200930805 九、發明說明 【發明所屬之技術領域】 本發明爲關於一種潤滑油組成物，其爲使用來自天然 油脂的燃料的內燃機中所使用的潤滑油組成物。 【先前技術】 現今，地球規模的環境規定愈趨嚴格，尤其汽車圍繞 φ 的環境下，燃費規定、排氣規定等逐漸嚴格。鑒於此背景 ，因地球暖化等的環境問題與對石油資源的枯竭之憂慮而 開始資源之保護。 另一方面，地球上存在之植物係吸收大氣中的二氧化 碳、水及太陽光進行光合作用，產生碳水化合物及氧。因 此，由以植物爲原料的植物油所製造之所謂的生物燃料， 以減少地球暖化之主因的二氧化碳、又減少汽車排放之大 氣污染物質的效果等觀點而言係大受注目。又，因植物生 ❹ 物質量的燃燒產生之二氧化碳係認爲爲一種不算增加地球 暖化氣體的碳中和（carbon neutral )，推測今後對烴系之 燃料的生物燃料的混合比例將增加（例如，參照文獻1 : 山根浩二著「生物柴油從天婦羅油炸鍋到燃料槽」東京圖 書出版社、2006年5月發行）。 於內燃機、尤其柴油機中，爲減輕因煤等的懸浮微粒 (particulate matter) ( ρΜ )或ΝΟx等之排出氣體成分 而導致環境污染的對策已成爲重要的課題。作爲其對策， 係於汽車內裝置柴油微粒過濾器（DPF)或淨化排出氣體 200930805 之觸媒（氧化或還原觸媒）等的淨化排出氣體之裝置可爲 有效。例如，在柴油機中生成之煤，附著於DPF後經由氧 化、燃燒可被去除。 其中，於柴油機設置DPF的情形，爲使於過濾器積存 的煤燃燒，一般進行燃料之後期噴射（post injection)。 藉由此後期噴射推測對引擎油的燃料稀釋增大，且引擎油 性能降低。尤其生物燃料係因其物性的關係而容易積存於 φ 引擎油中、且生物燃料劣化分解時產生極性化合物，故對 引擎零件（活塞等）的清淨性之不良影響大。例如，因燃 燒生成之金屬氧化物或硫酸鹽、羧酸鹽等而產生過濾器容 易孔堵塞的問題。又，所使用之引擎油的一部份係以燃燒 、排出氣體的方式被排出。因此，潤滑油中的金屬份或硫 份係盡可能以較低的爲佳。進而，減少潤滑油中的憐份及 硫份係於淨化排出氣體之觸媒之劣化對策方面而言亦爲佳 的。 φ 然而’至今尙未有提供十分適合於生物燃料的潤滑油 。又，單純地使潤滑油中之金屬份、磷份、或硫份等的含 量減少反而有損潤滑性之虞。 因此，本發明之主要目的係在於即使柴油機等之內燃 機中使用生物燃料或混合生物燃料的燃料，亦提供潤滑性 及引擎零件之清淨性優異的潤滑油組成物。 【發明內容】 爲解決前述之課題，本發明係爲提供以下表示之潤滑 -5- 200930805 油組成物。 (1) 一種潤滑油組成物’其爲使用燃料的內燃機中 所使用的潤滑油組成物， 其中燃料含有選自由天然油脂、天然油脂的氫化處理 物、天然油脂的酯交換物、及天然油脂之酯交換物的氫化 處理物之中之至少1種， 其特徵係潤滑油基油，爲以潤滑油組成物全量基準計 φ 配合5〜30質量％之l〇〇°C動黏度爲3〜8mm2/s的多元醇 酯（polyolester)及/或100°C動黏度爲3〜8mm2/s的多元 酸酯（polybasic acid ester)。 (2) 如前述之本發明的潤滑油組成物，其爲具有數 平均分子量500〜3500的聚丁烯基，且配合硼（B)與氮 (N )之質量比（B/N )爲0.5以上的聚丁烯基琥珀酸醯亞 胺化合物之硼衍生物、與鹼土類金屬系清淨劑的潤滑油組 成物。 φ ( 3 )如前述之本發明的潤滑油組成物，其中硫酸灰 份爲1 .1質量％以下的潤滑油組成物。 (4 )如前述之本發明的潤滑油組成物’其中以組成 物全量基準計配合0.3質量％以上之酚系抗氧化劑及/或胺 系抗氧化劑的潤滑油組成物。 (5 )如前述之本發明的潤滑油組成物’其中以組成 物全量基準計配合以硼換算量之〇_〇1質量％以上的前述聚 丁烯基琥珀酸醯亞胺化合物之硼衍生物的潤滑油組成物。 (6 )如前述之本發明的潤滑油組成物，其中以組成 -6- 200930805 物全量基準計硫含量爲0 · 5質量％以下的潤滑油組成物。 若依據本發明之潤滑油組成物，於使用燃料（由天然 油脂等所成之所謂的生物燃料）的內燃機中，即使引擎油 中混入生物燃料亦呈現對活塞等之引擎零件具優異的清淨 性。尤其，引擎變爲高溫時之高溫清淨性具優異。又，於 本發明之潤滑油組成物中，因可使D P F中殘存之灰份變少 ，故即使於附有DPF的柴油機使用時，亦不會降低DPF φ 的性能。 又’對於本發明中之天然油脂，係不限定於源自植物 者，亦可含有源自動物者。 發明之實施形態 以下，對於本發明，詳細地說明實施形態。 本發明係爲使用燃料的內燃機中所使用的潤滑油組成 物’其中燃料含有選自天然油脂、天然油脂的氫化處理物 ❹ 、天然油脂的酯交換物、及天然油脂之酯交換物的氫化處 理物之中之至少1種。 其中，天然油脂可使用自然界中廣泛存在之各種的動 植物油脂，以脂肪酸與甘油所成之酯爲主成分的植物油， 例如適於使用的有紅花油、大豆油、菜籽油、棕櫚油、棕 櫚仁油、棉籽油、椰子油、米糠油、芝麻油、蓖麻油、亞 麻仁油、橄欖油、桐油、山茶花油、花生油、木棉籽油、 可可油、木蠟、葵花油、玉米油等。 天然油脂的氫化處理物係指於適當的氫化觸媒的存在 200930805 下將前述之油脂進行所謂加氫者。 其中，氫化觸媒可列舉鎳系觸媒、鉑族（Pt，Pd，Rh，RU )系觸媒、鈷系觸媒、氧化鉻系觸媒、銅系觸媒、餓系觸 媒、銥系觸媒、鉬系觸媒等。又，作爲氫化觸媒，係將上 述觸媒組合2個以上使用亦佳。 天然油脂的酯交換物係指於適當的酯合成觸媒的存在 下，對構成天然油脂的三酸甘油酯進行酯交換反應所得的 φ 酯。例如，藉由使低級醇與油脂於上述酯合成觸媒的存在 下進行酯交換反應，可製造成爲生物燃料的脂肪酸酯。低 級醇係作爲酯化劑使用，可列舉甲醇、乙醇、丙醇、丁醇 、戊醇等碳數5以下的醇，而以反應性、成本之點而言以 甲醇爲佳。此種低級醇係一般對油脂而言使用當量以上的 量。 又，天然油脂之酯交換物的氫化處理物，係指於適當 的氫化觸媒的存在下將前述酯交換物進行加氫者。 φ 天然油脂、天然油脂的氫化處理物、天然油脂的酯交 換物、及天然油脂之酯交換物的氫化處理物，係添加於以 輕油等之烴所構成的燃料中成爲混合燃料亦可適於使用。 本發明之潤滑油組成物中所使用之潤滑油基油，至少 有使用多元醇酯及/或多元酸酯。 作爲多元醇酯’可列舉脂肪族多元醇與直鏈狀或分支 狀的脂肪酸所成之酯。作爲形成此多元醇酯的脂肪族多元 醇，係有新戊二醇、三羥甲基丙烷、二-三羥甲基丙烷、 三羥甲基乙烷、二-三羥甲基乙烷、季戊四醇、二季戊四 -8- 200930805 醇、及三季戊四醇等。又，作爲脂肪酸，可使用 12者，且尤其佳的脂肪酸係可列舉壬酸、癸酸、 十二酸、及十三酸。又，亦可使用上述之脂肪族 直鏈狀或分支狀的脂肪酸所成之部分酯。此等部 由適宜調整脂肪族多元醇與脂肪酸的反應莫耳數 應而求得。 本發明中之多元醇酯係100°C動黏度爲3〜 φ 且較佳爲4〜7mm2/s、更佳爲5〜6mm2/s。100°C 度爲3mm2/s以上則蒸發損失少，且又動黏度爲： 下，則可抑制因抗黏性而致之動力損失’可獲得 之效果。 作爲本發明中之多元酸酯’係羧酸成分以碳 之直鏈狀或分支狀的脂肪族二元酸爲佳’具體地 二酸、庚二酸、辛二酸、壬二酸、癸二酸、及具 同等性質者。又，作爲醇成分以碳數6〜15的脂 〇 佳，具體地可列舉已醇、庚醇、辛醇、壬醇、癸 醇、十二醇、十三醇、十四醇及十五醇，以及此 體。 本發明中之多元酸醋係100°c動黏度爲3〜 較佳爲4〜7mm2/s、更佳爲5〜6mm2/s。100°C時 爲3mm2/s以上則蒸發損失少’且又動黏度爲8m ，則可抑制因抗黏性而致之動力損失’可獲得改 效果。 上述之多元醇酯、多元酸酯係可各自作爲單 碳數8〜 Ί--酸、 多元醇與 分酯係藉 ，使之反 8mm2/s > 時之動黏 Smm2/s 以 改善燃費 數 6〜1 0 可列舉己 有與此等 肪族醇爲 醇、-(— 等之異構 8mm2/s， 之動黏度 m2/s以下 善燃費之 獨之基油 -9 - 200930805 使用或亦可混合使用。例如，亦可作爲複合酯（complex ester )使用。複合酯係指以多元酸與多元醇作爲原料所合 成之酯，通常原料中亦含有一元酸。於本發明中合適地可 使用有脂肪族多元醇、碳數8〜12之直鏈狀或分支狀的脂 肪族單羧酸、直鏈狀或分支狀的脂肪族二元酸、或由芳香 族二兀1酸、三元酸、四元酸所成之複合醋。 複合酯之形成所使用之脂肪族多元醇，係可使用三羥 φ 甲基丙烷、三羥甲基乙烷、季戊四醇、及二季戊四醇等。 又’作爲脂肪族單羧酸可列舉碳數8〜12的脂肪族單羧酸 ，例如十七酸、十八酸、十九酸、廿烷酸、二十二酸、及 廿四酸。作爲脂肪族二元酸，可列舉琥珀酸、己二酸、庚 二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二 酸、十三烷二酸、羧基十八烷酸、羧基甲基十八烷酸、及 廿二烷二酸等。又，作爲芳香族二元酸可列舉苯二甲酸、 異苯二甲酸等；作爲芳香族三元酸係有偏苯三甲酸等；作 φ 爲芳香族四元酸係有均苯四甲酸等。 使用複合酯作爲本發明之潤滑油組成物中所使用之潤 滑油基油時，較佳的黏度範圍亦與上述之多元醇酯或多元 酸酯相同。 用於製造上述之各種酯的酯化反應，例如使醇（多元 醇等）與羧酸（脂肪族多元酸或芳香族多元酸等）以所定 的比例反應即可。或者進行部分酯化，接著使其部分酯化 物與羧酸反應亦可，又亦可逆向進行酸的反應順序，或亦 可混合酸供予酯化反應。 -10- 200930805 上述之多元醇酯及/或多元酸酯的含量係以潤滑油組 成物全量基準計爲5〜30質量％、較佳爲10〜25質量％、 更佳爲10〜20質量％。多元醇酯及/或多元酸酯的含量低 於5質量％時，變高溫的引擎內之清淨性不足，另一方面 ，超過3 0質量％時對橡膠的影響變大而不佳。 又，基油方面係將作爲內燃機用潤滑油的基油所使用 的礦物油或合成油之中之任意者，混於上述之多元醇酯或 φ 多元酸酯作使用。 作爲礦物油，可列舉如將原油常壓蒸餾後而得之常壓 殘油予以減壓蒸餾所得的潤滑油餾份進行溶劑脫瀝青、溶 劑萃取、氫解作用、溶劑脫蠟、接觸脫蠟、加氫精製等之 1個以上的處理而純化爲礦物油、或者將蠟、GTL ( Gas-To-Liquid) WAX藉由異構化所製造的礦物油等。 另一方面，合成油係可列舉如聚丁烯、聚烯烴〔α-烯 烴均聚物或共聚物等〕、各種的醚（例如，聚苯基醚等） 〇 、聚乙二醇、烷基苯、烷基萘等。此等合成油之中，尤其 以黏度特性及蒸發性之點而言聚烯烴爲佳。 本發明中混合多元醇酯或多元酸酯所使用之基油，係 可使用1種上述礦物油、亦可組合2種以上。又，可使用 1種上述合成油、亦可組合2種以上使用。進而，亦可組 合1種以上之礦物油與1種以上之合成油。混合此等基油 來使用的情形，亦以於基油全體之l〇(TC動黏度爲3〜 8mm2/s的範圍爲佳。i〇〇°C時之動黏度爲3mm2/s以上時 則蒸發損失少，且又8mm2/S以下則可抑制因抗黏性而致 -11 - 200930805 之動力損失’可獲得改善燃費之效果。 混合多元醇酯或多元酸酯所使用之 使用環分析之％CA爲3以下且硫份的名 以下者。其中’環分析之％ C A係表示藉 算出之芳香族份的比例（百分比）。又 (Japanese Industrial Standard，以下中 測定之値。 0 %CA爲3以下，且硫份爲50質量 可提供一種潤滑油組成物，其爲呈現良 可抑制酸値的上升或淤渣生成，同時， 。更佳的硫份爲30質量ppm以下。又 以下、進而佳爲0.5以下。 又，多元醇酯或多元酸酯及混合此 度指數，爲70以上爲佳、更佳爲1〇〇 12〇以上。此黏度指數爲70以上的基油 〇 黏度變化爲小。 本發明之潤滑油組成物中，具有數 3500的聚丁烯基，且以含有硼（B) m (B/N)爲0.5以上之聚丁烯基琥珀酸 衍生物、與鹼土類金屬系清淨劑爲佳。 此種聚丁烯基琥珀酸醯亞胺化合物 ，使（a)以數平均分子量500〜3500 的琥珀酸或者其酐、（b)聚伸烷基聚S 物進行反應可得之。 礦物油，係較佳可 Γ量爲50質量ppm 由環分析n-d-M法 ，硫份爲依據JIS 3同）K 254 1進行 ppm以下的基油係 好的氧化穩定性且 對金屬之腐蝕性少 ，更佳的％CA爲1 等使用之基油的黏 以上、進而較佳爲 係因溫度之變化的 平均分子量 5 00〜 氮（N )之質量比 醯亞胺化合物的硼 的硼衍生物係例如 的聚丁烯基所取代 定、及（c)硼化合 -12- 200930805 作爲原料（a)，使用以聚丁烯基所取代之琥珀酸或 其酐°此聚丁烯基的數平均分子量（以下，有時略稱分子 量或Μη。）爲 500〜3500、較佳爲 1000〜3000。此聚丁 烯基的分子量低於5 00時，最終求得之琥珀酸醯亞胺化合 物的硼衍生物有無法充分溶解於潤滑油基油等的情形，又 ’分子量超過3500時，琥珀酸醯亞胺化合物變爲高黏度 ’有其操作上變困難的情形。 φ 以作爲原料（a)的聚丁烯基所取代之琥珀酸或其酐 ’係使該當於其聚丁烯基的分子量之聚丁烯與順丁烯二酸 酐以周知的方法進行反應即可。 作爲原料（b )係使用聚伸烷基聚胺，但以使用全體 之5莫耳％以上於末端具有環構造之聚伸烷基聚胺爲佳。 亦可原料（b)全體於末端具有環構造之聚伸烷基聚胺、 或者亦可爲末端具有環構造之聚伸烷基聚胺與末端不具有 環構造之聚伸烷基聚胺所成的混合物。末端具有環構造之 〇 聚伸烷基聚胺的比例爲5莫耳％以上時，本發明之目的之 引擎零件的清淨性更爲優異。聚伸烷基聚胺的比例若爲10 莫耳％以上 '進而20莫耳％以上，則更提昇清淨性，尤其 高溫下之清淨性具優異。 作爲原料（c )係使用硼化合物。此硼化合物，可列 舉如硼酸，硼酸酐、硼酸酯、氧化硼、鹵化硼等。其中亦 以硼酸爲特佳。 本發明中之聚丁烯基琥珀酸醯亞胺化合物的硼衍生物 ，可使上述原料（a)與原料（b)及原料（c)進行反應 -13- 200930805 求得。此反應方法係無特別限制，以周知的方法進行即可 。例如，以以下之方法使之反應，可求得目的物。首先， 使原料（a)與原料（b)反應，接著使其反應生成物與原 料（e)反應。關於原料（a)與原料（b)的反應中之原 料（a)與（b)的配合比例，以（a) ： (b)爲0.1〜1〇 -1 (莫耳比）爲佳、0.5〜2: 1 (莫耳比）爲更佳。又， 關於原料（a)與原料（b)的反應溫度，以約80〜250。〇 爲佳、約100〜2 OOt更佳。進行反應之際，在原料之操作 上 '或視需要而用於調整反應之溶劑，亦可使用例如烴油 等的有機溶劑。 接著，將如上述進行所得之原料（a)與（b)的反應 生成物與原料（c)進行反應。爲此反應原料（c)的硼化 合物之配合比例，係對聚伸烷基聚胺而言，一般以莫耳比 爲1:0.〇5〜10爲佳、1:0.5〜5更佳。又，關於反應溫 度，一般較佳爲約50〜250 °C、更佳爲1〇〇〜200 °C。再者 Φ ，進行反應之際，與原料（a)與（b)的反應相同地爲調 整操作上及反應，視需要亦可使用溶劑、例如烴油等的有 機溶劑。 經由上述反應，可獲得以生成物之以數平均分子量 200〜3 5 00的聚丁烯基所取代之琥珀酸醯亞胺化合物的硼 衍生物。本發明中，亦可單獨使用1種此種硼衍生物、亦 可組合2種以上使用。 本發明之潤滑油組成物中之聚丁烯基琥珀酸醯亞胺化 合物之硼衍生物的配合量，係以組成物全量基準計、以硼 -14- 200930805 (原子）換算之0.01質量°/❶以上者爲佳。更佳] 0.2質量％、進而佳爲0.01〜0.15質量％、最佳: 0.1質量％。 又，該硼衍生物中所含之硼，因存在有一定 故潤滑油組成物中即使混入生物燃料，於高溫的 仍可得高活塞清淨性。該硼衍生物的配合量低於 量％則無法獲得充分的高溫清淨性。又，硼含量 φ 質量％，亦無法顯現出對於高溫清淨性有更進一 缺乏實用性。 於是，該硼衍生物中之硼（B)與氮（N)的 B/N)係以0·5以上爲佳、更佳爲0.6以上、進 0_8以上。Β/Ν爲0.5以上時，於高溫下之引擎零 性可大幅提昇。 又，硼化琥珀酸醯亞胺系化合物係如上述地 a)與（b)進行反應，接著使其反應生成物與房 φ 反應而可求得，但改變反應順序，首先使原料（ )反應，其後使其反應生成物與（b)反應亦可 得目的之硼化琥珀酸醯亞胺化合物。 於本發明之潤滑油組成物中，以與前述之聚 珀酸醯亞胺化合物的硼衍生物同時配合鹼土類金 劑爲佳。 鹼土類金屬系清淨劑，適宜地可列舉如，鹼 磺酸鹽、鹼土類金屬酚鹽、鹼土類金屬水楊酸鹽 中選出之2種以上的混合物。 爲0 · 0 1〜 爲0.0 1〜 量以上， 內燃機中 〇.〇1 質 超過0.2 步提昇係 質量比（ 而較佳爲 件的清淨 使原料（ ί 料（C ) a)與（c 同樣地求 丁烯基琥 屬系清淨 土類金屬 及由此等 -15- 200930805 作爲鹼土類金屬磺酸鹽，可列舉將分子量300〜1,500 、較隹400〜7〇0的烷基芳香族化合物經由磺化而得的烷 基芳香族磺酸的鹼土類金屬鹽，尤其鎂鹽及/或鈣鹽等， 其中亦以鈣鹽較適於使用。 作爲鹼土類金屬酚鹽，可列舉烷基酚、烷基酚硫化物 、烷基酚之曼尼希（Mannich )反應物的鹼土類金屬鹽， 尤其鎂鹽及/或鈣鹽等，其中亦以鈣鹽較適於使用。 作爲鹼土類金屬水楊酸鹽，可列舉烷基水楊酸的鹼土 類金屬鹽、尤其鎂鹽及/或鈣鹽等，其中亦以鈣鹽較適於 使用。構成前述鹼土類金屬系清淨劑的烷基，以碳數4〜 30者爲佳、更佳爲6〜18的直鏈或分支烷基，此等可爲直 鏈或分支。又此等此亦可爲1級烷基、2級烷基或3級烷 基。 