JP4225782B2 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- JP4225782B2 JP4225782B2 JP2002563267A JP2002563267A JP4225782B2 JP 4225782 B2 JP4225782 B2 JP 4225782B2 JP 2002563267 A JP2002563267 A JP 2002563267A JP 2002563267 A JP2002563267 A JP 2002563267A JP 4225782 B2 JP4225782 B2 JP 4225782B2
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- lubricating oil
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Description
内燃機関からの排気ガスの排出を少なくする努力が増すにつれて、ガソリン出力エンジンおよびディーゼル出力エンジンの業者は、排気ガスを減らすために、排気ガス後処理装置(例えば、触媒コンバータ、微粒子トラップなど)を使用することにますます目を向けている。しかしながら、このような装置の使用に伴う問題には、比較的に高いレベルのイオウを含有する潤滑油組成物が最終的に分解して、これら潤滑剤の分解生成物(これは、イオウを含有する)が最終的に後処理装置に入り、しばしば、その装置の損傷の原因となることがある。さらに、ディーゼル燃料およびガソリン燃料中の許容できるイオウレベルは、15ppmに下げられると予想され、指定場所では、ゼロイオウ燃料が既に義務付けられている。従って、これらのエンジンの排気ガス中のイオウの相当部分は、その潤滑剤中のイオウに帰因すると予想できる。この結果、これらのエンジンで使用される潤滑油組成物中のイオウレベルを下げる圧力がかけられている。
本発明は、以下を含有する潤滑油組成物に関する:(A)基油;および(B)次式により表わされるリン含有化合物:
「ヒドロカルビル」との用語は、本発明の文脈内で、分子の残部に直接結合した炭素原子を有しそして炭化水素または主として炭化水素的な性質を有する基を示す。このような基には、以下が挙げられる:
(1)純粋な炭化水素基、すなわち、脂肪族基、脂環族基、芳香族基、脂肪族置換された芳香族基および脂環族置換された芳香族基、芳香族置換された脂肪族基および芳香族置換された脂環族基など、ならびに環式基。ここで、この環は、分子の他の部分により、完成されている(すなわち、いずれか2個の指示された置換基は、一緒になって、脂環族基を形成し得る)。例には、メチル、エチル、シクロヘキシル、フェニルなどが挙げられる。
本発明の潤滑油組成物は、1種以上の基油から構成され、これらは、一般に、主要量で存在している。この基油は、この潤滑油組成物の60重量%より多い量、または70重量%より多い量、または75重量%より多い量で存在し得る。
(A)基油
本発明の潤滑油組成物で使用される基油は、American Petroleum Institute(API) Base Oil Interchangeability Guidelinesで指定される群I〜Vの基油のいずれかから選択され得る。これらの5種の基油群は、以下のとおりである:
(B)リン含有化合物
リン含有化合物(B)は、次式により表わされる化合物である:
(C)アシル化窒素含有化合物
1実施形態では、本発明の潤滑油組成物は、さらに、少なくとも10個の脂肪族炭素原子の置換基を有するアシル化窒素含有化合物を含有する。これらの化合物は、典型的には、無灰分散剤として機能する。
(D)有機イオウ含有酸、カルボン酸、ラクトンまたはフェノールのアルカリ金属塩またはアルカリ土類金属塩
アルカリ金属塩またはアルカリ土類金属塩(D)は、有機イオウ含有酸、カルボン酸、ラクトンまたはフェノールの塩である。これらの塩は、中性またはオーバーベース化され得る。前者は、塩アニオン中に存在している酸性基を中和するのに、ちょうど十分な量の金属カチオンを含有する;後者は、過剰の金属カチオンを含有し、これらは、しばしば、塩基性塩、ハイパーベース化塩またはスーパーベース化塩と呼ばれている。
(R*)a−Ar*(CXXH)m (D−III)
ここで、式(D−III)では、R*は、4〜400個の脂肪族炭素原子を有する脂肪族炭化水素ベースの基であり、aは1〜4の整数であり、Ar*は、14個までの炭素原子を有する多価芳香族炭化水素核であり、各Xは、別個に、イオウ原子または酸素原子であり、そしてmは、1〜4の整数であるが、但し、R*およびaは、式(D−III)で表わされる各酸分子に対し、R*基により、平均して、少なくとも8個の脂肪族炭素原子が存在するような値である。
(R*)a−(Ar*)−(OH)m (D−IX)
ここで、式(D−IX)では、R*、a、Ar*およびmは、式(D−III)に関連して上で記述したものと同じ意味を有する。
(E)炭化水素置換サリゲニンのアルカリ金属塩またはアルカリ土類金属塩
炭化水素置換サリゲニンのアルカリ金属塩またはアルカリ土類金属塩は、次式により表わされる化合物であり得る:
−CHO:15〜100%または20〜60%または25〜50%
−CH2OH:0〜54%または4〜46%または10〜40%
−CH2−:0〜64%または18〜64%または20〜60%
