JP4973972B2 - 無段変速機用低摩擦摺動部材及びこれに用いる無段変速機油組成物 - Google Patents
無段変速機用低摩擦摺動部材及びこれに用いる無段変速機油組成物 Download PDFInfo
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- JP4973972B2 JP4973972B2 JP2004230038A JP2004230038A JP4973972B2 JP 4973972 B2 JP4973972 B2 JP 4973972B2 JP 2004230038 A JP2004230038 A JP 2004230038A JP 2004230038 A JP2004230038 A JP 2004230038A JP 4973972 B2 JP4973972 B2 JP 4973972B2
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- acid
- continuously variable
- variable transmission
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
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- 238000000638 solvent extraction Methods 0.000 description 1
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- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
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- HMFPLNNQWZGXAH-OCOZRVBESA-N trans-2-hexacosenoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCC\C=C\C(O)=O HMFPLNNQWZGXAH-OCOZRVBESA-N 0.000 description 1
- HSBSUGYTMJWPAX-HNQUOIGGSA-N trans-2-hexenedioic acid Chemical compound OC(=O)CC\C=C\C(O)=O HSBSUGYTMJWPAX-HNQUOIGGSA-N 0.000 description 1
- HOGWBMWOBRRKCD-BUHFOSPRSA-N trans-2-pentadecenoic acid Chemical compound CCCCCCCCCCCC\C=C\C(O)=O HOGWBMWOBRRKCD-BUHFOSPRSA-N 0.000 description 1
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 description 1
- HSBSUGYTMJWPAX-UHFFFAOYSA-N trans-Deltaalpha-Dihydromuconsaeure Natural products OC(=O)CCC=CC(O)=O HSBSUGYTMJWPAX-UHFFFAOYSA-N 0.000 description 1
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- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- 239000001993 wax Substances 0.000 description 1
Landscapes
- Transmissions By Endless Flexible Members (AREA)
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Description
CO2削減については、自動車の燃費の削減を図ることが大きな課題の1つであり、摺動材料と潤滑油が果たす役割は大きい。
摺動材料の役割は、無段変速機の摺動部位の中で摩擦摩耗環境が苛酷な部位に対して耐摩耗性に優れ且つ低い摩擦係数を発現することであり、最近では、種々の硬質薄膜材料の適用が進んできている。一般に硬質炭素薄膜は、空気中、潤滑油非存在下における摩擦係数が、窒素チタン(TiN)や窒化クロム(CrN)といった耐摩耗性の硬質被膜材料と比べて低いことから低摩擦摺動材料として期待されている。
このような硬質炭素薄膜の摩擦特性について、いくつかの報告がされている(例えば、非特許文献1及び2参照)。
加納 他「日本トライボロジー学会予稿集」1999年5月,p11〜12 加納、他(Kano et al.),ワールド・トライボロジー・コングレス(World Tribology Congress)2001.9,Vienna,Proceeding,p.342
また、本発明の無段変速機油組成物は、上述の如き無段変速機用低摩擦摺動部材に用いられる無段変速機油組成物であり、この無段変速機油組成物は、基油と、脂肪酸エステル又はアルコールとを含有し、該脂肪酸エステル又はアルコールを、組成物全量基準で0.05〜3.0%含有して成る。