又，作爲鹼土類金屬磺酸鹽、鹼土類金屬酚鹽及鹼土 類金屬水楊酸鹽，係使前述的烷基芳香族磺酸、烷基酚、 院基酣硫化物、院基酣之曼尼希（Mannich )反應物、院 基水楊酸等直接與鎂及/或鈣之鹼土類金屬的氧化物或氫 氧化物等的鹼土類金屬鹼反應，或藉由一度使鈉鹽或鉀鹽 等之鹼金屬鹽被取代爲鹼土類金屬鹽等而可獲得中性驗土 類金屬磺酸鹽、中性鹼土類金屬酚鹽及中性鹼土類金屬水 楊酸鹽，但不僅如此，亦含有鹼性鹼土類金屬磺酸鹽、驗 性鹼土類金屬酹鹽及鹼性鹼土類金屬水楊酸鹽，其係中性 鹼土類金屬磺酸鹽、中性鹼土類金屬酚鹽及中性鹼土類金 屬水楊酸鹽在水的存在下與過剩的鹼土類金屬鹽或鹼土類 -16- 200930805 金屬鹼經由加熱可得；或含有高鹼性鹼土類金屬磺酸鹽、 高鹼性鹼土類金屬酚鹽及高鹼性鹼土類金屬水楊酸鹽，其 係使中性鹼土類金屬磺酸鹽、中性鹼土類金屬酚鹽及中性 鹼土類金屬水楊酸鹽在碳酸氣體的存在下與鹼土類金屬之 碳酸鹽或硼酸鹽反應而可得。 本發明中，鹼土類金屬系清淨劑之較佳的配合量，以 鹼土類金屬換算量爲0.35質量％以下、更佳爲0.01〜0.35 φ 質量％、進而較佳爲0.1〜0.35質量％。鹼土類金屬系清淨 劑的配合量爲〇 . 〇 1質量％以上時，成爲具有氧化穩定性、 鹼値維持性及高溫清淨性之優異的潤滑油組成物。另一方 面，鹼土類金屬系清淨劑的配合量超過0.35質量％時，恐 有引起淨化排出氣體之觸媒的性能降低之虞。又，應用於 附有DPF的柴油機的情形，朝DPF的灰份附著量變多， 有使DPF之使用壽命變短之虞。 於本發明之潤滑油組成物中，作爲抗氧化劑係以配合 φ 酚系抗氧化劑及/或胺系抗氧化劑爲佳。 作爲酚系抗氧化劑，可列舉如十八基-3- ( 3,5-二-tert-丁基-4-羥基苯基）丙酸酯、4,4’-亞甲基雙（2,6-二-t-丁基酚）；4,4’-雙（2,6-二-t-丁基酚）；4,4’-雙（2-甲 基-6-t-丁基酚）；2,2’-亞甲基雙（4-乙基-6-t-丁基酚）； 2,2’-亞甲基雙（4-甲基-6-t-丁基酚）；4,4’-亞丁基雙（3-甲基-6-t-丁基酚）；4,4’-異亞丙基雙（2,6-二-t-丁基酚） ;2,2’-亞甲基雙（4-甲基-6-壬基酚）；2,2’-異亞丁基雙 (4,6-二甲基酚）；2，2’-亞甲基雙（4-甲基-6-環己基酚） -17- 200930805 ;2,6-二-t-丁基-4-甲基酚；2,6-二-卜丁基-4-乙基酚' 二甲基-6-t-丁 基酚；2,6-二-t-胺基-P-甲酚；2,6·二 基-4- (N，N，-二甲基胺基甲基酚）；4,4’-硫代雙（2_ 6 4-丁基酚）；4，4，-硫代雙（3-甲基-6-t-丁基酚）； 硫代雙（4-甲基-6-t-丁基酚）·，雙（3-甲基-4_羥基-5 基苄基）硫化物；雙（3,5-二-t-丁基-4-羥基苄基）硫 ;η-辛基-3- (4-羥基-3,5-二-t-丁基苯基）丙酸酯、n. φ 基-3- ( 4-羥基-3,5-二-t-丁基苯基）丙酸酯；2,2’ 〔二乙基-雙-3-(3,5-二-t-丁基-4-羥基苯基）丙酸酯 。此等中，尤其雙酚系及含酯基之酚系者爲合適。 又，作爲胺系抗氧化劑，可列舉如單辛基二苯基 單壬基二苯基胺等的單烷基二苯基胺系、4,4’ -二丁 苯基胺；4,4’ -二戊基二苯基胺；4,4’ -二己基二苯 ;4,4’ -二庚基二苯基胺；4,4’ -二辛基二苯基胺；4 二壬基二苯基胺等的二烷基二苯基胺系、四丁基二苯 〇 :四已基二苯基胺；四辛基二苯基胺；四壬基二苯基 的聚烷基二苯基胺系、及萘胺系者，具體地有α-萘胺 基-α-萘胺；又，丁基苯基-α_萘胺；戊基苯基-α_萘胺 基苯基-α-萘胺；庚基苯基-α-萘胺；辛基苯基-α_萘胺 基苯基-α-萘胺等的烷基取代之苯基-α_萘胺等。此等 二垸基二苯基胺系及萘胺系者爲合適。 又’其它的抗氧化劑係亦可使用鉬胺錯合物系抗 劑。作爲鉬胺錯合物系抗氧化劑，有6元的鉬化合物 體地係使三氧化鉬及/或鉬酸與胺化合物反應而成者 ；2,4--t-丁 甲基-2,2’-I - t - 丁 化物 -十八 -硫代 〕等 胺； 基二 基胺 ,4，- 基胺 胺等 :苯 ;己 :壬 中以 氧化 ，具 ，例 -18- 200930805 如可使用於日本特開2003 -25 2 8 87號公報中記載之製造方 法求得的化合物。作爲與6元之鉬化合物反應的胺化合物 ’係無特別限制，而具體地係可列舉單胺、二胺、聚胺及 烷醇胺。更具體地係可例示甲胺、乙胺、二甲胺、二乙胺 、甲基乙基胺、甲基丙基胺等的具有碳數1〜30之烷基（ 此等之烷基可爲直鏈狀或分支狀）的烷基胺；乙烯基胺、 丙烯基胺、丁烯基胺、辛烯基胺、及油烯基胺等的具有碳 ❹ 數2〜30之烯基（此等之烯基可爲直鏈狀或分支狀）的烯 基胺；甲醇胺、乙醇胺、甲醇乙醇胺、甲醇丙醇胺等的具 有碳數1〜30之烷醇（此等之烷醇可爲直鏈狀或分支狀） 的烷醇胺；亞甲二胺、乙二胺、丙二胺及丁二胺等的具有 碳數1〜30之伸烷基的伸烷基二胺；二乙三胺、三乙四胺 、四乙五胺、五乙六胺等的聚胺；十一基二乙胺、十一基 二乙醇胺、十二基二丙醇胺、油烯基二乙醇胺、油烯基丙 二胺、硬脂醯四乙五胺等的上述單胺、二胺、聚胺中具有 φ 碳數8〜20之烷基或烯基的化合物或咪唑啉等的雜環化合 物；此等化合物的環氧烷加成物：及此等混合物等。又， 可例示日本特公平3-2243 8號公報及特開2004-2866號公 報中所記載之琥珀酸醯亞胺之含硫之鉬錯合物等。 上述之抗氧化劑的配合量，以組成物全量基準計爲以 0.3質量％以上爲佳、0.5質量％以上更佳。另一方面，超 過2質量％時，有變成不溶於潤滑油基油之虞。因此，抗 氧化劑的配合量以組成物全量基準計爲以0.3〜2質量％的 範圍爲佳。 -19- 200930805 於本發明之潤滑油組成物中，在不損及本發明之 的範圍內，視需要亦可配合其它的添加劑，例如黏度 提昇劑、流動點下降劑、抗磨劑、無灰系摩擦減低劑 鏽劑、金屬惰性化劑、界面活性劑、及消泡劑等。 作爲黏度指數提昇劑，可列舉如聚甲基丙烯酸酯 散型聚甲基丙烯酸酯、烯烴系共聚物（例如，乙烯-共聚物等）、分散型烯烴系共聚物、苯乙烯系共聚物 Φ 如，苯乙烯-二烯共聚物、苯乙烯-異戊二烯共聚物等 。此等黏度指數提昇劑的配合量，以配合效果之觀點 ，以組成物全量基準計爲以0.5〜1 5質量％左右、較 1〜1 〇質量％。 作爲流動點下降劑，可列舉如質量平均分子量爲 〜50,000左右的聚甲基丙烯酸酯等。 作爲抗磨劑，可列舉如二硫代磷酸鋅、二硫代胺 鋅、磷酸鋅、二硫化物類、硫化烯烴類、硫化油脂類 φ 化酯類、硫代碳酸酯類、硫代胺甲酸酯類（例如， DTC )等的含硫之化合物；亞磷酸酯類、磷酸酯類、 酯類、及此等胺鹽或金屬鹽等的含磷之化合物；硫代 酸酯類、硫代磷酸酯類（例如，Mo-DTP)、硫代膦 類、及此等胺鹽或金屬鹽等的含硫及磷之抗磨劑。 作爲無灰系摩擦減低劑，可使用作爲潤滑油用之 系摩擦減低劑一般所使用之任意的化合物，可列舉如 子中具有至少1個碳數6〜30的烷基或烯基的脂肪酸 肪族醇、脂肪族醚、脂肪族酯、脂肪族胺及脂肪族醯 效果 指數 、防 、分 丙烯 (例 )等 而言 佳爲 5000 甲酸 、硫 Mo- 膦酸 亞磷 酸酯 無灰 於分 、脂 胺等 -20- 200930805 作爲防鏽劑，可列舉如石油磺酸鹽、烷基苯磺酸鹽、 二壬基萘磺酸鹽、烯基琥珀酸酯、多元醇酯等。此等防鏽 劑的配合量，以配合效果之觀點而言以組成物全量基準計 ’ 一般爲0.01〜1質量％左右、較佳爲0.05〜0.5質量％。 作爲金屬惰性化劑（銅腐蝕防止劑），可列舉如苯并 三唑系、甲苯基三唑系、噻二唑系、咪唑系及嘧啶系化合 〇 物等。於此之中以苯并三唑系化合物爲佳。因配合金屬惰 性化劑，故可抑制引擎零件之金屬腐鈾及氧化劣化。此等 金屬惰性化劑的配合量，以配合效果之觀點而言，以組成 物全量基準計較佳爲0.01〜0.1質量％、更佳爲0.03〜 0 · 0 5質量％。 作爲界面活性劑，可列舉如聚氧化乙烯烷基醚、聚氧 化乙烯烷基苯基醚及聚氧化乙烯烷基萘基醚等的聚伸烷基 乙二醇系非離子性界面活性劑等。 〇 作爲消泡劑，可列舉如矽油、氟矽油及氟烷基醚等’ 以消泡效果及經濟性之平衡等之觀點而言，依據組成物全 .量以配合0.005〜0.1質量％左右爲佳。 本發明之潤滑油組成物中，硫含量以組成物全量基準 計爲0.5質量％以下爲佳、〇_3質量％以下更佳、進而較佳 爲0.2質量％以下。硫含量爲0.5質量％以下時，可有效地 抑制淨化排出氣體之觸媒的性能降低。 本發明之潤滑油組成物中，磷含量以組成物全量基準 計爲0.12質量％以下爲佳、更佳爲〇·1質量％以下。磷含 -21 - 200930805 量爲〇. 1 2質量％以下時’可有效地抑制淨化排出氣體之觸 媒的性能降低。 又，本發明之潤滑油組成物中，硫酸灰份以1.1質量 %以下爲佳、1質量％以下爲更佳。硫酸灰份爲1 ·1質量％ 以下時，可有效地抑制淨化排出氣體之觸媒的性能降低° 又，於柴油機中，於DPF之過濾器堆積的灰份量少’可抑 制該過濾器之灰份堵塞，使DPF之壽命變長。又，此硫酸 φ 灰份係指於燃燒試料生成之碳化殘留物中加入硫酸後進行 加熱成爲恆量的灰份，一般爲用於了解潤滑油組成物中之 金屬系添加劑大約的量而使用。具體地’藉由JIS κ 2272 之「5 .硫酸灰份試驗方法」中所規定之方法來測定。 又，內燃機中潤滑油的蒸發性增大’係招致潤滑油本 身的消耗量增加且因此而潤滑油壽命降低、進而引起朝排 出氣體觸媒的飛散量增大導致觸媒能力·壽命的降低。從 此觀點而言，本發明之潤滑油組成物中’依據JPI ( JaPan 鲁 Petroleum Institute，以下相同）-5S-41-93 所測定之 NOACK蒸發量以1 5質量％以下爲佳、更佳爲13質量％以 下、進而較佳爲1 〇質量％以下。 【實施方式】 〔實施例〕 接著，藉由實施例進一步詳細說明本發明’但本發明 不受此等例子給任何限定。 -22- 200930805 〔實施例1〜7、比較例1〜4〕 調製具有表1中所示之配合組成的潤滑油組成物，進 行以下所示之熱管（hot tube )試驗。又，於潤滑油組成 物之調製使用的各成分之種類，係如下述。 (1)基油A:加氫精製基油、4(TC動黏度21mm2/s、 100°C動黏度4.5mm2/s、黏度指數127、％CA 0·0、硫含量 低於20質量ppm、N0ACK蒸發量13.3質量％BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricating oil composition which is a lubricating oil composition used in an internal combustion engine using a fuel derived from natural fats and oils. [Prior Art] Nowadays, the environmental regulations on the scale of the earth are becoming more and more strict, especially in the environment around the φ, the fuel consumption regulations and exhaust regulations are becoming stricter. In view of this background, resource protection has begun due to environmental problems such as global warming and worries about the depletion of petroleum resources. On the other hand, plants present on the earth absorb carbon dioxide, water and sunlight from the atmosphere for photosynthesis, producing carbohydrates and oxygen. Therefore, the so-called biofuels produced from plant-derived vegetable oils have attracted attention from the viewpoints of reducing carbon dioxide, which is the main cause of global warming, and reducing the effects of atmospheric pollutants emitted by automobiles. In addition, carbon dioxide produced by the combustion of plant biomass is considered to be a carbon neutral that does not increase the global warming gas, and it is speculated that the proportion of biofuel blended for hydrocarbon-based fuels will increase in the future ( For example, reference 1: Yamaguchi follows "Biodiesel from tempura frying pan to fuel tank" Tokyo Book Publishing House, issued in May 2006). In an internal combustion engine, particularly a diesel engine, measures to reduce environmental pollution caused by exhaust gas components such as particulate matter (ρΜ) or ΝΟx have become an important issue. As a countermeasure against this, an apparatus for purifying exhaust gas such as a diesel particulate filter (DPF) in an automobile or a catalyst (oxidation or reduction catalyst) for purifying the exhaust gas 200930805 can be used. For example, coal generated in a diesel engine can be removed by oxidation and combustion after being attached to the DPF. Among them, in the case where the diesel engine is provided with a DPF, in order to burn the coal accumulated in the filter, post-fuel injection is generally performed. By this late injection, it is presumed that the fuel dilution of the engine oil is increased, and the engine oil performance is lowered. In particular, biofuels are easily accumulated in φ engine oil due to their physical properties, and polar compounds are generated when biofuel is degraded and decomposed. Therefore, the adverse effects on the detergency of engine parts (pistons, etc.) are large. For example, there is a problem that the filter is easily clogged by a metal oxide or a sulfate, a carboxylate or the like which is generated by burning. Further, a part of the engine oil used is discharged by burning and exhausting gas. Therefore, the metal or sulfur in the lubricating oil is preferably as low as possible. Further, it is also preferable to reduce the pity and sulfur in the lubricating oil in terms of countermeasures