JP2010065194A - Grease composition for constant velocity joint and constant velocity joint - Google Patents
Grease composition for constant velocity joint and constant velocity joint Download PDFInfo
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- JP2010065194A JP2010065194A JP2008235059A JP2008235059A JP2010065194A JP 2010065194 A JP2010065194 A JP 2010065194A JP 2008235059 A JP2008235059 A JP 2008235059A JP 2008235059 A JP2008235059 A JP 2008235059A JP 2010065194 A JP2010065194 A JP 2010065194A
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- 239000004519 grease Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002562 thickening agent Substances 0.000 claims abstract description 14
- 239000002199 base oil Substances 0.000 claims abstract description 13
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 claims abstract description 11
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- COGHWIKGZJHSAG-UHFFFAOYSA-L zinc;2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Zn+2].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1.C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 COGHWIKGZJHSAG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000004359 castor oil Substances 0.000 claims abstract description 6
- 235000019438 castor oil Nutrition 0.000 claims abstract description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 235000019484 Rapeseed oil Nutrition 0.000 claims abstract description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 11
- 239000008158 vegetable oil Substances 0.000 claims description 11
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- 235000019871 vegetable fat Nutrition 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 abstract description 3
- 230000001050 lubricating effect Effects 0.000 abstract description 2
- 230000003405 preventing effect Effects 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 238000005299 abrasion Methods 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 159000000007 calcium salts Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000003112 inhibitor Substances 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
- 238000005259 measurement Methods 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- -1 alkyl aromatic sulfonic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000573 anti-seizure effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
Description
本発明は、等速ジョイント（ＣＶＪ）用グリース組成物及びこれを封入した等速ジョイントに関する。潤滑される等速ジョイント部分には、極めて高い面圧が発生し、ジョイント部分は、複雑なころがりすべり作用を受ける。このため、異常振動がしばしば発生する。本発明は、このような等速ジョイントを効率よく潤滑し、有効に摩擦を低減して振動の発生を防止し得る等速ジョイント用グリース組成物に関する。 The present invention relates to a grease composition for a constant velocity joint (CVJ) and a constant velocity joint in which the grease composition is enclosed. An extremely high surface pressure is generated in the constant velocity joint portion to be lubricated, and the joint portion is subjected to a complicated rolling and sliding action. For this reason, abnormal vibrations often occur. The present invention relates to a grease composition for a constant velocity joint that can efficiently lubricate such a constant velocity joint and effectively reduce friction to prevent vibrations.
このような等速ジョイントに用いられている潤滑グリースとしては、カルシウムコンプレックス石けんを増ちょう剤とするグリースや、リチウム石けんを増ちょう剤とし、例えば、硫化油脂、トリクレジルホスフェート、及びジチオリン酸亜鉛からなる群から選択された硫黄−リン系極圧剤を含有したグリースが挙げられる。
最近の自動車工業においては、車両の環境対策（ＣＯ2削減）を目的とした軽量化かつ居住空間の確保の点から、４輪駆動（ＦＦタイプ）車が急激に増加し、これに不可欠な等速ジョイント（ＣＶＪ）が広く用いられている。このＣＶＪの中で、プランジング型等速ジョイント、特にトリポート型等速ジョイント（ＴＪ）、ダブルオフセット型等速ジョイント（ＤＯＪ）等は、ある角度の付いた状態で、回転時に複雑なころがりすべり運動を行うため、軸方向にスライド抵抗を生じ、これがアイドリング時の振動、発進及び加速時の車体の横揺れ、特定速度での車内でのビート音、又はこもり音の起振源となっている。この問題の解決のため、種々の等速ジョイント（ＣＶＪ）自体の構造の改良もなされているが、ジョイントの占めるスペース、重さ、及びコスト面でその改良は難しく、振動低減性能に優れたグリースが要求されている。
Lubricating greases used in such constant velocity joints include greases using calcium complex soap as a thickener and lithium soap as a thickener, such as sulfurized fats and oils, tricresyl phosphate, and zinc dithiophosphate. Grease containing a sulfur-phosphorus extreme pressure agent selected from the group consisting of:
In the recent automobile industry, the number of four-wheel drive (FF type) vehicles has increased rapidly from the viewpoint of reducing the weight and securing the living space for the purpose of environmental measures (CO 2 reduction) of vehicles. Fast joints (CVJ) are widely used. Among these CVJs, plunging type constant velocity joints, especially tripod type constant velocity joints (TJ), double offset type constant velocity joints (DOJ), etc., have a complicated rolling sliding motion at an angle. For this reason, a slide resistance is generated in the axial direction, and this becomes a vibration source for idling vibration, vehicle body roll at start and acceleration, beat sound in a vehicle at a specific speed, or a booming sound. In order to solve this problem, the structure of various constant velocity joints (CVJ) itself has been improved, but it is difficult to improve the space, weight, and cost of the joint, and grease with excellent vibration reduction performance. Is required.
