JP2005528476A - 直接燃料噴射型クランク室排出式2ストロークエンジンに適した潤滑組成物 - Google Patents
直接燃料噴射型クランク室排出式2ストロークエンジンに適した潤滑組成物 Download PDFInfo
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- JP2005528476A JP2005528476A JP2003586266A JP2003586266A JP2005528476A JP 2005528476 A JP2005528476 A JP 2005528476A JP 2003586266 A JP2003586266 A JP 2003586266A JP 2003586266 A JP2003586266 A JP 2003586266A JP 2005528476 A JP2005528476 A JP 2005528476A
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Abstract
Description
本出願は、2002年4月19日に出願された米国仮出願第60/373,988号の優先権を主張する。
本発明は、直接燃料噴射型クランク室排出式2ストロークエンジンに有用な、潤滑組成物および燃料潤滑剤混合物に関する。火花点火式2ストローク内燃機関の使用は、20世紀の最後の30年間の間に急速に増加した。しかし、この成長は、主として従来の2ストロークエンジンに存在する高い排出レベルに起因して、現在、先細りにしている。従来の2ストロークエンジンの現在の世界的な人口は非常に多く、数千万に及ぶ。これらの2ストロークエンジンは、費用効果が高く、そして、荷重配分比に対して高い出力を有するので、2ストロークエンジンは、芝生および庭用の装置、ポータブルコントラクター装置(例えば、ポンプ)、ならびに、発電機、低コストの運搬用車両(例えば、モペット)、ならびに、商業用および娯楽用の車(オートバイ、船外機関、スノーモービル、個人用の船舶車両などが挙げられる)において非常に一般的に使用される。
本発明は、直接燃料噴射2ストロークエンジンを潤滑にするのに適切な潤滑組成物を提供し、この潤滑組成物は、以下:
(a)少なくとも40重量%の潤滑粘性油;
(b−1)0.5〜8重量%の、少なくとも1つの、アミンまたはアンモニアを有する脂肪族ヒドロカルビルモノカルボン酸アシル化剤の縮合生成物、および
(b−2)潤滑組成物に基づいて0.5〜8重量%の少なくとも1つのMannich分散剤;
(c)0〜45重量%の、100℃で2mm2s−1(cSt)未満の粘性を有する可燃性溶媒;ならびに、
(d)0〜3重量%の酸化防止剤;
を含み、ただし、(b−1)+(b−2)ならびに(b−1)および(b−2)以外の潤滑組成物中のあらゆる分散剤の総量が少なくとも約1.5重量%であり、さらにただし、潤滑組成物中の全窒素含量が約0.25〜約0.75重量%である。
本発明は、分散剤の混合物を含む、直接燃料噴射2ストロークエンジンを潤滑にするのに適した組成物を提供し、潤滑剤における全窒素含量は、0.25〜0.75%である。
本発明の第1の要素は、潤滑粘性油(天然または合成の潤滑油、および、それらの混合物を含む)である。潤滑粘性油の具体的な例は、米国特許第4,326,972号に記載される。
基油 粘性
分類 硫黄(%) 飽和(%) 指数
グループI >0.03 および/または <90 80〜120
グループII <0.03 および >90 80〜120
グループIII <0.03 および >90 >120
グループIV 全てポリαオレフィン(PAO)
グループV 全てグループI、II、IIIまたはIVに含まれない他のもの
グループI、IIおよびIIIは、ミネラルオイルベースストックである。次いで、潤滑粘性油は、天然または合成の潤滑油、およびこれらの混合物を含み得る。ミネラルオイルと合成オイルの混合物、特にポリαオレフィンオイルとポリエステルオイルが、しばしば使われる。
