスピンドルモータに適用されるとされている。また、特許文献4にあっては、低粘度でありながら高い引火点を持ち、蒸発し難く、耐熱性にすぐれた液体潤滑剤として、炭素数21〜29の炭化水素からなり、40℃動粘度が6〜16mm2／秒、100℃動粘度が4.9mm2／秒以下、引火点が180℃以上、流動点が-15℃以下である液体潤滑剤が提案されている。しかしながら、これらの潤滑油組成物は、近年要求される高い回転性能や耐熱性、低温特性などのすべてを満足させるものではない。さらに、特許文献1にあっては、含油軸受用組成物として、ポリオレフィンおよびポリオールエステルの重量比20/80〜80/20混合物が提案されている。ここで用いられている各成分の40℃動粘度は、ポリオレフィンについては5〜100mm2／秒、好ましくは15〜70mm2／秒、またポリオールエステルについては10〜100mm2／秒、好ましくは15〜70mm2／秒であるとされている。しかしながら、このような含油軸受用組成物は、低温特性の点において満足されるものではない。 For example, in Patent Document 3, monovalent saturated aliphatic alcohols having 6 to 10 carbon atoms and divalent saturated aliphatic carboxylic acid diesters having 10 carbon atoms are used as bearing lubricants having excellent durability and torque resistance. A lubricating oil composition containing 3 to 20% by weight of a low-viscosity lubricating oil having a kinematic viscosity at 40 ° C. of less than 11 mm 2 / sec is proposed. This is a fluid dynamic pressure bearing unit, a porous oil-impregnated bearing unit or a It is supposed to be applied to a spindle motor provided with a bearing unit. Further, in Patent Document 4, it is a low-viscosity, high-flash point, difficult to evaporate, and liquid lubricant with excellent heat resistance. There 6~16mm 2 / sec, 100 ° C. kinematic viscosity 4.9 mm 2 / sec or less, a flash point of 180 ° C. or higher, a liquid lubricant has been proposed pour point of -15 ° C. or less. However, these lubricating oil compositions do not satisfy all of the high rotational performance, heat resistance, and low-temperature characteristics required in recent years. Furthermore, Patent Document 1 proposes a mixture of polyolefin and polyol ester in a weight ratio of 20/80 to 80/20 as an oil-impregnated bearing composition. 40 ° C. The kinematic viscosity of each component, as used herein, 5 to 100 mm 2 / sec for polyolefin, preferably 15~70mm 2 / sec, and for polyol ester 10 to 100 mm 2 / s, preferably 15 to It is supposed to be 70mm 2 / sec. However, such an oil-impregnated bearing composition is not satisfactory in terms of low temperature characteristics.
潤滑油組成物を、常用回転数3000rpm未満の軸受用潤滑剤として使用する場合には、常温での潤滑性のみならず、バランスの良い高温潤滑性と低温時低トルク性とが要求仕様とされる。常温での潤滑性は、40℃動粘度で評価しており、潤滑性を重視する観点から約50〜70mm2／秒程度が好ましい数値とされている。高温潤滑性については、100℃動粘度の数値が5mm2／秒以下では、油膜切れが問題となる。また、蒸発損失は少ない程よいが、実際には150℃、100時間での蒸発損失が30重量％以下であることが適否の目安となる。一方、低温トルクについては、-40℃でのせん断応力値で優劣が評価され、この数値が小さい程低温特性が優れているとされる。 When a lubricating oil composition is used as a bearing lubricant with a normal rotational speed of less than 3000 rpm, not only lubricity at normal temperature but also high temperature lubrication with good balance and low torque at low temperature are required specifications. The The lubricity at normal temperature is evaluated by 40 ° C. kinematic viscosity, and about 50 to 70 mm 2 / sec is a preferable value from the viewpoint of emphasizing lubricity. Regarding high temperature lubricity, oil film breakage becomes a problem when the value of 100 ° C. kinematic viscosity is 5 mm 2 / sec or less. In addition, the smaller the evaporation loss, the better. In practice, however, the evaporation loss at 150 ° C. for 100 hours is 30% by weight or less. On the other hand, regarding low temperature torque, superiority or inferiority is evaluated by a shear stress value at −40 ° C., and the lower this value, the better the low temperature characteristics.