このため、ウレア系増ちょう剤、二硫化モリブデン、及び 酸化ワックスのカルシウム塩、石油スルホン酸のカルシウム塩、アルキル芳香族スルホン酸のカルシウム塩、サリシレートのカルシウム塩、フェネートのカルシウム塩、酸化ワックスの過塩基性カルシウム塩、石油スルホン酸の過塩基性カルシウム塩、アルキル芳香族スルホン酸の過塩基性カルシウム塩、サリシレートの過塩基性カルシウム塩、及びフェネートの過塩基性カルシウム塩からなる群から選択される少なくとも１種を含有する等速ジョイント用グリース組成物（特許文献１）や、さらにこれらの成分に加え、金属を含まない硫黄−リン系極圧剤、及びモリブデンジチオカーバメートを含有する等速ジョイント用グリース組成物（特許文献２）が提案されている。
また、基油、ジウレア系増ちょう剤、二硫化モリブデン、硫化ジアルキルジチオカルバミン酸モリブデン、石油スルホン酸のカルシウム塩、硫黄−リン系極圧剤、及び植物性油脂を含有する等速ジョイント用組成物も提案されている（特許文献３）。
しかし、従来の等速ジョイント用グリース組成物は、その摩擦係数低減効果及び振動発生防止効果は必ずしも十分とはいえない。
For this reason, urea-based thickeners, molybdenum disulfide, and calcium oxides of oxidized waxes, calcium salts of petroleum sulfonic acids, calcium salts of alkyl aromatic sulfonic acids, calcium salts of salicylates, calcium salts of phenates, and excess of oxidized waxes. Selected from the group consisting of basic calcium salt, petroleum sulfonic acid overbased calcium salt, alkyl aromatic sulfonic acid overbased calcium salt, salicylate overbased calcium salt, and phenate overbased calcium salt Grease composition for constant velocity joints containing at least one (Patent Document 1), and further for these constant velocity joints containing a metal-free sulfur-phosphorus extreme pressure agent and molybdenum dithiocarbamate in addition to these components A grease composition (Patent Document 2) has been proposed.
There is also a constant velocity joint composition containing a base oil, a diurea thickener, molybdenum disulfide, molybdenum disulfide dialkyldithiocarbamate, a calcium salt of petroleum sulfonic acid, a sulfur-phosphorus extreme pressure agent, and a vegetable oil. It has been proposed (Patent Document 3).
However, the conventional grease composition for constant velocity joints is not necessarily sufficient in the friction coefficient reduction effect and the vibration generation prevention effect.
従って、本発明の目的は、等速ジョイント用グリース組成物、特に、等速ジョイントを効率よく潤滑し、有効に摩耗を低減し振動の発生を防止し得る等速ジョイント用グリース組成物、及びこれを封入した等速ジョイントを提供することである。 Accordingly, an object of the present invention is to provide a grease composition for a constant velocity joint, in particular, a grease composition for a constant velocity joint that can efficiently lubricate the constant velocity joint, effectively reduce wear and prevent vibrations, and the like. It is to provide a constant velocity joint encapsulating.
本発明者等は、等速ジョイントの摩擦を低減し、振動を防止するグリース組成物の開発研究を種々行い、振動の発生し易い潤滑条件下で便用するグリースの性能評価を、振動摩擦摩耗試験機として知られるＴＥ７７試験機を用いて行った。その結果、等速ジョイントを起振源とした振動と、ＴＥ７７試験機で測定した特定の振動条件下の摩擦係数に特別な関係があることを見いだした。さらに、本発明者等は、基グリースにウレアグリースを用いて、各種極圧剤等の様々な組み合わせによって、上述の関係を検討した。その結果、基油、ウレア系増ちょう剤、硫化ジアルキルジチオカルバミン酸モリブデン、亜鉛ジチオホスフェート、塩基価が５０ｍｇＫＯＨ／ｇ以下のジノニルナフタレンスルホン酸の亜鉛塩、硫黄−リン系極圧剤および植物性油脂を含有するグリース組成物が、低摩擦係数の望ましい潤滑特性を示すことを見いだし、さらに、実際の等速ジョイントを用いた強制力試験においても、従来の等速ジョイント用グリースとは異なり、振動の発生を顕著に防止し得ることを確認し、本発明を完成するに至った。 The present inventors have conducted various researches and developments on grease compositions that reduce the friction of constant velocity joints and prevent vibrations, and evaluate the performance of greases used for stool under lubrication conditions where vibrations are likely to occur. The test was performed using a TE77 tester known as a tester. As a result, it has been found that there is a special relationship between the vibration using the constant velocity joint as the vibration source and the coefficient of friction measured under a specific vibration condition measured with a TE77 testing machine. Furthermore, the present inventors examined the above relationship by using urea grease as the base grease and various combinations of various extreme pressure agents and the like. As a result, base oil, urea-based thickener, sulfurized molybdenum dialkyldithiocarbamate, zinc dithiophosphate, zinc salt of dinonylnaphthalenesulfonic acid having a base number of 50 mgKOH / g or less, sulfur-phosphorus extreme pressure agent and vegetable oil It has been found that a grease composition containing a desirable lubricant characteristic with a low coefficient of friction, and even in a forced force test using an actual constant velocity joint, unlike conventional constant velocity joint grease, It was confirmed that the occurrence can be remarkably prevented, and the present invention has been completed.