本発明はまた、少なくとも2つの特定の分散剤を含み、必要に応じて1つ以上の追加の分散剤を含む。第1の特定の分散剤は、脂肪ヒドロカルビルモノカルボン酸アシル化剤(例えば、脂肪酸)とアミンまたはアンモニアとの縮合生成物である。
このような潤滑組成物に一般に(必ずではなく)存在する別の材料は、潤滑剤中、または、従来は潤滑剤と混合される燃料中の添加物の溶解を援助するための溶媒である。代表的に、このような物質は、約105℃未満の引火点を有する可燃性溶媒(潤滑粘性油以外)であり、ここで潤滑剤の残っている成分は、可溶性である。溶媒は、炭化水素溶媒、すなわち、たとえ、比較的少数のヘテロ原子が分子中に存在し得ようとも、代表的に炭化水素特性を主として示すものである。溶媒は、好ましくは、炭化水素であり、そして、好ましくは、主として非芳香族(例えば、アルカン)特性を有する。従って、溶媒は、好ましくは、20重量%未満の芳香族成分を含み、そして、好ましくは、多核性の芳香族成分を実質的に含まない。(十分大量の芳香族炭化水素は、燃焼の際の煙に寄与し得、従って、時折あまり望ましくない。)特に適当な溶媒は、灯油である。これは、180〜300℃の沸騰範囲を有する芳香族を含まない石油蒸留物である。別の有用な溶媒は、Stoddard溶媒である。これは、154〜202℃の沸騰範囲を有する。
一般に存在する別の物質は、酸化防止剤である。酸化防止剤(特にヒンダードフェノールおよび芳香族アミンが挙げられる)は、種々の型の化学物質を含む。
本発明の任意の組成物はまた、金属清浄剤(detergent)を含み得る。金属清浄剤は、代表的にオーバーベースの物質である、他に、オーバーベースの塩、または、スーパーベースの塩と称される(一般に単相であり、金属および金属と反応する特定の酸性有機化合物の化学量論に従う中和のために存在する、過剰な金属含有量によって特徴付けられる均質なニュートンの系である)。オーバーベースの物質は、上記の酸性物質、化学量論的に過剰な金属塩基、およびフェノールまたはアルコールのような開始剤について、酸性物質(代表的には、無機酸または低級カルボン酸、好ましくは二酸化炭素)を、酸性有機化合物、少なくとも1つの不活性有機溶剤を含む反応媒体(ミネラルオイル、ナフサ、トルエン、キシレンなど)を含む混合物と反応させることによって調製される。酸性有機物質は、通常十分な炭素原子数(代表的には1つ以上のヒドロカルビル置換基)を有し、オイルに溶解度を供給する。本発明のために有用な金属清浄剤は、代表的には、中性塩であるか、または、2未満の金属比率(金属対酸基の比、過剰塩基の測定値)を有する。
1.)CaまたはMgスルホン酸塩、中性またはオーバーベース;
2.)CaまたはMg石炭酸塩、好ましくは中性であるが、必要に応じてオーバーベース;
3.)Na、CaまたはLiグリオキシレート、好ましくは中性であるが、必要に応じてオーバーベース;
4.)Ca、MgまたはNaサリチル酸塩、好ましくは中性であるが、必要に応じてオーバーベース;
5.)CaまたはMgサリゲニン生成物、米国特許第6,310,990号に記載されるように好ましくは中性であるが、必要に応じてオーバーベース;
6.)例えば、米国特許第6,174,844号に記載されるような金属カリックスアーレン、中性またはオーバーベース;
7.)クラウンエーテル、すなわち、酸素原子が金属イオンを配位する環状エーテル、中性またはオーバーベース。
(a)主要な量の潤滑粘性油
(b)以下の分散剤を含む、4〜25%(従来の希釈油を含む量)の量で存在する追加用パッケージ:
1.)Mannich塩基(例えば、ホルムアルデヒドおよびエチレンジアミンと反応した高ビニリデンポリブテン置換フェノール);
2.)アルキルアミノフェノール(例えば、ポリブテニル基が約1000の数平均分子量を有する4−ポリブテニルアミノフェノール;および
3.)脂肪酸の縮合生成物(例えば、テトラエチレンペンタアミンのようなポリアミンを有するイソステアリン酸(イミダゾリン成分を含むと考えられている));
(c)可燃性溶媒(例えば、0〜35%のレベルで存在する灯油またはStoddard溶媒)、この溶媒は、1000℃で2.0cSt未満の粘性を有し、好ましくは、1000℃で1.5cSt未満または1cSt未満の粘性を有する;ならびに
