KR20120099065A - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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Publication number
KR20120099065A
KR20120099065A KR1020127013971A KR20127013971A KR20120099065A KR 20120099065 A KR20120099065 A KR 20120099065A KR 1020127013971 A KR1020127013971 A KR 1020127013971A KR 20127013971 A KR20127013971 A KR 20127013971A KR 20120099065 A KR20120099065 A KR 20120099065A
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KR
South Korea
Prior art keywords
group
lubricating oil
acid
oil composition
compound
Prior art date
Application number
KR1020127013971A
Other languages
Korean (ko)
Inventor
히데끼 가마노
Original Assignee
이데미쓰 고산 가부시키가이샤
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Publication of KR20120099065A publication Critical patent/KR20120099065A/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

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Abstract

기유에, 특정한 황 함유 화합물 및 특정한 극성기 함유 화합물을 배합함으로써, 저인분, 저황분, 저황산회분으로서도 내마모성이 우수하고, 또한 DLC 처리를 실시한 접동부에 사용하는 경우에서도 우수한 마찰 저감 효과를 발현하는 윤활유 조성물을 제공한다.By blending a specific sulfur-containing compound and a specific polar group-containing compound with the base oil, it is excellent in wear resistance even as low phosphorus, low sulfur and low sulfuric acid ash, and exhibits an excellent friction reduction effect even when used in sliding parts subjected to DLC treatment. It provides a lubricating oil composition.

Description

윤활유 조성물{LUBRICATING OIL COMPOSITION}Lubricant composition {LUBRICATING OIL COMPOSITION}

본 발명은 윤활유 조성물에 관한 것이다. 더욱 상세하게는, 저인분, 저황분, 저황산회분에서도 내마모성이 우수한 윤활유 조성물이며, 또한 다이아몬드 라이크 카본(DLC) 처리를 실시한 접동부에 사용하는 경우에도 우수한 마찰 저감 효과를 발현하는 윤활유 조성물에 관한 것이다. The present invention relates to a lubricating oil composition. More specifically, the present invention relates to a lubricating oil composition which is excellent in wear resistance even in low phosphorus, low sulfur and low sulfuric acid ash, and exhibits an excellent friction reducing effect even when used in a sliding part subjected to diamond-like carbon (DLC) treatment. will be.

현재의 자동차 등의 엔진에는 배출 가스를 청정화하기 위해서 산화 촉매, 3원 촉매, NOx 흡장형 환원 촉매, 디젤 파티큘레이트 필터(DPF) 등이 사용되고 있다. 이들 배출 가스 정화 장치는 엔진유 중의 금속분, 인분, 황분에 의해 악영향을 받는 것이 알려져 있고, 이들 성분을 저감시키는 것이 장치의 열화 대책상 요구된다. In an engine such as an automobile, an oxidation catalyst, a ternary catalyst, a NO x storage type reduction catalyst, a diesel particulate filter (DPF), and the like are used to clean exhaust gas. It is known that these exhaust gas purification apparatuses are adversely affected by metal powder, phosphorus powder and sulfur powder in engine oil, and reducing these components is required for deterioration countermeasure of the apparatus.

또한, 최근의 자동차 등에 관해서는, 저연비화를 목적으로 하는 여러가지 기술 개발이 행해지고 있고, 예를 들면 엔진 등의 접동부에 있어서의 표면 처리 기술을 들 수 있다. In addition, in recent years, various technologies have been developed for the purpose of reducing fuel consumption, and for example, surface treatment techniques in sliding parts such as engines are mentioned.

그런데, 종래부터 가솔린 엔진, 디젤 엔진, 가스 엔진 등에 사용하는 내연 기관용 윤활유의 내마모제 겸 산화 방지제로서, 디티오인산 아연(Zn-DTP)이 오랜 세월 사용되고 있고, 현재도 내연 기관용 윤활유가 중요한 필수 첨가제로 여겨지고 있다. By the way, zinc dithiophosphate (Zn-DTP) has been used for many years as an anti-wearing agent and antioxidant of lubricating oils for internal combustion engines used in gasoline engines, diesel engines, gas engines, and the like. It is considered.

그러나, 디티오인산 아연은 분해하면 황산이나 인산을 발생하기 때문에 엔진유 중의 염기성 화합물을 소모해서 윤활유의 열화를 촉진하여, 오일 갱신 기간을 극단적으로 단축시키는 경우가 있다. 또한, 디티오인산 아연은 고온 조건에서 슬러지화하고, 엔진 내부의 청정성을 악화시키는 경우가 있다. 또한, 디티오인산 아연은 분자 중에 금속분(아연)과 함께, 인분 및 황분을 다량으로 포함하고 있는 점에서, 배출 가스 정화 장치에 대한 악영향의 원인이 되는 것을 생각할 수 있다. 따라서, 디티오인산 아연을 사용하지 않아도 내마모성이 우수한 윤활유 조성물의 개발이 요망된다. However, since zinc dithiophosphate decomposes, sulfuric acid and phosphoric acid generate | occur | produce, in some cases, the basic compound in engine oil is consumed, the deterioration of lubricating oil is accelerated | stimulated, and an oil renewal period may be shortened extremely. In addition, zinc dithiophosphate may sludge under high temperature conditions, and may deteriorate the cleanliness inside an engine. In addition, since zinc dithiophosphate contains a large amount of phosphorus and sulfur in addition to metal powder (zinc) in a molecule | numerator, it can be considered that it causes a bad influence to an exhaust gas purification apparatus. Therefore, development of a lubricating oil composition excellent in wear resistance is desired even without using zinc dithiophosphate.

또한, 상기한 바와 같이 접동부에 있어서의 표면 처리 기술의 개발이 진행되고 있는 상황에서는, 윤활유 조성물에 관해서도 개량이 한층 더 요구되고 있다. 예를 들어, 종래의 윤활유를 DLC 처리를 실시한 접동부에 사용한 경우에는 기대한 만큼의 마찰 저감 효과가 발현되지 않는 경우가 있었다. 따라서, 한층 저연비화를 달성하기 위해 DLC 처리를 실시한 접동부에 사용하는 경우에도 우수한 마찰 저감 효과를 발현하는 윤활유 조성물이 요망된다. Moreover, in the situation where development of the surface treatment technique in a sliding part is advanced as mentioned above, improvement is further calculated | required also regarding a lubricating oil composition. For example, when the conventional lubricating oil was used for the sliding part which performed the DLC process, the friction reduction effect as expected might not be expressed. Therefore, a lubricating oil composition which expresses the outstanding friction reducing effect is desired also when used for the sliding part which carried out DLC process in order to achieve further low fuel consumption.

이들 과제를 해결할 목적으로, 종래부터 각종 윤활유용 첨가제나 윤활유 조성물이 제안되어 있다. 예를 들어, 특허문헌 1 내지 3에는 특정한 구조를 갖는 디술피드 화합물을 주성분으로 하는 윤활유용 첨가제나 윤활유 조성물이 기재되어 있다. 특허문헌 4에는 환원 촉매의 피독 물질인 황, 인을 감소시키고, 또한 마모 방지 성능이 우수하다고 하는 엔진유가 기재되어 있다. 특허문헌 5에는, 다이아몬드를 이용한 접동면을 갖고, 특정한 첨가제를 함유하는 윤활유 조성물을 개재시킨 저마찰 접동 기구가 기재되어 있다. In order to solve these problems, conventionally, various lubricating oil additives and lubricating oil compositions have been proposed. For example, Patent Literatures 1 to 3 describe additives for lubricating oils and lubricating oil compositions which contain a disulfide compound having a specific structure as a main component. Patent document 4 describes the engine oil which reduces sulfur and phosphorus which are poisoning substances of a reduction catalyst, and is excellent in abrasion prevention performance. Patent Document 5 describes a low friction sliding mechanism having a sliding surface using diamond and interposing a lubricating oil composition containing a specific additive.

일본 특허 공개 제2004-262964호 공보Japanese Patent Laid-Open No. 2004-262964 일본 특허 공개 제2004-262965호 공보Japanese Patent Laid-Open No. 2004-262965 일본 특허 공개 제2008-056876호 공보Japanese Patent Publication No. 2008-056876 일본 특허 공개 제2007-131792호 공보Japanese Patent Publication No. 2007-131792 일본 특허 공개 제2008-56735호 공보Japanese Patent Publication No. 2008-56735

이와 같이, 각종 윤활유용 첨가제나 윤활유 조성물의 개발이 지금까지 행해져 왔지만, 윤활유에 관해서는 촉매 피독에 관한 성능, 내마모성 및 마찰 저감 효과 등 다수의 요구 성능을 동시에 만족하는 것이 통상 요구되기 때문에, 상기 문헌에 기재되는 윤활유 조성물도 충분한 것이라고는 할 수 없었다. 특히 디티오인산 아연은 내마모성이나 산화 방지성을 향상시킬 때 매우 유용한 첨가제였기 때문에 해당 화합물을 사용하지 않고 종래와 동등하거나 또는 그 이상의 성능을 갖는 윤활유 조성물을 얻는 것은 곤란했었다. As described above, development of various lubricant additives and lubricating oil compositions has been conducted so far, but since it is usually required to satisfy a large number of required performances such as performance on catalyst poisoning, abrasion resistance, and a friction reducing effect, lubricating oil is generally required. The lubricating oil composition described in the above was not sufficient. In particular, since zinc dithiophosphate was a very useful additive when improving abrasion resistance and antioxidant resistance, it was difficult to obtain a lubricating oil composition having the same or better performance than the conventional one without using the compound.

본 발명은 상기 사정을 감안하여 이루어진 것으로, 저인분, 저황분, 저황산회분에서도 내마모성이 우수한 윤활유 조성물로서, DLC 처리를 실시한 접동부에 사용하는 경우에도 우수한 마찰 저감 효과를 더욱 발현하는 윤활유 조성물을 제공하는 것을 목적으로 하는 것이다. The present invention has been made in view of the above circumstances, and as a lubricating oil composition having excellent abrasion resistance even in low servings, low sulfur powders and low sulfuric acid ashes, a lubricating oil composition which further exhibits an excellent friction reducing effect even when used in a sliding part subjected to DLC treatment is used. The purpose is to provide.

본 발명자들은 예의 연구를 거듭한 결과, 특정한 황 함유 화합물 및 특정한 극성기 함유 화합물을 병용함으로써, 상기 목적을 달성할 수 있는 것을 발견했다. 본 발명은 이러한 지견에 기초하여 완성한 것이다. MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, the present inventors discovered that the said objective can be achieved by using together a specific sulfur containing compound and a specific polar group containing compound. The present invention has been completed based on these findings.

즉 본 발명은, That is,

1. 기유에, (A) 하기의 화학식 I 및 II로 나타내는 황 함유 화합물로부터 선택되는 적어도 1종과, (B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물을 배합해서 이루어지는 윤활유 조성물. 1. In the base oil, (A) at least 1 sort (s) chosen from the sulfur containing compound represented by following formula (I) and (II), (B) at least 1 sort (s) of polar group chosen from an amino group, an amide group, and a hydroxyl group, and C3-C24 The lubricating oil composition formed by mix | blending the polar group containing compound which has an alkyl group.

Figure pct00001
Figure pct00001

(R1 내지 R12는 각각 독립적으로 수소 원자; 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기 및 아릴기로부터 선택되는 탄화수소기; 또는 이들 탄화수소기 중에 산소 원자, 질소 원자 및 황 원자로부터 선택되는 원자를 포함하여 이루어지는 헤테로 원자 함유기를 나타내고, Y는 각각 독립적으로 -O-, -S-, -SO-, -SO2-, -(C=O)O-, -(C=O)NH-, -O(C=O)NH-, -C(=O)-, -N(H)-, -NHCONH-, -N=N-, -NH-C(=NH)-NH-, -S-C(=O)-, -NH-C(=S)- 및 -NH-C(=S)-NH-로부터 선택되는 2가의 기를 나타내고, x는 1 내지 3의 정수이며, n은 각각 독립적으로 1 내지 5의 정수임),(R 1 to R 12 are each independently a hydrogen atom; a hydrocarbon group selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group; or an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom in these hydrocarbon groups) And a hetero atom-containing group comprising a compound, and each Y independently represents -O-, -S-, -SO-, -SO 2 -,-(C = O) O-,-(C = O) NH-, -O (C = O) NH-, -C (= O)-, -N (H)-, -NHCONH-, -N = N-, -NH-C (= NH) -NH-, -SC ( = O)-, -NH-C (= S)-and -NH-C (= S) -NH- represent a divalent group selected, x is an integer of 1 to 3, n is each independently 1 to Is an integer of 5),

2. 상기 (B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물이, 글리세린 부분 지방산 에스테르, 글리세린모노에테르 화합물, 아민 화합물 및 아미드 화합물로 이루어지는 군으로부터 선택되는 적어도 1종의 화합물인 상기 1에 기재된 윤활유 조성물,2. The polar group-containing compound having at least one polar group selected from the amino group, the amide group and the hydroxyl group and an alkyl group having 3 to 24 carbon atoms is selected from the group consisting of glycerin partial fatty acid esters, glycerin monoether compounds, amine compounds and amide compounds. The lubricating oil composition according to the above 1 which is at least one compound selected from the group consisting of

3. 상기 (B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물이, 하기 화학식 III 또는 IV로 나타내는 글리세린 지방산 모노에스테르, 또는 하기 화학식 V 또는 VI으로 나타내는 글리세린모노에테르 화합물인 상기 1에 기재된 윤활유 조성물,3. The glycerin fatty acid monoester represented by the following general formula (III) or (V) wherein the polar group-containing compound having at least one polar group selected from the amino group, the amide group and the hydroxyl group and an alkyl group having 3 to 24 carbon atoms is represented by the following general formula (III) or (IV): Or the lubricating oil composition according to the above 1, which is a glycerin monoether compound represented by VI,

Figure pct00002
Figure pct00002

(R13 및 R14는 각각 독립적으로 탄소수 3 내지 24의 알킬기를 나타냄)(R 13 and R 14 each independently represent an alkyl group having 3 to 24 carbon atoms)

4. 상기 (B)아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물이, 하기 화학식 VII로 나타내는 아민 화합물 또는 하기 화학식 VIII로 나타내는 아미드 화합물인 상기 1에 기재된 윤활유 조성물,4. The polar group-containing compound having at least one polar group selected from the above (B) amino group, an amide group and a hydroxyl group and an alkyl group having 3 to 24 carbon atoms is an amine compound represented by the following general formula (VII) or an amide compound represented by the following general formula (VIII) The lubricating oil composition according to the above 1,

Figure pct00003
Figure pct00003

(R15 및 R17은 각각 독립적으로 탄소수 3 내지 24의 알킬기를 나타내고, R16 및 R18은 각각 독립적으로 수소 원자 또는 탄소수 2 내지 4의 직쇄 알킬기의 말단 수소 원자가 수산기로 치환되어 이루어지는 기를 나타냄)(R 15 and R 17 each independently represent an alkyl group having 3 to 24 carbon atoms, and R 16 and R 18 each independently represent a group in which a terminal hydrogen atom of a hydrogen atom or a straight chain alkyl group having 2 to 4 carbon atoms is substituted with a hydroxyl group)

5. 윤활유 조성물 전량 기준으로 인 함유량이 0.5 질량% 이하, 황산회분이 0.6 질량% 이하인 상기 1 내지 4 중 어느 한 항에 기재된 윤활유 조성물,5. The lubricant composition according to any one of the above 1 to 4, wherein the phosphorus content is 0.5% by mass or less and sulfuric acid ash is 0.6% by mass or less based on the total amount of the lubricant composition,

6. 윤활유 조성물 전량 기준으로 인 함유량이 0 질량%, 황산회분이 0.1 질량% 이하인 상기 1 내지 5 중 어느 한 항에 기재된 윤활유 조성물, 및6. The lubricating oil composition according to any one of the above 1 to 5, wherein the phosphorus content is 0% by mass and the sulfuric acid ash is 0.1% by mass or less based on the total amount of the lubricating oil composition, and

7. 다이아몬드 라이크 카본(DLC) 처리를 실시한 접동부용 윤활유 조성물인 상기 1 내지 6 중 어느 한 항에 기재된 윤활유 조성물7. The lubricating oil composition according to any one of the above 1 to 6, which is a lubricating oil composition for a sliding part subjected to a diamond-like carbon (DLC) treatment.