本発明は、上記知見に基づいてなされたもので、下記の等速ジョイント用グリース組成物及びこれを封入した等速ジョイントを提供するものである。
１．下記の成分を含有する等速ジョイント用グリース組成物。
（ａ）基油、
（ｂ）次式で表されるジウレア系増ちょう剤、
Ｒ1−ＮＨ−ＣＯ−ＮＨ−Ｃ6Ｈ4−ｐ−ＣＨ2−Ｃ6Ｈ4−ｐ−ＮＨ−ＣＯ−ＮＨＲ2
（Ｒ1及びＲ2は独立して、炭素原子数８〜１８のアルキル基である）
（ｃ）次式で表される硫化ジアルキルジチオカルバミン酸モリブデン、
（Ｒ3Ｒ4Ｎ−ＣＳ−Ｓ）2−Ｍｏ2ＯmＳn
（式中、Ｒ3及びＲ4は独立して、炭素数１〜２４のアルキル基を表し、ｍは０〜３、ｎは４〜１であり、ｍ＋ｎ＝４である。）
（ｄ）亜鉛ジチオホスフェート、
（ｅ）塩基価が５０ｍｇＫＯＨ／ｇ以下のジノニルナフタレンスルホン酸亜鉛、
（ｆ）硫黄−リン系極圧剤、及び
（ｇ）ひまし油及びなたね油からなる群から選ばれる少なくとも１種の植物性油脂。
２．全組成物中、ジウレア系増ちょう剤の含有量が１〜２５質量％、硫化ジアルキルジチオカルバミン酸モリブデンの含有量が０．１〜５質量％、亜鉛ジチオホスフェートの含有量が０．１〜５質量％、ジノニルナフタレンスルホン酸亜鉛の含有量が０．１〜１０質量％、硫黄−リン系極圧剤の含有量が０．１〜５質量％、及び植物性油脂の含有量が０．１〜５質量％である上記１記載の等速ジョイント用グリース組成物。
３．固定型等速ジョイントである上記１又は２記載の等速ジョイント用グリース組成物。
４．上記１〜３のいずれか１項記載の等速ジョイント用グリース組成物を封入した等速ジョイント。
The present invention has been made based on the above findings, and provides the following grease composition for a constant velocity joint and a constant velocity joint in which the grease composition is enclosed.
1. A grease composition for a constant velocity joint containing the following components:
(A) base oil,
(B) a diurea thickener represented by the following formula:
R 1 -NH-CO-NH- C 6 H 4 -p-CH 2 -C 6 H 4 -p-NH-CO-NHR 2
(R 1 and R 2 are each independently an alkyl group having 8 to 18 carbon atoms)
(C) molybdenum disulfide dialkyldithiocarbamate represented by the following formula:
(R 3 R 4 N-CS -S) 2 -Mo 2 O m S n
(In the formula, R 3 and R 4 independently represent an alkyl group having 1 to 24 carbon atoms, m is 0 to 3, n is 4 to 1, and m + n = 4.)
(D) zinc dithiophosphate,
(E) zinc dinonylnaphthalenesulfonate having a base number of 50 mgKOH / g or less,
(F) Sulfur-phosphorus extreme pressure agent, and (g) at least one vegetable oil selected from the group consisting of castor oil and rapeseed oil.
2. In all compositions, the content of diurea thickener is 1 to 25% by mass, the content of molybdenum dialkyldithiocarbamate is 0.1 to 5% by mass, and the content of zinc dithiophosphate is 0.1 to 5% by mass. %, Content of zinc dinonylnaphthalenesulfonate 0.1 to 10% by mass, content of sulfur-phosphorus extreme pressure agent 0.1 to 5% by mass, and content of vegetable oil and fat 0.1 The grease composition for constant velocity joints according to 1 above, which is ˜5 mass%.
3. 3. The grease composition for a constant velocity joint according to the above 1 or 2, which is a fixed type constant velocity joint.
4). The constant velocity joint which enclosed the grease composition for constant velocity joints of any one of said 1-3.