本発明の目的は、耐熱性にすぐれたポリオールエステル油を主成分とし、その耐熱性を実質的に損なうことなく、低温特性を改善せしめた、常用回転数3000rpm未満の軸受用潤滑油組成物を提供することにある。 An object of the present invention is to provide a lubricating oil composition for bearings having a normal rotational speed of less than 3000 rpm, which has a polyol ester oil having excellent heat resistance as a main component and has improved low temperature characteristics without substantially impairing the heat resistance. It is to provide.
かかる本発明の目的は、40℃動粘度が15〜40mm2／秒のポリオールエステル油と40℃動粘度が15〜40mm2／秒の炭化水素油との混合物からなる低粘度基油および40℃動粘度が350mm2／秒以上の高粘度炭化水素油の基油混合物であって、ポリオールエステル油が基油混合物中60〜75重量％を占め、さらに粘度指数向上剤を潤滑油組成物中5〜10重量％の割合で含有させた潤滑油組成物によって達成される。ここで、常用回転数とは、モーターを起動した後、安定状態となった時点で平均的に用いられる回転数を指している。 Such object of the present invention, 40 ° C. kinematic viscosity of 15 to 40 mm 2 / sec polyol ester oil and 40 ° C. kinematic viscosity mixture low viscosity base oil and 40 ° C. consisting of hydrocarbon oil 15 to 40 mm 2 / s A base oil mixture of a high-viscosity hydrocarbon oil having a kinematic viscosity of 350 mm 2 / sec or more, wherein the polyol ester oil accounts for 60 to 75% by weight in the base oil mixture, and a viscosity index improver is added to the lubricating oil composition. This is achieved by a lubricating oil composition contained in a proportion of ˜10% by weight. Here, the normal rotational speed refers to the rotational speed that is used on average when the motor is started and becomes stable.
本発明に係る潤滑油組成物は、耐熱性を維持するために、低粘度基油の主成分をポリオールエステル油とし、またポリオールエステル油に比べて低温特性が良好な合成炭化水素油を高粘度基油とし、さらに低粘度基油の一部を合成炭化水素油で置換して用いることにより、低温特性をさらに改善せしめることができる。また、ポリオールエステル油を主成分として用いることにより、粘度指数向上剤配合時の溶解性の向上や高温時のスラッジの発生を抑制することもできる。かかる潤滑油組成物は、常用回転数が3000rpm未満である軸受用途、例えば自動車電装機器モータ用軸受などに好適に使用される。 In order to maintain heat resistance, the lubricating oil composition according to the present invention uses a low-viscosity base oil as a main component of a polyol ester oil, and a high-viscosity synthetic hydrocarbon oil having good low-temperature characteristics as compared with a polyol ester oil. By using a base oil and substituting a part of the low-viscosity base oil with a synthetic hydrocarbon oil, the low-temperature characteristics can be further improved. Further, by using a polyol ester oil as a main component, it is possible to improve the solubility at the time of blending the viscosity index improver and to suppress the generation of sludge at a high temperature. Such a lubricating oil composition is suitably used for bearing applications having a normal rotational speed of less than 3000 rpm, such as automobile electrical equipment motor bearings.
基油混合物中60〜75重量％を占める主成分としてのポリオールエステル油は、多価アルコール、例えばトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、ネオペンチルグリコール等と炭素数4〜18の脂肪族飽和モノカルボン酸、例えばC8〜C12混合物、C9、C18カルボン酸等とのエステルであり、エステル化はポリオール基の一部または全部について行われる。 Polyol ester oil as the main component, which accounts for 60 to 75 wt% in the base oil mixture, polyhydric alcohols, for example trimethylol propane, pentaerythritol, dipentaerythritol, neopentyl glycol and an aliphatic saturated having 4 to 18 carbon atoms An ester with a monocarboxylic acid, such as a C 8 -C 12 mixture, C 9 , C 18 carboxylic acid, etc., and esterification is carried out on some or all of the polyol groups.