(d)酸化防止剤(例えば、0〜3%の量の芳香族アミン)。
1.)Mannich塩基;
2.)ポリアミンを有する脂肪酸の縮合生成物;および
3.)PIBポリアミン(例えば、塩化ポリイソブテン中間体としての、ポリイソブテン(
a.6.6%(60%化学物質、40%の希釈油)のポリブテニルアミノフェノール
b.4%(希釈油なし)のイソステアリン酸とテトラエチレンペンタアミンの縮合生成物
c.6.2%(70%化学物質、30%の希釈油)の上記のモノスクシンイミド
d.1.0%の芳香族アミン酸化防止剤
e.0.3%のグリセロールモノオレイン酸塩(摩擦モディファイヤ)
f.0.06%の防錆剤
g.28%の溶媒
h.5%(希釈油なし)のポリイソブテン(
i.48.8%の基油
2.実施例2は、下記を含むオイルである:
a.4.97%(60%化学物質)のアルキルアミノフェノール(実施例1と同様)
b.5.03%の縮合生成物(実施例1と同様)
c.5.0%(70%の化学物質)のモノスクシンイミド(実施例1と同様)
d.28%の溶媒
e.5%のポリイソブテン
f.52%の基油
3.実施例3は、下記を含むオイルである:
a.6.0%(60%化学物質)のアルキルアミノフェノール(実施例1と同様)
b.5%の縮合生成物(実施例1と同様)
c.5%(67%化学物質、34%の希釈油)の上記と同じMannich塩基
d.0.6%(60%化学物質、40%の希釈油)のアルキルフェノール/グリオキシル酸反応生成物のNa塩、TBN(総塩基数)51
e.1.0%の芳香族アミン酸化防止剤
f.0.34%のモノオレイン酸グリセロール
g.0.06%の防錆剤
h.28%の溶媒
i.8%のポリイソブテン
j.48%の基油
実施例3の組成物は、処方者が新しい生成物(特定のパフォーマンス標的を満たし得るか、または超え得る)を産生するのを支援するように設計されている、2サイクル処方物最適化ツールを用いて得られる。回帰モデル(例えば、線形または部分的に線形)が、WestbendTM134エンジンおよびYamahaTMYZ125エンジンにおけるパフォーマンス試験結果に匹敵する処方変数を作成する。処方変数の例としては、添加剤の量、混合物の化学的性質/物理的性質、および、基油記述子が挙げられる。回帰モデルは、標準の統計的モデリング実行と共に、Bayesianモデル平均化アルゴリズム(Meyer,R.DanielおよびWilkinson,Robert G.(1998)、「Bayesian variable assessment」、Communications in Statistics、Part A−Theory and Methods、27,2675−2705)を用いて作成される。次いで、このモデルは、ウェブベースの最適化ツールにそれから組み込まれる。ツールのユーザーは、熟慮するために、一連の化学添加剤と共にベース流体システムの選択を特定する。ユーザーはまた、WestbendTM134および/またはYamahaTMYZ125試験についての処理速度定数、総コスト定数、および、最小パフォーマンスターゲットを指定し得る。線形プログラミング技術を使って、このシステムは、これらの必要条件を満たす最適な処方物を見出す。最適な処方物は、コストを最小限にするか、または、上記のパフォーマンス試験の1つの局面に関してパフォーマンスを最大限にするものである。最適性(すなわち、目的の関数)のこの選択は、ツールのユーザーによって選択される。実施例3における添加物組成物は、WestbendTMおよびYamahaTMの室内エンジンにおいて試験し、ピストンワニス、リングスティック、および、ピストンクラウン沈澱物についての予測された試験結果および実際の試験結果を、以下の表に示し、ここで、結果は、1〜10のスケール上の人事考課単位(merit rating unit)で表し、10は、非常にクリーンであり、そして、1は非常に汚い。
(手順1)
実地試験は、以下の様式の船外エンジンを用いて行なう:
1.全てのエンジン/発動機は、OrbitalTMまたはFichtTM設計のいずれかの直接燃料噴射システムを有する。エンジンは、新品であるか、またはOEMの認証を受けた機械工によって再建され、そして、86.8kW〜168kW(115HP〜225HP)のサイズで変化する。