本発明の等速ジョイント用グリース組成物は、等速ジョイントを効率よく潤滑し、有効に摩耗を低減し振動の発生を顕著に防止し得る。また従来の等速ジョイント用グリース組成物と比較して耐ジョイントフレーキング特性に優れている。 The grease composition for a constant velocity joint of the present invention can efficiently lubricate the constant velocity joint, effectively reduce wear, and remarkably prevent the occurrence of vibration. In addition, it has superior joint flaking resistance compared to conventional grease compositions for constant velocity joints.
以下、本発明の等速ジョイント用グリース組成物について詳述する。
本発明のグリース組成物は、下記成分（ａ）、（ｂ）、（ｃ）、（ｄ）、（ｅ）、（ｆ）、及び（ｇ）を含有する。
（ａ）基油、
（ｂ）次式で表されるジウレア系増ちょう剤、
Ｒ1−ＮＨ−ＣＯ−ＮＨ−Ｃ6Ｈ4−ｐ−ＣＨ2−Ｃ6Ｈ4−ｐ−ＮＨ−ＣＯ−ＮＨＲ2
（Ｒ1及びＲ2は独立して、炭素原子数８〜１８のアルキル基である）
（ｃ）次式で表される硫化ジアルキルジチオカルバミン酸モリブデン、
（Ｒ3Ｒ4Ｎ−ＣＳ−Ｓ）2−Ｍｏ2ＯmＳn
（式中、Ｒ3及びＲ4は独立して、炭素数１〜２４のアルキル基を表し、ｍは０〜３、ｎは４〜１であり、ｍ＋ｎ＝４である。）
（ｄ）亜鉛ジチオホスフェート、
（ｅ）塩基価が５０ｍｇＫＯＨ／ｇ以下のジノニルナフタレンスルホン酸亜鉛
（ｆ）硫黄−リン系極圧剤、及び
（ｇ）ひまし油及びなたね油からなる群から選ばれる少なくとも１種の植物性油脂。
Hereinafter, the grease composition for constant velocity joints of the present invention will be described in detail.
The grease composition of the present invention contains the following components (a), (b), (c), (d), (e), (f), and (g).
(A) base oil,
(B) a diurea thickener represented by the following formula:
R 1 -NH-CO-NH- C 6 H 4 -p-CH 2 -C 6 H 4 -p-NH-CO-NHR 2
(R 1 and R 2 are each independently an alkyl group having 8 to 18 carbon atoms)
(C) molybdenum disulfide dialkyldithiocarbamate represented by the following formula:
(R 3 R 4 N-CS -S) 2 -Mo 2 O m S n
(In the formula, R 3 and R 4 independently represent an alkyl group having 1 to 24 carbon atoms, m is 0 to 3, n is 4 to 1, and m + n = 4.)
(D) zinc dithiophosphate,
(E) zinc dinonylnaphthalenesulfonate having a base number of 50 mgKOH / g or less (f) sulfur-phosphorus extreme pressure agent, and (g) at least one vegetable oil selected from the group consisting of castor oil and rapeseed oil.
上記（ａ）成分の基油としては、鉱物油、エーテル系合成油、エステル系合成油及び炭化水素系合成油等の通常に使用されている潤滑油またはそれらの混合油が挙げられるが、これらに限定されるものではない。コストの点から、鉱物油を用いるのが好ましく、また、鉱物油を主成分とし、これに合成油を混合した基油を用いるのが好ましい。
上記基油の１００℃における動粘度は、好ましくは５〜３０ｍｍ2／ｓであり、より好ましくは７〜２０ｍｍ2／ｓである。５ｍｍ2／ｓ未満では、等速ジョイント（ＣＶＪ）内で油膜を形成せず高速耐久性が不充分となる傾向があり、３０ｍｍ2／ｓを超えるとＣＶＪ内の発熱のため高速耐久性が低下する傾向がある。
Examples of the base oil of the component (a) include commonly used lubricating oils such as mineral oils, ether-based synthetic oils, ester-based synthetic oils and hydrocarbon-based synthetic oils, or mixed oils thereof. It is not limited to. From the viewpoint of cost, it is preferable to use a mineral oil, and it is preferable to use a base oil in which a mineral oil is a main component and a synthetic oil is mixed.
The kinematic viscosity at 100 ° C. of the base oil is preferably 5 to 30 mm 2 / s, more preferably 7 to 20 mm 2 / s. If it is less than 5 mm 2 / s, oil film is not formed in the constant velocity joint (CVJ) and high-speed durability tends to be insufficient. If it exceeds 30 mm 2 / s, high-speed durability is reduced due to heat generation in the CVJ. Tend to.
上記（ｂ）成分のジウレア系増ちょう剤は、ジフェニルメタンジイソシアネートと炭素数８〜１８のアルキルアミン、例えば、オクチルアミンとの反応により得られる。上記ジイソシアネートとアミンとを反応させる方法には特に制限はなく、従来公知の方法により実施することができる。 The diurea type thickener of the said (b) component is obtained by reaction with diphenylmethane diisocyanate and a C8-C18 alkylamine, for example, octylamine. There is no restriction | limiting in particular in the method of making the said diisocyanate and amine react, It can implement by a conventionally well-known method.