用いられるポリオールエステル油の40℃動粘度は、15〜40mm2／秒の範囲でなければならず、このような動粘度への調節はポリオールのエステル化の程度や多価アルコールと脂肪族飽和モノカルボン酸との組合せの選択などによって行われる。また、動粘度がこれ以下では、耐引火性、耐揮発性、耐荷重性などに不具合が生ずる場合があり、一方これ以上の動粘度のものを用いると、低温流動性が損なわれる場合がみられることがある。 The 40 ° C. kinematic viscosity of the polyol ester oil used must be in the range of 15 to 40 mm 2 / sec. Adjustment to such kinematic viscosity can be achieved by adjusting the degree of esterification of the polyol, polyhydric alcohol and aliphatic saturated mono This is done by selecting a combination with a carboxylic acid. Also, if the kinematic viscosity is less than this, there may be a problem with flammability, volatilization resistance, load resistance, etc. On the other hand, if a kinematic viscosity higher than this is used, the low temperature fluidity may be impaired. May be.
低粘度基油としては、耐熱性および粘度指数向上剤配合時の溶解性が良好で、高温時のスラッジの発生を抑制する作用を有するポリオールエステル油に同動粘度範囲の炭化水素油を低粘度基油中15〜38重量％、好ましくは15〜30重量％の割合で混合したものが用いられる。40℃動粘度が15〜40mm2／秒の範囲の炭化水素油としては、エチレン、プロピレン、イソブチレン、1-デセン、1-ドデセン等の炭素数1〜18のα-オレフィンと他のα-オレフィンとの単独重合体オリゴマーまたはα-オレフィンの共重合体オリゴマーが用いられる。このようにポリオールエステル油に低粘度炭化水素油を15重量％以上の割合で混合して用いることにより、さらに低温特性を良化させることができるといった効果が得られる。一方、38重量％以上の割合で用いると、蒸発損失率が増加し、高温寿命が悪化するようになる。 The low-viscosity base oil has good heat resistance and solubility when blended with a viscosity index improver, and has a low viscosity viscosity with a hydrocarbon oil in the same kinematic viscosity range as a polyol ester oil that has the effect of suppressing sludge generation at high temperatures. A mixture of 15 to 38% by weight, preferably 15 to 30% by weight in the base oil is used. Examples of hydrocarbon oils having a kinematic viscosity at 40 ° C. in the range of 15 to 40 mm 2 / sec include α-olefins having 1 to 18 carbon atoms such as ethylene, propylene, isobutylene, 1-decene and 1-dodecene, and other α-olefins. Homopolymer oligomers and α-olefin copolymer oligomers are used. Thus, by mixing and using a low-viscosity hydrocarbon oil in a proportion of 15% by weight or more in the polyol ester oil, the effect of further improving the low temperature characteristics can be obtained. On the other hand, if it is used at a ratio of 38% by weight or more, the evaporation loss rate increases and the high-temperature life is deteriorated.
