JP2021155740A - Lubricant composition - Google Patents

Abstract

To provide a lubricant composition that has an extended shudder prevention life without lowering the inter-metal friction coefficient even when the viscosity is lowered.SOLUTION: Provided is a lubricant composition characterized in containing: (A) a lubricant base oil; (C)(C-1) a succinimide compound or a boronated succinimide compound having a mass average molecular weight of 4,000 to 7,000, (C-2) a succinimide compound or a boronated succinimide compound having a mass average molecular weight of more than 7,000 to 10,000; and (D) phosphorus based extreme-pressure agent, and in which the lubricant composition does not contain zinc dithiophosphate and may optionally contain a sulfur based extreme-pressure agent, provided that the content of the sulfur based extreme-pressure agent is not more than 0.1 mass% in the lubricant composition.SELECTED DRAWING: None

Description

The present invention relates to a lubricating oil composition, particularly a lubricating oil composition characterized in that it is suitably used for an automobile transmission. More specifically, the present invention relates to a lubricating oil composition for a continuously variable transmission.

Lubricating oil compositions are widely used in the automobile field such as for internal combustion engines, automatic transmissions, and gear oils. In recent years, in order to achieve fuel efficiency, it has been required to reduce the viscosity of the lubricating oil composition. Further, a continuously variable transmission (CTV) has been widely used in place of a stepped automatic transmission, and a metal belt type CVT that uses a metal belt and a pulley for power transmission has become common.

One method for improving the fuel efficiency of continuously variable transmission vehicles is to expand the operating conditions of the lockup clutch, and it is required to extend the shudder prevention life of the lockup clutch. However, if the amount of the friction modifier is increased in order to extend the shudder prevention life, there arises a problem that the coefficient of friction between metals between the metal belt and the pulley is lowered, the belt grip performance is lowered, and the torque transmission ability is lowered. As described above, the shadder prevention performance and the coefficient of friction between metals are in a trade-off relationship, and it is required to achieve both sufficient torque characteristics and shadder prevention performance at a high level. When the viscosity of the lubricating oil composition for a transmission is reduced, there is also a problem that a sufficient coefficient of friction between metals cannot be obtained and a sufficiently large torque cannot be secured.

For example, Patent Documents 1 to 5 describe conventional lubricating oil compositions for continuously variable transmissions. Patent Document 1 describes a lubricating oil composition in which a specific boron-free succinate imide compound and a phosphorus-based compound are blended and does not contain zinc dialkyldithiophosphate, and is used between a metal belt or a chain and a pulley. It states that the coefficient of friction can be significantly improved, a high coefficient of friction can be maintained for a long period of time, and the clutch plate is not clogged. Patent Document 2 describes a lubricant composition containing a sulfonate-based cleaning agent, a salicylate-based cleaning agent, and a boron-containing succinimide-based additive in a specific amount and a specific amount ratio, and maintains sufficient torque transmission capacity and shifting characteristics. However, it states that it has excellent shudder prevention performance. Patent Document 3 describes a lubricating oil composition containing a specific amount of a boronized alkyl succinimide and / or a borated alkenyl succinimide having a specific weight average molecular weight, and a metal-based cleaning agent having a linear alkyl group. However, it is stated that it has a high coefficient of friction between metals and is excellent in shifting characteristics and shudder prevention performance. Patent Document 4 describes a lubricating oil composition containing a specific sulfolane derivative, one or more selected from calcium sulfonate and calcium phenate, and a specific amount of a specific viscosity index improver, and has a high coefficient of metal friction. , It is stated that both fuel saving and component durability due to low viscosity are achieved. Patent Document 5 provides a high coefficient of friction between metals and anti-shudder properties by blending at least four types of additives such as calcium salicylate, a phosphorus-based anti-friction agent, a friction modifier, and a dispersed viscosity index improver as essential components. It states that they are compatible.

Japanese Unexamined Patent Publication No. 2006-056934 JP-A-2007-126541 Japanese Unexamined Patent Publication No. 2009-215395 Japanese Unexamined Patent Publication No. 2010-180278 Japanese Unexamined Patent Publication No. 2000-355695

In view of the above circumstances, a first object of the present invention is to provide a lubricating oil composition having an extended shudder prevention life without lowering the coefficient of friction between metals even when the viscosity is lowered.

As a result of diligent studies, the present inventors have combined two types of succinimide compounds or boring succinimide compounds having a specific mass average molecular weight as ashless dispersants, and further use a phosphorus-based extreme pressure agent in combination. As a result, it has been found that the shade prevention life can be extended without lowering the coefficient of friction between metals even when the viscosity is lowered, and the present invention has been achieved.