上記（ｅ）成分の塩基価が５０ｍｇＫＯＨ／ｇ以下のジノニルナフタレンスルホン酸の亜鉛塩は、エンジン油等の潤滑油に用いられる金属系清浄分散剤や防錆剤として知られている、潤滑油留分中の芳香族炭化水素成分のスルホン化によって得られる。塩基価が５０ｍｇＫＯＨ／ｇを越えると摩擦係数が高くなる傾向がある。 The zinc salt of dinonylnaphthalenesulfonic acid having a base number of the above component (e) of 50 mgKOH / g or less is a lubricating oil known as a metal-based detergent dispersant or rust inhibitor used in lubricating oils such as engine oils. Obtained by sulfonation of aromatic hydrocarbon components in the fraction. When the base number exceeds 50 mgKOH / g, the friction coefficient tends to increase.
上記（ｆ）成分の、硫黄−リン系極圧剤として好ましいものは、硫黄分１５〜３５重量％及びリン分０．５〜３質量％のものであり、硫黄成分とリン成分の比率を調整することにより、優れた摩耗防止性能や焼き付き防止性能を発揮させることができる。硫黄成分が上記範囲より多いとジョイントが腐食し易くなり、リン成分が上記範囲より多いとジョイントの摩耗防止効果が得られ難くなる。また両者とも上記範囲より少ない場合は、目的とする摩耗防止性能や焼き付き防止性能を十分に発揮させることが困難になる。
上記（ｇ）成分の植物性油脂としては、特にひまし油が好ましい。
The component (f) is preferably a sulfur-phosphorus extreme pressure agent having a sulfur content of 15 to 35% by weight and a phosphorus content of 0.5 to 3% by mass, and adjusting the ratio of the sulfur component and the phosphorus component. By doing so, excellent wear prevention performance and anti-seizure performance can be exhibited. If the sulfur component is more than the above range, the joint is easily corroded, and if the phosphorus component is more than the above range, it is difficult to obtain the joint wear prevention effect. Moreover, when both are less than the said range, it will become difficult to fully exhibit the target wear prevention performance and image sticking prevention performance.
As the vegetable oil of component (g), castor oil is particularly preferable.
本発明の等速ジョイント用グリース組成物において、等速ジョイント用グリース組成物の全質量に対して、（ｂ）成分のジウレア系増ちょう剤の含有量は、好ましくは１〜２５質量％、さらに好ましくは５〜１５質量％、（ｃ）成分の硫化ジアルキルジチオカルバミン酸モリブデンの含有量は、好ましくは０．１〜５質量％、さらに好ましくは０．５〜５質量％、（ｄ）成分の亜鉛ジチオホスフェートの含有量は、好ましくは０．１〜５質量％、さらに好ましくは０．５〜５質量％、（ｅ）成分の塩基価が５０ｍｇＫＯＨ／ｇ以下のジノニルナフタレンスルホン酸亜鉛の含有量は、好ましくは０．１〜１０質量％、さらに好ましくは１〜７質量％、（ｆ）成分の硫黄−リン系極圧剤の含有量は、好ましくは０．１〜５質量％、さらに好ましくは０．１〜２質量％、（ｇ）成分の植物性油脂の含有量は、好ましくは０．１〜５質量％、さらに好ましくは０．５〜５質量％である。
上記（ｂ）成分のジウレア系増ちょう剤の含有量が１質量％未満であると、増ちょう効果が少なくなり、グリース化しにくくなり、２５質量％を越えると、得られた組成物が硬くなりすぎ所期の効果が得られなくなる場合があるので、上記範囲内とすることが好ましい。
上記（ｃ）成分の硫化ジアルキルジチオカルバミン酸モリブデンの含有量が０．１質量％未満であると、所期の効果を得ることが困難になり、５質量％を越えて含有させても効果の増大がない場合があるので、上記範囲内とすることが好ましい。
上記（ｄ）成分の亜鉛ジチオホスフェートの含有量が０．１質量％未満であると、所期の効果を得ることが困難になり、５質量％を越えて含有させても効果の増大がない場合があるので、上記範囲内とすることが好ましい。
上記（ｅ）成分のジノニルナフタレンスルホン酸亜鉛の含有量が０．１質量％未満であると、所期の効果を得ることが困難になり、１０質量％を越えて含有させても効果の増大がない場合があるので、上記範囲内とすることが好ましい。
上記（ｆ）成分の硫黄−リン系極圧剤の含有量が０．１質量％未満であると、所期の効果を得ることが困難になり、５質量％を越えて含有させても効果の増大がない場合があるので、上記範囲内とすることが好ましい。
上記（ｇ）成分の植物性油脂の含有量が０．１質量％未満であると、所期の効果を得ることが困難になり、５質量％を越えて含有させても効果の増大がない場合があるので、上記範囲内とすることが好ましい。
In the grease composition for constant velocity joints of the present invention, the content of the diurea thickener as the component (b) is preferably 1 to 25% by mass relative to the total mass of the grease composition for constant velocity joints, Preferably, the content of molybdenum sulfide dialkyldithiocarbamate as component (c) is preferably 5 to 15% by mass, more preferably 0.5 to 5% by mass, and zinc as component (d). The content of dithiophosphate is preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, and the content of (e) zinc dinonylnaphthalene sulfonate having a base number of 50 mgKOH / g or less Is preferably 0.1 to 10% by mass, more preferably 1 to 7% by mass, and the content of the sulfur-phosphorus extreme pressure agent as component (f) is preferably 0.1 to 5% by mass, more preferably 0.1 to 2 wt%, the content of vegetable oils (g) component is preferably 0.1 to 5 mass%, more preferably 0.5 to 5 mass%.