을 제공하는 것이다. To provide.

본 발명에 따르면, 저인분, 저황분, 저황산회분에서도 내마모성이 우수한 윤활유 조성물로서, 또한 DLC 처리를 실시한 접동부에 사용하는 경우에도 우수한 마찰 저감 효과를 발현하는 윤활유 조성물이 제공된다. According to the present invention, there is provided a lubricating oil composition which exhibits excellent friction reducing effect even when used in a sliding part subjected to DLC treatment as a lubricating oil composition having excellent wear resistance even in low phosphorus, low sulfur powder and low sulfuric acid ash.

본 발명의 윤활유 조성물은 기유에 특정한 황 함유 화합물 및 특정한 극성기 함유 화합물을 배합해서 이루어지는 것을 특징으로 한다. The lubricating oil composition of this invention mix | blends a specific sulfur containing compound and a specific polar group containing compound with base oil, It is characterized by the above-mentioned.

[기유] [Base oil]

본 발명에서 이용하는 기유로서는 특별히 제한은 없고, 종래 윤활유의 기유로 사용되고 있는 광유나 합성 오일 중에서 임의의 것을 적절하게 선택하여 사용할 수 있다. There is no restriction | limiting in particular as base oil used by this invention, Arbitrary thing can be suitably selected and used from mineral oil or synthetic oil conventionally used as base oil of lubricating oil.

상기 광유로서는 예를 들어 원유를 상압 증류해서 얻어지는 상압 잔유를 감압 증류해서 얻어진 윤활유 증류분을 용제 탈력, 용제 추출, 수소화 분해, 용제 탈왁스, 접촉 탈왁스, 수소화 정제 등 중의 1개 이상의 처리를 행하여 정제한 광유, 또는 왁스, GTL 왁스를 이성화함으로써 제조되는 광유 등을 들 수 있다. As said mineral oil, the lubricating oil distillate obtained by depressurizing the atmospheric residual oil obtained by atmospheric distillation of crude oil, for example, is subjected to one or more processes of solvent dehydration, solvent extraction, hydrocracking, solvent dewaxing, contact dewaxing, hydrorefining, etc. Refined mineral oil, or wax, mineral oil manufactured by isomerizing GTL wax, etc. are mentioned.

한편, 상기 합성 오일로서는 예를 들어 폴리부텐, 폴리올레핀[α-올레핀 단독 중합체나 공중합체(예를 들어 에틸렌-α-올레핀 공중합체) 등], 각종 에스테르(예를 들어, 폴리올에스테르, 이염기산에스테르, 인산에스테르 등), 각종 에테르(예를 들어, 폴리페닐에테르 등), 폴리글리콜, 알킬벤젠, 알킬나프탈렌 등을 들 수 있다. 이들 합성 오일 중, 특히 폴리올레핀, 폴리올에스테르가 바람직하다. On the other hand, as said synthetic oil, for example, polybutene, polyolefin [alpha-olefin homopolymer or copolymer (for example, ethylene-alpha-olefin copolymer), etc.], various esters (for example, polyol ester, dibasic acid ester) , Phosphate esters, and the like), various ethers (for example, polyphenyl ether, etc.), polyglycol, alkylbenzene, alkylnaphthalene, and the like. Among these synthetic oils, polyolefins and polyol esters are particularly preferable.

본 발명에서는 기유로서 상기 광유를 1종 단독으로 사용할 수도 있고, 2종 이상을 조합해서 사용할 수도 있다. 또한, 상기 합성 오일을 1종 사용할 수도 있고, 2종 이상을 조합해서 사용할 수도 있다. 나아가, 광유 1종 이상과 합성 오일 1종 이상을 조합해서 사용할 수도 있다. In this invention, the said mineral oil may be used individually by 1 type, or may be used in combination of 2 or more type as base oil. Moreover, 1 type may be used for the said synthetic oil, and may be used for it in combination of 2 or more type. Furthermore, one or more mineral oils and one or more synthetic oils may be used in combination.

기유의 점도에 대해서는 특별히 제한은 없지만, 100 ℃에 있어서의 동점도가 2 내지 30㎟/s의 범위인 것이 바람직하고, 보다 바람직하게는 3 내지 15㎟/s의 범위, 더욱 바람직하게는 4 내지 10㎟/s의 범위이다. Although there is no restriction | limiting in particular about the viscosity of base oil, It is preferable that dynamic viscosity in 100 degreeC is the range of 2-30 mm <2> / s, More preferably, it is the range of 3-15 mm <2> / s, More preferably, it is 4-10. It is in the range of mm 2 / s.

100 ℃에 있어서의 동점도가 2㎟/s 이상이면 증발 손실이 적고, 또한 30㎟/s 이하이면, 점성 저항에 의한 동력 손실이 억제되어, 연비 개선 효과를 얻을 수 있다. If kinematic viscosity in 100 degreeC is 2 mm <2> / s or more, evaporation loss will be small, and if it is 30 mm <2> / s or less, power loss by a viscous resistance is suppressed and a fuel efficiency improvement effect can be obtained.

또한, 기유로서는 환 분석에 의한 %CA가 3.0 이하에서 황분의 함유량이 50 질량 ppm 이하인 것이 바람직하게 사용된다. 여기서, 환 분석에 의한 %CA란, 환 분석 n-d-M법으로 산출한 방향족분의 비율(백분율)을 나타낸다. 또한, 황분은 JIS K 2541에 준거해서 측정한 값이다. In addition, the base oil as a% C A by a ring analysis is used when the content of sulfur to preferably 50 mass ppm or less 3.0 or less. Here,% C A by ring analysis shows the ratio (percentage) of the aromatic content computed by the ring analysis ndM method. In addition, sulfur content is the value measured based on JISK2541.

%CA가 3.0 이하에서 황분이 50 질량ppm 이하의 기유는, 양호한 산화 안정성을 갖고, 산값의 상승이나 슬러지의 생성을 억제할 수 있는 윤활유 조성물을 제공할 수 있다. 보다 바람직한 %CA는 1.0 이하, 더욱 바람직하게는 0.5 이하이고, 또한 더욱 바람직한 황분은 30 질량ppm 이하이다. % C A is the base oil of not more than 50 mass ppm sulfur minutes at 3.0 or less, has good oxidation stability, it is possible to provide a lubricant composition capable of suppressing the formation of sludge and increase in acid value. More preferably,% C A is 1.0 or less, still more preferably 0.5 or less, and still more preferably 30 ppm by mass or less.

또한, 기유의 점도 지수는 70 이상이 바람직하고, 보다 바람직하게는 100 이상, 더욱 바람직하게는 120 이상이다. 이 점도 지수가 70 이상의 기유는 온도 변화에 의한 점도 변화가 적다. In addition, the viscosity index of the base oil is preferably 70 or more, more preferably 100 or more, and still more preferably 120 or more. Base oils with a viscosity index of 70 or more have little change in viscosity due to temperature change.

(황 함유 화합물) (Sulfur-containing compound)

본 발명의 윤활유 조성물에서는, 하기 화학식 I 또는 II로 표시되는 황 함유 화합물이 배합된다. In the lubricating oil composition of this invention, the sulfur containing compound represented by following formula (I) or (II) is mix | blended.

Figure pct00004
Figure pct00004

화학식 I 및 II에서, R1 내지 R12는 각각 독립적으로 수소 원자; 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기 및 아릴기로부터 선택되는 탄화수소기; 또는 이들 탄화수소기 중에 산소 원자, 질소 원자 및 황 원자로부터 선택되는 원자를 포함하여 이루어지는 헤테로 원자 함유기를 나타낸다. In formulas (I) and (II), R 1 to R 12 each independently represent a hydrogen atom; A hydrocarbon group selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group; Or a hetero atom-containing group including an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom in these hydrocarbon groups.

R1 내지 R12로 표시되는 알킬기는 탄소수 1 내지 30의 알킬기가 바람직하고, 탄소수 1 내지 24의 알킬기가 보다 바람직하다. 알킬기의 구체예로서는, 예를 들어 n-부틸기, 이소부틸기, sec-부틸기, tert-부틸기, 각종 헥실기, 각종 옥틸기, 각종 데실기, 각종 도데실기, 각종 테트라데실기, 각종 헥사데실기, 각종 옥타데실기 및 각종 이코실기 등을 들 수 있다. 또한, 알킬기는 방향족기로 치환되어 있을 수도 있고, 예를 들어 벤질기, 페네틸기 등을 들 수 있다. The alkyl group represented by R 1 to R 12 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples of the alkyl group include, for example, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, and various hexa Decyl group, various octadecyl groups, various icosyl groups, and the like. Moreover, the alkyl group may be substituted by the aromatic group, for example, a benzyl group, a phenethyl group, etc. are mentioned.

R1 내지 R12로 표시되는 시클로알킬기는 탄소수 3 내지 30의 시클로알킬기가 바람직하고, 탄소수 3 내지 24의 시클로알킬기가 더욱 바람직하다. 시클로알킬기의 구체예로서는, 시클로프로필기, 시클로펜틸기, 시클로헥실기, 메틸시클로펜틸기, 디메틸시클로펜틸기, 메틸에틸시클로펜틸기, 디에틸시클로펜틸기, 메틸시클로헥실기, 디메틸시클로헥실기, 메틸에틸시클로헥실기 및 디에틸시클로헥실기 등을 들 수 있다. 또한, 시클로알킬기는 방향족기로 치환되어 있을 수도 있고, 예를 들어 페닐시클로펜틸기, 페닐시클로헥실기 등을 들 수 있다. The cycloalkyl group represented by R 1 to R 12 is preferably a cycloalkyl group having 3 to 30 carbon atoms, and more preferably a cycloalkyl group having 3 to 24 carbon atoms. Specific examples of the cycloalkyl group include cyclopropyl group, cyclopentyl group, cyclohexyl group, methylcyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, A methyl ethyl cyclohexyl group, a diethyl cyclohexyl group, etc. are mentioned. In addition, the cycloalkyl group may be substituted by the aromatic group, for example, a phenylcyclopentyl group, a phenylcyclohexyl group, etc. are mentioned.

R1 내지 R12로 표시되는 알케닐기는 탄소수 2 내지 30의 알케닐기가 바람직하고, 탄소수 2 내지 24의 알케닐기가 보다 바람직하다. 알케닐기의 구체예로서는, 예를 들어 비닐기, 알릴기, 1-부테닐기, 2-부테닐기, 3-부테닐기, 1-메틸비닐기, 1-메틸알릴기, 1,1-디메틸알릴기, 2-메틸알릴기, 노네닐기, 데세닐기, 옥타데세닐기 등을 들 수 있다. 또한, 알케닐기는 방향족기로 치환되어 있을 수도 있다. The alkenyl group represented by R 1 to R 12 is preferably an alkenyl group having 2 to 30 carbon atoms, and more preferably an alkenyl group having 2 to 24 carbon atoms. As a specific example of an alkenyl group, For example, a vinyl group, an allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methyl allyl group, nonenyl group, decenyl group, octadecenyl group, etc. are mentioned. In addition, the alkenyl group may be substituted by the aromatic group.

R1 내지 R12로 표시되는 시클로알케닐기는 탄소수 3 내지 30의 시클로알케닐기가 바람직하고, 탄소수 3 내지 24의 시클로알케닐기가 보다 바람직하다. 시클로알케닐기의 구체예로서는, 시클로부테닐기, 메틸시클로부테닐기 등을 들 수 있다. 또한, 시클로알케닐기는 방향족기로 치환되어 있을 수도 있다. The cycloalkenyl group represented by R 1 to R 12 is preferably a cycloalkenyl group having 3 to 30 carbon atoms, and more preferably a cycloalkenyl group having 3 to 24 carbon atoms. As a specific example of a cycloalkenyl group, a cyclobutenyl group, a methylcyclobutenyl group, etc. are mentioned. In addition, the cycloalkenyl group may be substituted by the aromatic group.

R1 내지 R12로 표시되는 아릴기는 탄소수 6 내지 30의 아릴기가 바람직하고, 탄소수 6 내지 24의 아릴기가 보다 바람직하다. 아릴기의 구체예로서는, 페닐기, 톨릴기, 크실릴기, 나프틸기, 부틸페닐기, 옥틸페닐기, 노닐페닐기 등을 들 수 있다. The aryl group represented by R 1 to R 12 is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 24 carbon atoms. As a specific example of an aryl group, a phenyl group, tolyl group, xylyl group, naphthyl group, butylphenyl group, octylphenyl group, nonylphenyl group, etc. are mentioned.

화학식 I 및 II에 있어서, Y는 각각 독립적으로 -O-, -S-, -SO-, -SO2-, -(C=O)O-, -(C=O)NH-, -O(C=O)NH-, -C(=O)-, -N(H)-, -NHCONH-, -N=N-, -NH-C(=NH)-NH-, -S-C(=O)-, -NH-C(=S)- 및 -NH-C(=S)-NH-로부터 선택되는 2가의 기를 나타낸다. In formulas (I) and (II), each Y independently represents —O—, —S—, —SO—, —SO 2 —, — (C═O) O—, — (C═O) NH—, —O ( C = O) NH-, -C (= O)-, -N (H)-, -NHCONH-, -N = N-, -NH-C (= NH) -NH-, -SC (= O) -, A divalent group selected from -NH-C (= S)-and -NH-C (= S) -NH-.

화학식 I 및 II에 있어서, x는 1 내지 3의 정수이고, 2가 바람직하다. n은 각각 독립적으로 1 내지 5의 정수이며, 1 또는 2가 바람직하다. In general formula (I) and (II), x is an integer of 1-3, 2 is preferable. n is respectively independently an integer of 1-5, 1 or 2 is preferable.