上述の如く、本発明の無段変速機用低摩擦摺動部材は、無段変速機油組成物の存在下で互いに摺動する部材の一方又は両方の摺動面に、硬質炭素薄膜による被覆を施して成る摺動部位を有する。かかる無段変速機油組成物が、基油と、脂肪酸エステル又はアルコールとを含有している。これにより、一方又は両方の摺動面に、硬質炭素薄膜による被覆を施して成る摺動部材が、従来よりも極めて低摩擦で摺動し得る。
このDLC材料は、非晶質のものであって、炭素同士の結合形態がダイヤモンド構造(SP3結合)とグラファイト結合(SP2結合)の両方から成る。具体的には、炭素元素だけから成るa−C(アモルファスカーボン)、水素を含有するa−C:H(水素アモルファスカーボン)、及びチタン(Ti)やモリブデン(Mo)等の金属元素を一部に含むMeCなどを好適に用いることができる。
この場合、成膜時に水素を含まないガスを用いるだけでなく、場合によっては反応容器や基材保持具のベーキングや基材表面のクリーニングを十分に行ったうえで成膜することが被膜中の水素量を減らすために望ましい。
本発明に用いる無段変速機油組成物としては、基油(ベースオイル)に、脂肪酸エステル又はアルコールを含有させたものを用いることが望ましく、このような潤滑油を硬質炭素薄膜が被覆された摺動面に介在させる。これによって、極めて優れた低摩擦特性が発揮される。
鉱油としては、具体的には、原油を常圧蒸留及び減圧蒸留して得られた作動油留分を溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、水素化精製、硫酸洗浄、白土処理等の精製処理等を適宜組み合わせて精製したパラフィン系又はナフテン系等の油やノルマルパラフィン等が使用でき、溶剤精製、水素化精製処理したものが一般的であるが、芳香族分をより低減することが可能な高度水素化分解プロセスやGTL Wax(ガス・トウー・リキッド・ワックス)を異性化した手法で製造したものを用いることがより好ましい。
なお、ここで言う全芳香族含有量とは、ASTM D2549に規定される方法に準拠して測定される芳香族留分(aromatics fraction)含有量を意味している。
1.1 1価アルコール類
1.2 2価アルコール類
1.3 3価以上のアルコール類
1.4 上記1〜3から選ばれるアルコール類のアルキレンオキサイド付加物
1.5 上記1〜4から選ばれる1種又は2種以上の混合物
2.1 脂肪族モノカルボン酸類(脂肪酸類)
2.2 脂肪族多価カルボン酸類
2.3 炭素環カルボン酸類
2.4 複素環式カルボン酸類
2.5 上記1〜4から選ばれる2種以上の混合物
3.1 飽和又は不飽和脂肪族エーテル類
3.2 芳香族エーテル類
3.3 環式エーテル類
3.4 上記1〜4から選ばれる2種以上の混合物
4.1 脂肪酸モノカルボン酸類(脂肪酸類)のエステル
4.2 脂肪族多価カルボン酸類のエステル
4.3 炭素環カルボン酸類のエステル
4.4 複素環式カルボン酸類のエステル
4.5 アルコール類又はエステル類のアルキレンオキサイド付加物
4.6 上記1〜5から選ばれる任意の混合物
なお、上記4.1〜4.5に挙げたエステル類としては、ヒドロキシル基又はカルボキシル基が全てエステル化された完全エステルでもよく、ヒドロキシル基又はカルボキシル基が一部残存した部分エステルであってもよい。
これらのうち、100℃における動粘度が1〜100mm2/sのものは潤滑油基油として使用することができ、通常、上記脂肪酸エステル系無灰摩擦調整剤と区別することができる。これらの例としては、例えば、トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール2−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等の、炭素数3〜40、好ましくは炭素数4〜18、特に好ましくは4〜12の3価以上のポリオール類、特にネオペンチル構造を有する3価以上のポリオール類と、炭素数1〜40、好ましくは炭素数4〜18、特に好ましくは6〜12のモノカルボン酸から選ばれる1種又は2種以上との単一エステル類あるいはコンプレックスエステル類等のポリオールエステル類及びこれらの混合物、あるいは、さらにアルキレンオキサイドを付加させたもの等が挙げられる。これらはヒドロキシル基又はカルボキシル基が全てエステル化された完全エステルでもよく、ヒドロキシル基又はカルボンキシル基が一部残存した部分エステルでもよいが、完全エステルであることが好ましく、そのヒドロキシル基価は通常100mgKOH/g以下、より好ましくは50mgKOH/g以下、特に好ましくは10mgKOH/g以下である。
また、これら潤滑油基油の100℃における動粘度は、好ましくは2〜60mm2/s、特に好ましくは3〜50mm2/sである。
これらの中では、アルコール類及びカルボン酸類並びにこれらの誘導体から選ばれる1種又は2種以上と、アミン化合物との反応生成物(例えばマンニッヒ反応生成物、アシル化反応生成物、アミド等)が好ましい例として挙げられる。