When the content of the diurea thickener as the component (b) is less than 1% by mass, the thickening effect is reduced and it becomes difficult to form a grease. When the content exceeds 25% by mass, the obtained composition becomes hard. Since the desired effect may not be obtained, it is preferable to be within the above range.
When the content of the molybdenum sulfide dialkyldithiocarbamate as the component (c) is less than 0.1% by mass, it is difficult to obtain the desired effect, and even if the content exceeds 5% by mass, the effect is increased. Therefore, it is preferable to be within the above range.
When the content of zinc dithiophosphate as the component (d) is less than 0.1% by mass, it is difficult to obtain the desired effect, and even if the content exceeds 5% by mass, the effect is not increased. In some cases, it is preferable to be within the above range.
When the content of zinc dinonylnaphthalene sulfonate as the component (e) is less than 0.1% by mass, it is difficult to obtain the desired effect, and even if the content exceeds 10% by mass, the effect can be obtained. Since there may be no increase, it is preferably within the above range.
When the content of the sulfur-phosphorus extreme pressure agent as the component (f) is less than 0.1% by mass, it is difficult to obtain the desired effect, and even if the content exceeds 5% by mass, the effect is achieved. Since there is a case where there is no increase in the thickness, it is preferable to be within the above range.
When the content of the vegetable oil of component (g) is less than 0.1% by mass, it is difficult to obtain the desired effect, and there is no increase in effect even if the content exceeds 5% by mass. In some cases, it is preferable to be within the above range.
本発明の等速ジョイント用グリース組成物には、上記（ａ）〜（ｇ）成分に加え、更に各種潤滑油やグリースに一般的に用いられている酸化防止剤、防錆剤、ポリマー添加剤を添加することができる。また、上記成分以外の極圧剤、摩擦緩和剤、耐摩耗剤及び固体潤滑剤等の添加剤を添加することができる。上記添加剤を含有させる場合、その含有量は、等速ジョイント用グリース組成物の全質量中、好ましくは０．１〜１０質量％である。 In addition to the above components (a) to (g), the grease composition for constant velocity joints of the present invention further includes antioxidants, rust inhibitors and polymer additives generally used in various lubricating oils and greases. Can be added. In addition to the above components, additives such as extreme pressure agents, friction modifiers, antiwear agents and solid lubricants can be added. When it contains the said additive, the content is 0.1-10 mass% preferably in the total mass of the grease composition for constant velocity joints.
以下、本発明を実施例により更に詳細に説明する。なお、本発明の範囲は、かかる実施例に限定されないことはいうまでもない。
実施例１
容器に基油４４０ｇとジフェニルメタン−４，４′−ジイソシアネート５８.９ｇをとり、混合物を７０〜８０℃に加熱した。別容器に基油４４０ｇとオクチルアミン６１.１ｇをとり、７０〜８０℃に加熱後、先の容器に加え、よく攪拌しながら、３０分間反応させた。その後攪拌しながら、１６０℃まで昇温し、放冷後、ベース脂肪族アミンジウレアグリースを得た。このベースグリースに、表１に示す配合で、添加剤を添加し、適宜基油を加え、得られる混合物を、三段ロールミルにて、ちょう度No. 1 グレードに調整した。
グリースの基油として、以下の特性を有する鉱油を使用した。
粘度 ４０℃ １５７ mm2／ｓ
１００℃ １４ mm2／ｓ
粘度指数 ８８
Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the scope of the present invention is not limited to such examples.
Example 1
A container was charged with 440 g of base oil and 58.9 g of diphenylmethane-4,4′-diisocyanate, and the mixture was heated to 70-80 ° C. In a separate container, 440 g of base oil and 61.1 g of octylamine were taken, heated to 70-80 ° C., added to the previous container, and allowed to react for 30 minutes with good stirring. Thereafter, the temperature was raised to 160 ° C. while stirring, and after cooling, a base aliphatic amine diurea grease was obtained. Additives were added to this base grease in the formulation shown in Table 1, base oil was added as appropriate, and the resulting mixture was adjusted to a consistency No. 1 grade with a three-stage roll mill.