That is, the present invention
(A) Lubricating oil base oil,
(C) (C-1) Succinimide compound or borated succinimide compound having a mass average molecular weight of 4,000 to 7,000,
(C-2) A lubricating oil composition comprising (C-2) a succinate imide compound or a boring succinate imide compound having a mass average molecular weight of more than 7,000 to 10,000, and (D) a phosphorus-based extreme pressure agent. Therefore, the lubricating oil composition does not contain zinc dithiophosphate and may optionally contain a sulfur-based extreme pressure agent, except that the content of the sulfur-based extreme pressure agent is 0.1 in the lubricating oil composition. The lubricating oil composition having a mass% or less.

Further, in order to improve fuel efficiency, it is required to reduce the viscosity at low temperature (for example, 40 ° C.), which affects the fuel efficiency, while maintaining the viscosity at high temperature (for example, 100 ° C.) as much as possible, that is, a high viscosity index is required. The conventional stepless transmission lubricating oil composition has a problem that the polymer chains of the base oil and the viscosity index improver are cut by mechanical shearing, which causes a decrease in high-temperature viscosity with running.

By further specifying the composition of the lubricating oil base oil and the viscosity index improver in the lubricating oil composition, the present inventors have the effect of extending the shudder prevention life without lowering the coefficient of friction between metals, and shearing. We have found that stability can be improved.
That is, the present invention further
(A) Lubricating oil base oil,
(C) (C-1) Succinimide compound or borated succinimide compound having a mass average molecular weight of 4,000 to 7,000,
(C-2) A lubricating oil composition comprising (C-2) a succinate imide compound or a boronized succinate imide compound having a mass average molecular weight of more than 7,000 to 10,000, and (D) a phosphorus-based extreme pressure agent. Therefore, the lubricating oil composition does not contain zinc dithiophosphate and may optionally contain a sulfur-based extreme pressure agent, except that the content of the sulfur-based extreme pressure agent is 0.1 in the lubricating oil composition. It is less than% by mass and
A poly-α-olefin or α-olefin copolymer having a ^{kinematic viscosity of 6 to 80 mm 2} / s at 100 ° C. as a part or all of the component (A) was added to the total weight of the lubricating oil composition. Provided are a lubricating oil composition containing ~ 30% by weight and (B) further comprising a polymethacrylate having a mass average molecular weight of 15,000 to 40,000.

上記式において、Ｒ^１は互いに独立に炭素数４０〜４００のアルキル基またはアルケニル基であり、ｍは１〜２０の整数であり、ｎは０〜２０の整数である。
（４）１００℃における動粘度３〜１０ｍｍ^２／ｓを有する。
（５）粘度指数１５０以上を有する。
（６）（Ｄ）リン系極圧剤が、酸性リン酸エステル、酸性亜リン酸エステル、リン酸エステル、亜リン酸エステル、及びこれらのアミン塩、リン酸、及び亜リン酸から選ばれる少なくとも１種以上である。
（７）（Ｄ）リン系極圧剤が、酸性リン酸エステル、酸性亜リン酸エステル、リン酸エステル、亜リン酸エステル、及びこれらのアミン塩の中から選ばれる少なくとも１種以上と、リン酸及び亜リン酸から選ばれる少なくとも１種以上との組合せである。
（８）さらに、（Ｅ）金属清浄剤を含有する。
（９）さらに、（Ｆ）エーテルスルホラン化合物を含有する。
（１０）無段変速機用である。 Further, a preferred embodiment of the lubricating oil composition of the present invention has at least one of the following characteristics (1) to (10).
(1) A part or all of the component (C-1) and the component (C-2) are borated succinimide compounds.
(2) The component (C-1) and the component (C-2) each contain boron by 0.1 to 3 mass with respect to the mass of the component (C-1) or the component (C-2). It is contained in an amount of%.
(3) The succinimide compound is represented by the following formula (1) or (2).

In the above formula, R ¹ is an alkyl group or an alkenyl group having 40 to 400 carbon atoms independently of each other, m is an integer of 1 to 20, and n is an integer of 0 to 20.
(4) It has a kinematic viscosity of 3 to 10 mm ² / s at 100 ° C.
(5) Has a viscosity index of 150 or more.
(6) At least the phosphorus-based extreme pressure agent selected from acidic phosphoric acid ester, acidic phosphite ester, phosphoric acid ester, phosphite ester, and amine salts, phosphoric acid, and phosphite thereof. One or more.
(7) The phosphorus-based extreme pressure agent contains at least one selected from acidic phosphoric acid ester, acidic phosphoric acid ester, phosphoric acid ester, phosphoric acid ester, and amine salts thereof, and phosphorus. It is a combination with at least one selected from acid and phosphite.
(8) Further contains (E) a metal cleaning agent.
(9) Further contains (F) an ether sulfolane compound.
(10) For continuously variable transmissions.