ここでいうアミン化合物としては、アンモニア、モノアミン、ジアミン、ポリアミンが挙げられる。より具体的には、アンモニア;メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、ヘキサデシルアミン、ヘプタデシルアミン、オクタデシルアミン、ステアリルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、ジノニルアミン、ジデシルアミン、ジウンデシルアミン、ジドデシルアミン、ジトリデシルアミン、ジテトラデシルアミン、ジペンタデシルアミン、ジヘキサデシルアミン、ジヘプタデシルアミン、ジオクタデシルアミン、メチルエチルアミン、メチルプロピルアミン、メチルブチルアミン、エチルプロピルアミン、エチルブチルアミン、及びプロピルブチルアミン等の炭素数1〜30のアルキル基(これらのアルキル基は直鎖状でも分枝状でもよい)を有するアルキルアミン;エテニルアミン、プロペニルアミン、ブテニルアミン、オクテニルアミン、及びオレイルアミン等の炭素数2〜30のアルケニル基(これらのアルケニル基は直鎖状でも分枝状でもよい)を有するアルケニルアミン;メタノールアミン、エタノールアミン、プロパノールアミン、ブタノールアミン、ペンタノールアミン、ヘキサノールアミン、ヘプタノールアミン、オクタノールアミン、ノナノールアミン、メタノールエタノールアミン、メタノールプロパノールアミン、メタノールブタノールアミン、エタノールプロパノールアミン、エタノールブタノールアミン、及びプロパノールブタノールアミン等の炭素数1〜30のアルカノール基(これらのアルカノール基は直鎖状でも分枝状でもよい)を有するアルカノールアミン;メチレンジアミン、エチレンジアミン、プロピレンジアミン、及びブチレンジアミン等の炭素数1〜30のアルキレン基を有するアルキレンジアミン;ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等のポリアミン;ウンデシルジエチルアミン、ウンデシルジエタノールアミン、ドデシルジプロパノールアミン、オレイルジエタノールアミン、オレイルプロピレンジアミン、ステアリルテトラエチレンペンタミン等の上記モノアミン、ジアミン、ポリアミンに炭素数8〜20のアルキル基又はアルケニル基を有する化合物やN−ヒロドキシエチルオレイルイミダゾリン等の複素環化合物;これらの化合物のアルキレンオキシド付加物;及びこれらの混合物等が例示できる。
これら含酸素有機化合物の誘導体の中でも、オレイン酸アミドのような炭素数8〜20のカルボン酸アミド類が好ましい例として挙げられる。
上記ポリブテニルコハク酸イミドとしては、次の一般式(1)及び(2)
また、上記一般式におけるnは、清浄性に優れる点から1〜5の整数、より望ましくは2〜4の整数であることがよい。更に、上記ポリブテンは、製造過程の触媒に起因して残留する微量のフッ素分や塩素分を吸着法や十分な水洗等の適切な方法により、50ppm以下、より望ましくは10ppm以下、特に望ましくは1ppm以下まで除去してから用いることもよい。
また、上記含酸素有機化合物としては、具体的には、例えばギ酸、酢酸、グリコール酸、プロピオン酸、乳酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、マルガリン酸、ステアリン酸、オレイン酸、ノナデカン酸及びエイコサン酸等の炭素数1〜30のモノカルボン酸、シュウ酸、フタル酸、トリメリット酸及びピロメリット酸等の炭素数2〜30のポリカルボン酸並びにこれらの無水物、又はエステル化合物、炭素数2〜6のアルキレンオキサイド及びヒドロキシ(ポリ)オキシアルキレンカーボネート等が挙げられる。
なお、これら金属系清浄剤の全塩基価及び添加量は、要求される無段変速機油の性能に応じて任意に選択できる。通常は、過塩素酸法で0〜500mgKOH/g、望ましくは150〜400mgKOH/gであり、その添加量は組成物全量基準で、通常0.1〜10%である。
これら粘度指数向上剤の分子量は、せん断安定性を考慮して選定することが必要である。具体的には、粘度指数向上剤の数平均分子量は、例えば分散型又は非分散型ポリメタクリレートでは5000〜1000000、好ましくは100000〜800000が良く、ポリイソブチレン又はその水素化物では800〜5000、エチレン−α−オレフィン共重合体及びその水素化物では800〜300000、好ましくは10000〜200000が良い。また、かかる粘度指数向上剤は、単独で又は複数種を任意に組合せて含有させることができるが、通常その含有量は、組成物全量基準で0.1〜40.0%であることが望ましい。
また、他の無灰分散剤としては、数平均分子量が900〜3500のポリブテニル基を有するポリブテニルベンジルアミン、ポリブテニルアミン、数平均分子量が900未満のポリブテニル基を有するポリブテニルコハク酸イミド等及びそれらの誘導体等が挙げられる。
さらに、上記摩耗防止剤又は極圧剤としては、ジスルフィド、硫化油脂、硫化オレフィン、炭素数2〜20の炭化水素基を1〜3個有するリン酸エステル、チオリン酸エステル、亜リン酸エステル、チオ亜リン酸エステル及びこれらのアミン塩等が挙げられる。
更にまた、上記防錆剤としては、アルキルベンゼンスルフォネート、ジノニルナフタレンスルフォネート、アルケニルコハク酸エステル、多価アルコールエステル等が挙げられる。
また、上記非イオン系界面活性剤及び抗乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル及びポリオキシエチレンアルキルナフチルエーテル等のポリアルキレングリコール系非イオン系界面活性剤等が挙げられる。