A mineral oil having the following characteristics was used as the base oil of the grease.
Viscosity 40 ° C 157 mm 2 / s
100 ° C 14 mm 2 / s
Viscosity index 88
比較例１〜６
実施例１において、成分（ｄ）を添加しなかった他は同様にして比較例１のグリースを調製した。
実施例１において、成分（ｅ）を添加しなかった他は同様にして比較例２のグリースを調製した。
実施例１において、成分（ｆ）を添加しなかった他は同様にして比較例３のグリースを調製した。
実施例１において、成分（ｇ）を添加しなかった他は同様にして比較例４のグリースを調製した。
実施例１において、成分（ｅ）及び（ｇ）を添加しなかった他は同様にして比較例５のグリースを調製した。
実施例１において、成分（ｅ）、（ｆ）及び（ｇ）を添加しなかった他は同様にして比較例６のグリースを調製した。
比較例７は市販のＭｏＤＴＣを含有するウレアグリースである。
なお、表中に示す各成分は以下のとおりであり、表中の数字は質量％を示す。
ＭｏＤＴＣ（硫化ジアルキルジチオカルバミン酸モリブデン）（商品名：サクラルーブ600 旭電化工業社製）
亜鉛ジチオホスフェート（商品名：Lubrizol 1395 日本ルーブリゾール社製）
ジノニルナフタレンスルホン酸亜鉛（塩基価：30ｍｇＫＯＨ／ｇ）
硫黄−リン系極圧剤（商品名 Lubrizol 810 日本ルーブリゾール社製）
植物性油脂（ひまし油）
Comparative Examples 1-6
A grease of Comparative Example 1 was prepared in the same manner as in Example 1 except that component (d) was not added.
A grease of Comparative Example 2 was prepared in the same manner as in Example 1 except that component (e) was not added.
A grease of Comparative Example 3 was prepared in the same manner as in Example 1 except that component (f) was not added.
A grease of Comparative Example 4 was prepared in the same manner as in Example 1 except that component (g) was not added.
A grease of Comparative Example 5 was prepared in the same manner as in Example 1 except that components (e) and (g) were not added.
A grease of Comparative Example 6 was prepared in the same manner as in Example 1 except that components (e), (f) and (g) were not added.
Comparative Example 7 is a commercially available urea grease containing MoDTC.
In addition, each component shown in the table | surface is as follows, and the number in a table | surface shows the mass%.
MoDTC (Molybdenum dialkyldithiocarbamate) (trade name: SakuraLube 600, manufactured by Asahi Denka Kogyo Co., Ltd.)
Zinc dithiophosphate (trade name: Lubrizol 1395 made by Nippon Lubrizol)
Zinc dinonylnaphthalenesulfonate (base number: 30mgKOH / g)
Sulfur-phosphorus extreme pressure agent (trade name: Lubrizol 810, manufactured by Nihon Lubrizol)
Vegetable oil (castor oil)
上記等速ジョイント用グリース組成物につき、以下に示す試験方法で物性の評価を行った。
ＴＥ７７試験
テストピース ボール：直径 １７．５mm（ＳＵＪ−２）
プレート：６０ｍｍ×４０ｍｍ×４ｍｍ（ＳＣＭ）
試験条件 荷重：１００Ｎ
周波数：２０Ｈｚ
振幅：１．０mm
時間：１０分
試験温度：４０℃
測定項目 摩擦係数
強制力試験
下記条件にて実ジョイントでの強制力試験を行い、強制力を測定した。
試験条件 回転数：２００ｒｐｍ
トルク：５００Ｎｍ
ジョイント角度：１０°
運転時間：２ｍｉｎ．
ジョイントタイプ：トリポート型等速ジョイント
測定項目 ジョイント強制力を測定し、市販ウレアグリースを基準としての増減率で評価した。
The physical properties of the grease composition for constant velocity joints were evaluated by the following test methods.
TE77 test Test piece Ball: Diameter 17.5mm (SUJ-2)
Plate: 60mm x 40mm x 4mm (SCM)
Test conditions Load: 100N
Frequency: 20Hz
Amplitude: 1.0 mm
Time: 10 minutes
Test temperature: 40 ° C
Measurement item Friction coefficient forcing test
The forcible force test at the actual joint was conducted under the following conditions, and the forcible force was measured.
Test conditions Rotation speed: 200rpm
Torque: 500Nm
Joint angle: 10 °
Operating time: 2 min.
Joint type: Tripport type constant velocity joint Measurement item Joint forcing force was measured, and the rate of increase / decrease based on commercially available urea grease was evaluated.