高粘度炭化水素油としては、良好な低温特性を示す、上記の如きα-オレフィン単独重合体のオリゴマーまたはα-オレフィンと他のα-オレフィンとの共重合体オリゴマーであって、その40℃動粘度が350mm2／秒以上、好ましくは350〜1000mm2／秒のものが用いられる。40℃動粘度がこれ以下のものを用いると、異なる粘度の基油混合による良好な低温特性が得られなくなる。ここで、高粘度炭化水素油は全炭化水素油中、5〜50重量％、好ましくは10〜45重量％となるような割合で用いられる。高粘度炭化水素油の混合割合がこれより少ないと、中粘度基油を単一に配合した場合に比べて製品粘度が低くなりすぎるようになり、また耐揮発性が悪化するようになる。一方、高粘度炭化水素油の混合割合がこれより多いと、中粘度基油の単一配合の場合と比べて低温特性への効果があらわれにくくなってしまう。 The high-viscosity hydrocarbon oil is an α-olefin homopolymer oligomer or a copolymer oligomer of an α-olefin and another α-olefin, which exhibits good low-temperature characteristics, and operates at 40 ° C. viscosity 350 mm 2 / sec or more, preferably is used as the 350~1000mm 2 / sec. If a material having a kinematic viscosity of 40 ° C. or lower is used, good low temperature characteristics cannot be obtained by mixing base oils having different viscosities. Here, the high-viscosity hydrocarbon oil is used in a ratio of 5 to 50% by weight, preferably 10 to 45% by weight, based on the total hydrocarbon oil. When the mixing ratio of the high-viscosity hydrocarbon oil is less than this, the product viscosity becomes too low as compared with the case where the medium-viscosity base oil is blended singly, and the volatility resistance deteriorates. On the other hand, when the mixing ratio of the high-viscosity hydrocarbon oil is higher than this, the effect on the low-temperature characteristics is less likely to appear as compared with the case of a single blend of the medium-viscosity base oil.
これらの低粘度基油と高粘度基油とを基油混合物として用いることにより、より低温度のトルクを低く抑えることができる。すなわち、ポリオールエステル油のすぐれた耐熱性を実質的に損なうことなく、低温特性を改善させることができる。また、40℃動粘度が15〜40mm2／秒の低粘度基油と350mm2／秒以上の高粘度基油とを基油混合物として用いることにより、その中間の40℃動粘度を有する単一成分からなる基油よりも、低温粘度をさらに低下せしめることができる。かかる観点から、ポリオールエステル油は基油混合物中60〜75重量％、好ましくは65〜75重量％の割合で用いられる。また、ポリオールエステルの混合割合がこれ以下では、十分な耐蒸発損失特性が低下するばかりか、かえって40℃動粘度が上がり、低温特性が悪化することがある。 By using these low-viscosity base oil and high-viscosity base oil as a base oil mixture, the torque at a lower temperature can be kept low. That is, the low temperature characteristics can be improved without substantially impairing the excellent heat resistance of the polyol ester oil. Further, by the 40 ° C. kinematic viscosity using a 15 to 40 mm 2 / s low viscosity base oil and 350 mm 2 / sec or more high viscosity base oil as a base oil mixtures, single with 40 ° C. kinematic viscosity of the intermediate The low-temperature viscosity can be further reduced as compared with a base oil composed of components. From this viewpoint, the polyol ester oil is used in a proportion of 60 to 75% by weight, preferably 65 to 75% by weight in the base oil mixture. On the other hand, when the mixing ratio of the polyol ester is less than this, not only the sufficient evaporation loss characteristic is lowered, but also the 40 ° C. kinematic viscosity is increased, and the low temperature characteristic may be deteriorated.