試験は、手順1を用いて以下の結果を得る:
a.主要なOEMからのプレミアム高窒素含有2サイクル船外オイルをこのデータセットのための参照例として使用する。
タンク試験を、以下を例外として、船外エンジンおよび手順1に記載したものと同じ手順を用いて行なう:
1.テストエンジンは、船体開放(open−hull)ボート上でよりむしろ、予定された温度範囲で保持された水で満たされている大きなスチールタンクでエンジンを吊るすフレームに取付けられる。
試験は、手順2を用いて以下の結果を与える:
b.拡張されたDFIパフォーマンスのために設計、および販売される高窒素含有OEMオイル、このデータセットのための参照例として使用される。
結果は、実施例1および3(低窒素含量を有する)が、高窒素含有OEMオイルと同等であるか、またはより良いパフォーマンスをもたらすことを示す。これらの実施例の両方が、トップおよび第2のリングの重炭素における非常に有意な減少によって増強されたパフォーマンスを示す。堆積物のこれらの減少は、リングジャッキ持ち上げ、および、引き続くエンジンの焼付を妨げ得る。
炭化水素置換基、すなわち、脂肪族(例えば、アルキルまたはアルケニル)、脂環式(例えば、シクロアルキル、シクロアルケニル)置換基、ならびに、芳香族、脂肪族および脂環式置換芳香族置換基、ならびに、環が分子の別の部分を介して完成される環式置換基(例えば、2つの置換基は、共に環を形成する);
置換された炭化水素置換基、すなわち、本発明の文脈において置換基の主たる炭化水素特性を変更しない非炭化水素基を含む置換基(例えば、ハロ(特に、クロロおよびフルオロ)、ヒドロキシアルコキシ、メルカプト、アルキルメルカプト、ニトロ、ニトロソ、および、スルホキシ);
ヘテロ置換基、すなわち、本発明の文脈において、主たる炭化水素特性を有する一方で、別の場合、炭素原子から成る環または鎖において炭素以外を含む、置換基。ヘテロ原子としては、硫黄、酸素、窒素が挙げられ、そして、ピリジル、フリル、チエニル、および、イミダゾリルとして置換基を包含する。一般に、2つ未満、好ましくは1つの非炭化水素置換基が、ヒドロカルビル基における10個の炭素原子毎について存在する;代表的に、ヒドロカルビル基には非炭化水素置換基がない。
Claims (9)
- 直接燃料噴射2ストロークエンジンを潤滑にするのに適当な潤滑組成物であって、該潤滑組成物は、以下:
(a)少なくとも約40重量%の潤滑粘性油;
(b−1)約0.5〜約8重量%の、少なくとも1つの、アミンまたはアンモニアを有する脂肪族ヒドロカルビルモノカルボン酸アシル化剤の縮合生成物脂肪、および
(b−2)潤滑組成物に基づいて約0.5〜約8重量%の少なくとも1つのMannich分散剤;
(c)0〜約45重量%の、100℃で2mm2s−1(cSt)未満の粘性を有する可燃性溶媒、ならびに、
(d)0〜約3重量%の酸化防止剤;
を含み、ただし、(b−1)+(b−2)ならびに(b−1)および(b−2)以外の潤滑組成物中のあらゆる分散剤の総量が少なくとも約1.5重量%であり、さらに、潤滑組成物中の全窒素含量が約0.25〜約0.75重量%である、潤滑組成物。 - (b−3)約0.5〜約8重量%の(b−1)および(b−2)以外の型の少なくとも1つの追加の分散剤をさらに含む、請求項1に記載の潤滑組成物。
- 前記追加の分散剤(b−3)が、アルキルアミノフェノール分散剤、モノ−スクシンイミド分散剤、ヒドロカルビル−アミン分散剤、ポリエーテル分散剤、または、連結されたフェノール分散剤である、請求項2に記載の潤滑組成物。
- 前記(b−1)の縮合生成物が、ポリアミンと共に約12〜約24個の炭素原子を有する脂肪酸の縮合生成物である、請求項1に記載の潤滑組成物。
- 前記脂肪酸がイソステアリン酸を含み、前記ポリアミンがテトラエチレンペンタアミンを含む、請求項4に記載の潤滑組成物。
- 前記(b−2)のMannich分散剤が、ポリブテン置換フェノール、ホルムアルデヒド、および、エチレンジアミンまたはジメチルアミンの反応生成物である、請求項1に記載の潤滑組成物。