화학식 I로 표시되는 황 함유 화합물로서는, 예를 들어 이하의 식으로 표시되는 화합물을 들 수 있다. As a sulfur containing compound represented by General formula (I), the compound represented by the following formula is mentioned, for example.

Figure pct00005
Figure pct00005

Figure pct00006
Figure pct00006

Figure pct00007
Figure pct00007

Figure pct00008
Figure pct00008

Figure pct00009
Figure pct00009

Figure pct00010
Figure pct00010

Figure pct00011
Figure pct00011

Figure pct00012
Figure pct00012

또한, 이하의 화합물도 화학식 I로 표시되는 화합물의 예로서 예를 들어 비스(메톡시카르보닐메틸)디술피드, 비스(에톡시카르보닐메틸)디술피드, 비스(n-프로폭시카르보닐메틸)디술피드, 비스(이소프로폭시카르보닐메틸)디술피드, 비스(n-부톡시카르보닐메틸)디술피드, 비스(n-옥톡시카르보닐메틸)디술피드, 비스(n-도데실옥시카르보닐메틸)디술피드, 비스(시클로프로폭시카르보닐메틸)디술피드, 1,1-비스(2-메톡시카르보닐에틸)디술피드, 1,1-비스(3-메톡시카르보닐-n-프로필)디설파이드, 1,1-비스(4-메톡시카르보닐-n-부틸)디설파이드, 1,1-비스(2-에톡시카르보닐에틸)디술피드, 1,1-비스(2-n-프로폭시카르보닐에틸)디술피드, 1,1-비스(2-이소프로폭시카르보닐에틸)디술피드, 1,1-비스(2-시클로프로폭시카르보닐에틸)디술피드 등을 들 수 있다. In addition, the following compounds are also mentioned as an example of the compound represented by general formula (I), for example, bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl). Disulfide, bis (isopropoxycarbonylmethyl) disulfide, bis (n-butoxycarbonylmethyl) disulfide, bis (n-octoxycarbonylmethyl) disulfide, bis (n-dodecyloxycarbonyl Methyl) disulfide, bis (cyclopropoxycarbonylmethyl) disulfide, 1,1-bis (2-methoxycarbonylethyl) disulfide, 1,1-bis (3-methoxycarbonyl-n-propyl ) Disulfide, 1,1-bis (4-methoxycarbonyl-n-butyl) disulfide, 1,1-bis (2-ethoxycarbonylethyl) disulfide, 1,1-bis (2-n-pro Foxicarbonylethyl) disulfide, 1, 1-bis (2-isopropoxycarbonylethyl) disulfide, 1, 1-bis (2-cyclopropoxycarbonylethyl) disulfide, etc. are mentioned.

화학식 II로 표시되는 화합물의 구체예로서는, 디티오말산테트라메틸, 디티오말산테트라에틸, 디티오말산테트라-1-프로필, 디티오말산테트라-2-프로필, 디티오말산테트라-1-부틸, 디티오말산테트라-2-부틸, 디티오말산테트라 이소부틸, 디티오말산테트라-1-헥실, 디티오말산테트라-1-옥틸, 디티오말산테트라-1-(2-에틸)헥실, 디티오말산테트라-1-(3,5,5-트리메틸)헥실, 디티오말산테트라-1-데실, 디티오말산테트라-1-도데실, 디티오말산테트라-1-헥사데실, 디티오말산테트라-1-옥타데실, 디티오말산테트라벤질, 디티오말산테트라-α-(메틸)벤질, 디티오말산테트라-α,α-디메틸벤질, 디티오말산테트라-1-(2-메톡시)에틸, 디티오말산테트라-1-(2-에톡시)에틸, 디티오말산테트라-1-(2-부톡시)에틸, 디티오말산테트라-1-(2-에톡시)에틸, 디티오말산테트라-1-(2-부톡시-부톡시)에틸, 디티오말산테트라-1-(2-페녹시)에틸 등을 들 수 있다. Specific examples of the compound represented by the formula (II) include dithiomal acid tetramethyl, dithiomal acid tetraethyl, dithiomal acid tetra-1-propyl, dithiomal acid tetra-2-propyl, dithiomal acid tetra-1-butyl, and dithi. Tetra-2-butyl, dithiomalic acid tetra isobutyl, dithiomalic acid tetra-1-hexyl, dithiomalic acid tetra-1-octyl, dithiomalic acid tetra-1- (2-ethyl) hexyl, dithiomalic acid Tetra-1- (3,5,5-trimethyl) hexyl, dithiomal acid tetra-1-decyl, dithiomal acid tetra-1-dodecyl, dithiomal acid tetra-1-hexadecyl, dithiomal acid tetra-1 Octadecyl, dithiomalic acid tetrabenzyl, dithiomalic acid tetra-α- (methyl) benzyl, dithiomalic acid tetra-α, α-dimethylbenzyl, dithiomalic acid tetra-1- (2-methoxy) ethyl, dithi Tetramalte-1- (2-ethoxy) ethyl, dithiomalatetetra-1- (2-butoxy) ethyl, dithiomalatetetra-1- (2-ethoxy) ethyl, dithiomalatetetra-1 -(2-butoxy-butox ), And the like, ethyl dithiocarbamic acid tetrahydro-1- (2-phenoxy) acetate.

본 발명에서는 이들 화학식 I 또는 II로 표시되는 황 함유 화합물을 1종 단독으로 사용할 수도 있고, 2종 이상을 혼합하여 사용할 수도 있다. 또한 해당 황 함유 화합물의 배합량은 조성물 전량 기준으로 0.01 내지 5.0 질량%가 바람직하고, 0.1 내지 2.0 질량%가 보다 바람직하다. 배합량이 0.01 질량% 이상인 것으로, 충분한 내마모성이 얻어지고, 5.0 질량%를 초과한 경우, 첨가량에 적당한 효과를 얻지 못할 경우가 있다. In this invention, these sulfur containing compounds represented by general formula (I) or (II) may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, 0.01-5.0 mass% is preferable on the basis of a composition whole quantity, and, as for the compounding quantity of this sulfur containing compound, 0.1-2.0 mass% is more preferable. When a compounding quantity is 0.01 mass% or more, sufficient abrasion resistance is obtained and when it exceeds 5.0 mass%, a suitable effect may not be acquired for an addition amount.

[극성기 함유 화합물] [Polar group-containing compound]

본 발명의 윤활유 조성물에 있어서는, 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 특정 범위의 탄소수의 알킬기를 갖는 극성기 함유 화합물이 배합된다. In the lubricating oil composition of the present invention, a polar group-containing compound having at least one polar group selected from an amino group, an amide group and a hydroxyl group and an alkyl group having a specific range of carbon atoms is blended.

본 발명에서 사용하는 극성기 함유 화합물은 탄소수 3 내지 24, 바람직하게는 탄소수 8 내지 20의 알킬기를 갖는 화합물이다. 탄소수가 3 미만의 경우는 해당 화합물의 용해성이 낮아진다. 또한, 탄소수의 증가에 따라 통상은 보다 우수한 마찰 저감 효과를 얻을 수 있지만, 24를 초과하면 탄소수의 증가에 적당한 효과를 얻기 어렵게 된다. The polar group-containing compound used in the present invention is a compound having an alkyl group having 3 to 24 carbon atoms, preferably 8 to 20 carbon atoms. When carbon number is less than 3, the solubility of this compound will become low. In addition, although an excellent friction reduction effect is usually obtained with an increase in the number of carbons, if it exceeds 24, it becomes difficult to obtain a suitable effect for increasing the number of carbons.

상기 극성기 함유 화합물로서는, 예를 들어 글리세린 부분 지방산에스테르, 글리세린모노에테르화합물, 아민 화합물 및 아미드 화합물로 이루어지는 군으로부터 선택되고, 또한 상기 알킬기를 함유하는 화합물을 들 수 있다. As said polar group containing compound, the compound selected from the group which consists of a glycerol partial fatty acid ester, a glycerol monoether compound, an amine compound, and an amide compound, and also contains the said alkyl group is mentioned, for example.

상기 글리세린 부분 지방산 에스테르는, 예를 들어 글리세린과 지방산과의 반응으로 얻어지는 화합물이고, 해당 지방산으로서는 아세트산, 프로피온산, 부탄산(부티르산), 펜탄산(발레르산), 이소펜탄산(이소발레르산), 헥산산(카프로산), 헵탄산, 이소헵탄산, 옥탄산(카프릴산), 2-에틸헥산산, 이소옥탄산, 노난산(펠라르곤산), 이소노난산, 데칸산(카프르산), 이소데칸산, 운데칸산, 이소운데칸산, 도데칸산(라우르산), 이소도데칸산, 트리데칸산, 이소트리데칸산, 테트라데칸산(미리스트산), 헥사데칸산(팔미트산), 옥타데칸산(스테아르산), 이소스테아르산, 에이코산(아라킨산), 도코산산(베헨산), 테트라코산산(리그노세르산), 헥타코산산(세로트산), 옥타코산산(몬탄산), 10-운데센산, 조마린산, 올레산, 엘라이드산, 리놀산, 리놀렌산, 가드렌산, 에루크산, 셀라콜레인산 등을 들 수 있다. 또한, 천연 유지로 얻어지는 혼합 지방산일 수도 있다. 이들 지방산 중에서도, 윤활유의 마찰 저감의 관점에서, 탄소수 10 내지 18의 지방산이 바람직하고, 탄소수 10 내지 12의 포화 지방산이 보다 바람직하고, 올레산 및 엘라이드산이 더욱 바람직하고, 올레산이 가장 바람직하다. The said glycerin partial fatty acid ester is a compound obtained by reaction of glycerin with a fatty acid, for example, acetic acid, propionic acid, butanoic acid (butyric acid), pentanic acid (valeric acid), isopentanic acid (isovaleric acid), Hexanoic acid (caproic acid), heptanoic acid, isoheptanoic acid, octanoic acid (caprylic acid), 2-ethylhexanoic acid, isooctanoic acid, nonanoic acid (pelargonic acid), isononanoic acid, decanoic acid (capric acid) , Isodecanoic acid, undecanoic acid, isoundecanoic acid, dodecanoic acid (lauric acid), isododecaneic acid, tridecanoic acid, isotridecanoic acid, tetradecanoic acid (milistic acid), hexadecanoic acid (palmitic acid) ), Octadecanoic acid (stearic acid), isostearic acid, eicosane (arachinic acid), docosanic acid (behenic acid), tetracoic acid (lignoseric acid), heptaconic acid (serotic acid), octacoic acid (Montanic Acid), 10-Undecenoic Acid, Jomarinic Acid, Oleic Acid, Elide Acid, Linoleic Acid, Linolenic Acid, Gardenic Acid, Erucic Acid And cellolacholeic acid. It may also be a mixed fatty acid obtained by natural fats and oils. Among these fatty acids, from the viewpoint of reducing friction of the lubricating oil, fatty acids having 10 to 18 carbon atoms are preferable, saturated fatty acids having 10 to 12 carbon atoms are more preferable, oleic acid and elic acid are more preferable, and oleic acid is most preferred.

상기 글리세린 부분 지방산 에스테르로서는, 예를 들어 하기 화학식 III 및 IV로 표시되는 글리세린 지방산 모노에스테르를 들 수 있다. 이들 화합물은 지방산과 글리세린과의 직접 에스테르화 반응이나 유지와 글리세린과의 에스테르 교환 반응 등에 의해 얻을 수 있다. As said glycerin partial fatty acid ester, the glycerin fatty acid monoester represented by following formula (III) and (IV) is mentioned, for example. These compounds can be obtained by the direct esterification reaction of fatty acids and glycerin, the transesterification reaction of fats and oils, and glycerin.

Figure pct00013
Figure pct00013

화학식 III 및 IV에 있어서, R13은 각각 독립적으로 탄소수 3 내지 24의 알킬기를 나타낸다. 본 발명에 있어서는 화학식 III 또는 IV로 표시되는 글리세린 지방산 모노에스테르를 단독으로 사용할 수도 있고, 이들의 혼합물일 수도 있다. 또한, 이들 글리세린 지방산 모노에스테르를 사용하는 경우에 있어서, 글리세린 지방산디에스테르나 글리세린 지방산 트리에스테르가 혼입되어 있을 수도 있다. In the general formulas (III) and (IV), each R 13 independently represents an alkyl group having 3 to 24 carbon atoms. In the present invention, the glycerin fatty acid monoester represented by the general formula (III) or (IV) may be used alone, or a mixture thereof. In the case of using these glycerin fatty acid monoesters, glycerin fatty acid diesters and glycerin fatty acid triesters may be mixed.

상기 글리세린모노에테르 화합물은 예를 들어 글리세린과 지방족 알코올의 반응에서 얻어지는 화합물로서, 해당 지방족 알코올로서는 프로판올, 부탄올, 올레일알코올, 스테아릴알코올 등을 들 수 있다. 이들 중에서 윤활유의 마찰 저감의 관점에서, 올레일알코올 및 스테아릴알코올이 바람직하고, 올레일알코올이 특히 바람직하다. The said glycerin monoether compound is a compound obtained by reaction of glycerin and an aliphatic alcohol, for example, propanol, butanol, oleyl alcohol, stearyl alcohol, etc. are mentioned. Among them, oleyl alcohol and stearyl alcohol are preferred from the viewpoint of friction reduction of lubricating oil, and oleyl alcohol is particularly preferable.

상기 글리세린모노에테르 화합물로서는 예를 들어 하기 화학식 V 및 VI으로 표시되는 글리세린모노에테르 화합물을 들 수 있다. As said glycerin monoether compound, the glycerin monoether compound represented by following formula (V) and VI is mentioned, for example.

Figure pct00014
Figure pct00014

화학식 V 및 VI에 있어서, R14는 각각 독립적으로 탄소수 3 내지 24의 알킬기를 나타내며, 본 발명에 있어서는 화학식 V 또는 VI으로 표시되는 글리세린모노에테르 화합물을 단독으로 사용할 수도 있고, 이들 혼합물일 수도 있다. 또한, 이들 글리세린모노에테르 화합물을 사용하는 경우에 있어서, 글리세린디에테르나 글리세린트리에테르가 혼입되어 있을 수도 있다. In the formulas (V) and (VI), each R 14 independently represents an alkyl group having 3 to 24 carbon atoms, and in the present invention, a glycerin monoether compound represented by the formula (V) or (VI) may be used alone, or a mixture thereof. In addition, when using these glycerin monoether compounds, the glycerin diether and the glycerin triether may be mixed.

상기 아민 화합물로서는 예를 들어 알킬아민 화합물이나 알칸올아민 화합물을 들 수 있다. 알킬아민 화합물에 있어서의 알킬기로서는, 상기 지방산 중에 포함되는 알킬기를 들 수 있다. 해당 아민 화합물로서는, 예를 들어 하기 화학식 VII로 표시되는 아민 화합물을 들 수 있다. As said amine compound, an alkylamine compound and an alkanolamine compound are mentioned, for example. As an alkyl group in an alkylamine compound, the alkyl group contained in the said fatty acid is mentioned. As this amine compound, the amine compound represented by following General formula (VII) is mentioned, for example.