against deterioration of the catalyst for purifying the exhaust gas. Φ However, there has not been a lubricant that is very suitable for biofuels. Further, simply reducing the content of the metal component, the phosphorus component, or the sulfur component in the lubricating oil adversely affects the lubricity. Therefore, the main object of the present invention is to provide a lubricating oil composition excellent in lubricity and detergency of engine parts even in the case of using a biofuel or a fuel mixed with biofuel in an internal combustion engine such as a diesel engine. SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a lubricating composition of the following -5-200930805 oil composition. (1) A lubricating oil composition which is a lubricating oil composition used in an internal combustion engine using a fuel, wherein the fuel contains a transesterified product selected from natural fats and oils, natural fats and oils, natural fats and oils, and natural fats and oils. At least one of the hydrogenated products of the transesterified product is characterized in that the lubricating base oil is 以 with a total amount of the lubricating oil composition, and the dynamic viscosity of the mixture is 5 to 30% by mass, and the dynamic viscosity is 3 to 8 mm 2 . /s polyolster (polyoleic acid ester) and / or 100 ° C dynamic viscosity of 3 ~ 8mm2 / s polybasic acid ester (polybasic acid ester). (2) The lubricating oil composition of the present invention as described above, which is a polybutenyl group having a number average molecular weight of 500 to 3,500, and a mass ratio (B/N) of boron (B) to nitrogen (N) is 0.5. A lubricating oil composition of a boron derivative of the above polybutenyl succinic acid imide compound and an alkaline earth metal-based detergent. Φ (3) The lubricating oil composition of the present invention as described above, wherein the ash content of the lubricating oil is 1.1% by mass or less. (4) A lubricating oil composition of the present invention, wherein a lubricating oil composition of 0.3% by mass or more of a phenol-based antioxidant and/or an amine-based antioxidant is added in an amount based on the total amount of the composition. (5) The above-mentioned lubricating oil composition of the present invention, wherein the boron derivative of the above polybutenyl succinic acid imide compound is added in an amount of 〇_〇1% by mass or more based on the total amount of the composition. Lubricant composition. (6) The lubricating oil composition of the present invention as described above, wherein the lubricating oil composition has a sulfur content of 0.5% by mass or less based on the total amount of the composition -6-200930805. According to the lubricating oil composition of the present invention, in an internal combustion engine using a fuel (a so-called biofuel made of natural oil or the like), even if the engine oil is mixed with the biofuel, it exhibits excellent detergency to engine parts such as pistons. . In particular, the high-temperature detergency is excellent when the engine is turned to a high temperature. Further, in the lubricating oil composition of the present invention, since the amount of ash remaining in the D P F can be reduced, the performance of the DPF φ is not lowered even when used in a diesel engine with a DPF. Further, the natural fats and oils in the present invention are not limited to those derived from plants, and may also be derived from animals. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The present invention relates to a lubricating oil composition used in an internal combustion engine using a fuel, wherein the fuel contains a hydrotreating agent selected from the group consisting of natural fats and oils, hydrotreated substances of natural fats and oils, transesterified natural fats, and transesterified products of natural fats and oils. At least one of the objects. Among them, natural oils and fats can be used as various vegetable oils and fats widely found in nature, and vegetable oils mainly composed of fatty acid and glycerin. For example, safflower oil, soybean oil, rapeseed oil, palm oil, and palm are suitable for use. Kernel oil, cottonseed oil, coconut oil, rice bran oil, sesame oil, castor oil, linseed oil, olive oil, tung oil, camellia oil, peanut oil, kapok seed oil, cocoa butter, wood wax, sunflower oil, corn oil, etc. The hydrotreated product of natural oils and fats refers to the so-called hydrogenation of the aforementioned oils and fats in the presence of a suitable hydrogenation catalyst at 200930805. Among them, examples of the hydrogenation catalyst include a nickel-based catalyst, a platinum group (Pt, Pd, Rh, RU)-based catalyst, a cobalt-based catalyst, a chromium oxide-based catalyst, a copper-based catalyst, a hungry catalyst, and a lanthanide system. Catalyst, molybdenum-based catalyst, etc. Further, as the hydrogenation catalyst, it is also preferred to use two or more of the above catalyst combinations. The transesterified product of natural fats and oils refers to a φ ester obtained by transesterifying a triglyceride constituting a natural fat or oil in the presence of a suitable ester synthesis catalyst. For example, a fatty acid ester which is a biofuel can be produced by performing a transesterification reaction between a lower alcohol and a fat or oil in the presence of the above ester synthesis catalyst. The lower alcohol is used as the esterifying agent, and examples thereof include an alcohol having 5 or less carbon atoms such as methanol, ethanol, propanol, butanol or pentanol, and methanol is preferred in terms of reactivity and cost. Such a lower alcohol is generally used in an amount equivalent to or more than the equivalent amount of the fat or oil. Further, the hydrotreated product of the transesterified product of natural fats and oils refers to the hydrogenation of the above-mentioned transesterified product in the presence of a suitable hydrogenation catalyst. Hydration of natural oils and fats, hydrolyzed products of natural oils and fats, transesterified products of natural oils and fats, and transesterified products of natural oils and fats, added to fuels composed of hydrocarbons such as light oils For use. The lubricating base oil used in the lubricating oil composition of the present invention is at least a polyol ester and/or a polybasic acid ester. The polyol ester' may, for example, be an ester of an aliphatic polyol and a linear or branched fatty acid. As the aliphatic polyol forming the polyol ester, there are neopentyl glycol, trimethylolpropane, di-trimethylolpropane, trimethylolethane, di-trimethylolethane, pentaerythritol. , Dipenta-4-8- 200930805 Alcohol, and tripentaerythritol. Further, as the fatty acid, 12 may be used, and particularly preferred fatty acid compounds include capric acid, capric acid, dodecanoic acid, and tridecanoic acid. Further, a partial ester of the above fatty linear or branched fatty acid may be used. These parts are determined by adjusting the number of moles of the reaction between the aliphatic polyol and the fatty acid. The polyol ester in the present invention has a dynamic viscosity at 100 ° C of 3 to φ and preferably 4 to 7 mm 2 /s, more preferably 5 to 6 mm 2 /s. When the degree of 100 ° C is 3 mm 2 /s or more, the evaporation loss is small, and the dynamic viscosity is: under, the