JP4594626B2 - 内燃機関潤滑油用又は駆動系潤滑油用潤滑油組成物 - Google Patents
内燃機関潤滑油用又は駆動系潤滑油用潤滑油組成物 Download PDFInfo
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- JP4594626B2 JP4594626B2 JP2004024309A JP2004024309A JP4594626B2 JP 4594626 B2 JP4594626 B2 JP 4594626B2 JP 2004024309 A JP2004024309 A JP 2004024309A JP 2004024309 A JP2004024309 A JP 2004024309A JP 4594626 B2 JP4594626 B2 JP 4594626B2
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- Prior art keywords
- acid
- lubricating oil
- oil
- internal combustion
- combustion engine
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- 239000003112 inhibitor Substances 0.000 description 4
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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Description
しかしながら、金属系清浄剤は燃料と共にその一部が燃焼されるため、金属系清浄剤に含まれる金属分が種々の問題を引き起こしている。具体的には、排ガスと共に放出された金属分が排ガス触媒に付着し、排ガス浄化性能を低下させたり、また、ディーゼルエンジンにおいては、ディーゼル微粒子除去装置(DPF)の粒子状物質(PM)除去性能を低下させるばかりか、DPFの再利用を阻害するという問題がある。そのため、金属系清浄剤の添加量を低減することが大きな課題となっている。
本発明は、上記のような課題を解決するためになされたものであり、カルシウムやマグネシウムなどの金属分を含有せず、清浄性能に優れる潤滑油添加剤及びそれを含有する潤滑油組成物を提供することを目的としている。
即ち、本発明は、塩基価が少なくとも10mgKOH/gであり且つ下記の一般式(1)
なお、本発明における「金属」とは、「典型金属元素」及び「遷移金属元素」を指す。
この第四級アンモニウム塩の塩基価は、スラッジ分散性や酸中和性の観点から高いことが好ましいが、あまりに塩基価が高いと潤滑油の摩擦係数を上昇させる、あるいは基油への溶解性が悪くなる恐れがあり好ましくない。このため、第四級アンモニウム塩の塩基価は、30〜600mgKOH/gであることが好ましく、50〜300mgKOH/gであることが更に好ましい。
ここで、本発明における塩基価は、第四級アンモニウム塩1g中に含まれる塩基性成分を中和するのに要する塩酸と当量の水酸化カリウムのミリグラム(mg)数であり、JIS K2501(石油製品及び潤滑油−中和価試験方法)の全塩基価測定方法により測定することができる。
このようなアニオン性基としては、例えば、炭酸、ホウ酸、ケイ酸などの無機化合物;モノメチル炭酸、モノエチル炭酸などの炭酸エステル類;ギ酸、酢酸、プロピオン酸、ブタン酸(酪酸)、ペンタン酸(吉草酸)、イソペンタン酸(イソ吉草酸)、ヘキサン酸(カプロン酸)、ヘプタン酸、イソヘプタン酸、オクタン酸(カプリル酸)、2−エチルヘキサン酸、イソオクタン酸、ノナン酸(ペラルゴン酸)、イソノナン酸、デカン酸(カプリン酸)、イソデカン酸、ウンデカン酸、イソウンデカン酸、ドデカン酸(ラウリン酸)、イソドデカン酸、トリデカン酸、イソトリデカン酸、テトラデカン酸(ミリスチン酸)、ヘキサデカン酸(パルミチン酸)、オクタデカン酸(ステアリン酸)、イソステアリン酸、エイコサン酸(アラキン酸)、ドコサン酸(ベヘン酸)、テトラコサン酸(リグノセリン酸)、ヘキサコサン酸(セロチン酸)、オクタコサン酸(モンタン酸)、10−ウンデセン酸、ゾーマリン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸、ガドレン酸、エルカ酸、セラコレイン酸、天然油脂から得られる混合脂肪酸、マロン酸、コハク酸、マレイン酸、安息香酸、メチル安息香酸、エチル安息香酸、ブチル安息香酸、ヒドロキシ安息香酸、ナフタレンカルボン酸、ジフェニルカルボン酸、テレフタル酸、ナフタレンジカルボン酸、トリメリット酸、ピロメリット酸などの有機カルボン酸由来のもの及び水酸基が挙げられる。中でも、原料入手の容易さ及び油への溶解性の観点から、炭酸、炭酸エステル、ホウ酸及び有機カルボン酸由来のもの及び水酸基が好ましい。