Figure pct00015
Figure pct00015

화학식 VII에 있어서, R15는 탄소수 3 내지 24의 알킬기를 나타내며, R16은 각각 독립적으로 수소 원자 또는 탄소수 2 내지 4의 직쇄 알킬기의 말단 수소 원자가 수산기로 치환되어 이루어지는 기[예를 들어, -(CH2)2-OH]를 나타내며, 본 발명에 있어서는 화학식 VII로 표시되는 아민 화합물을 단독으로 사용할 수도 있고, 혼합물로 사용할 수도 있다. In formula (VII), R 15 represents an alkyl group having 3 to 24 carbon atoms, and R 16 each independently represents a group in which a terminal hydrogen atom of a hydrogen atom or a linear alkyl group having 2 to 4 carbon atoms is substituted with a hydroxyl group [for example,-( CH 2 ) 2 —OH], and in the present invention, the amine compound represented by the formula (VII) may be used alone or in a mixture.

상기 아민 화합물의 구체예로서는, 모노에탄올아민, 디에탄올아민, 트리에탄올아민, N-메틸에탄올아민, N,N-디메틸에탄올아민, N-에틸에탄올아민, N,N-디에틸에탄올아민, N-이소프로필에탄올아민, N,N-디이소프로필에탄올아민, 모노이소프로판올아민, 디이소프로판올아민, 트리이소프로판올아민, N-메틸이소프로판올아민, N,N-디메틸이소프로판올아민, N-에틸이소프로판올아민, N,N-디에틸이소프로판올아민, N-이소프로필이소프로판올아민, N,N-디이소프로필이소프로판올아민, 모노n-프로판올아민, 디n-프로판올아민, 트리n-프로판올아민, N-메틸n-프로판올아민, N,N-디메틸 n-프로판올아민, N-에틸n-프로판올아민, N,N-디에틸n-프로판올아민, N-이소프로필n-프로판올아민, N,N-디이소프로필n-프로판올아민, 모노부탄올아민, 디부탄올아민, 트리부탄올아민, N-메틸부탄올아민, N,N-디메틸부탄올아민, N-에틸부탄올아민, N,N-디에틸부탄올아민, N-이소프로필부탄올아민, N,N-디이소프로필부탄올아민 등을 들 수 있다. Specific examples of the amine compound include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N-ethylethanolamine, N, N-diethylethanolamine, and N-iso Propylethanolamine, N, N-diisopropylethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N, N-dimethylisopropanolamine, N-ethylisopropanolamine, N, N- Diethylisopropanolamine, N-isopropylisopropanolamine, N, N-diisopropylisopropanolamine, monon-propanolamine, din-propanolamine, trin-propanolamine, N-methyln-propanolamine, N, N-dimethyl n-propanolamine, N-ethyln-propanolamine, N, N-diethyln-propanolamine, N-isopropyln-propanolamine, N, N-diisopropyln-propanolamine, monobutanol Amine, dibutanolamine, tributanolamine, N-methyl moiety There may be mentioned all-amine, N, N- dimethyl-butanol amine, N- ethyl-butanol amine, N, N- diethyl-butanol amine, N- isopropyl-butanol amine, N, N- diisopropyl amine, such as butanol.

상기 아미드 화합물로서는, 1 내지 4가의 카르복실산과 알킬아민 또는 알칸올아민을 반응시켜서 얻어지는 화합물을 들 수 있다. As said amide compound, the compound obtained by making 1- tetravalent carboxylic acid, alkylamine, or alkanolamine react is mentioned.

상기 1가의 카르복실산을 구성하는 알킬기로서는 예를 들어 헥실기, 헵틸기, 옥틸기, 노닐기, 데실기, 운데실기, 도데실기, 트리데실기, 테트라데실기, 펜타데실기, 헥사데실기, 헵타데실기, 옥타데실기, 노나데실기, 이코실기, 펜타이코실기, 도코실기, 트리코실기, 테트라코실기, 펜타코실기, 헥사코실기, 헵타코실기, 옥타코실기, 노나코실기 및 트리아콘틸기 등을 들 수 있다. As an alkyl group which comprises the said monovalent carboxylic acid, for example, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl, octadecyl, nonadecyl, isocyl, pentacosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and A triacontyl group, etc. are mentioned.

1가 카르복실산으로서는 카프로산, 카프릴산, 카프르산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라킨산, 베헨산 및 리그노세르산 등을 들 수 있고, 또한, 2 내지 4가의 카르복실산으로서는 옥살산, 프탈산, 트리멜리트산, 피로멜리트산 등의 폴리카르복실산을 들 수 있다. Examples of the monovalent carboxylic acid include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachinic acid, behenic acid, and lignoseric acid. As polyhydric carboxylic acid, polycarboxylic acid, such as oxalic acid, a phthalic acid, trimellitic acid, a pyromellitic acid, is mentioned.

상기 아미드 화합물로서는, 예를 들어 하기 화학식 VIII로 표시되는 아미드 화합물을 들 수 있다. As said amide compound, the amide compound represented by following formula (VIII) is mentioned, for example.

Figure pct00016
Figure pct00016

화학식 VIII에서, R17은 탄소수 3 내지 24의 알킬기를 나타내며, R18은 각각 독립적으로 수소 원자 또는 탄소수 2 내지 4의 직쇄 알킬기의 말단 수소 원자가 수산기로 치환되어 이루어지는 기[예를 들어, -(CH2)2-OH]를 나타낸다. 본 발명에 있어서는 화학식 VIII로 표시되는 아미드 화합물을 단독으로 사용할 수도 있고, 혼합물로 사용할 수도 있다. In formula (VIII), R 17 represents an alkyl group having 3 to 24 carbon atoms, and R 18 each independently represents a group in which a terminal hydrogen atom of a hydrogen atom or a straight alkyl group having 2 to 4 carbon atoms is substituted with a hydroxyl group [for example,-(CH 2 ) 2 -OH]. In the present invention, the amide compound represented by the formula (VIII) may be used alone or in a mixture.

상기 아미드 화합물의 구체예로서는, 올레산모노에탄올아미드, 올레산디에탄올 아미드, 올레산모노프로판올아미드, 올레산디프로판올아미드 등을 들 수 있다. Specific examples of the amide compound include oleic acid monoethanolamide, oleic acid diethanol amide, oleic acid monopropanolamide, oleic acid dipropanolamide and the like.

본 발명에 있어서의 극성기 함유 화합물은 상기 극성기 함유 화합물과, 몰리브덴 화합물과의 반응으로 얻어지는 화합물일 수도 있다. 해당 몰리브덴 화합물로서는 예를 들어 산화몰리브덴, 할로겐화 몰리브덴, 몰리브덴산 등을 들 수 있다. 이 반응에 있어서는, 몰리브덴 화합물은 상기 극성기 함유 화합물 1몰에 대하여, 바람직하게는 0.01 내지 10몰의 몰비로, 보다 바람직하게는 0.05 내지 5몰의 몰비로 사용된다. The polar group-containing compound in the present invention may be a compound obtained by the reaction between the polar group-containing compound and the molybdenum compound. As this molybdenum compound, molybdenum oxide, molybdenum halide, molybdate acid, etc. are mentioned, for example. In this reaction, the molybdenum compound is preferably used in a molar ratio of 0.01 to 10 moles, more preferably 0.05 to 5 moles per mole of the polar group-containing compound.

상기 반응에 있어서는 용제 예를 들어 탄화수소 오일, 헥산, 헵탄, 옥탄, 톨루엔, 크실렌 등의 유기 용제를 사용할 수 있다. In the said reaction, a solvent, for example, organic solvents, such as a hydrocarbon oil, hexane, heptane, an octane, toluene, xylene, can be used.

상기 반응의 반응 온도는 특별히 제한은 없지만, 바람직하게는 50 내지 250 ℃, 보다 바람직하게는 100 내지 200 ℃이다. Although the reaction temperature of the said reaction does not have a restriction | limiting in particular, Preferably it is 50-250 degreeC, More preferably, it is 100-200 degreeC.

본 발명에 있어서의 극성기 함유 화합물은 상기 극성기 함유 화합물과 붕소 화합물과의 반응으로 얻어지는 화합물일 수도 있다. 해당 붕소 화합물로서는 예를 들어 산화붕소, 할로겐화붕소, 붕산, 붕산 무수물, 붕산 에스테르 등을 들 수 있다. 이 반응에 있어서는 붕소 화합물은 상기 극성기 함유 화합물 1몰에 대하여, 바람직하게는 0.01 내지 10몰의 몰비로, 보다 바람직하게는 0.05 내지 5몰의 몰비로 사용된다. The polar group containing compound in this invention may be a compound obtained by reaction of the said polar group containing compound and a boron compound. Examples of the boron compound include boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, and the like. In this reaction, the boron compound is preferably used in a molar ratio of 0.01 to 10 moles, more preferably 0.05 to 5 moles per mole of the polar group-containing compound.

상기 반응에 있어서는 용제, 예를 들어 탄화수소 오일, 헥산, 헵탄, 옥탄, 톨루엔, 크실렌 등의 유기 용제를 사용할 수 있다. In the said reaction, a solvent, for example, organic solvents, such as a hydrocarbon oil, hexane, heptane, an octane, toluene, xylene, can be used.

상기 반응의 반응 온도는 특별히 제한은 없지만, 바람직하게는 50 내지 250 ℃, 보다 바람직하게는 100 내지 200 ℃이다. Although the reaction temperature of the said reaction does not have a restriction | limiting in particular, Preferably it is 50-250 degreeC, More preferably, it is 100-200 degreeC.

본 발명에 있어서는, 극성기 함유 화합물을 1종 단독으로 사용할 수도 있고, 2종 이상을 혼합하여 사용할 수도 있다. 또한 극성기 함유 화합물의 배합량은, 조성물 전량 기준으로 0.01 내지 5.0 질량%가 바람직하고, 0.1 내지 2.0 질량%가 더욱 바람직하다. 배합량이 0.01 질량% 이상인 것으로 충분한 마찰 저감 효과가 얻어지고, 5.0 질량% 이상이 되면 용해된 나머지가 생기는 경우가 있다. In this invention, a polar group containing compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, 0.01-5.0 mass% is preferable on the basis of a composition whole quantity, and, as for the compounding quantity of a polar group containing compound, 0.1-2.0 mass% is more preferable. When the compounding amount is 0.01% by mass or more, a sufficient friction reducing effect is obtained, and when the amount is 5.0% by mass or more, the dissolved residue may occur.

본 발명의 윤활유 조성물에 있어서는, 그 효과를 저해하지 않는 범위에서 종래 공지된 첨가제를 배합할 수도 있다. 첨가제로서는, 산화 방지제, 무회계 분산제, 금속계 청정제, 점도 지수 향상제, 유동점 강하제, 금속 불활성화제, 방청제 및 소포제 등을 들 수 있다. In the lubricating oil composition of this invention, you may mix | blend a conventionally well-known additive in the range which does not inhibit the effect. Examples of the additive include antioxidants, ashless dispersants, metal cleaners, viscosity index improvers, pour point depressants, metal deactivators, rust inhibitors and antifoaming agents.

상기 산화 방지제로서는, 인을 포함하지 않는 산화 방지제가 바람직하고, 예를 들어 페놀계 산화 방지제, 아민계 산화 방지제, 몰리브덴 아민 착체계 산화 방지제, 황계 산화 방지제 등을 들 수 있다. As said antioxidant, antioxidant which does not contain phosphorus is preferable, For example, a phenolic antioxidant, an amine antioxidant, a molybdenum amine complex system antioxidant, sulfur type antioxidant, etc. are mentioned.

페놀계 산화 방지제로서는 예를 들어 4,4'-메틸렌비스(2,6-디-t-부틸페놀), 4,4'-비스(2,6-디-t-부틸페놀), 4,4'-비스(2-메틸-6-t-부틸페놀), 2,2'-메틸렌비스(4-에틸-6-t-부틸페놀), 2,2'-메틸렌비스(4-메틸-6-t-부틸페놀), 4,4'-부틸리덴비스(3-메틸-6-t-부틸페놀), 4,4'-이소프로필리덴비스(2,6-디-t-부틸페놀), 2,2'-메틸렌비스(4-메틸-6-노닐페놀), 2,2'-이소부틸리덴비스(4,6-디메틸페놀), 2,2'-메틸렌비스(4-메틸-6-시클로헥실페놀), 2,6-디-t-부틸-4-메틸페놀, 2,6-디-t-부틸-4-에틸페놀, 2,4-디메틸-6-t-부틸페놀, 2,6-디-t-아밀-p-크레졸, 2,6-디-t-부틸-4-(N,N'-디메틸아미노메틸페놀), 4,4'-티오비스(2-메틸-6-t-부틸페놀), 4,4'-티오비스(3-메틸-6-t-부틸페놀), 2,2'-티오비스(4-메틸-6-t-부틸페놀), 비스(3-메틸-4-히드록시-5-t-부틸벤질)술피드, 비스(3,5-디-t-부틸-4-히드록시벤질)술피드, n-옥틸-3-(4-히드록시-3,5-디-t-부틸페닐)프로피오네이트, n-옥타데실-3-(4-히드록시-3,5-디-t-부틸페닐)프로피오네이트, 2,2'-티오[디에틸-비스-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트] 등을 들 수 있다. As a phenolic antioxidant, 4,4'- methylenebis (2,6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4, for example '-Bis (2-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6- t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6- Cyclohexylphenol), 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 2, 6-di-t-amyl-p-cresol, 2,6-di-t-butyl-4- (N, N'-dimethylaminomethylphenol), 4,4'-thiobis (2-methyl-6- t-butylphenol), 4,4'-thiobis (3-methyl-6-t-ë-tylphenol), 2,2'-thiobis (4-methyl-6-t-butylinol), bis (3- Methyl-4-hydroxy-5-t-butylbenzyl) sulfide, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, n-octyl-3- (4-hydroxy -3,5-di-t-butylphenyl) propionate, n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,2'-thio [Diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] etc. are mentioned.

이들 중에서 특히 비스페놀계 및 에스테르기 함유 페놀계인 것이 바람직하다. Among these, it is especially preferable that they are bisphenol type and ester group containing phenol type.