effect of the power loss due to the anti-adhesive property can be suppressed. The polybasic acid ester component in the present invention is preferably a linear or branched aliphatic dibasic acid of carbon. Specifically, diacid, pimelic acid, suberic acid, sebacic acid, and cerium Acid, and of the same nature. Further, the alcohol component is preferably a lipid having 6 to 15 carbon atoms, and specific examples thereof include an alcohol, a heptanol, an octanol, a decyl alcohol, a decyl alcohol, a dodecanol, a tridecyl alcohol, a tetradecanol, and a pentadecyl alcohol. And this body. The polybasic acid vinegar of the present invention has a dynamic viscosity at 100 ° C of 3 to preferably 4 to 7 mm 2 /s, more preferably 5 to 6 mm 2 /s. When the temperature is 3 mm 2 /s or more at 100 ° C, the evaporation loss is small, and the dynamic viscosity is 8 m, the power loss due to the anti-adhesive property can be suppressed. The above polyol esters and polybasic acid esters can each be used as a single carbon number 8 Ί-acid, a polyhydric alcohol and a partial ester system, so as to reverse the dynamic viscosity Smm2/s at 8 mm 2 /s > 6~1 0 can be used as the base oil -9 - 200930805 which has the same as the alcohol, alcohol, -(-, etc., heterogeneous 8mm2/s, the dynamic viscosity m2/s or less For example, it can also be used as a complex ester, which is an ester synthesized by using a polybasic acid and a polyhydric alcohol as a raw material, and usually contains a monobasic acid as a raw material. An aliphatic polyhydric alcohol, a linear or branched aliphatic monocarboxylic acid having a carbon number of 8 to 12, a linear or branched aliphatic dibasic acid, or an aromatic dicarboxylic acid or a tribasic acid, A complex vinegar made of a quaternary acid. The aliphatic polyol used for the formation of a complex ester can be used as trihydroxy φ methyl propane, trimethylolethane, pentaerythritol, dipentaerythritol, etc. The monocarboxylic acid may, for example, be an aliphatic monocarboxylic acid having a carbon number of 8 to 12, such as heptadecanoic acid or octadecanoic acid. , nineteen acid, decanoic acid, behenic acid, and perylenetetracarboxylic acid. As the aliphatic dibasic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , undecanedioic acid, dodecanedioic acid, tridecanedioic acid, carboxy octadecanoic acid, carboxymethyl octadecanoic acid, and decanedioic acid, etc. Also, as an aromatic dibasic acid Examples of the phthalic acid, the isophthalic acid, and the like; the aromatic tribasic acid is trimellitic acid; the φ is the aromatic tetrabasic acid, and the pyromellitic acid is used. The complex ester is used as the lubricating oil of the present invention. The lubricating base oil used in the composition preferably has the same viscosity range as the above-mentioned polyol ester or polybasic acid ester. The esterification reaction for producing the above various esters, for example, an alcohol (polyol, etc.) It may be reacted with a carboxylic acid (aliphatic polybasic acid or aromatic polybasic acid, etc.) in a predetermined ratio, or may be partially esterified, and then a part of the esterified product may be reacted with a carboxylic acid, or may be reversely reacted with an acid. The order may be mixed with an acid to provide an esterification reaction. -10- 200930805 The content of the alcohol ester and/or the polybasic acid ester is 5 to 30% by mass, preferably 10 to 25% by mass, more preferably 10 to 20% by mass based on the total amount of the lubricating oil composition. Polyol ester and/or When the content of the polybasic acid ester is less than 5% by mass, the detergency in the engine which becomes high in temperature is insufficient, and on the other hand, when the content exceeds 30% by mass, the influence on the rubber becomes large, and the base oil is used as the base oil. Any of mineral oil or synthetic oil used for the base oil of the lubricating oil for internal combustion engines is used in combination with the above polyol ester or φ polybasic acid ester. As the mineral oil, for example, the crude oil is distilled under normal pressure. The atmospheric oil residue obtained by vacuum distillation is subjected to solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing, contact dewaxing, hydrotreating, and the like to be purified into minerals. Oil, or mineral oil produced by isomerization of wax, GTL (Gas-To-Liquid) WAX. On the other hand, examples of the synthetic oil include polybutene, polyolefin (α-olefin homopolymer or copolymer, etc.), various ethers (for example, polyphenyl ether, etc.), polyethylene glycol, and alkyl group. Benzene, alkylnaphthalene, and the like. Among these synthetic oils, polyolefin is preferred in particular in terms of viscosity characteristics and evaporability. In the present invention, the base oil to be used in the case of mixing the polyol ester or the polybasic acid ester may be one or more kinds of the above-mentioned mineral oils. Further, one type of the above synthetic oil may be used, or two or more types may be used in combination. Further, one or more kinds of mineral oils and one or more kinds of synthetic oils may be combined. When the base oil is mixed and used, it is also preferably in the range of 3 to 8 mm 2 /s of the TC dynamic viscosity of the whole base oil. When the dynamic viscosity at i 〇〇 ° C is 3 mm 2 /s or more, The evaporation loss is small, and below 8mm2/S, the power loss of -11 - 200930805 can be suppressed due to the anti-adhesion property. The effect of improving the fuel consumption can be obtained. The % of the ring analysis used for the mixed polyol ester or polyester ester CA is below 3 and the name of the sulfur is below. Among them, the % of the ring analysis indicates the proportion (percentage) of the calculated aromatics. (Japanese Industrial Standard, the following is measured. 0 % CA is 3 In the following, the sulfur content is 50% to provide a lubricating oil composition, which is capable of suppressing the rise of acid strontium or sludge formation, and more preferably having a sulfur content of 30 ppm by mass or less. Further, the polyol ester or the polybasic acid ester and the blending index are preferably 70 or more, more preferably 1〇〇12〇 or more. The viscosity change of the base oil having a viscosity index of 70 or more is small. The lubricating oil composition of the present invention has a number of 3,500 The butenyl group is preferably a polybutenyl succinic acid derivative containing boron (B) m (B/N) of 0.5 or more and an alkaline earth metal-based detergent. The amine compound is obtained by reacting (a) succinic acid having a number average molecular weight of 500 to 3,500 or an anhydride thereof, and (b) a polyalkylene poly(S). The mineral oil is preferably a mass of 50 ppm by mass. By the ring analysis ndM method, the sulfur content is based on JIS 3 and K 254 1 and the base oil of ppm or less is excellent in oxidation stability and less corrosive to metals, and more preferably, the %CA is 1 used. More preferably, the viscosity is greater than or equal to the average molecular weight of the change in temperature of 500 00 to the mass of nitrogen (N), and the boron derivative of boron of the quinone imine compound is substituted, for example, a polybutenyl group, and (c) Boron compound-12-200930805 As the raw material (a), succinic acid or its anhydride substituted with a polybutenyl group is used. The number average molecular weight (hereinafter, abbreviated as molecular weight or Μη) of the polybutenyl group is 500. 