更に、上記金属不活性化剤としては、イミダゾリン、ピリミジン誘導体、ベンゾトリアゾール及びチアジアゾール等が挙げられる。
更にまた、上記消泡剤としては、シリコーン、フルオロシリコーン及びフルオロアルキルエーテル等が挙げられる。
なお、これら添加剤を本発明に用いる潤滑油組成物に含有する場合は、その含有量は、組成物全量基準で、他の摩擦調整剤、他の無灰分散剤、摩耗防止剤又は極圧剤、防錆剤、及び抗乳化剤は0.01〜5%、並びに金属不活性化剤は0.0005〜1%の範囲から適宜選択できる。
材料は、SCM420浸炭鋼を用い、LFW−1試験用のFalex社が規定する寸法(下記の(LFW−1試験条件)を参照。)のブロックとリングを作製した。
・ブロック
SCM420鋼から成る素材に、浸炭、低温焼戻し処理後、摺動表面をラッピングテープを用いて研磨し、表面粗さをRa0.03μmに仕上げた。得られたブロックの表面に、必要に応じてPVD処理又はCVD処理により、コーティング材を膜厚が1.1μmになるようにコーティングし、更にラッピングテープを用いて表面粗さをRa0.03μmに仕上げた。
・リング
SCM420鋼から成る素材に、浸炭、低温焼戻し処理後、摺動表面をラッピングテープを用いて研磨し、表面粗さをRa0.04μmに仕上げた。得られたブロックとリングの仕様を表1に示す。
基油としてパラフィン系鉱油(100℃における動粘度が4.3mm2/s)を使用し、脂肪酸エステル系、脂肪族アミン系、アミド系及びアルコール系の摩擦調整剤とCVTF添加剤パッケージとポリメタクリレートを適宜添加して、CVTF組成物を調製した。得られたCVTF組成物と上記摺動部材とを組み合わせて実施例1〜7及び比較例1〜6の摺動部材を得た。各例の仕様を表2に示す。なお、表2中、脂肪酸エステルとしてはグリセリンモノオレートを用い、また、市販のCVTFとしては日産純正油(NS−2)を用いた(このCVTFには、摩擦調整剤が含有されている。)。更に、用いたCVTFパッケージ添加物には、摩擦調整剤が含有されている。
ASTM D2714に規定されているLFW−1試験方法に準拠し、下記の試験条件で試験時間60分後の摩擦力から各例の摩擦係数を算出した。得られた結果を表2に併記する。
(LFW−1試験条件)
・試験装置 :Falex Block−on−Ring Friction
and Wear Testing Machine
・試験片 :ブロック(FalexタイプH−60形状)
:リング(FalexタイプS−10形状)
・すべり速度:0.26m/s
・荷重 :222.5N
・油温 :110℃
・試験時間 :60分
Claims (9)
- 無段変速機油組成物の存在下で互いに摺動する部材の少なくとも一方の摺動面に硬質炭素薄膜を被覆して成る摺動部位を有する無段変速機用低摩擦摺動部材であって、
上記硬質炭素薄膜の水素含有量が20原子%以下であり、
上記無段変速機油組成物が、基油と、脂肪酸エステル又はアルコールとを含んでいることを特徴とする無段変速機用低摩擦摺動部材。 - 上記硬質炭素薄膜の水素含有量が10原子%以下であることを特徴とする請求項1に記載の無段変速機用低摩擦摺動部材。
- 上記硬質炭素薄膜の水素含有量が5原子%以下であることを特徴とする請求項1に記載の無段変速機用低摩擦摺動部材。
- 上記硬質炭素薄膜の水素含有量が0.5原子%以下であることを特徴とする請求項1に記載の無段変速機用低摩擦摺動部材。
- 上記硬質炭素薄膜の被覆前における基材の表面粗さがRaで0.1μm以下であることを特徴とする請求項1〜4のいずれか1つの項に記載の無段変速機用低摩擦摺動部材。
- 上記硬質炭素薄膜は、表面硬さが、マイクロビッカース硬さ(10g荷重)でHv1000〜3500、厚さが0.3〜2.0μmであることを特徴とする請求項1〜5のいずれか1つの項に記載の無段変速機用低摩擦摺動部材。
- 請求項1〜6のいずれか1つの項に記載の無段変速機用低摩擦摺動部材に用いられる無段変速機油組成物であって、
上記無段変速機油組成物が基油と、脂肪酸エステル又はアルコールとを含有し、該脂肪酸エステル又はアルコールを、組成物全量基準で0.05〜3.0%含有していることを特徴とする無段変速機油組成物。 - ポリブテニルコハク酸イミド及び/又はその誘導体を含有することを特徴とする請求項7に記載の無段変速機油組成物。
- 上記ポリブテニルコハク酸イミド及び/又はその誘導体の含有量が、組成物全量基準で0.1〜15%であることを特徴とする請求項8に記載の無段変速機油組成物。
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US10/921,291 US7318514B2 (en) | 2003-08-22 | 2004-08-19 | Low-friction sliding member in transmission, and transmission oil therefor |
CNB2004100641577A CN1296467C (zh) | 2003-08-22 | 2004-08-20 | 变速器中的低摩擦滑动件及用于该滑动件的变速器油 |
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