또한, 상기 아민계 산화 방지제로서는 예를 들어 모노옥틸디페닐아민, 모노노닐디페닐아민 등의 모노알킬디페닐아민계; 4,4'-디부틸디페닐아민, 4,4'-디펜틸디페닐아민, 4,4'-디헥실디페닐아민, 4,4'-디헵틸디페닐아민, 4,4'-디옥틸디페닐아민, 4,4'-디노닐디페닐아민 등의 디알킬디페닐아민계; 테트라부틸디페닐아민, 테트라헥실디페닐아민; 테트라옥틸디페닐아민, 테트라노닐디페닐아민 등의 폴리알킬디페닐아민계; 및 α-나프틸아민, 페닐-α-나프틸아민, 또한 부틸페닐-α-나프틸아민, 펜틸페닐-α-나프틸아민, 헥실페닐-α-나프틸아민, 헵틸페닐-α-나프틸아민, 옥틸페닐-α-나프틸아민, 노닐페닐-α-나프틸아민 등의 알킬 치환 페닐-α-나프틸아민 등을 들 수 있다. Moreover, as said amine antioxidant, For example, Monoalkyl diphenylamine type, such as monooctyl diphenylamine and monononyl diphenylamine; 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine Dialkyl diphenylamines such as 4,4'-dinonyldiphenylamine; Tetrabutyldiphenylamine, tetrahexyldiphenylamine; Polyalkyldiphenylamines such as tetraoctyldiphenylamine and tetranonyldiphenylamine; And α-naphthylamine, phenyl-α-naphthylamine, but also butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthyl And alkyl substituted phenyl-α-naphthylamines such as amines, octylphenyl-α-naphthylamine and nonylphenyl-α-naphthylamine.

이들 중에서 디알킬디페닐아민계 및 나프틸아민계인 것이 바람직하다. It is preferable that they are dialkyl diphenylamine type and naphthylamine type among these.

상기 몰리브덴 아민 착체계 산화 방지제로서는, 6가의 몰리브덴 화합물, 구체적으로는 3산화몰리브덴 및/또는 몰리브덴산과 아민 화합물을 반응시켜서 이루어지는 것, 예를 들어 일본 특허 공개 제2003-252887호 공보에 기재된 제조 방법으로 얻어지는 화합물을 사용할 수 있다. As said molybdenum amine complex antioxidant, it is made by reacting a hexavalent molybdenum compound, specifically molybdenum trioxide and / or molybdate acid, and an amine compound, for example by the manufacturing method of Unexamined-Japanese-Patent No. 2003-252887. The compound obtained can be used.

상기 6가의 몰리브덴 화합물과 반응시키는 아민 화합물로서는 특별히 제한되지 않지만, 구체적으로는, 모노아민, 디아민, 폴리아민 및 알칸올아민을 들 수 있다. 보다 구체적으로는, 메틸아민, 에틸아민, 디메틸아민, 디에틸아민, 메틸에틸 아민, 메틸프로필아민 등의 탄소수 1 내지 30의 알킬기(이들 알킬기는 직쇄상이거나 분지상일 수도 있다)를 갖는 알킬아민; 에테닐아민, 프로페닐아민, 부테닐아민, 옥테닐아민 및 올레일아민 등의 탄소수 2 내지 30의 알케닐기(이들 알케닐기는 직쇄상이거나 분지상일 수도 있다)를 갖는 알케닐아민; 메탄올아민, 에탄올아민, 메탄올에탄올아민, 메탄올프로판올아민 등의 탄소수 1 내지 30의 알칸올기(이들 알칸올기는 직쇄상이거나 분지상일 수도 있다)를 갖는 알칸올아민; 메틸렌디아민, 에틸렌디아민, 프로필렌디아민 및 부틸렌디아민 등의 탄소수 1 내지 30의 알킬렌기를 갖는 알킬렌디아민; 디에틸렌트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타민, 펜타에틸렌헥사민 등의 폴리아민; 운데실디에틸아민, 운데실디에탄올아민, 도데실디프로판올아민, 올레일디에탄올아민, 올레일프로필렌디아민, 스테아릴테트라에틸렌펜타민 등의 상기 모노아민, 디아민, 폴리아민에 탄소수 8 내지 20의 알킬기 또는 알케닐기를 갖는 화합물이나 이미다졸린 등의 복소환 화합물; 이들 화합물의 알킬렌옥시드 부가물; 및 이들 혼합물 등을 예시할 수 있다. Although it does not restrict | limit especially as an amine compound made to react with the said hexavalent molybdenum compound, Specifically, a monoamine, a diamine, a polyamine, and an alkanolamine are mentioned. More specifically, Alkylamine which has a C1-C30 alkyl group (These alkyl groups may be linear or branched), such as methylamine, ethylamine, dimethylamine, diethylamine, methylethyl amine, and methylpropylamine; Alkenylamines having alkenyl groups having 2 to 30 carbon atoms (the alkenyl groups may be linear or branched) such as ethenylamine, propenylamine, butenylamine, octenylamine and oleylamine; Alkanolamines having an alkanol group having 1 to 30 carbon atoms (these alkanol groups may be linear or branched) such as methanol amine, ethanol amine, methanol ethanol amine and methanol propanol amine; Alkylenediamines having an alkylene group having 1 to 30 carbon atoms such as methylenediamine, ethylenediamine, propylenediamine and butylenediamine; Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; An alkyl group having 8 to 20 carbon atoms or alkenyl to the above monoamines, diamines, and polyamines, such as undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine, oleyl diethanolamine, oleylpropylenediamine, and stearyltetraethylenepentamine Heterocyclic compounds such as a compound having a group and imidazoline; Alkylene oxide adducts of these compounds; And these mixture etc. can be illustrated.

또한, 일본 특허 공고 평3-22438호 공보 및 일본 특허 공개 제2004-2866호 공보에 기재되어 있는 숙신산 이미드의 황 함유 몰리브덴 착체 등을 예시할 수 있다. Moreover, the sulfur containing molybdenum complex of the succinic acid imide described in Unexamined-Japanese-Patent No. 3-22438 and Unexamined-Japanese-Patent No. 2004-2866 can be illustrated.

상기 황계 산화 방지제로서는 예를 들면 페노티아진, 펜타에리트리톨-테트라키스-(3-라우릴티오프로피오네이트), 디도데실설파이드, 디옥타데실설파이드, 디도데실티오디프로피오네이트, 디옥타데실티오디프로피오네이트, 디미리스틸티오디프로피오네이트, 도데실옥타데실티오디프로피오네이트, 2-머캅토벤조이미다졸 등을 들 수 있다. Examples of the sulfur-based antioxidant include phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropionate), dododecyl sulfide, dioctadecyl sulfide, didodecylthiodipropionate, dioctade Silthiodipropionate, dimyristyl thiodipropionate, dodecyl octadecyl thiodipropionate, 2-mercaptobenzoimidazole, and the like.

이들 산화 방지제 중에서도, 금속분이나 황분을 저감시키는 관점에서, 페놀계 산화 방지제 및 아민계 산화 방지제가 바람직하다. 또한, 상기 산화 방지제는 1종을 단독으로 사용할 수도 있고, 2종 이상을 혼합하여 사용할 수도 있다. 이 중에서도 산화 안정성의 효과라는 관점에서, 페놀계 산화 방지제 1종 또는 2종 이상과 아민계 산화 방지제 1종 또는 2종 이상과의 혼합물이 바람직하다. Among these antioxidants, phenolic antioxidants and amine antioxidants are preferable from the viewpoint of reducing metal powder and sulfur powder. In addition, the said antioxidant may be used individually by 1 type, and may mix and use 2 or more types. Among these, from the viewpoint of the effect of oxidation stability, a mixture of one or two or more phenolic antioxidants and one or two or more amine antioxidants is preferable.

산화 방지제의 배합량은 조성물 전량 기준으로, 0.1 내지 5 질량%의 범위가 바람직하고, 0.1 내지 3 질량%의 범위가 보다 바람직하다. The range of 0.1-5 mass% is preferable on the basis of a composition whole quantity, and, as for the compounding quantity of antioxidant, the range of 0.1-3 mass% is more preferable.

또한, 상기 무회 분산제로서는, 윤활유에 사용되는 임의의 무회 분산제를 사용할 수 있지만, 예를 들어 하기 화학식 IX로 표시되는 모노 타입의 숙신산 이미드 화합물, 또는 하기 화학식 X으로 표시되는 비스 타입의 숙신산 이미드 화합물을 들 수 있다. As the ashless dispersant, any ashless dispersant used for lubricating oil can be used, but for example, a mono-type succinic acid imide compound represented by the following general formula (IX) or a bis-type succinic acid imide represented by the following general formula (X) The compound can be mentioned.

Figure pct00017
Figure pct00017

상기 화학식 IX, X에 있어서, R19, R21 및 R24는 각각 수 평균 분자량 500 내지 4,000의 알케닐기 또는 알킬기이고, R21 및 R24는 동일하거나 상이할 수도 있으며, R19, R21 및 R24의 수 평균 분자량은 바람직하게는 1,000 내지 4,000이다. In Formulas IX and X, R 19 , R 21, and R 24 each represent an alkenyl group or alkyl group having a number average molecular weight of 500 to 4,000, and R 21 and R 24 may be the same or different, and R 19 , R 21, and The number average molecular weight of R 24 is preferably 1,000 to 4,000.

상기 R19, R21 및 R24의 수 평균 분자량이 500 이상이면, 기유에 대한 용해성이 양호하고, 4,000 이하이면 분산성이 저하될 우려는 없다. Wherein R 19, R 21 and R 24 is a number-average molecular weight of not less than 500, it is excellent in solubility in a base oil, and 4,000 minutes or less there is no danger of acid is decreased.

또한, R20, R22 및 R23은 각각 탄소수 2 내지 5의 알킬렌기이며, R22 및 R23은 동일하거나 상이할 수도 있고, r은 1 내지 10의 정수를 나타내며, s는 0 또는 1 내지 10의 정수를 나타낸다. 또한, 상기 r은 바람직하게는 2 내지 5, 보다 바람직하게는 3 내지 4이다. r이 1 이상이면 분산성이 양호하고, r이 10 이하이면, 기유에 대한 용해성도 양호하다. R 20 , R 22 and R 23 are each an alkylene group having 2 to 5 carbon atoms, R 22 and R 23 may be the same or different, r represents an integer of 1 to 10, and s is 0 or 1 to 1 The integer of 10 is shown. Also, the r is preferably 2 to 5, more preferably 3 to 4. Dispersibility is favorable when r is 1 or more, and solubility to base oil is also favorable when r is 10 or less.

또한 화학식 X에 있어서, s는 바람직하게는 1 내지 4, 보다 바람직하게는 2 내지 3이다. s가 1 내지 4의 범위 내이면, 분산성 및 기유에 대한 용해성의 점에서 바람직하다. In the formula (X), s is preferably 1 to 4, more preferably 2 to 3. If s is in the range of 1-4, it is preferable at the point of dispersibility and solubility to base oil.

상기 알케닐기로서는, 폴리부테닐기, 폴리이소부테닐기, 에틸렌-프로필렌 공중합체를 들 수 있고, 알킬기로서는 이들을 수소 첨가한 것이다. 바람직한 알케닐기의 대표예로서는, 폴리부테닐기 또는 폴리이소부테닐기를 들 수 있다. 상기 폴리부테닐기는, 1-부텐과 이소부텐의 혼합물 또는 고순도의 이소부텐을 중합시킨 것으로서 얻어진다. As said alkenyl group, a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer are mentioned, As an alkyl group, these are hydrogenated. As a representative example of a preferable alkenyl group, a polybutenyl group or a polyisobutenyl group is mentioned. The polybutenyl group is obtained by polymerizing a mixture of 1-butene and isobutene or isobutene of high purity.

또한, 바람직한 알킬기의 대표예는, 폴리부테닐기 또는 폴리이소부테닐기를 수소 첨가한 것이다. Moreover, the typical example of a preferable alkyl group is hydrogenated polybutenyl group or polyisobutenyl group.

상기 알케닐숙신산 이미드 화합물 또는 알킬숙신산 이미드 화합물은 통상, 폴리올레핀과 무수 말레산과의 반응에서 얻어지는 알케닐숙신산 무수물, 또는 그것을 수소 첨가해서 얻어지는 알킬 숙신산 무수물을 폴리아민과 반응시킴으로써 제조할 수 있다. 또한, 상기 모노 타입의 숙신산 이미드 화합물 및 비스 타입의 숙신산 이미드 화합물은 상기 알케닐숙신산 무수물 또는 알킬 숙신산 무수물과 폴리아민과의 반응 비율을 바꿈으로써 제조할 수 있다. The alkenylsuccinic acid imide compound or the alkyl succinic acid imide compound can generally be produced by reacting an alkenylsuccinic anhydride obtained by reaction of a polyolefin with maleic anhydride or an alkyl succinic anhydride obtained by hydrogenation thereof with a polyamine. The mono-type succinic acid imide compound and the bis-type succinic acid imide compound can be produced by changing the reaction ratio of the alkenylsuccinic anhydride or alkyl succinic anhydride and polyamine.

상기 폴리올레핀을 형성하는 올레핀 단량체로서는, 탄소수 2 내지 8의 α-올레핀의 1종 또는 2종 이상을 혼합해서 사용할 수 있지만, 이소부텐과 부텐-1과의 혼합물을 바람직하게 사용할 수 있다.As an olefin monomer which forms the said polyolefin, although 1 type (s) or 2 or more types of C2-C8 alpha olefin can be mixed and used, the mixture of isobutene and butene-1 can be used preferably.

또한, 상기 폴리아민으로서는, 에틸렌디아민, 프로필렌디아민, 부틸렌디아민, 펜틸렌디아민 등의 단일 디아민; 디에틸렌트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타민, 펜타에틸렌헥사민, 디(메틸에틸렌)트리아민, 디부틸렌트리아민, 트리부틸렌테트라민, 펜타펜틸렌헥사민 등의 폴리알킬렌폴리아민; 아미노에틸피페라진 등의 피페라진 유도체 등을 들 수 있다. Moreover, as said polyamine, Single diamine, such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine; Polyalkylenes such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine, tributylenetetramine, pentapentylenehexamine Polyamines; Piperazine derivatives, such as amino ethyl piperazine, etc. are mentioned.

또한, 무회 분산제로서는, 상기 알케닐 또는 알킬 숙신산 이미드 화합물 외에, 그의 붕소 유도체 및/또는 이들을 유기산으로 변성한 것을 사용할 수도 있다. As the ashless dispersant, in addition to the alkenyl or alkyl succinic acid imide compounds, boron derivatives thereof and / or those modified with organic acids can also be used.

알케닐 또는 알킬 숙신산 이미드 화합물의 붕소 유도체는, 통상법에 의해 제조된 것을 사용할 수 있다. 예를 들어, 상기 폴리올레핀을 무수 말레산과 반응시켜서 알케닐숙신산 무수물로 한 후, 또한 상기의 폴리아민과 산화 붕소, 할로겐화 붕소, 붕산, 붕산 무수물, 붕산 에스테르, 붕소산의 암모늄염 등의 붕소 화합물을 반응시켜서 얻어지는 중간체와 반응시켜서 이미드화 시킴으로써 얻어진다. The boron derivative of an alkenyl or alkyl succinic acid imide compound can use the thing manufactured by the conventional method. For example, the polyolefin is reacted with maleic anhydride to form alkenylsuccinic anhydride, and then the polyamine and boron compounds such as boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, and ammonium salt of boric acid are reacted. It is obtained by making it imidize by making it react with the obtained intermediate.