〜3500, preferably 1000~3000. When the molecular weight of the polybutenyl group is less than 500, the final succinic acid is obtained. The boron derivative of the quinone imine compound may not be sufficiently dissolved in the lubricating base oil or the like, and when the molecular weight exceeds 3,500, the yttrium succinimide compound becomes high in viscosity, which may become difficult to handle. The succinic acid or its anhydride which is substituted with the polybutenyl group of the starting material (a) may be reacted with maleic anhydride having a molecular weight of the polybutenyl group by a known method. The raw material (b) is a polyalkylene polyamine, but it is preferably a polyalkylene polyamine having a ring structure of 5 mol% or more at the end. The raw material (b) may be a polyalkylene polyamine having a ring structure at the end, or may be a polyalkylene polyamine having a ring structure at the terminal end and a polyalkylene polyamine having a ring structure at the terminal end. mixture. When the ratio of the fluorene-polyalkylamine having a ring structure at the end is 5 mol% or more, the engine part of the object of the present invention is more excellent in detergency. When the proportion of the polyalkylene polyamine is 10 mol% or more and further 20 mol% or more, the detergency is further improved, and the detergency at a high temperature is excellent. As the raw material (c), a boron compound is used. The boron compound may, for example, be boric acid, boric anhydride, boric acid ester, boron oxide, boron halide or the like. Among them, boric acid is also preferred. The boron derivative of the polybutenyl succinic acid imide compound of the present invention can be obtained by reacting the above raw material (a) with the raw material (b) and the raw material (c) -13-200930805. The reaction method is not particularly limited and may be carried out by a known method. For example, the object can be obtained by reacting it in the following manner. First, the raw material (a) is allowed to react with the raw material (b), and then the reaction product is reacted with the raw material (e). The mixing ratio of the raw materials (a) and (b) in the reaction between the raw material (a) and the raw material (b) is preferably 0.1 to 1 〇 -1 (mole ratio) of (a): (b), 0.5. ~2: 1 (Morbi) is better. Further, the reaction temperature of the raw material (a) and the raw material (b) is about 80 to 250. 〇 is better, about 100~2 OOt is better. When the reaction is carried out, an organic solvent such as a hydrocarbon oil may be used in the operation of the raw material or, if necessary, a solvent for adjusting the reaction. Next, the reaction product of the raw materials (a) and (b) obtained as described above is reacted with the raw material (c). For this reason, the compounding ratio of the boron compound of the starting material (c) is preferably a molar ratio of 1:0. 〇5 to 10, more preferably 1:0.5 to 5, for the polyalkylene polyamine. Further, the reaction temperature is usually preferably from about 50 to 250 ° C, more preferably from 1 to 200 ° C. Further, when Φ is carried out, the reaction is carried out in the same manner as in the reaction of the raw materials (a) and (b), and a solvent, for example, an organic solvent such as a hydrocarbon oil may be used. Through the above reaction, a boron derivative of a succinic acid succinimide compound substituted with a polybutenyl group having a number average molecular weight of 200 to 3,500 can be obtained. In the present invention, one type of such a boron derivative may be used alone or two or more types may be used in combination. The blending amount of the boron derivative of the polybutenyl succinic acid imide compound in the lubricating oil composition of the present invention is 0.01 mass% in terms of boron-14-200930805 (atoms) based on the total amount of the composition. The above is better. More preferably, it is 0.2 mass%, more preferably 0.01 to 0.15 mass%, and most preferably 0.1 mass%. Further, boron contained in the boron derivative may have high piston detergency at a high temperature even if a biofuel is mixed in the lubricating oil composition. When the blending amount of the boron derivative is less than the amount of %, sufficient high-temperature detergency cannot be obtained. Further, the boron content φ mass% does not show a further lack of practicality for high-temperature detergency. Therefore, in the boron derivative, boron (B) and nitrogen (N) B/N) are preferably 0.5 or more, more preferably 0.6 or more, and further preferably 0-8 or more. When Β/Ν is 0.5 or more, the engine zero at high temperatures can be greatly improved. Further, the bismuth borate succinimide compound is obtained by reacting a) with (b) as described above, and then reacting the reaction product with the house φ, but changing the reaction sequence, first reacting the raw material ( ) Thereafter, the reaction product is reacted with (b) to obtain a desired boride succinimide compound. In the lubricating oil composition of the present invention, it is preferred to mix an alkaline earth metal agent with the boron derivative of the above-described bismuth sub-imide compound. The alkaline earth metal-based detergent may, for example, be a mixture of two or more selected from the group consisting of an alkali sulfonate, an alkaline earth metal phenate, and an alkaline earth metal salicylate. It is 0 · 0 1~ is 0.01 1~ or more, and the internal combustion engine has a quality ratio of more than 0.2 steps. (It is better to clean the material so that the raw material (C (a) a) is the same as (c) The butene-based sulphate-based cleansing earth metal and the like -15-200930805, as an alkaline earth metal sulfonate, an alkyl aromatic compound having a molecular weight of 300 to 1,500 and less than 400 to 7 〇 0 is sulfonated. The alkaline earth metal salt of the alkyl aromatic sulfonic acid obtained, especially the magnesium salt and/or the calcium salt, etc., wherein the calcium salt is also suitable for use. As the alkaline earth metal phenate, an alkylphenol or an alkane is mentioned. Alkaline earth metal salts of phenolic sulphates, Mannich reactants of alkylphenols, especially magnesium salts and/or calcium salts, among which calcium salts are also suitable for use. As alkaline earth metal salicylic acid The salt may, for example, be an alkaline earth metal salt of an alkylsalicylic acid, particularly a magnesium salt and/or a calcium salt, and the calcium salt is preferably used. The alkyl group constituting the alkaline earth metal-based detergent is a carbon number. 