In particular, the lubricating oil composition lubricates a poly-α-olefin or α-olefin copolymer having a ^{kinematic viscosity of 6 to 80 mm 2} / s at 100 ° C. as a part or all of the component (A). It is preferably contained in an amount of 5 to 30% by mass based on the total mass of the oil composition, and preferably contains the (E) ether sulfolane compound. Synthetic base oils have a lower affinity for oil seal rubbers called packings and gaskets than mineral oils, and higher molecular weight (higher viscosity) base oils have a lower affinity. If the affinity is low, the swelling of the seal rubber is reduced, and conversely, it is easy to shrink. As a result, there is a problem that the sealing property is lowered and oil leakage occurs. By adopting the lubricating oil composition of the present invention, the swelling property of the seal rubber can be further ensured.

The lubricating oil composition of the present invention can extend the shudder prevention life without lowering the coefficient of friction between metals. This effect can be achieved even if the kinematic viscosity of the lubricating oil composition at 100 ° C. is lowered to about 5.0. Further, according to the present invention, it is possible to provide a lubricating oil composition having further improved shear stability in addition to the effect. Furthermore, the swelling property of the seal rubber can be ensured. The lubricating oil composition of the present invention can be particularly preferably used as a lubricating oil composition for continuously variable transmissions.

Hereinafter, each component will be described.

(A) Lubricating oil base oil As the lubricating oil base oil in the present invention, a conventionally known lubricating oil base oil can be used, and there are mineral oils, synthetic oils, and mixed oils thereof. ^{In particular, a polyα-olefin or α-olefin copolymer having a kinematic viscosity of 6 to 80 mm 2} / s at 100 ° C. as a part or all of the lubricating oil base oil is added to the mass of the entire lubricating oil composition. The content is preferably 5 to 30% by mass, more preferably the lower limit is 6% by mass, more preferably 8% by mass, and the upper limit is 25% by mass, more preferably 20% by mass. If the content of the base oil is less than the lower limit, a sufficient viscosity index, that is, fuel efficiency and protection performance to mechanical elements cannot be obtained at the same time, and if the content exceeds the upper limit, the shear stability is lowered and the rubber is compatible. (Rubber shrinkage) may occur.

The poly-α-olefin and α-olefin copolymer ^{preferably have a kinematic viscosity of 6 to 80 mm 2} / s at 100 ° C., preferably 8 to 80 mm ² / s, and more preferably 8 to 60 mm ² / s. It is s, more preferably 9 to 40 mm ² / s. If the kinematic viscosity at 100 ° C is less than the lower limit, the viscosity index, that is, fuel saving and protection performance to mechanical elements cannot be achieved at the same time, and if the kinematic viscosity at 100 ° C exceeds the upper limit, shear stability is not obtained. It is not preferable because the compatibility of rubber and rubber deteriorates (rubber shrinkage).

The poly-α-olefin or α-olefin copolymer may be a (co) polymer or (co) oligomer of an α-olefin and has the above-mentioned kinematic viscosity, and conventionally known lubricating oil base oils are used. Can be used. The α-olefin is selected from, for example, a linear or branched olefin hydrocarbon having 2 to 14 carbon atoms, preferably 4 to 12 carbon atoms. For example, 1-octene oligomer, 1-decene oligomer, ethylene-propylene oligomer, isobutene oligomer and hydrides thereof can be mentioned. Further, the poly-α-olefin or α-olefin copolymer may be produced by using a metallocene catalyst. The mass average molecular weight of the (co) polymer or (co) oligomer may be such that the kinematic viscosity at 100 ° C. satisfies the above range. For example, it has a mass average molecular weight of 1,000 to 10,000, preferably 1,100 to 7,000. As the poly-α-olefin or α-olefin copolymer, one type may be used alone, or two or more types may be used in combination.

The lubricating oil composition of the present invention may contain another lubricating oil base oil in combination with the above poly α-olefin or α-olefin copolymer. These lubricating oil base oils are not particularly limited, and conventionally known mineral oil-based base oils and synthetic base oils other than the above-mentioned poly α-olefins and α-olefin copolymers can be used.