また、モノエタノールアミン、ジエタノールアミン、N−メチルエタノールアミン、N−エチルエタノールアミン、N−プロピルエタノールアミン、N−イソプロピルエタノールアミン、N−ブチルエタノールアミン、N−シクロヘキシルエタノールアミン、N−ベンジルエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、N−シクロヘキシルイソプロパノールアミン、N−ベンジルイソプロパノールアミン、モノブタノールアミン、ジブタノールアミン等の第一級又は第二級アルカノールアミンを、ハロゲン化炭化水素や硫酸ジアルキル等で三級化した後、脂肪酸、脂肪酸クロライド又は脂肪酸エステルと反応させて、アミン化合物の水酸基をエステル化させることにより、第三級アミンエステル化合物を得ることもできる。
基油としては、潤滑油の基油として一般的に用いられているものであればよく、鉱油、炭化水素系合成油及びこれらの混合物が挙げられる。より具体的には、ポリ−α−オレフィン、エチレン−α−オレフィン共重合体、ポリブテン、アルキルベンゼン、アルキルナフタレン、ポリアルキレングリコール、ポリフェニルエーテル、アルキル置換ジフェニルエーテル、ポリオールエステル、二塩基酸エステル、リン酸エステル、亜リン酸エステル、炭酸エステル、シリコーン油、フッ素化油等の合成油、パラフィン系鉱油、ナフテン系鉱油又はこれらを精製した精製鉱油類等が挙げられる。
まず、下記に示す配合の基準油を調製した。次に、下記の基準油及び各添加剤を用いて下記の表1に示す配合にて、実施例1〜5及び比較例1〜5の潤滑油組成物を調製した。なお、実施例1〜5及び比較例1〜4においては、潤滑油組成物の全塩基価が5mgKOH/gになるように、添加剤を添加した。
鉱油系高度VI油
動粘度4.1mm2/s(100℃)、18.3mm2/s(40℃)、粘度指数(VI)=126
[基準油配合表]
基油 100質量部
コハク酸イミド系分散剤 5.0質量部
フェノール系酸化防止剤 0.3質量部
アミン系酸化防止剤 0.3質量部
ジチオリン酸亜鉛 1.0質量部
(A−1:本発明品)
重炭酸ジオレイルジメチルアンモニウム
塩基価:92mgKOH/g
金属分:0%
(A−2:本発明品)
ジオレイルジメチルアンモニウムプロピオン酸
塩基価:90mgKOH/g
金属分:0%
(A−3:本発明品)
重炭酸トリドデシルモノメチルアンモニウム
塩基価:93mgKOH/g
金属分:0%
(A−4:本発明品)
金属分:0%
(B−1:比較品)
カルシウムスルホネート
塩基価:300mgKOH/g
金属分:12.6%
(B−2:比較品)
カルシウムスルホネート
塩基価:100mgKOH/g
金属分:4.3%
(B−3:比較品)
マグネシウムサリシレート
塩基価:200mgKOH/g
金属分:3.1%
(B−4:比較品)
ジオレイルジモノメチルアミン
塩基価:105mgKOH/g
金属分:0%
(B−5:比較品)
ジオレイルジメチルアンモニウムクロライド
塩基価:0mgKOH/g
金属分:0%
JIS K−2514(潤滑油−酸化安定度試験方法)に準拠して、触媒として銅板と鉄板を入れたガラス容器に、試料250mlを入れ、1300rpmで空気を巻き込むように攪拌しながら、165.5℃で1週間加熱した。試験前及び試験後の潤滑油組成物について、動粘度(40℃)及び全塩基価を測定した。試験前の動粘度および試験後の動粘度から動粘度差を求め、試験前の全塩基価及び試験後の全塩基価から全塩基価の減少量を求めた。また、試験後の潤滑油組成物をろ過し、トルエンで洗浄後に乾燥して、生成したスラッジ量を測定した。
試験前後の動粘度差が小さく、全塩基価の減少量が少ないものほど酸化安定性が高いことを示し、生成したスラッジ量が少ないほど金属への腐食が少なく、且つ分散性が高いことを示す。これらの結果を表1に示す。
これに対して、105mgKOH/gの塩基価を有する第三級アミン化合物(B−4)を添加した比較例4及び塩基価が0mgKOH/gである第四級アンモニウム塩(B−5)を添加した比較例5は、酸化安定性およびスラッジ分散性が劣っていた。
Claims (3)
- 塩基価が少なくとも10mgKOH/gであり且つ下記の一般式(1)
- 前記Xが、炭酸エステルである請求項1に記載の内燃機関潤滑油用又は駆動系潤滑油用潤滑油組成物。
- 前記第四級アンモニウム塩の塩基価が30〜600mgKOH/gである請求項1又は2に記載の内燃機関潤滑油用又は駆動系潤滑油用潤滑油組成物。
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JP2004024309A JP4594626B2 (ja) | 2004-01-30 | 2004-01-30 | 内燃機関潤滑油用又は駆動系潤滑油用潤滑油組成物 |
CA002552671A CA2552671A1 (en) | 2004-01-30 | 2005-01-25 | Lubricating oil additive and lubricating oil composition containing same |
US10/587,020 US20070155636A1 (en) | 2004-01-30 | 2005-01-25 | Lubricating oil additive and lubricating oil composition containing the same |