4 to 30 is preferred, more preferably 6 to 18 linear or branched alkyl, these may be straight or divided Further, this may also be a 1-stage alkyl group, a 2-stage alkyl group or a 3-stage alkyl group. Further, as an alkaline earth metal sulfonate, an alkaline earth metal phenate, and an alkaline earth metal salicylate, The above-mentioned alkyl aromatic sulfonic acid, alkyl phenol, sulfonium sulfide, Mannich reactant, and hospital-based salicylic acid are directly related to magnesium and/or calcium alkaline earth metals. Neutral soil metal sulfonate can be obtained by reacting an alkaline earth metal base such as an oxide or a hydroxide, or by substituting an alkali metal salt such as a sodium salt or a potassium salt for an alkaline earth metal salt. Neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate, but not only this, but also alkaline alkaline earth metal sulfonate, alkaline earth metal strontium salt and alkaline alkaline earth metal salicylate It is a neutral alkaline earth metal sulfonate, a neutral alkaline earth metal phenate and a neutral alkaline earth metal salicylate in the presence of water with excess alkaline earth metal salt or alkaline earth class-16-200930805 metal base Available via heating; or contains an overbased alkaline earth metal sulfonate, an overbased alkaline earth Is a phenolate and an overbased alkaline earth metal salicylate, which is a neutral alkaline earth metal sulfonate, a neutral alkaline earth metal phenate and a neutral alkaline earth metal salicylate in the presence of carbonic acid gas In the present invention, the amount of the alkaline earth metal-based detergent is preferably 0.35% by mass or less, more preferably 0.01 to 0.35, in terms of the amount of the alkaline earth metal-based detergent. 5% by mass, and more preferably 0.1 to 0.35% by mass. The amount of the alkaline earth metal-based detergent is 〇. 〇1% by mass or more, and is excellent in oxidative stability, alkali hydrazine maintenance, and high-temperature detergency. On the other hand, when the amount of the alkaline earth metal-based detergent is more than 0.35% by mass, the performance of the catalyst for purifying the exhaust gas may be degraded. Further, in the case of a diesel engine equipped with a DPF, the amount of ash adhering to the DPF is increased, and the service life of the DPF is shortened. In the lubricating oil composition of the present invention, it is preferred to blend φ phenol-based antioxidant and/or amine-based antioxidant as an antioxidant. Examples of the phenolic antioxidant include octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 4,4'-methylenebis (2,6). -di-t-butylphenol); 4,4'-bis(2,6-di-t-butylphenol); 4,4'-bis(2-methyl-6-t-butylphenol) ; 2,2'-methylenebis(4-ethyl-6-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-butylphenol); , 4'-butylidene bis(3-methyl-6-t-butylphenol); 4,4'-isopropylidene bis(2,6-di-t-butylphenol); 2,2' -methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylene bis(4,6-dimethylphenol); 2,2'-methylenebis(4- Methyl-6-cyclohexylphenol) -17- 200930805; 2,6-di-t-butyl-4-methylphenol; 2,6-di-b-butyl-4-ethylphenol' dimethyl-6 -t-butylphenol; 2,6-di-t-amino-P-cresol; 2,6.diyl-4-(N,N,-dimethylaminomethylphenol); 4'-thiobis(2_6-4-butylphenol); 4,4,-thiobis(3-methyl-6-t-butylphenol); thiobis(4-methyl-6-) T-butylphenol)·, bis(3-methyl-4-hydroxy-5-benzyl) sulfide; bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide; η- Xin -3- (4-hydroxy-3,5-di-t-butylphenyl)propionate, n. φ-yl-3-(4-hydroxy-3,5-di-t-butylphenyl) Propionate; 2,2'[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. Among these, bisphenol-based and ester-containing phenolic compounds are suitable. Further, examples of the amine-based antioxidant include a monoalkyldiphenylamine type such as monooctyldiphenylmonodecyldiphenylamine and 4,4'-dibutylphenylamine; 4,4' -dipentyldiphenylamine; 4,4'-dihexyldiphenyl; 4,4'-diheptyldiphenylamine; 4,4'-dioctyldiphenylamine; 4 dimercaptoyl a dialkyldiphenylamine system such as phenylamine, tetrabutyldibenzoquinone: tetrahexyldiphenylamine; tetraoctyldiphenylamine; tetradecyldiphenyl polyalkyldiphenyl Amine-based and naphthylamine-based, specifically α-naphthylamino-α-naphthylamine; further, butylphenyl-α-naphthylamine; pentylphenyl-α-naphthylaminophenyl-α- Naphthylamine; heptylphenyl-α-naphthylamine; alkyl-substituted phenyl-α-naphthylamine such as octylphenyl-α-naphthylaminophenyl-α-naphthylamine. These dimercaptodiphenylamine and naphthylamine are suitable. Further, other antioxidants may also be used as a molybdenum amine complex inhibitor. As a molybdenum amine complex antioxidant, a 6-membered molybdenum compound is obtained by reacting molybdenum trioxide and/or molybdic acid with an amine compound; 2,4--t-butylmethyl-2,2'- I-t-butylate-octadecyl-thio]amine; bis-diamine, 4,-ylamine, etc.: benzene; hexyl: oxime to oxidize, with, -18-200930805, can be used in Japan A compound obtained by the production method described in JP-A-2003-25 2 8 87. The amine compound ' reacted with a 6-membered molybdenum compound' is not particularly limited, and specific examples thereof include a monoamine, a diamine, a polyamine, and an alkanolamine. More specifically, an alkyl group having 1 to 30 carbon atoms such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine or methylpropylamine can be exemplified (the alkyl groups may be a linear or branched alkylamine; an alkenyl group having a carbon number of 2 to 30, such as a vinylamine, an allylamine, a butenylamine, an octenylamine, or an oleylamine; The alkenyl group may be a linear or branched alkenylamine; an alkanol having 1 to 30 carbon atoms such as methanolamine, ethanolamine, methanolethanolamine or methanol propanolamine (the alkanols may be linear) Alkanolamine; or alkylenediamine having a carbon number of from 1 to 30; methylenediamine, ethylenediamine, propylenediamine, and butanediamine; Polyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.; undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine, oleyldiethanolamine, oleylpropane a compound having an alkyl group or an alkenyl group having a carbon number of 8 to 20 or a heterocyclic compound such as an imidazoline in the above monoamine, diamine or polyamine such as a diamine or a stearin tetraethylene pentaamine; Epoxy Adducts of: and mixtures of these. Further, the sulfur-containing molybdenum complex of succinimide succinate described in Japanese Patent Publication No. Hei 3-2243 8 and JP-A-2004-2866 can be exemplified. The amount of the above-mentioned antioxidant is preferably 0.3% by mass or more and more preferably 0.5% by mass or more based on the total amount of the composition. On the other hand, when it exceeds 2% by mass, it becomes insoluble in the lubricating base oil. Therefore, the amount of the antioxidant to be added is preferably in the range of 0.3 to 2% by mass based on the total amount of the composition. -19- 200930805 In the lubricating oil composition of the present invention, other additives such as a viscosity increasing agent, a pour point depressant, an anti-wear agent, and an ash-free agent may be blended as needed within the range not impairing the present invention. It is a friction reducing agent rusting agent, a metal inerting agent, a surfactant, and an antifoaming agent. Examples of the viscosity index-enhancing agent include polymethacrylate-based polymethacrylate, olefin-based copolymer (for example, ethylene-copolymer, etc.), dispersed olefin-based copolymer, and styrene-based copolymer Φ. , styrene-diene copolymer, styrene-isoprene copolymer, and the like. The blending amount of the viscosity index-increasing agent is about 0.5 to 15% by mass, more preferably 1 to 1% by mass based on the total amount of the composition, from the viewpoint of the effect. Examples of the pour point depressant include polymethacrylates having a mass average molecular weight of about 50,000 or