以上の各基油成分からなる潤滑油組成物中には、さらに約5〜10重量％、好ましくは約6〜10重量％の粘度指数向上剤が添加される。これ以上の添加割合では、それぞれの使用条件下において低温特性の低下や40℃動粘度が高くなりすぎ、一方これ以下の添加割合では、高温潤滑性が得られなくなる。粘度指数向上剤としては、例えばポリメタクリレート、エチレン-プロピレン共重合体、ポリイソブチレン、ポリアルキルスチレン、スチレン-イソプレン水素化共重合体等が用いられる。このうち、下記特許文献５に記載されているメタクリレート系重合物および該重合物を溶解させる合成油溶媒からなる粘度指数向上剤が低温特性、耐熱特性に優れるため、好適に使用される。メタクリレート系重合物の分子量は、十分な粘度指数向上を実現するために、重量平均分子量(Mw)が10,000〜1,000,000のものが用いられる。さらに、せん断安定性、ハンドリング性、摩擦摩耗特性といった観点から、好ましくはMw10,000〜500,000のものが用いられる。
メタクリレート系重合物の溶媒として使用可能な合成油は、特に限定されないが、好ましくは合成炭化水素油、エステル油またはこれらの混合物等が挙げられる。また、潤滑油組成物の基油として使用されるものの少なくとも一成分と同一種類のものを溶媒として用いることにより、さらに本発明が目的とする特性に合致する潤滑油組成物を得ることが可能となる。なお、合成油基油の特性を損なわないものであれば、合成油については同種異種を問わず、異なる粘度のものを使用することができる。メタクリレート系重合物は、通常、固形分として約0.5〜40重量％、好ましくは約1.5〜30重量％の割合となるように溶媒中に溶解されて用いられる。 Synthetic oil that can be used as a solvent for the methacrylate polymer is not particularly limited, and preferred examples include synthetic hydrocarbon oil, ester oil, and mixtures thereof. Further, by using as the solvent the same kind of at least one component used as the base oil of the lubricating oil composition, it is possible to obtain a lubricating oil composition that further meets the target characteristics of the present invention. Become. In addition, as long as it does not impair the characteristics of the synthetic base oil, those having different viscosities can be used regardless of whether they are of the same type or different types. The methacrylate polymer is usually used by being dissolved in a solvent so that the solid content is about 0.5 to 40% by weight, preferably about 1.5 to 30% by weight.
潤滑油組成物中にはさらに、その効果に影響を与えない範囲内で、酸化防止剤、金属不活性化剤としての腐食防止剤、防錆剤等従来の潤滑油に添加されている添加剤を添加することができる。 Additives added to conventional lubricating oils such as antioxidants, corrosion inhibitors as metal deactivators, rust inhibitors, etc., as long as they do not affect the effect of the lubricating oil composition Can be added.
酸化防止剤としては、例えば2,6-ジ第3ブチル-4-メチルフェノール、4,4′-メチレンビス(2,6-ジ第3ブチルフェノール)等のフェノール系の酸化防止剤、アルキルジフェニルアミン、トリフェニルアミン、フェニル-α-ナフチルアミン、フェノチアジン、アルキル化フェニル-α-ナフチルアミン、アルキル化フェニチアジン等のアミン系の酸化防止剤などが挙げられる。他に、リン系酸化防止剤、イオウ系酸化防止剤等も用いられる。腐食防止剤としては、例えばベンゾトリアゾール、ベンゾイミダゾール、チアジアゾール等が挙げられる。また防錆剤としては、例えば芳香族スルホン酸または飽和脂肪族ジカルボン酸のCa塩またはNa塩、脂肪酸、脂肪酸アミン、アルキルスルホン酸金属塩、アルキルスルホン酸アミン塩、酸化パラフィン、ポリオキシアルキルエーテル等が挙げられる。 Examples of the antioxidant include phenolic antioxidants such as 2,6-ditertiarybutyl-4-methylphenol and 4,4′-methylenebis (2,6-ditertiarybutylphenol), alkyldiphenylamine, Examples include amine-based antioxidants such as phenylamine, phenyl-α-naphthylamine, phenothiazine, alkylated phenyl-α-naphthylamine, and alkylated phenothiazine. In addition, phosphorus antioxidants, sulfur antioxidants, and the like are also used. Examples of the corrosion inhibitor include benzotriazole, benzimidazole, thiadiazole and the like. Examples of the rust preventive agent include Ca salt or Na salt of aromatic sulfonic acid or saturated aliphatic dicarboxylic acid, fatty acid, fatty acid amine, alkyl sulfonic acid metal salt, alkyl sulfonic acid amine salt, oxidized paraffin, polyoxyalkyl ether, etc. Is mentioned.