이 붕소 유도체 중의 붕소 함유량에는, 특별히 제한은 없지만, 붕소로서 바람직하게는 0.05 내지 5 질량%의 범위, 보다 바람직하게는 0.1 내지 3 질량%의 범위이다. Although there is no restriction | limiting in particular in the boron content in this boron derivative, As boron, Preferably it is the range of 0.05-5 mass%, More preferably, it is the range of 0.1-3 mass%.

또한, 상기 무회 분산제의 배합량은 윤활유 조성물 전량 기준으로, 0.5 내지 15 질량%의 범위가 바람직하고, 보다 바람직하게는 1 내지 10 질량%의 범위, 더욱 바람직하게는 3 내지 7 질량%의 범위이다. In addition, the amount of the ashless dispersant is preferably in the range of 0.5 to 15% by mass, more preferably in the range of 1 to 10% by mass, still more preferably in the range of 3 to 7% by mass, based on the total amount of the lubricating oil composition.

배합량이 0.5 질량% 미만의 경우는, 고온 하에 있어서의 염기가 유지성에 대한 효과가 적고, 한편, 15 질량%를 초과하는 경우는, 윤활유 조성물의 저온 유동성이 대폭 악화되기 때문에 각각 바람직하지 않다. When the compounding amount is less than 0.5% by mass, the base under high temperature has little effect on the retention, while when the amount exceeds 15% by mass, the low-temperature fluidity of the lubricating oil composition is greatly deteriorated, which is not preferable.

상기 금속계 청정제로서는, 윤활유에 사용되는 임의의 알칼리토류 금속계 청정제가 사용 가능해서 예를 들어 알칼리토류 금속 술포네이트, 알칼리토류 금속 페네이트, 알칼리토류 금속살리실레이트 및 이들 중에서 선택되는 2종 이상의 혼합물 등을 들 수 있다. As the metal-based cleaning agent, any alkaline earth metal-based cleaning agent used for lubricating oil can be used, and for example, alkaline earth metal sulfonate, alkaline earth metal phenate, alkaline earth metal salicylate and mixtures of two or more selected from these, etc. Can be mentioned.

상기 알칼리토류 금속 술포네이트로서는, 분자량이 바람직하게는 300 내지 1,500, 보다 바람직하게는 400 내지 700의 알킬 방향족 화합물을 술폰화함으로써 얻어지는 알킬 방향족 술폰산의 알칼리토류 금속염, 특히 마그네슘염 및/또는 칼슘 염 등을 들 수 있으며, 그 중에서 칼슘염이 바람직하게 사용된다. As the alkaline earth metal sulfonate, preferably an alkaline earth metal salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of preferably 300 to 1,500, more preferably 400 to 700, in particular magnesium salt and / or calcium salt, etc. And calcium salts are used preferably.

상기 알칼리토류 금속 페네이트로서는, 알킬페놀, 알킬페놀설파이드, 알킬페놀의 만니히 반응물의 알칼리토류 금속염, 특히 마그네슘염 및/또는 칼슘 염 등을 들 수 있어 그 중에서 칼슘염이 특히 바람직하게 사용된다. Examples of the alkaline earth metal phenate include alkali earth metal salts, especially magnesium salts and / or calcium salts of Mannich reactants of alkylphenols, alkylphenol sulfides and alkylphenols, and calcium salts are particularly preferably used.

상기 알칼리토류 금속살리실레이트로서는, 알킬 살리실산의 알칼리토류 금속염, 특히 마그네슘염 및/또는 칼슘염 등을 들 수 있고, 그 중에서 칼슘염이 바람직하게 사용된다. Examples of the alkaline earth metal salicylate include alkaline earth metal salts of alkyl salicylic acid, in particular magnesium salts and / or calcium salts, among which calcium salts are preferably used.

상기 알칼리토류 금속계 청정제를 구성하는 알킬기로서는, 탄소수 4 내지 30인 것이 바람직하고, 보다 바람직하게는 6 내지 18의 직쇄 또는 분지 알킬기이고 이들은 직쇄상이거나 분지상일 수도 있다. As an alkyl group which comprises the said alkaline-earth metal type detergent, it is preferable that it is C4-C30, More preferably, it is a 6-18 group or branched alkyl group, These may be linear or branched.

이들은 또한 1급 알킬기, ２급 알킬기 또는 3급 알킬기일 수도 있다. They may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.

또한, 알칼리토류 금속 술포네이트, 알칼리토류 금속 페네이트 및 알칼리토류 금속 살리실레이트로서는, 상기한 알킬 방향족 술폰산, 알킬페놀, 알킬페놀 설파이드, 알킬페놀의 만니히 반응물, 알킬 살리실산 등을, 직접 마그네슘 및/또는 칼슘의 알칼리토류 금속의 산화물이나 수산화물 등의 알칼리토류 금속 염기와 반응시키거나, 또는 일단 나트륨염이나 칼륨염 등의 알칼리 금속염으로 하고나서 알칼리토류 금속염과 치환시킴으로써 얻어지는 중성 알칼리토류 금속 술포네이트, 중성 알칼리토류 금속 페네이트 및 중성 알칼리토류 금속 살리실레이트 뿐만 아니라, 중성 알칼리토류 금속 술포네이트, 중성 알칼리토류 금속 페네이트 및 중성 알칼리토류 금속살리실레이트와 과잉의 알칼리토류 금속염이나 알칼리토류 금속 염기를 물의 존재 하에서 가열함으로써 얻어지는 염기성 알칼리토류 금속 술포네이트, 염기성 알칼리토류 금속 페네이트 및 염기성 알칼리토류 금속 살리실레이트나, 탄산 가스의 존재 하에서 중성 알칼리토류 금속 술포네이트, 중성 알칼리토류 금속 페네이트 및 중성 알칼리토류 금속 살리실레이트를 알칼리토류 금속의 탄산염 또는 붕산염을 반응시킴으로써 얻어지는 과염기성 알칼리토류 금속 술포네이트, 과염기성 알칼리토류 금속 페네이트 및 과염기성 알칼리토류 금속 살리실레이트도 포함된다. In addition, as alkaline earth metal sulfonate, alkaline earth metal phenate, and alkaline earth metal salicylate, the above-mentioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reactant of alkylphenol, alkyl salicylic acid, etc. can be directly added to magnesium and A neutral alkaline earth metal sulfonate obtained by reacting with an alkaline earth metal base such as an oxide or hydroxide of an alkaline earth metal of calcium or an alkali metal salt such as sodium salt or potassium salt and then replacing the alkaline earth metal salt with Not only neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates, but also neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates and excess alkaline earth metal salts or alkaline earth metal bases In the presence of water Basic alkaline earth metal sulfonates, basic alkaline earth metal phenates and basic alkaline earth metal salicylates obtained by heating, neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salins in the presence of carbon dioxide gas Also included are overbased alkaline earth metal sulfonates, overbased alkaline earth metal phenates and overbased alkaline earth metal salicylates obtained by reacting the silates with carbonates or borates of alkaline earth metals.

본 발명에서 사용하는 금속계 청정제로서는, 조성물 중의 황분을 저감시킬 목적으로 알칼리토류 금속 살리실레이트나 알칼리토류 금속 페네이트가 바람직하고, 이 중에서도 과염기성 살리실레이트나 과염기성 페네이트가 바람직하고, 특히 과염기성 칼슘살리실레이트가 바람직하다. As the metal-based cleaning agent used in the present invention, alkaline earth metal salicylates and alkaline earth metal phenates are preferred for the purpose of reducing the sulfur content in the composition, and among these, overbased salicylates and overbased phenates are particularly preferred. Overbased calcium salicylates are preferred.

본 발명에서 사용하는 금속계 청정제의 전 염기가는 10 내지 500mgKOH/g의 범위가 바람직하고, 보다 바람직하게는 15 내지 450mgKOH/g의 범위이며, 이들 중에서 선택되는 1종 또는 2종 이상 병용할 수 있다. The total base value of the metallic detergent used in the present invention is preferably in the range of 10 to 500 mgKOH / g, more preferably in the range of 15 to 450 mgKOH / g, and may be used in combination of one or two or more selected from these.

또한, 여기에서 말하는 전 염기가란, JIS K 2501 「석유제품 및 윤활유-중화 가 시험 방법」의 7.에 준거해서 측정되는 전위차 적정법(염기가?과염소산법)에 의한 전 염기가를 의미한다. In addition, all-base value here means all-base value by the potentiometric titration method (base-perchloric acid method) measured based on 7. of JISK2501 "petroleum product and lubricating oil-neutralization test method."

또한, 본 발명에 있어서 사용하는 금속계 청정제로서는, 그 금속비에 특별히 제한은 없고, 통상 20 이하의 것을 1종 또는 2종 이상 혼합해서 사용할 수 있지만, 금속비가 바람직하게는 3 이하, 보다 바람직하게 1.5 이하, 특히 바람직하게는 1.2이하의 금속계 청정제를 사용하는 것이 산화 안정성이나 염기가 유지성 및 고온 청정성 등에 의해 우수하기 때문에 특히 바람직하다. In addition, as a metal type cleaning agent used in this invention, there is no restriction | limiting in particular in the metal ratio, Usually, 20 or less types can be used 1 type or in mixture of 2 or more types, Preferably, metal ratio is 3 or less, More preferably, 1.5 Hereinafter, it is particularly preferable to use a metallic detergent of 1.2 or less because it is excellent in oxidative stability, base stability, high temperature cleanability, and the like.

또한, 여기에서 말하는 금속비란, 금속계 청정제에 있어서의 (금속 원소의 가수)×(금속 원소 함유량(몰%))/(비누기 함유량(몰%))으로 표시되고, 금속 원소란 칼슘, 마그네슘 등을, 비누기란 술폰산기, 페놀기 및 살리실산기 등을 의미한다. In addition, the metal ratio here is represented by (the valence of a metal element) x (metal element content (mol%)) / (soap content (mol%)) in a metal type detergent, and a metal element is calcium, magnesium, etc. The soap group means a sulfonic acid group, a phenol group and a salicylic acid group.

상기 금속계 청정제의 배합량은 윤활유 조성물 전량 기준으로, 0.01 내지 20 질량%의 범위가 바람직하고, 0.1 내지 10 질량%의 범위가 보다 바람직하고, 0.5 내지 5 질량%의 범위가 더욱 바람직하다. As for the compounding quantity of the said metal type cleaning agent, the range of 0.01-20 mass% is preferable on the basis of the lubricating oil composition whole quantity, The range of 0.1-10 mass% is more preferable, The range of 0.5-5 mass% is further more preferable.

배합량이 0.01 질량% 미만인 경우, 고온 청정성이나 산화 안정성, 염기가 유지성 등의 성능이 얻기 어려워지기 때문에 바람직하지 않다. 한편, 20 질량% 이하이면 통상 그 첨가량에 적당한 효과를 얻을 수 있지만, 해당 금속계 청정제의 배합량의 상한에 대해서는 상기의 범위에 관계없이, 배합량을 가능한 한 낮게 하는 것이 긴요하다. 그것에 의하여 윤활유 조성물의 금속분, 즉 황산회분을 적게 하고, 자동차의 배출 가스 정화 장치의 열화를 방지할 수 있다. When the compounding amount is less than 0.01% by mass, it is not preferable because performances such as high temperature cleanliness, oxidative stability, and base stability are difficult to obtain. On the other hand, if it is 20 mass% or less, a moderate effect can normally be acquired with the addition amount, but it is important to make a compounding quantity as low as possible about the upper limit of the compounding quantity of the said metal type cleaning agent irrespective of said range. Thereby, metal powder, ie, sulfuric acid ash of a lubricating oil composition can be reduced, and deterioration of the exhaust gas purification apparatus of an automobile can be prevented.

또한, 금속계 청정제는 상기의 규정량을 함유할 뿐, 단독 또는 2종 이상을 조합해서 사용할 수도 있다. In addition, a metallic detergent contains only the said prescribed amount and can also be used individually or in combination of 2 or more types.

구체적으로는, 상기 금속계 청정제 중에서는 과염기성 칼슘 살리실레이트 또는 과염기성 칼슘 페네이트가 상기 무회계 분산제 중에서는 상기 폴리부테닐숙신산 비스이미드가 특히 바람직하다. 또한, 상기 과염기성 칼슘살리실레이트 및 과염기성 칼슘 페네이트의 전 염기가는 100 내지 500mgKOH/g의 범위인 것이 바람직하고, 200 내지 500mgKOH/g의 범위가 보다 바람직하다. Specifically, in the metal-based detergent, overbased calcium salicylate or overbased calcium phenate is particularly preferable in the ashless dispersant. The total base value of the overbased calcium salicylate and overbased calcium phenate is preferably in the range of 100 to 500 mgKOH / g, more preferably in the range of 200 to 500 mgKOH / g.

상기 점도 지수 향상제로서는 예를 들어 폴리메타크릴레이트, 분산형 폴리 메타크릴레이트, 올레핀계 공중합체(예를 들어, 에틸렌-프로필렌 공중합체 등), 분산형 올레핀계 공중합체, 스티렌계 공중합체(예를 들어, 스티렌-디엔 공중합체, 스티렌-이소프렌 공중합체 등) 등을 들 수 있다. Examples of the viscosity index improver include polymethacrylates, dispersed polymethacrylates, olefin copolymers (for example, ethylene-propylene copolymers), dispersed olefin copolymers, and styrene copolymers (for example, For example, a styrene diene copolymer, a styrene isoprene copolymer, etc. can be mentioned.

점도 지수 향상제의 배합량은 배합 효과의 관점에서, 윤활유 조성물 전량 기준으로, 0.5 내지 15 질량%의 범위가 바람직하고, 보다 바람직하게는 1 내지 10 질량%의 범위이다. From the viewpoint of the blending effect, the blending amount of the viscosity index improver is preferably in the range of 0.5 to 15 mass%, more preferably in the range of 1 to 10 mass%.

상기 유동점 강하제로서는 예를 들어 중량 평균 분자량이 5000 내지 50,000정도의 폴리메타크릴레이트 등을 들 수 있다. Examples of the pour point depressant include polymethacrylate having a weight average molecular weight of about 5000 to 50,000.

유동점 강하제의 배합량은 배합 효과의 관점에서, 윤활유 조성물 전량 기준으로, 0.1 내지 2 질량%의 범위가 바람직하고, 보다 바람직하게는 0.1 내지 1 질량%의 범위이다. From the viewpoint of the blending effect, the blending amount of the pour point lowering agent is preferably in the range of 0.1 to 2% by mass, more preferably in the range of 0.1 to 1% by mass, based on the total amount of the lubricating oil composition.

상기 금속 불활성화제로서는, 예를 들어 벤조트리아졸계, 톨릴트리아졸계, 티아디아졸계 및 이미다졸계 화합물 등을 들 수 있다. As said metal deactivator, a benzotriazole type, tolyl triazole type, a thiadiazole type, an imidazole type compound, etc. are mentioned, for example.