so. Examples of the antiwear agent include zinc dithiophosphate, zinc dithiocarbamide, zinc phosphate, disulfides, sulfurized olefins, sulfurized fats and oils, thiolated esters, thiocarbonates, and thiouric acid. Sulfur-containing compounds such as esters (for example, DTC); phosphites, phosphates, esters, and phosphorus-containing compounds such as such amine salts or metal salts; thioesters, phosphorothioates Sulfur-containing (for example, Mo-DTP), thiophosphine, and sulfur and phosphorus-containing antiwear agents such as these amine salts or metal salts. As the ashless friction reducing agent, any compound generally used as a friction reducing agent for lubricating oil can be used, and examples thereof include fatty acids having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms. Alcohol, aliphatic ether, aliphatic ester, aliphatic amine and aliphatic hydrazine effect index, anti-, propylene (for example), etc., preferably 5000 formic acid, sulfur Mo-phosphonic acid phosphite ashless, fat Amine, etc. -20- 200930805 Examples of the rust inhibitor include petroleum sulfonate, alkylbenzenesulfonate, dinonylnaphthalenesulfonate, alkenyl succinate, and polyhydric alcohol ester. The amount of the rust inhibitor to be added is generally from 0.01 to 1% by mass, preferably from 0.05 to 0.5% by mass, based on the total amount of the composition. The metal inerting agent (copper corrosion preventing agent) may, for example, be a benzotriazole-based, a tolyltriazole-based, a thiadiazole-based, an imidazole-based or a pyrimidine-based compound. Among them, a benzotriazole-based compound is preferred. Due to the metal inerting agent, the metal humus and oxidative degradation of engine parts can be suppressed. The blending amount of the metal inerting agent is preferably 0.01 to 0.1% by mass, more preferably 0.03 to 0.5% by mass based on the total amount of the composition, from the viewpoint of the compounding effect. Examples of the surfactant include a polyalkylene glycol-based nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylnaphthyl ether. 〇 〇 〇 〇 〇 〇 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以good. In the lubricating oil composition of the present invention, the sulfur content is preferably 0.5% by mass or less based on the total amount of the composition, more preferably 3% by mass or less, still more preferably 0.2% by mass or less. When the sulfur content is 0.5% by mass or less, the performance of the catalyst for purifying the exhaust gas can be effectively suppressed from being lowered. In the lubricating oil composition of the present invention, the phosphorus content is preferably 0.12% by mass or less, more preferably 〇·1% by mass or less based on the total amount of the composition. Phosphorus contains -21 - 200930805 When the amount is 〇. 2 2% by mass or less, the performance of the catalyst for purifying the exhaust gas can be effectively suppressed. Further, in the lubricating oil composition of the present invention, the ash sulfate component is preferably 1.1% by mass or less and more preferably 1% by mass or less. When the ash sulfate fraction is 1:1 mass% or less, the performance of the catalyst for purifying the exhaust gas can be effectively suppressed. Further, in the diesel engine, the amount of ash accumulated in the filter of the DPF is small, and the ash of the filter can be suppressed. The blockage makes the life of the DPF longer. Further, the sulfuric acid φ ash portion is obtained by adding sulfuric acid to the carbonized residue formed by the combustion sample and heating it to a constant amount of ash, and is generally used for understanding the approximate amount of the metal-based additive in the lubricating oil composition. Specifically, it is measured by the method specified in "5. Sulfuric acid ash test method" of JIS κ 2272. Further, the increase in the evaporability of the lubricating oil in the internal combustion engine increases the consumption of the lubricating oil itself, and thus the life of the lubricating oil decreases, and the amount of scattering of the exhaust gas catalyst increases, resulting in a decrease in catalyst capacity and life. From this point of view, in the lubricating oil composition of the present invention, the amount of NOACK evaporation measured according to JPI (JPP Petroleum Institute, the same below)-5S-41-93 is preferably 15 mass% or less, more preferably 13 The mass% or less is further preferably 1% by mass or less. [Embodiment] [Embodiment] Next, the present invention will be described in further detail by way of examples, but the invention is not limited thereto. -22-200930805 [Examples 1 to 7 and Comparative Examples 1 to 4] A lubricating oil composition having the compounding composition shown in Table 1 was prepared, and the hot tube test shown below was carried out. Further, the types of the respective components used for the preparation of the lubricating oil composition are as follows. (1) Base oil A: hydrorefined base oil, 4 (TC dynamic viscosity 21mm2/s, 100°C dynamic viscosity 4.5mm2/s, viscosity index 127, %CA 0·0, sulfur content less than 20 mass ppm, N0ACK evaporation 13.3% by mass
0 (2)基油 B:PAO、40°C 動黏度 17.5mm2/s、100°C 動黏度3.9mm2/s、黏度指數120、NOACK蒸發量15質量 % (3)基油C:酯油（多元醇（polyol)脂肪酸酯。多 元醇成分爲三羥甲基丙烷；脂肪酸成分係使用椰子油 （ C8〜C12 )經精製（refine )者。）、40 °C動黏度 19.8mm2/s、100 °C 動黏度 4.3 mm2/s、黏度指數 139、 NOACK蒸發量3質量％、皂化値〇.lmgKOH/g φ (4)基油D:十三基己二酸酯、40°C動黏度27mm2/s 、：100°C動黏度5.3mm2/s、黏度指數132、NOACK蒸發量 4質量％ (5) 黏度指數提昇劑··聚甲基丙烯酸酯、質量平均 分子量420,000、樹脂量39質量％ (6) 流動點下降劑：聚烷基甲基丙烯酸酯、質量平 均分子量6,000 (7 )金屬系清淨劑：高鹼性鈣水楊酸鹽、鹼値（過 氯酸法）225mgK〇H/g、鈣含量7.8質量％、硫含量〇·3質 -23- 200930805 量％ (8) 聚丁烯基琥珀酸單醯亞胺A:聚丁烯基的數平 均分子量10 00、氮含量1.76質量％、硼含量2.0質量％、 B/N= 1 . 1 (9) 聚丁烯基琥珀酸雙醯亞胺B:聚丁烯基的數平 均分子量2000、氮含量0.99質量％、Β/Ν = 0 (10 )酚系抗氧化劑：十八基 3- ( 3,5-tert-丁基- 4-φ 羥基苯基）丙酸酯 (π )胺系抗氧化劑：二烷基二苯基胺、氮含量4.62 質量％ (12 )二烷基二硫代磷酸鋅：Ζη含量9.0質量％、磷 含量8.2質量％、硫含量17.1質量％、烷基；第2級丁基 與第2級己基的混合物 (13)銅腐蝕防止劑：1-〔ν，Ν -雙（2 -乙基己基）胺 基甲基〕甲基苯并三唑 ❹ (1〇生物柴油燃料：菜籽油甲基酯 (1 5 )其它的添加劑：防鏽劑、界面活性劑及消泡劑 關於各潤滑油組成物的性質測定及熱管試驗，如以下 地進行。 (鈣含量） 依據JPI-5S-38-92進行測定。 (硼含量） -24- 200930805 依據JPI-5S-38-92進行測定。 (氮含量） 依據JIS K2609進行測定。 (磷含量） 依據JPI-5S-3 8-92進行測定。 ❹ (硫含量） 依據JIS K2541進行測定》 (硫酸灰份） 依據JIS K2272進行測定。 (Noack ) 〇 依據JPI-5S-41-93進行測定。 .(熱管試驗） 內之燃料與 物（新油） 酯交換而獲 在280 °C及 行測定。又 影饗’故使 作爲試驗用的潤滑油組成物，假設內燃機 潤滑油的混合比例，對於前述之各潤滑油組成 使用配合生物燃料（經由甲基醇將菜籽油進行 得之燃料）5質量％的混合油。試驗溫度設定 32〇°C，對於其它條件係依據JPI-5S_5 5 -99進 ’熱管試驗係亦會受黏度指數提昇劑的量而有 -25- 200930805 各實施例·比較例中黏度指數提昇劑的配合量固定。幾乎 朝向試驗後的玻璃管的附著物量變少，顯示清淨性爲良好 〇 各潤滑油組成物的性質及熱管試驗的結果示於表1。