EP05709314A EP1717298A4 (en) | 2004-01-30 | 2005-01-25 | LUBRICANT ADDITIVE AND THIS LUBRICANT OIL COMPOSITION |
PCT/JP2005/000913 WO2005073351A1 (ja) | 2004-01-30 | 2005-01-25 | 潤滑油添加剤及びそれを含有する潤滑油組成物 |
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JP2004024309A JP4594626B2 (ja) | 2004-01-30 | 2004-01-30 | 内燃機関潤滑油用又は駆動系潤滑油用潤滑油組成物 |
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JP2005213452A5 JP2005213452A5 (ja) | 2007-01-25 |
JP4594626B2 true JP4594626B2 (ja) | 2010-12-08 |
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US (1) | US20070155636A1 (ja) |
EP (1) | EP1717298A4 (ja) |
JP (1) | JP4594626B2 (ja) |
CA (1) | CA2552671A1 (ja) |
WO (1) | WO2005073351A1 (ja) |
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JP4927349B2 (ja) * | 2005-05-11 | 2012-05-09 | 出光興産株式会社 | 冷凍機油組成物、これを用いた圧縮機及び冷凍装置 |
WO2007128740A1 (en) * | 2006-05-03 | 2007-11-15 | Shell Internationale Research Maatschappij B.V. | Lubricating oil composition |
EP1970432A1 (en) * | 2006-12-19 | 2008-09-17 | Castrol Limited | Lubricating oil compositions and uses |
JP2010053352A (ja) * | 2008-07-31 | 2010-03-11 | Sanyo Chem Ind Ltd | 潤滑油添加剤及び潤滑油組成物 |
KR102005477B1 (ko) * | 2009-05-15 | 2019-07-30 | 더루우브리졸코오포레이션 | 4차 암모늄 아미드 및/또는 에스테르 염 |
US20120010112A1 (en) | 2010-07-06 | 2012-01-12 | Basf Se | Acid-free quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
JP5808775B2 (ja) * | 2013-07-05 | 2015-11-10 | 株式会社椿本チエイン | チェーン用潤滑剤組成物及びチェーン |
US9677020B2 (en) * | 2014-06-25 | 2017-06-13 | Afton Chemical Corporation | Hydrocarbyl soluble quaternary ammonium carboxylates and fuel compositions containing them |
US10358616B2 (en) | 2015-04-09 | 2019-07-23 | The Lubrizol Corporation | Lubricants containing quaternary ammonium compounds |
EP3325585B1 (en) * | 2015-07-20 | 2023-03-29 | The Lubrizol Corporation | Zinc-free lubricating composition |
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- 2005-01-25 CA CA002552671A patent/CA2552671A1/en not_active Abandoned
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US20070155636A1 (en) | 2007-07-05 |
WO2005073351A1 (ja) | 2005-08-11 |
EP1717298A4 (en) | 2012-07-11 |
CA2552671A1 (en) | 2005-08-11 |
EP1717298A1 (en) | 2006-11-02 |
JP2005213452A (ja) | 2005-08-11 |
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