式(E−1)で表わされる化合物は、マグネシウム塩であり得、この化合物の調製中にマグネシウムが存在することは、上記X成分およびY成分の所望の比を達成する際に重要であると考えられている。(この化合物を調製した後、そのMg金属は、公知方法により、水素、他の金属またはアンモニウム(もし望ましいなら)で置き換えることができる)。この組成物中のMgイオンの数は、0.1〜1.0、1実施形態では、0.2または0.4〜0.9、1実施形態では、0.6〜0.8の平均値「n」により、特徴付けられる。
攪拌機、ストッパー、サーモウェルおよび還流冷却器を備えた5Lの四ッ口丸底フラスコに、以下を充填する:希釈油(鉱油)670g、ドデシルフェノール1000g、およびNaOH(3g)の水(40g)溶液。この混合物を、攪拌しながら、35℃まで加熱する。35℃に達したら、この混合物に、パラホルムアルデヒド(90%)252gを加え、攪拌を続ける。5分後、MgO(5g)およびさらなる希釈油102gを加える。この混合物を79℃まで加熱し、その温度で、30分間保持する。第二増分のMgO(58g)を加え、そのバッチを、さらに加熱し、そして90〜100℃で、1時間維持する。その後、この混合物を、28L/時間(1.0 std.ft3/時間)の窒素流下にて、120℃まで加熱する。120℃に達したら、希釈油252gを加え、その混合物を、2.7kPa(20torr)の圧力で、120℃で、1時間にわたって、ストリッピングし、次いで、濾過する。得られた生成物は、1.5重量%のマグネシウムを含有し、そして63のTBNを有する。この生成物を1Dおよび2D 1H/13C NMRで分析すると、29モル%のアルデヒド含量、38モル%のメチレン架橋含量、12モル%のエーテル架橋含量および21モル%のヒドロキシメチル含量が明らかとなる。
(A部)
攪拌機、ストッパー、サーモウェルおよび還流冷却器を備えた5Lの四ッ口丸底フラスコに、以下を充填する:希釈油(鉱油)670gおよびドデシルフェノール1000g。この混合物を、攪拌しながら、35℃まで加熱する。35℃に達したら、この混合物に、パラホルムアルデヒド(90%)252gを加え、攪拌を続ける。5分後、Ca(OH)2(7.3g)およびさらなる希釈油102gを加える。この混合物を79℃まで加熱し、その温度で、30分間保持する。第二増分のCa(OH)2(104g)を加え、そのバッチを、さらに加熱し、そして90〜100℃で、1時間維持する。その後、この混合物を、28L/時間(1.0 std.ft3/時間)の窒素流下にて、120℃まで加熱する。120℃に達したら、希釈油252gを加える。その混合物を、窒素流下にて、150℃で、ストリッピングし、そして濾過により単離する。得られた生成物は、14モル%のアルデヒド官能性を含む。
攪拌機、サーモウェル、還流冷却器および水面下チューブを備えた12Lの四ッ口フラスコに、A部の生成物5000g、ポリイソブテン(Mn=1000)置換無水コハク酸315g、Ca(OH)2(376g)およびアルコール混合物(これは、88〜96重量%のエチルアルコール、4〜5%のイソプロピルアルコールおよび0〜8%の水を含有する)863gを充填する。この混合物を63℃まで加熱し、そして氷酢酸10gを加える。この混合物を、約60℃で、1時間保持する。この混合物に、3時間にわたって、約0.5std.ft3/時間で、56.4の直接塩基価となるまで、二酸化炭素を吹き込む。第二増分のCa(OH)2(370g)を加え、この混合物に、7時間にわたって、39.8の直接塩基価となるまで、同様に、二酸化炭素を吹き込む。この混合物を、1.5std.ft3/時間の窒素下にて、145℃まで再ストリッピングし、その温度で、1時間にわたって、2.0std.ft3/時間で維持する。その生成物をトルエンで希釈し、遠心分離し、得られた固形物からデカントし、そして130〜140℃および60mmHgの真空までストリッピングする。この生成物を濾過すると、205のTBNを示し、これは、7.2重量%のCaを含有している。
(F)リン含有金属塩
このリン含有金属塩は、典型的には、極圧(EP)添加剤として機能し、本発明の潤滑油組成物に添加され得るが、但し、この添加により潤滑油組成物に寄与するリンの量は、その潤滑油組成物の0.08重量%を超えず、イオウの量は、0.25重量%を超えない。これらのEP添加剤を製造する際に有用なリン含有酸は、次式により表わされ得る:
(G)分散剤粘度指数調整剤
分散剤粘度指数調整剤(G)は、多機能添加剤であり、これは、粘度改良特性および分散特性の両方を提供する。これらの添加剤は、当該技術分野で公知であり、市販されている。
(H)他の任意の添加剤
本発明の潤滑油組成物は、上で言及したアシル化窒素含有化合物(C)および分散剤粘度指数調整剤(G)に加えて、1種以上の無灰型の清浄剤または分散剤を含有し得る。
以下の実施例1〜6は、本発明をさらに開示するために提供されている。実施例C−1は、本発明の範囲内ではないが、比較のために提供されている。各実施例は、以下の表で開示した潤滑油組成物から成る。以下の表では、各々の例示した潤滑油組成物の成分(消泡剤を除く)に関連した全ての数値は、重量%の濃度である。この消泡剤の濃度は、ppmで表わされている。例示した潤滑油組成物は、1つ以上の以下の試験を使用して試験され、このような試験の結果もまた、以下の表で報告されている。
この電動弁列摩耗試験は、実物大のシリンダーヘッドを使用し、これを、AC電動モーターで駆動し、そしてCamilleデータ獲得および制御コンピューターシステムで作動する。その試験の順序は、100回の1時間サイクルから成り、各サイクルでは、2つの段階がある。段階1は、800rpmで、5分間運転する。段階2は、1500rpmで、10分間運転する。そのオイル試料は、酸化剤、水および燃料により、汚染される。摩耗の測定は、全12個のカムローブを測定することにより、行なう。摩耗は、失われた材料のミクロン数で表わす。