組成物の調製は、以上の各成分を所定量添加し、十分に混合する方法等によって行われる。 The composition is prepared by a method of adding a predetermined amount of each of the above components and mixing them sufficiently.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１〜２、比較例１
40℃動粘度
基油A：トリメチロールプロパン完全C8〜C12カルボン酸エステル 18mm2／秒
〃 B：合成炭化水素油(イノビーン製品PAO 4) 19mm2／秒
〃 C： 〃 (同社製品PAO 6) 31mm2／秒
〃 D： 〃 (同社製品PAO 40) 390mm2／秒
〃 E： 〃 (同社製品PAO 10) 68mm2／秒
以上の基油中の2種または3種 97.9重量部、ポリメタクリレート系粘度指数向上剤(基油A中にて合成、Mw:250,000)8重量部、アミン系酸化防止剤(チバ・スペシャルティ・ケミカルズ社製品イルガノックスL57)1重量部およびベンゾトリアゾール系腐食防止剤(同社製品イルガメット39)0.1重量部を混合し、酸化防止剤および腐食防止剤含有潤滑油組成物(合計100重量部)を得た。
Examples 1-2, Comparative Example 1
40 ° C. Kinematic viscosity base oil A: Trimethylolpropane complete C 8 to C 12 carboxylic acid ester 18 mm 2 / sec 秒 B: Synthetic hydrocarbon oil (Inobean product PAO 4) 19 mm 2 / sec 〃 C: 〃 (Company product PAO 6 ) 31 mm 2 / s 〃 D: 〃 (its products PAO 40) 390 mm 2 / s 〃 E: 〃 (two or 97.9 parts by weight of its products PAO 10) 68mm 2 / s or more base oil, polymethacrylate System viscosity index improver (synthesized in base oil A, Mw: 250,000) 8 parts by weight, amine antioxidant (Ciba Specialty Chemicals product Irganox L57) 1 part by weight and benzotriazole corrosion inhibitor ( The company's product Irgamet 39) 0.1 parts by weight was mixed to obtain an antioxidant and corrosion inhibitor-containing lubricating oil composition (total 100 parts by weight).
比較例２
3種の基油91.9重量部、ポリメタクリレート系粘度指数向上剤(基油A中にて合成、Mw:250,000)7.0重量部、アミン系酸化防止剤(イルガノックスL57)1.0重量部およびベンゾトリアゾール系腐食防止剤(同社製品イルガメット39)0.1重量部を混合し、潤滑油組成物(合計100重量部)を得た。
Comparative Example 2
3 base oils 91.9 parts, polymethacrylate viscosity index improver (synthesized in base oil A, Mw: 250,000) 7.0 parts, amine antioxidant (Irganox L57) 1.0 part and benzotriazole 0.1 parts by weight of a corrosion inhibitor (the company's product Irgamet 39) was mixed to obtain a lubricating oil composition (100 parts by weight in total).
以上の各実施例および比較例の潤滑油組成物について、次の各項目の測定を行った。
動粘度：40℃および100℃における動粘度を、JIS K2283に準拠して測定
粘度指数：JIS K2283に準拠して測定
蒸発損失率：0.3gの潤滑油組成物を37mm径のアルミニウム製皿に均一に塗布し、
150℃の恒温槽中に100時間静置した後取り出し、その重量減少量から 蒸発損失率を算出
低温特性：-40℃で軸受を回転させたときのトルク特性を想定し、レオメータを使
用して評価
-40℃、せん断速度1000s-1においてコーン(25mm径、1/25°)を回転させ
、回転直後(0.1秒後)および60秒後のせん断応力を測定
For the lubricating oil compositions of the above Examples and Comparative Examples, the following items were measured.
Kinematic viscosity: Measure the kinematic viscosity at 40 ° C and 100 ° C according to JIS K2283 Viscosity index: Measure according to JIS K2283 Evaporation loss ratio: 0.3 g of lubricating oil composition is uniformly on a 37 mm diameter aluminum dish Apply to
Evaporation loss rate is calculated from the weight loss after leaving it in a thermostatic bath at 150 ° C for 100 hours. Low temperature characteristics: Use a rheometer assuming the torque characteristics when the bearing is rotated at -40 ° C.