금속 불활성제의 배합량은, 윤활유 조성물 전량 기준으로, 0.01 내지 3 질량%의 범위가 바람직하고, 보다 바람직하게는 0.01 내지 1 질량%의 범위이다. As for the compounding quantity of a metal deactivator, the range of 0.01-3 mass% is preferable on the basis of the lubricating oil composition whole quantity, More preferably, it is the range of 0.01-1 mass%.

상기 방청제로서는 예를 들어 석유 술포네이트, 알킬벤젠술포네이트, 디노닐나프탈렌술포네이트, 알케닐숙신산에스테르, 다가 알코올에스테르 등을 들 수 있다. As said rust inhibitor, a petroleum sulfonate, alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinic acid ester, polyhydric alcohol ester, etc. are mentioned, for example.

이들 방청제의 배합량은 배합 효과의 관점에서, 윤활유 조성물 전량 기준으로 0.01 내지 1 질량%의 범위가 바람직하고, 보다 바람직하게는 0.05 내지 0.5 질량%의 범위이다. From the viewpoint of the blending effect, the blending amount of these rust inhibitors is preferably in the range of 0.01 to 1% by mass, more preferably in the range of 0.05 to 0.5% by mass.

상기 소포제로서는, 예를 들어 실리콘유, 플루오로 실리콘유 및 플루오로알킬에테르 등을 들 수 있고, 배합량은, 소포 효과 및 경제성의 균형 등의 점에서, 윤활유 조성물 전량 기준으로 0.005 내지 0.5 질량%의 범위가 바람직하고, 보다 바람직하게는 0.01 내지 0.2 질량%의 범위이다. Examples of the antifoaming agent include silicone oil, fluoro silicone oil, fluoroalkyl ether, and the like, and the compounding amount is 0.005 to 0.5% by mass based on the total amount of the lubricating oil composition in view of the balance of defoaming effect and economic efficiency. A range is preferable, More preferably, it is the range of 0.01-0.2 mass%.

본 발명의 윤활유 조성물에 있어서는, 또한 필요에 따라 마찰 조정제, 내마모제, 극압제를 배합할 수도 있다. 또한 이 마찰 조정제는, 본 발명의 필수 성분인 극성기 함유 화합물 이외의 화합물을 가리킨다. 마찰 조정제의 배합량은, 윤활유 조성물 전량 기준으로 0.01 내지 2 질량%의 범위가 바람직하고, 보다 바람직하게는 0.01 내지 1 질량%의 범위이다. In the lubricating oil composition of this invention, you may mix | blend a friction modifier, an antiwear agent, and an extreme pressure agent further as needed. In addition, this friction modifier points out compounds other than the polar group containing compound which is an essential component of this invention. As for the compounding quantity of a friction modifier, the range of 0.01-2 mass% is preferable on the basis of the lubricating oil composition whole quantity, More preferably, it is the range of 0.01-1 mass%.

상기 내마모제 또는 극압제로서는, 디티오인산 아연, 인산 아연, 디티오카르밤산 아연, 디티오카르밤산 몰리브덴, 디티오인산 몰리브덴, 디술피드류(본 발명에서 사용하는 화학식 I 또는 II로 표시되는 황 함유 화합물 외의 것을 가리키고, 예를 들어 디벤질디술피드)를 들 수 있다. 황화 올레핀류, 황화 유지류, 황화 에스테르류, 티오카르보네이트류, 티오카바메이트류, 폴리설파이드류 등의 황 함유 화합물; 아인산에스테르류, 인산에스테르류, 포스폰산 에스테르류 및 이들 아민염 또는 금속염 등의 인 함유 화합물; 티오아인산에스테르류, 티오인산에스테르류, 티오포스폰산 에스테르류 및 이들 아민 염 또는 금속염 등의 황 및 인 함유 내마모제 등을 들 수 있다. Examples of the antiwear or extreme pressure agent include zinc dithiophosphate, zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, and disulfides (sulfur-containing represented by the formula (I) or (II) used in the present invention). Points other than a compound are mentioned, for example, dibenzyl disulfide). Sulfur-containing compounds such as sulfided olefins, sulfurized fats and oils, sulfided esters, thiocarbonates, thiocarbamates and polysulfides; Phosphorus-containing compounds such as phosphite esters, phosphate esters, phosphonic acid esters, and these amine salts and metal salts; Sulfur and phosphorus containing antiwear agents, such as thiophosphoric acid ester, thiophosphoric acid ester, thiophosphonic acid ester, these amine salt, or a metal salt, etc. are mentioned.

내마모제 또는 극압제를 배합할 경우, 그 배합량은 내마모제 또는 극압제를 배합하는 것에 의한 윤활유 중의 인분이나 황분 및 금속분의 함유량이 과대해지지 않도록 유의할 필요가 있다. When mix | blending an antiwear agent or extreme pressure agent, it is necessary to care about the compounding quantity so that content of phosphorus, sulfur, and metal powder in lubricating oil by mix | blending an antiwear agent or extreme pressure agent may not become excessive.

본 발명의 윤활유 조성물은 상기한 조성으로 이루어지는 것이지만, 그 성상으로서 이하를 만족하는 것이 바람직하다. Although the lubricating oil composition of this invention consists of said composition, it is preferable to satisfy the following as a property.

(1) 황산회분(JIS K2272)이 0.6 질량% 이하, 보다 바람직하게는 0.1 질량% 이하인 것, 및(1) sulfuric acid ash (JIS K2272) is 0.6 mass% or less, more preferably 0.1 mass% or less, and

(2) 인 함유량(JIS-5S-38-92)이, 0.5 질량% 이하, 보다 바람직하게는 0 질량% 인 것. (2) Phosphorus content (JIS-5S-38-92) is 0.5 mass% or less, More preferably, it is 0 mass%.

또한, 상기 외에 이하를 만족하는 것이 더욱 바람직하다. Moreover, it is more preferable to satisfy the followings other than the above.

(3) 황 함유량(JIS K2541)이 0.4 질량% 이하, 보다 바람직하게는 0.2 질량% 이하인 것. (3) Sulfur content (JIS K2541) is 0.4 mass% or less, More preferably, it is 0.2 mass% or less.

(4) 붕소 함유량이 0.4 질량% 이하, 보다 바람직하게는 0.2 질량% 이하인 것. (4) Boron content is 0.4 mass% or less, More preferably, it is 0.2 mass% or less.

이들 성상을 만족하는 본 발명의 윤활유 조성물은 자동차 엔진의 산화 촉매, 3원 촉매, NOx 흡장형 환원 촉매, 디젤 파티큘레이트 필터(DPF) 등의 열화를 억제할 수 있다. The lubricating oil composition of the present invention, which satisfy these properties can be prevented from being deteriorated such as a car engine an oxidation catalyst, three-way catalysts, NO x occlusion type reducing catalyst, a diesel particulate filter (DPF).

본 발명의 윤활유 조성물은 상기 황 함유 화합물 및 극성기 함유 화합물을 조합하여 사용하는 것으로서, 이 병용의 결과, 각각의 단독 사용시를 훨씬 초과하는 내마모성 및 마찰 저감 효과를 발현한다. 따라서, 종래부터 윤활유 첨가제로서 자주 사용되어 온 디티오인산 아연을 배합하지 않아도 충분히 우수한 윤활 성능을 갖는 윤활유 조성물을 얻을 수 있고, 상기 황산회분 등의 성상을 달성하는 것이 용이해진다. 또한, 후술하는 바와 같이 본 발명의 윤활유 조성물은, DLC 처리를 실시한 접동부에 사용하는 경우에도 우수한 마찰 저감 효과를 나타내는 것이다. The lubricating oil composition of the present invention uses a combination of the sulfur-containing compound and the polar group-containing compound, and as a result of this combination, it exhibits abrasion resistance and friction reducing effect far exceeding each use alone. Therefore, a lubricating oil composition having sufficiently good lubricating performance can be obtained without blending zinc dithiophosphate, which has conventionally been frequently used as a lubricating oil additive, and it becomes easy to achieve properties such as sulfuric acid ash. Moreover, as mentioned later, the lubricating oil composition of this invention shows the outstanding friction reduction effect also when using for the sliding part which performed the DLC process.

본 발명의 윤활유 조성물은 2륜차, 4륜차, 발전용, 선박용 등의 가솔린 엔진, 디젤 엔진, 가스 엔진 등의 내연 기관용 윤활유로서 바람직하게 사용할 수 있고, 저인분, 저황분, 저황산회분이기 때문에, 특히 배출 가스 정화 장치를 장착한 내연 기관용에 바람직하다. Since the lubricating oil composition of this invention can be used suitably as lubricating oil for internal combustion engines, such as gasoline engines, diesel engines, and gas engines, such as a two-wheeled vehicle, a four-wheeled vehicle, power generation, and a ship, and since it is low phosphorus, low sulfur, and low sulfuric acid ash, It is especially suitable for the internal combustion engine equipped with the exhaust gas purification apparatus.

또한 본 발명의 윤활유 조성물은, 상기 이외의 용도에 있어서도 바람직하게 사용된다. 특히 본 발명의 윤활유 조성물이 우수한 내마모성 및 마찰 저감 효과를 발현하는 것으로부터, 예를 들어 내연 기관, 자동 변속기, 무단 변속기, 수동 변속기, 파워 스티어링, 쇼크 업소버, 압축기, 냉매 압축기, 냉동기, 유압 펌프 및 클러치 풀리 등의 윤활용으로 이용된다. 즉, 본 발명의 윤활유 조성물은, 내연 기관 오일, 자동 변속기유, 무단 변속기 오일, 수동 변속기 오일, 파워스티어링 오일, 쇼크 업소버 오일, 압축기 오일, 냉동기유, 유압 펌프 오일, 클러치 풀리용 윤활유 및 그리스 등에 사용할 수 있다. Moreover, the lubricating oil composition of this invention is used suitably also in the use of that excepting the above. In particular, since the lubricating oil composition of the present invention exhibits excellent wear resistance and friction reducing effect, for example, an internal combustion engine, an automatic transmission, a continuously variable transmission, a manual transmission, a power steering, a shock absorber, a compressor, a refrigerant compressor, a refrigerator, a hydraulic pump, and Used for lubrication of clutch pulleys. That is, the lubricating oil composition of the present invention includes an internal combustion engine oil, an automatic transmission oil, a continuously variable transmission oil, a manual transmission oil, a power steering oil, a shock absorber oil, a compressor oil, a freezer oil, a hydraulic pump oil, a lubricant for a clutch pulley, grease and the like. Can be used.

본 발명의 윤활유 조성물은, 접동면이 강철 등의 금속일 경우 뿐만 아니라, 접동면의 적어도 일부에 DLC막을 갖는 경우에도 마찰 저감 효과나 우수한 내마모성을 발현한다. The lubricating oil composition of the present invention exhibits a friction reducing effect and excellent wear resistance not only when the sliding surface is a metal such as steel, but also when the sliding surface has a DLC film on at least part of the sliding surface.

해당 DLC막은 마찰 저감 효과를 높이는 관점에서, 수소 함유량이 40 원자% 이하의 것이 바람직하고, 30 원자% 이하의 것이 보다 바람직하고, 20 원자% 이하의 것이 특히 바람직하다. From the viewpoint of enhancing the friction reducing effect, the DLC film preferably has a hydrogen content of 40 atomic% or less, more preferably 30 atomic% or less, and particularly preferably 20 atomic% or less.

접동면에 DLC막을 갖는 접동 부재의 상대 부재에 대해서는 특별히 제한은 없고 예를 들어 동일하게 DLC막을 갖는 접동 부재일 수도 있고 철이나 철합금 부재, 알루미늄 합금 부재 또는 수지나 고무재 등의 유기 재료일 수도 있다. There is no restriction | limiting in particular about the relative member of the sliding member which has a DLC film | membrane in a sliding surface, For example, it may be a sliding member which has a DLC film | membrane similarly, or may be an organic material, such as iron, an iron alloy member, an aluminum alloy member, resin, or a rubber material have.

<실시예>  <Examples>

이어서, 실시예 및 비교예에 의해 본 발명을 더욱 상세하게 설명하지만, 본 발명은 이들 실시예에 한정되는 것은 아니다. Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

<성상, 성능의 측정 방법>  <Method of measuring appearance, performance>

이하의 실시예, 비교예에 있어서의 윤활유 조성물의 성상 및 성능은 다음 방법에 의해서 구했다. The properties and the performance of the lubricating oil composition in the following examples and comparative examples were determined by the following method.

(1) 동점도 (1) kinematic viscosity

JIS K 2283에 준거해서 측정했다. It measured based on JISK2283.

(2) 인 함유량 (2) phosphorus content

JPI-5S-38-92에 준거해서 측정했다. It measured based on JPI-5S-38-92.

(3) 황 함유량 (3) sulfur content

JIS K 2541에 준거해서 측정했다. It measured based on JISK2541.

(4) 붕소 함유량 (4) boron content

JPI-5S-38-92에 준거해서 측정했다. It measured based on JPI-5S-38-92.

(5) 황산회분 (5) sulfuric acid ash

JIS K 2272에 준거해서 측정했다. It measured based on JISK2272.

(6) 왕복 이동 마찰시험 (6) Reciprocating friction test

왕복 이동 마찰 시험기에서, 시험판 및 시험구로서 이하를 이용하여 하기의 조건으로 시험을 행하고, 마찰 계수를 구했다. In the reciprocating friction tester, the test was performed under the following conditions as a test plate and a test tool, and the friction coefficient was obtained.

? 시험판: SUJ-2제 판  ? Trial: SUJ-2

? 시험구: DLC(수소 함유량:20%) 처리를 실시한 SUJ-2제 1/2인치 구  ? Test sphere: 1/2 inch sphere made of SUJ-2 treated with DLC (hydrogen content: 20%)

[시험 조건]  [Exam conditions]

? 시험 온도: 100 ℃  ? Test temperature: 100 ℃

? 하중: 200g  ? Load: 200g

? 진폭: 10mm  ? Amplitude: 10mm

? 접동 속도: 1.0mm/sec  ? Sliding Speed: 1.0mm / sec

(7) 마찰 마모 시험 (7) friction wear test

왕복 이동 마찰시험기에서, 시험판 및 시험구로서 이하를 사용하여 하기의 조건으로 시험을 행하고, 시험판의 마모 자국 폭을 측정했다. In the reciprocating friction tester, the test was performed under the following conditions as a test plate and a test tool, and the wear mark width of the test plate was measured.

? 시험판: SUJ-2제 판  ? Trial: SUJ-2

? 시험구: SUJ-2제 구(직경 10 mm)  ? Test mouth: sphere made of SUJ-2 (diameter 10mm)

[시험 조건] [Exam conditions]

? 시험 온도: 100 ℃  ? Test temperature: 100 ℃

? 하중: 200 N  ? Load: 200 N

? 진폭: 10 mm  ? Amplitude: 10 mm

? 진동수: 10 Hz  ? Frequency: 10 Hz

? 시험 시간: 30 분  ? Test time: 30 minutes

실시예 1 내지 7, 비교예 1 내지 9 Examples 1 to 7, Comparative Examples 1 to 9

제1의 표에 나타낸 기유 및 첨가제를 제1의 표에 나타내는 비율로 배합하여, 윤활유 조성물을 제조했다. 그 조성물의 성상?조성 및 성능을 제1의 표에 나타낸다. The base oil and additive shown in the 1st table were mix | blended in the ratio shown in a 1st table, and the lubricating oil composition was produced. The properties, compositions and performances of the composition are shown in the first table.