この試験は、重負荷ディーゼル弁列摩耗性能を決定するために、CH−4 Cummins M−11ディーゼルエンジンを使用する。CH−4 Cummins M−11は、ターボチャージャー付きのインライン6気筒11リットルエンジンである。このエンジン試験は、4段階に分けられる。第一および第三段階では、このエンジンには、燃料を過剰に入れ、遅延タイミングで作動して、加速状態で、すすを発生させる。第二および第四段階は、摩耗を引き起こすために、低速および高トルクで運転する。
Claims (8)
- 以下を含有する、潤滑油組成物であって:
(A)基油;
(B)次式により表わされるリン含有化合物であって:
(E)次式により表わされる化合物:
該潤滑油組成物は、0.01〜0.25重量%のイオウ含量により、特徴付けられる、
組成物。 - 前記組成物が、(C)少なくとも10個の脂肪族炭素原子の置換基を有するアシル化窒素含有化合物をさらに含有する、請求項1に記載の組成物。
- 前記組成物が、(D)有機イオウ含有酸、カルボン酸、ラクトンまたはフェノールのアルカリ金属塩またはアルカリ土類金属塩をさらに含有する、請求項1に記載の組成物。
- 前記潤滑油組成物が、(G)分散剤粘度指数調整剤をさらに含有する、請求項1に記載の組成物。
- 式(B−I)では、R1、R2およびR3が、独立して、芳香族基またはアルキル芳香族基であり、そしてa、bおよびcが、それぞれ、1である、請求項1に記載の組成物。
- (B)が、リン酸トリ(アルキルフェノール)または亜リン酸トリフェニルである、請求項1に記載の組成物。
- 前記潤滑油組成物が、少なくとも1種の無灰清浄剤または分散剤、腐食防止剤、酸化防止剤、粘度調整剤、流動点降下剤、摩擦調整剤、流動調整剤、銅不動態化剤または消泡剤をさらに含有する、請求項1に記載の組成物。
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US6588393B2 (en) * | 2000-09-19 | 2003-07-08 | The Lubrizol Corporation | Low-sulfur consumable lubricating oil composition and a method of operating an internal combustion engine using the same |
US7165107B2 (en) * | 2001-01-22 | 2007-01-16 | Sun Microsystems, Inc. | System and method for dynamic, transparent migration of services |
EP1439217B1 (en) * | 2001-10-12 | 2012-06-20 | Nippon Oil Corporation | Lubricating oil composition for internal combustion engine |
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JP5099868B2 (ja) * | 2002-06-10 | 2012-12-19 | ザ ルブリゾル コーポレイション | 内燃機関を潤滑し、該機関の排出制御システムの効率を改善する方法 |
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2002
- 2002-01-31 US US10/061,978 patent/US6764982B2/en not_active Expired - Fee Related
- 2002-01-31 JP JP2002563267A patent/JP4225782B2/ja not_active Expired - Fee Related
- 2002-01-31 AU AU2002243800A patent/AU2002243800B2/en not_active Ceased
- 2002-01-31 EP EP02709308.7A patent/EP1360264B1/en not_active Expired - Lifetime
- 2002-01-31 CA CA002434332A patent/CA2434332A1/en not_active Abandoned
- 2002-01-31 WO PCT/US2002/003144 patent/WO2002062929A2/en active IP Right Grant
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JP2004521175A (ja) | 2004-07-15 |
WO2002062929A2 (en) | 2002-08-15 |
WO2002062929A3 (en) | 2003-02-13 |
US6764982B2 (en) | 2004-07-20 |
CA2434332A1 (en) | 2002-08-15 |
AU2002243800B2 (en) | 2007-03-15 |
US20020151442A1 (en) | 2002-10-17 |
EP1360264A2 (en) | 2003-11-12 |
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