成分（ｄ）〜（ｇ）を含有する本発明の実施例１のグリース組成物は、成分（ｄ）〜（ｇ）のいずれかの成分を含まない比較例１〜６のグリース組成物と比較して、著しい摩擦係数低減効果及び振動発生防止効果を示すことがわかる。 The grease composition of Example 1 of the present invention containing the components (d) to (g) is compared with the grease compositions of Comparative Examples 1 to 6 that do not contain any of the components (d) to (g). Thus, it can be seen that a significant friction coefficient reducing effect and vibration generation preventing effect are exhibited.
Claims (4)
（ａ）基油、
（ｂ）次式で表されるジウレア系増ちょう剤、
Ｒ1−ＮＨ−ＣＯ−ＮＨ−Ｃ6Ｈ4−ｐ−ＣＨ2−Ｃ6Ｈ4−ｐ−ＮＨ−ＣＯ−ＮＨＲ2
（Ｒ1及びＲ2は独立して、炭素原子数８〜１８のアルキル基である）
（ｃ）次式で表される硫化ジアルキルジチオカルバミン酸モリブデン、
（Ｒ3Ｒ4Ｎ−ＣＳ−Ｓ）2−Ｍｏ2ＯmＳn
（式中、Ｒ3及びＲ4は独立して、炭素数１〜２４のアルキル基を表し、ｍは０〜３、ｎは４〜１であり、ｍ＋ｎ＝４である。）
（ｄ）亜鉛ジチオホスフェート、
（ｅ）塩基価が５０ｍｇＫＯＨ／ｇ以下のジノニルナフタレンスルホン酸亜鉛、
（ｆ）硫黄−リン系極圧剤、及び
（ｇ）ひまし油及びなたね油からなる群から選ばれる少なくとも１種の植物性油脂。 A grease composition for a constant velocity joint containing the following components:
(A) base oil,
(B) a diurea thickener represented by the following formula:
R 1 -NH-CO-NH- C 6 H 4 -p-CH 2 -C 6 H 4 -p-NH-CO-NHR 2
(R 1 and R 2 are independently an alkyl group having 8 to 18 carbon atoms)
(C) molybdenum disulfide dialkyldithiocarbamate represented by the following formula:
(R 3 R 4 N-CS -S) 2 -Mo 2 O m S n
(In the formula, R 3 and R 4 independently represent an alkyl group having 1 to 24 carbon atoms, m is 0 to 3, n is 4 to 1, and m + n = 4.)
(D) zinc dithiophosphate,
(E) zinc dinonylnaphthalenesulfonate having a base number of 50 mgKOH / g or less,
(F) sulfur-phosphorus extreme pressure agent, and (g) at least one vegetable oil selected from the group consisting of castor oil and rapeseed oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008235059A JP5344422B2 (en) | 2008-09-12 | 2008-09-12 | Grease composition for constant velocity joint and constant velocity joint |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130109483A1 (en) * | 2010-08-05 | 2013-05-02 | Kazuhiko Yoshida | Fixed-type constant velocity universal joint |
| KR20150046079A (en) * | 2012-08-28 | 2015-04-29 | 에누티에누 가부시키가이샤 | Grease composition for constant velocity joints, and constant velocity joint in which grease composition for constant velocity joints is sealed |
| WO2022113239A1 (en) | 2020-11-26 | 2022-06-02 | 協同油脂株式会社 | Grease composition for constant-velocity joint |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130109483A1 (en) * | 2010-08-05 | 2013-05-02 | Kazuhiko Yoshida | Fixed-type constant velocity universal joint |
| US8771086B2 (en) * | 2010-08-05 | 2014-07-08 | Ntn Corporation | Fixed-type constant velocity universal joint |
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| CN104583381A (en) * | 2012-08-28 | 2015-04-29 | Ntn株式会社 | Grease composition for constant velocity joints, and constant velocity joint in which grease composition for constant velocity joints is sealed |
| US20150218483A1 (en) * | 2012-08-28 | 2015-08-06 | Ntn Corporation | Grease composition for constant velocity joints, and constant velocity joint in which grease composition for constant velocity joints is sealed |
| EP2891705A4 (en) * | 2012-08-28 | 2016-03-30 | Ntn Toyo Bearing Co Ltd | Grease composition for constant velocity joints, and constant velocity joint in which grease composition for constant velocity joints is sealed |
| KR102097268B1 (en) * | 2012-08-28 | 2020-04-06 | 에누티에누 가부시키가이샤 | Grease composition for constant velocity joints, and constant velocity joint in which grease composition for constant velocity joints is sealed |
| WO2022113239A1 (en) | 2020-11-26 | 2022-06-02 | 協同油脂株式会社 | Grease composition for constant-velocity joint |
| EP4253507A4 (en) * | 2020-11-26 | 2024-04-17 | Kyodo Yushi Co., Ltd. | Grease composition for constant-velocity joint |
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