- 主要な量の液体燃料組成物と混合された請求項1に記載の潤滑剤。
- 直接燃料噴射2サイクルエンジンを潤滑にする方法であって、該エンジンに請求項1に記載の潤滑組成物を供給する工程を包含する、方法。
- 前記潤滑組成物が主要な量の液体燃料組成物と混合され、そして、その結果生じる混合物がエンジンに供給される、請求項8に記載の方法。
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PCT/US2003/011955 WO2003089555A1 (en) | 2002-04-19 | 2003-04-17 | Lubricant composition suitable for direct fuel injected, crankcase-scavenged two-stroke engines |
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JP2003586266A Expired - Lifetime JP4630550B2 (ja) | 2002-04-19 | 2003-04-17 | 直接燃料噴射型クランク室排出式2ストロークエンジンに適した潤滑組成物 |
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JP2008031289A (ja) * | 2006-07-28 | 2008-02-14 | Showa Shell Sekiyu Kk | エンジン用潤滑油組成物 |
JP2011515538A (ja) * | 2008-03-19 | 2011-05-19 | ザ ルブリゾル コーポレイション | 重質燃料によって駆動される2ストロークエンジンを潤滑するのに適切な潤滑添加組成物 |
JP2014080628A (ja) * | 2008-03-19 | 2014-05-08 | Lubrizol Corp:The | 重質燃料によって駆動される2ストロークエンジンを潤滑するのに適切な潤滑添加組成物 |
JP2016531995A (ja) * | 2013-09-19 | 2016-10-13 | ザ ルブリゾル コーポレイションThe Lubrizol Corporation | 直噴エンジン用潤滑剤組成物 |
JP2020153427A (ja) * | 2019-03-19 | 2020-09-24 | 住友重機械工業株式会社 | 減速装置、減速装置の腐食防止方法、潤滑剤、潤滑剤の製造方法および添加剤 |
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EP1497399A1 (en) | 2005-01-19 |
WO2003089556A1 (en) | 2003-10-30 |
JP2005523374A (ja) | 2005-08-04 |
CA2482757A1 (en) | 2003-10-30 |
CA2482754C (en) | 2013-01-08 |
EP1497400A1 (en) | 2005-01-19 |
AU2003234139B2 (en) | 2008-11-13 |
AU2003228577A1 (en) | 2003-11-03 |
AU2003228577B2 (en) | 2008-11-06 |
JP4630550B2 (ja) | 2011-02-09 |
US7900590B2 (en) | 2011-03-08 |
WO2003089555A1 (en) | 2003-10-30 |
US20050139174A1 (en) | 2005-06-30 |
EP1497399B1 (en) | 2018-08-15 |
CA2482754A1 (en) | 2003-10-30 |
CA2482757C (en) | 2012-06-12 |
AU2003234139A1 (en) | 2003-11-03 |
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