Use to evaluate
Rotate the cone (25mm diameter, 1/25 °) at -40 ° C and shear rate 1000s -1
Measure shear stress immediately after rotation ( after 0.1 seconds) and after 60 seconds
得られた結果は、基油の組成(重量％)と共に、次の表に示される。
表
実施例１ 実施例２ 比較例１ 比較例２
〔基油組成；重量％〕
(低粘度基油)
基油A 72.6 72.9 73.3 26.1
〃 B 16.4
〃 C 20.8 73.9
(高粘度基油)
基油D 11.0 6.3
(中粘度基油)
基油E 26.7
〔測定項目〕
動粘度
40℃ (mm2／秒) 57.7 60.3 59.9 61.0
100℃ (mm2／秒) 12.1 12.5 12.1 12.0
粘度指数 (-) 211 201 203 199
蒸発損失率 (重量％) 27.3 21.5 9.1 41.6
低温特性
回転直後せん断応力(Pa) 8250 8580 9710 8910
60秒後せん断応力 (Pa) 7560 7640 8600 7990
The results obtained are shown in the following table together with the base oil composition (wt%).
table
Example 1 Example 2 Comparative Example 1 Comparative Example 2
[Base oil composition; wt%]
(Low viscosity base oil)
Base oil A 72.6 72.9 73.3 26.1
〃 B 16.4
〃 C 20.8 73.9
(High viscosity base oil)
Base oil D 11.0 6.3
(Medium viscosity base oil)
Base oil E 26.7
〔Measurement item〕
Kinematic viscosity
40 ℃ (mm 2 / sec.) 57.7 60.3 59.9 61.0
100 ℃ (mm 2 / sec) 12.1 12.5 12.1 12.0
Viscosity index (-) 211 201 203 199
Evaporation loss rate (wt%) 27.3 21.5 9.1 41.6
Low temperature properties Shear stress immediately after rotation (Pa) 8250 8580 9710 8910
Shear stress after 60 seconds (Pa) 7560 7640 8600 7990
以上の結果から、次のようなことがいえる。
(1) 本発明に係る常用回転数3000rpm未満の軸受に用いられる潤滑油組成物(実施例1〜2)は、40℃動粘度が約60mm2／秒程度に設定され、ポリオールエステル油が基油混合物中60〜75重量％の割合で用いられても、特定の基油混合物を用いているため低温特性が改善されており、自動車電装機器モータ軸受向け用途に使用することができる。
(2) 炭化水素油として中粘度基油のみを用いると(比較例1)、低温特性が低下するようになる。
(3) 炭化水素油として低粘度基油のみを用い、さらにポリオールエステル量が少ないと(比較例2)、蒸発損失が多くなり、却って低温特性も悪化する傾向となる。
From the above results, the following can be said.
(1) The lubricating oil compositions (Examples 1 and 2) used for bearings having a normal rotational speed of less than 3000 rpm according to the present invention have a kinematic viscosity at 40 ° C. set to about 60 mm 2 / second, and are based on a polyol ester oil. Even if it is used at a ratio of 60 to 75% by weight in the oil mixture, the low temperature characteristics are improved because a specific base oil mixture is used, and the oil mixture can be used for applications for motor vehicle electrical equipment motor bearings.
(2) When only a medium viscosity base oil is used as the hydrocarbon oil (Comparative Example 1), the low temperature characteristics are lowered.
(3) When only a low-viscosity base oil is used as the hydrocarbon oil and the amount of polyol ester is small (Comparative Example 2), the evaporation loss increases and the low-temperature characteristics tend to deteriorate.
本発明に係る潤滑油組成物は、常用回転数3000rpm未満の軸受、例えばブロワー、換気ファン、パワーウィンドウ、スライドドア、パワーシート、ドアミラー、ヘッドライトの光軸調整装置等の自動車電装機器のモータ軸受用として好適に用いられる。 The lubricating oil composition according to the present invention is a bearing having a normal rotational speed of less than 3000 rpm, for example, a motor bearing of an automobile electrical equipment such as a blower, a ventilation fan, a power window, a sliding door, a power seat, a door mirror, and an optical axis adjusting device for a headlight. It is preferably used as an application.
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