0 (2) Base oil B: PAO, 40 ° C dynamic viscosity 17.5 mm 2 / s, 100 ° C dynamic viscosity 3.9 mm 2 / s, viscosity index 120, NOACK evaporation 15% by mass (3) Base oil C: ester oil ( Polyol fatty acid ester. The polyol component is trimethylolpropane; the fatty acid component is refined using coconut oil (C8~C12).), 40 °C dynamic viscosity 19.8mm2/s, 100 °C dynamic viscosity 4.3 mm2 / s, viscosity index 139, NOACK evaporation 3% by mass, saponification 値〇.lmgKOH / g φ (4) base oil D: tridecyl adipate, 40 ° C dynamic viscosity 27mm2 / s , 100 ° C dynamic viscosity 5.3 mm 2 / s, viscosity index 132, NOACK evaporation 4% by mass (5) viscosity index improver · polymethacrylate, mass average molecular weight 420,000, resin amount 39% by mass (6 Flow point depressant: polyalkyl methacrylate, mass average molecular weight 6,000 (7) metal detergent: high alkaline calcium salicylate, alkali hydrazine (perchloric acid method) 225 mg K 〇 H / g, calcium Content: 7.8% by mass, sulfur content 〇·3 -23- 200930805 Quantities (8) Polybutenyl succinic acid monoterpene imine A: polybutenyl group number average molecular weight 10 00, nitrogen content 1.76 %, boron content 2.0% by mass, B/N = 1.1 (9) Polybutenyl succinic acid bisinimide B: polybutenyl group number average molecular weight 2000, nitrogen content 0.99 mass%, Β / Ν = 0 (10) phenolic antioxidant: octadecyl 3-(3,5-tert-butyl-4-φhydroxyphenyl)propionate (π) amine antioxidant: dialkyldiphenylamine, Nitrogen content 4.62% by mass (12) Zinc dialkyldithiophosphate: Ζη content 9.0% by mass, phosphorus content 8.2% by mass, sulfur content 17.1% by mass, alkyl group; mixture of butyl group and second-grade hexyl group (13) Copper corrosion inhibitor: 1-[ν,Ν-bis(2-ethylhexyl)aminomethyl]methylbenzotriazolium (1〇 biodiesel fuel: rapeseed oil methyl ester (1 5) Other additives: rust inhibitor, surfactant, and antifoaming agent The properties of each lubricating oil composition and the heat pipe test were carried out as follows. (Calcium content) The measurement was carried out in accordance with JPI-5S-38-92. (Bon content) -24- 200930805 Measured according to JPI-5S-38-92 (Nitrogen content) Measured in accordance with JIS K2609. (Phosphorus content) Measured according to JPI-5S-3 8-92. Measurement "(sulfate ash) was measured according to JIS K2541 based on JIS K2272. (Noack) 测定 Measured according to JPI-5S-41-93. The fuel in the (heat pipe test) was transesterified with the product (new oil) and measured at 280 °C. In addition, it is used as a lubricating oil composition for testing, assuming that the mixing ratio of the lubricating oil of the internal combustion engine is used, and the above-mentioned lubricating oil composition is used in combination with biofuel (fuel obtained by using rapeseed oil via methyl alcohol) 5 mass. % mixed oil. The test temperature is set at 32 °C. For other conditions, the heat pipe test system will also be affected by the amount of viscosity index improver according to JPI-5S_5 5 -99. -25-200930805 Each Example · Comparative Example Viscosity Index Lifting Agent The amount of the compound is fixed. The amount of adhering matter of the glass tube almost toward the test was small, and the detergency was good. 性质 The properties of each lubricating oil composition and the results of the heat pipe test are shown in Table 1.
-26- 200930805 〔I—I谳〕 f M 寸 79.61 1 1 3.00 6.50 0.30 I 2.82 I 1 5.00 0.50 0.50 1.22 0.05 0.50 100.00 0.22 ! 0.02 I 0.09 I 〇 ο.ιο I 1 0.97 1 1 π·〇 1 丨而1 1 153.5 1 cn 79.61 1 3.00 1 6.50 0.30 2.82 1 5.00 0.50 0.50 1.22 0.05 0.50 100.00 I 0.22 1 0.02 I | 0.09 I (Ν 〇 0.10 1 0.97 J 〇\ 1 155.5 j CN 62.61 20.00 1 1 6.50 I 0.30 1___ — 2.82 1 5.00 0.50 0.50 | —1.22—— 0.05 I 0.50 I 100.00 | 0.22 1 0·00」 0.07 <Ν 〇 0.10 1 0.96」 1 10.5 〇 ON 1 83.3 1 82.61 1 1 1 L6.50 I [0.30 1 | 2.82 I 1 1 5.00 1 1 0.50 I 0.50 L—L22 1 0.05 1 0.50 I [100.00 | 0.22 1 [〇.〇〇 1 0.07 (Ν 〇 1 ο.ιο I 1 0.96 j Ui-2 1 1 10.3 1 1 157.8 J 實施例 卜 1 61.61 20.00 1 6.50 0.30 2.82 1.00 5.00 0.50 0.50 1.22 0.05 0.50 1 100.001 0.22 1 | 0.02 1 [〇.〇9 1 〇 〇:ι〇 0.97 〇〇 OS 0 寸· 61.61 | 1 1 20.00 6.50 1 0.30 1 2.82J 1.00 5.00 1 0.50 I 0.50 1.22 | (Ml 1 0.50J 100.00I | 0.22 1 ! 〇.〇2 | 0.09」 <Ν ο 0.10 1 0.97 1 0 Os 0 — 61.61 1 20.00 1 6.50 0.30 2.82 1.00 5.00 0.50 0.50 1.22 0.05 1 0.50 100.00 0.22 1 ! 〇.〇2 | 009 04 Ο 1 ο.ιο 1 1 0.97 »—Η ο ON cn 寸 1 62.61 20.00 1 6.50 0.30 1_ 2.82 1 5.00 0.50 0.50 1.22 0.05 1 0.50 | I100.00 I | 0.22 1 | 〇.〇〇 | | 0.07 1 (Ν Ο 1 ο.ιο 1 1 0.96 1 00 ο 1 26.6 j m 62.61 1 10.00 10.00 6.50 0.30 2.82 1 5.00 0.50 0.50 1.22 0.05 0.50 | 100.00 1 ί 0.22 1 | 〇.〇〇 | | 0.07 1 CN Ο 1 ο.ιο 1 0.96 1 00 ο 1 26.2 1 CN 62.61 1 1 20.00 6.50 1 0.30 ^ 2.82 1 5.00 1 Γ〇.50 0.50 | | 1.22 | 1 0.05 1 0.50 | 1100.001 | 0.22 1 | 〇.〇〇 | | 0.07 1 CN Ο 1 ο.ιο 1 1 0.96 1 00 ο 1 28.0 1 | 62.61 1 1 Γ20.00 1 1 1 6.50 1 「0.30 1 「2.82 1 1 1 5.00 ] | 0.50 1 | 0.50 | | 1.22 | 1 0.05 1 | 0.50 | 1100.001 | 0.22 1 | 〇.〇〇 | | 0.07 | CN Ο (ΧΙΟ」 1 0.96 卜 00 00 ο 1 25.2 基油A 基油B 基油c 基油D 黏度指數提昇劑 流動點下降劑 金屬系清淨劑 聚丁烯基琥珀酸單醯亞胺A 聚丁烯基琥珀酸雙醯亞胺B 酚系抗氧化劑 胺系抗氧化劑 二烷基二硫代磷酸鋅 銅腐蝕防止劑 其它 合計 鈣含量 硼含量 氮含量 硫含量 磷含量 硫酸灰份 Noack 熱管試驗/附著物量（mg) 新油95%+生物柴油燃料5%@280°C 新油95%+生物柴油燃料5%@320°C 配合組成 償量％) 組成物的性質 (質量％) 1 1 -27- 200930805 〔評估結果〕 如表1之熱管試驗結果可知地’使用本發明之潤滑油 組成物的實施例1〜7中可知即使於新油中添加生物燃料 ，熱管內的附著量亦不怎麼變多，且引擎的清淨性亦具優 異。另一方面，比較例1、2係沒有使用作爲基油的多元 醇酯或多元酸酯’故附著量非常地多。又，如比較例3、4 ’即使使用多元醇酯或多元酸酯作爲基油，其配合量少亦 〇 幾乎不見防止附著的效果，無法期待對於引擎之清淨性。 ❹ -28--26- 200930805 [I—I谳] f M inch 79.61 1 1 3.00 6.50 0.30 I 2.82 I 1 5.00 0.50 0.50 1.22 0.05 0.50 100.00 0.22 ! 0.02 I 0.09 I 〇ο.ιο I 1 0.97 1 1 π·〇1 丨And 1 1 153.5 1 cn 79.61 1 3.00 1 6.50 0.30 2.82 1 5.00 0.50 0.50 1.22 0.05 0.50 100.00 I 0.22 1 0.02 I | 0.09 I (Ν 〇0.10 1 0.97 J 〇\ 1 155.5 j CN 62.61 20.00 1 1 6.50 I 0.30 1___ — 2.82 1 5.00 0.50 0.50 | —1.22 — 0.05 I 0.50 I 100.00 | 0.22 1 0·00” 0.07 <Ν 〇0.10 1 0.96” 1 10.5 〇ON 1 83.3 1 82.61 1 1 1 L6.50 I [0.30 1 2.82 I 1 1 5.00 1 1 0.50 I 0.50 L—L22 1 0.05 1 0.50 I [100.00 | 0.22 1 [〇.〇〇1 0.07 (Ν 1 ο.ιο I 1 0.96 j Ui-2 1 1 10.3 1 1 157.8 J Example 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.30 1 2.82J 1.00 5.00 1 0.50 I 0.50 1.22 | (Ml 1 0.50J 100.00I | 0.22 1 ! 〇.〇2 | 0.09" <Ν ο 0.10 1 0.97 1 0 Os 0 — 61.61 1 20.00 1 6.50 0.30 2.82 1.00 5.00 0.50 0.50 1.22 0.05 1 0.50 100.00 0.22 1 ! 〇.〇2 | 009 04 Ο 1 ο.ιο 1 1 0.97 »—Η ο ON cn inch 1 62.61 20.00 1 6.50 0.30 1_ 2.82 1 5.00 0.50 0.50 1.22 0.05 1 0.50 | I100.00 I | 0.22 1 | 〇.〇〇| | 0.07 1 (Ν Ο 1 ο.ιο 1 1 0.96 1 00 ο 1 26.6 jm 62.61 1 10.00 10.00 6.50 0.30 2.82 1 5.00 0.50 0.50 1.22 0.05 0.50 | 100.00 1 ί 0.22 1 | 〇.〇〇| | 0.07 1 CN Ο 1 ο.ιο 1 0.96 1 00 ο 1 26.2 1 CN 62.61 1 1 20.00 6.50 1 0.30 ^ 2.82 1 5.00 1 Γ〇.50 0.50 | 1.22 | 1 0.05 1 0.50 | 1100.001 | 0.22 1 | 〇.〇〇| | 0.07 1 CN Ο 1 ο.ιο 1 1 0.96 1 00 ο 1 28.0 1 | 62.61 1 1 Γ20.00 1 1 1 6.50 1 "0.30 1 "2.82 1 1 1 5.00 ] | 0.50 1 | 0.50 | | 1.22 | 1 0.05 1 | 0.50 | 1100.001 | 0.22 1 | 〇.〇〇| | 0.07 | CN Ο (ΧΙΟ) 1 0.96 00 00 ο 1 25.2 Oil A Base oil B Base oil c Base oil D Viscosity index improver Flow point descent agent Metal-based detergent Polybutenyl succinic acid monoterpene imine A Polybutenyl succinic acid bis-imide B phenolic Antioxidant Amine Antioxidant Zinc Dialkyldithiophosphate Copper Corrosion Inhibitor Other Total Calcium Content Boron Content Nitrogen Content Sulfur Content Phosphorus Content Ash Sulfate Noack Heat Pipe Test/Amount of Attachment (mg) New Oil 95%+Biodiesel Fuel 5%@280°C New oil 95%+Biodiesel fuel 5%@320°C Coordination composition %) Properties of the composition (% by mass) 1 1 -27- 200930805 [Evaluation results] Heat pipe test as shown in Table 1. As a result, it can be seen that in Examples 1 to 7 in which the lubricating oil composition of the present invention is used, even if biofuel is added to the fresh oil, the amount of adhesion in the heat pipe is not so large, and the detergency of the engine is also excellent. On the other hand, in Comparative Examples 1 and 2, the polyol ester or the polybasic acid ester as the base oil was not used, so the amount of adhesion was extremely large. Further, in Comparative Examples 3 and 4', even when a polyol ester or a polybasic acid ester was used as the base oil, the amount of the mixture was small, and the effect of preventing adhesion was hardly observed, and the detergency against the engine could not be expected. ❹ -28-