Figure pct00018
Figure pct00018

Figure pct00019
Figure pct00019

[주] [week]

?기유: 수소화 정제기유, 40 ℃ 동점도 21 ㎟/s, 100 ℃ 동점도 4.5 ㎟/s, 점도지수 127, %CA 0.0, 황 함유량 20 질량ppm 미만, 노악(NOACK) 증발량 13.3 질량% Base oil: Hydrogenated refined base oil, 40 ℃ kinematic viscosity 21 mm2 / s, 100 ℃ kinematic viscosity 4.5 mm2 / s, viscosity index 127,% C A 0.0, sulfur content less than 20 mass ppm, NOACK evaporation 13.3 mass%

? 황 함유 화합물 A: 1,1-비스(옥톡시카르보닐메틸)디술피드  ? Sulfur-containing compound A: 1,1-bis (octoxycarbonylmethyl) disulfide

? 황 함유 화합물 B: 디티오말산테트라-1-헥실  ? Sulfur-containing compound B: dithiomalate tetra-1-hexyl

? 극성기 함유 화합물 A: 글리세린모노올레이트  ? Polar group-containing compound A: glycerin monooleate

? 극성기 함유 화합물 B: 올레산디에탄올 아미드  ? Polar group-containing compound B: oleic acid diethanol amide

? 극성기 함유 화합물 C: 글리세린 모노올레일에테르  ? Polar group-containing compound C: glycerin monooleyl ether

? 극성기 함유 화합물 D: N,N-디폴리옥시에틸렌-N-올레일 아민  ? Polar group-containing compound D: N, N-dipolyoxyethylene-N-oleyl amine

? 극성기 함유 화합물 E: 글리세린모노올레이트의 붕산과의 반응물  ? Polar group-containing compound E: reaction product of glycerin monooleate with boric acid

? 극성기 함유 화합물 F: 올레산디에탄올 아미드의 붕산과의 반응물  ? Polar group-containing compound F: reaction product of oleic acid diethanol amide with boric acid

? 점도 지수 향상제: 폴리메타크릴레이트, 중량 평균 분자량 420,000, 수지량 39 질량%  ? Viscosity index improver: Polymethacrylate, weight average molecular weight 420,000, resin amount 39 mass%

? 유동점 강하제: 폴리알킬메타크릴레이트, 중량 평균 분자량 6,000  ? Pour point depressant: Polyalkyl methacrylate, weight average molecular weight 6,000

? 폴리부테닐숙신산 이미드: 폴리부테닐기의 수 평균 분자량 1000, 질소 함유량 1.76 질량%, 붕소 함유량 1.9 질량%  ? Polybutenyl succinic acid imide: Number average molecular weight 1000 of a polybutenyl group, 1.76 mass% of nitrogen content, 1.9 mass% of boron content

?페놀계 산화 방지제: 옥타데실-3-(3,5-디-tert-부틸-4-히드록시페닐)프로피오네이트  Phenolic antioxidant: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

?아민계 산화 방지제: 디알킬디페닐아민, 질소 함유량 4.62 질량%  Amine-based antioxidants: dialkyldiphenylamine, nitrogen content 4.62 mass%

?디알킬디티오인산 아연: Zn 함유량 9.0 질량%, 인 함유량 8.2 질량%, 황 함유량 17.1 질량%, 알킬기(제２급 부틸기와 제２급 헥실기의 혼합물)  Zinc dialkyl dithiophosphate: Zn content 9.0 mass%, phosphorus content 8.2 mass%, sulfur content 17.1 mass%, alkyl group (mixture of secondary butyl group and secondary hexyl group)

?기타: 소포제, 금속 불활성화제  Others: defoamer, metal deactivator

제1의 표, 제2의 표에 나타낸 바와 같이, 실시예 1 내지 7의 윤활유 조성물은 황 함유 화합물 및 극성기 함유 화합물의 병용에 의한 상승 효과에 의해, 낮은 마찰 계수 및 낮은 마모 자국 직경값을 나타내고 있다. As shown in the first and second tables, the lubricating oil compositions of Examples 1 to 7 exhibit low friction coefficient and low wear mark diameter values due to the synergistic effect of the combination of the sulfur-containing compound and the polar group-containing compound. have.

즉, 극성기 함유 화합물을 갖지 않는 비교예 1에 있어서는 마찰 계수가 0.140이며, 황 함유 화합물을 갖지 않는 비교예 2 내지 7에 있어서는 마찰 계수가 0.124 내지 0.128임에도 불구하고 이들을 조합함으로써 마찰 계수를 0.110 내지 0.117(실시예 1 내지 7)까지 저감화할 수 있다. 또한, 극성기 함유 화합물을 갖지 않는 비교예 1에 있어서는 마모 자국 직경값이 0.52이며, 황 함유 화합물을 갖지 않는 비교예 2 내지 7에 있어서는 마모 자국 직경값이 0.60 내지 0.65에도 불구하고 이들을 조합함으로써 마모 자국 직경값을 0.42 내지 0.46(실시예 1 내지 7)으로까지 저감화할 수 있다. That is, in Comparative Example 1 having no polar group-containing compound, the friction coefficient was 0.140. In Comparative Examples 2 to 7, which did not have sulfur-containing compound, the friction coefficient was 0.110 to 0.117 by combining them even though the friction coefficient was 0.124 to 0.128. It can be reduced to (Examples 1 to 7). In addition, in Comparative Example 1 having no polar group-containing compound, the wear mark diameter value was 0.52. In Comparative Examples 2 to 7, which did not have a sulfur-containing compound, the wear mark diameter was combined by combining them despite the 0.60 to 0.65 wear mark diameter. The diameter value can be reduced to 0.42 to 0.46 (Examples 1 to 7).

또한 실시예 1 내지 7과 비교예 8과의 대비에서 알 수 있는 바와 같이, 본원 발명의 첨가제의 병용에 의해 발현하는 효과는, 디알킬디티오인산 아연을 단독으로 배합한 경우의 효과를 상회하는 것이다. 또한 비교예 9에서 나타낸 바와 같이, 본원 발명에서 사용하는 황 함유 화합물 대신 디알킬디티오인산 아연을 사용해서 극성기 함유 화합물과 병용해도, 실시예 1 내지 7로 나타나는 것과 같은 낮은 마찰 계수 및 낮은 마모 자국 직경값은 얻어지지 않는다. In addition, as can be seen from the comparison between Examples 1 to 7 and Comparative Example 8, the effect expressed by the use of the additive of the present invention is greater than the effect of combining zinc dialkyldithiophosphate alone. will be. In addition, as shown in Comparative Example 9, even when used in combination with the polar group-containing compound using zinc dialkyldithiophosphate instead of the sulfur-containing compound used in the present invention, low friction coefficient and low wear marks as shown in Examples 1 to 7 The diameter value is not obtained.

상기한 바와 같이 특정한 황 함유 화합물 및 특정한 극성기 함유 화합물을 병용함으로써, 디알킬디티오인산 아연이 갖는 내마모성을 초과할 수 있고, 이 결과, 저인분, 저황분, 저황산회분으로서도 내마모성이 우수한 윤활유 조성물로서, 우수한 마찰 저감 효과를 발현하는 윤활유 조성물을 얻을 수 있다. By using a specific sulfur-containing compound and a specific polar group-containing compound as described above, the wear resistance of zinc dialkyldithiophosphate can be exceeded. As a result, a lubricating oil composition excellent in wear resistance even as low phosphorus, low sulfur and low sulfuric acid ash As the lubricant composition, an excellent friction reducing effect can be obtained.

<산업상 이용가능성>  Industrial Applicability

본 발명에 따르면, 저인분, 저황분, 저황산회분으로서도 내마모성이 우수한 윤활유 조성물로서, 또한 DLC 처리를 실시한 접동부에 사용하는 경우에도 우수한 마찰 저감 효과를 발현하는 윤활유 조성물이 제공된다. 따라서, 본 발명의 윤활유 조성물은 가솔린 엔진, 디젤 엔진, 가스 엔진 등, 내연 기관용 윤활유 조성물로서 특히 바람직하게 이용할 수 있다.According to the present invention, there is provided a lubricating oil composition exhibiting excellent friction reducing effect even when used as a lubricating oil composition excellent in wear resistance even in low phosphorus, low sulfur powder and low sulfuric acid ash. Therefore, the lubricating oil composition of this invention can be used especially preferably as a lubricating oil composition for internal combustion engines, such as a gasoline engine, a diesel engine, and a gas engine.

Claims (7)

기유에,
(A) 하기의 화학식 I 및 II로 나타내는 황 함유 화합물로부터 선택되는 적어도 1종과,
(B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물
을 배합해서 이루어지는 윤활유 조성물.
Figure pct00020

(R1 내지 R12는 각각 독립적으로 수소 원자; 알킬기, 시클로알킬기, 알케닐기, 시클로알케닐기 및 아릴기로부터 선택되는 탄화수소기; 또는 이들 탄화수소기 중에 산소 원자, 질소 원자 및 황 원자로부터 선택되는 원자를 포함하여 이루어지는 헤테로 원자 함유기를 나타내고, Y는 각각 독립적으로 -O-, -S-, -SO-, -SO2-, -(C=O)O-, -(C=O)NH-, -O(C=O)NH-, -C(=O)-, -N(H)-, -NHCONH-, -N=N-, -NH-C(=NH)-NH-, -S-C(=O)-, -NH-C(=S)- 및 -NH-C(=S)-NH-로부터 선택되는 2가의 기를 나타내고, x는 1 내지 3의 정수이며, n은 각각 독립적으로 1 내지 5의 정수임) Base oil,
(A) at least one selected from sulfur-containing compounds represented by the following formulas (I) and (II),
(B) a polar group-containing compound having at least one polar group selected from an amino group, an amide group and a hydroxyl group and an alkyl group having 3 to 24 carbon atoms
Lubricating oil composition formed by blending.
Figure pct00020

(R 1 to R 12 are each independently a hydrogen atom; a hydrocarbon group selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group; or an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom in these hydrocarbon groups) And a hetero atom-containing group comprising a compound, and each Y independently represents -O-, -S-, -SO-, -SO 2 -,-(C = O) O-,-(C = O) NH-, -O (C = O) NH-, -C (= O)-, -N (H)-, -NHCONH-, -N = N-, -NH-C (= NH) -NH-, -SC ( = O)-, -NH-C (= S)-and -NH-C (= S) -NH- represent a divalent group selected, x is an integer of 1 to 3, n is each independently 1 to Is an integer of 5) 제1항에 있어서, 상기 (B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물이, 글리세린 부분 지방산 에스테르, 글리세린모노에테르 화합물, 아민 화합물 및 아미드 화합물로 이루어지는 군으로부터 선택되는 적어도 1종의 화합물인 윤활유 조성물. The polar group-containing compound according to claim 1, wherein the polar group-containing compound having at least one polar group selected from the amino group, the amide group and the hydroxyl group and an alkyl group having 3 to 24 carbon atoms is a glycerin partial fatty acid ester, a glycerin monoether compound, or an amine compound. And at least one compound selected from the group consisting of amide compounds. 제1항에 있어서, 상기 (B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물이, 하기 화학식 III 또는 IV로 나타내는 글리세린 지방산 모노에스테르, 또는 하기 화학식 V 또는 VI으로 나타내는 글리세린모노에테르 화합물인 윤활유 조성물.
Figure pct00021

(R13 및 R14는 각각 독립적으로 탄소수 3 내지 24의 알킬기를 나타냄) The glycerin fatty acid monoester according to claim 1, wherein the (B) polar group-containing compound having at least one polar group selected from an amino group, an amide group and a hydroxyl group and an alkyl group having 3 to 24 carbon atoms is represented by the following general formula (III) or (IV): Or a glycerol monoether compound represented by the following formula (V) or (VI).
Figure pct00021

(R 13 and R 14 each independently represent an alkyl group having 3 to 24 carbon atoms) 제1항에 있어서, 상기 (B) 아미노기, 아미드기 및 수산기로부터 선택되는 적어도 1종의 극성기 및 탄소수 3 내지 24의 알킬기를 갖는 극성기 함유 화합물이, 하기 화학식 VII로 나타내는 아민 화합물 또는 하기 화학식 VIII로 나타내는 아미드 화합물인 윤활유 조성물.
Figure pct00022

(R15 및 R17은 각각 독립적으로 탄소수 3 내지 24의 알킬기를 나타내고, R16 및 R18은 각각 독립적으로 수소 원자 또는 탄소수 2 내지 4의 직쇄 알킬기의 말단 수소 원자가 수산기로 치환되어 이루어지는 기를 나타냄)The polar group-containing compound according to claim 1, wherein the polar group-containing compound having at least one polar group selected from the amino group, the amide group and the hydroxyl group and an alkyl group having 3 to 24 carbon atoms is represented by the amine compound represented by the following general formula (VII) or the general formula (VIII) The lubricating oil composition which is an amide compound shown.
Figure pct00022

(R 15 and R 17 each independently represent an alkyl group having 3 to 24 carbon atoms, and R 16 and R 18 each independently represent a group in which a terminal hydrogen atom of a hydrogen atom or a straight chain alkyl group having 2 to 4 carbon atoms is substituted with a hydroxyl group) 제1항 내지 제4항 중 어느 한 항에 있어서, 윤활유 조성물 전량 기준으로 인 함유량이 0.5 질량% 이하, 황산회분이 0.6 질량% 이하인 윤활유 조성물. The lubricating oil composition of any one of Claims 1-4 whose phosphorus content is 0.5 mass% or less and sulfuric acid ash 0.6 mass% or less on the basis of the lubricating oil composition whole quantity. 제1항 내지 제5항 중 어느 한 항에 있어서, 윤활유 조성물 전량 기준으로 인 함유량이 0 질량%, 황산회분이 0.1 질량% 이하인 윤활유 조성물. The lubricating oil composition of any one of Claims 1-5 whose phosphorus content is 0 mass% and sulfuric acid ash content of 0.1 mass% or less on the basis of the lubricating oil composition whole quantity. 제1항 내지 제6항 중 어느 한 항에 있어서, 다이아몬드 라이크 카본(DLC) 처리를 실시한 접동부용 윤활유 조성물인 윤활유 조성물.The lubricating oil composition according to any one of claims 1 to 6, which is a lubricating oil composition for a sliding part subjected to a diamond-like carbon (DLC) treatment.
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US20120238481A1 (en) 2012-09-20
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CN102639684A (en) 2012-08-15
JPWO2011068137A1 (en) 2013-04-18

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