As the mineral oil-based base oil, the lubricating oil distillate obtained by atmospheric distillation and vacuum distillation of crude oil is subjected to solvent desorption, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid. Paraffin-based, naphthen-based, etc. lubricating oil base oils that have been refined by appropriately combining refining treatments such as washing and white clay treatment, and lubricating oil base oils obtained by isomerizing and removing wax obtained by solvent dewaxing. Can be mentioned. The kinematic viscosity of the mineral oil-based base oil is not particularly limited, but in order to obtain a lubricating oil composition having a low viscosity, it is preferably ^{1 to 5 mm 2 / s.}

As the synthetic base oil, isoparaffin, alkylbenzene, alkylnaphthalene, monoester, diester, polyol ester, polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl ether, GTL base oil and the like can be used. The kinematic viscosity of the synthetic base oil is not particularly limited. It is also possible to use a poly-α-olefin or α-olefin copolymer having a kinematic viscosity at 100 ° C. of ^{less than 6 mm 2} / s or more than 80 mm ^{2 / s.} In order to obtain a lubricating oil composition having a low viscosity, the kinematic viscosity of the synthetic base oil is preferably 1 to 6 ^{mm 2 / s.}

As the base oil that can be used in combination, one type may be used alone, or two or more types may be used. When using two or more types, use two or more types of mineral oil-based base oil, use two or more types of synthetic base oil, and use one or more types of mineral oil-based base oil and one or more types of synthetic base oil. Is possible. Among them, the single use of mineral oil-based base oil, the use of two or more kinds of mineral oil-based ^{base oil, the single use of synthetic base oil having a kinematic viscosity of 1 to 6 mm or less than 2} / s at 100 ° C., and the kinematic viscosity at 100 ° C. It is preferable to use two or more kinds of synthetic base oils having a ^{thickness of 1 to} 6 mm and less than 2 / s.

Further, in order to obtain a lubricating oil composition having a low viscosity, the overall lubricating oil base oil has a kinematic viscosity at 100 ° C. of ^{2 to} 7 mm 2 / s, preferably 2.3 to ⁶ mm 2 / s, particularly 2 It is preferable to have .5-5.6 mm ^{2 / s.}

(B) Viscosity Index Improver The lubricating oil composition of the present invention can contain a conventionally known viscosity index improver. Preferably, the viscosity index improver contains polymethacrylate having a mass average molecular weight of 15,000 to 40,000. The lower limit of the mass average molecular weight is preferably 17,000, more preferably 18,000. The upper limit of the mass average molecular weight is preferably 38,000, more preferably 36,000. If the mass average molecular weight is less than the lower limit, the effect of improving the viscosity index is insufficient, and if the mass average molecular weight is more than the upper limit, the effect of improving the viscosity index can be obtained, but the shear stability. Is not preferable because it worsens. The content of the polymethacrylate is not limited, but is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, still more preferably 2 to 10% by mass in the lubricating oil composition.

One type of polymethacrylate may be used alone, or two or more types may be used in combination. The content when two or more kinds are used in combination is not limited. The total content of the polymethacrylate is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, still more preferably 2 to 10% by mass in the lubricating oil composition.

The lubricating oil composition of the present invention may contain another viscosity index improver in addition to the above polymethacrylate. Other viscosity index improvers include polymethacrylates having a mass average molecular weight of less than 15,000, polymethacrylates having a mass average molecular weight of more than 40,000, polyisobutylene and its hydrogenated products, and styrene-diene hydrogenated copolymers. Examples include coalescing, styrene-maleic anhydride copolymers and polyalkylstyrene. When another viscosity index improver is contained, the blending amount is preferably 0.1 to 15% by mass in the lubricating oil composition.

(C) Imide Compound Succinimide or Imide Borone Succinimide Compound The lubricating oil composition of the present invention is characterized by containing two specific imide compounds succinimide or imide boronized succinimide compound as an ashless dispersant. do. That is, in the present invention, the lubricating oil composition has a (C-1) mass average molecular weight of 4,000 to 7,000, preferably 5,000 to 7,000. And (C-2) a succinimide compound having a mass average molecular weight of more than 7,000 to 10,000, preferably 7,100 to 9,600, or a boronized succinimide compound in combination. And. In the following, the component (C-1) may be referred to as a first succinimide compound, and the component (C-2) may be referred to as a second succinimide compound. At least one of the above component (C-1) and the above component (C-2) may be a part or all of the borated succinimide compound. Further, both the component (C-1) and the component (C-2) may be a borated succinimide compound.

The component (C) is preferably added to the composition in an amount of 0.5 to 3% by mass, more preferably 0.6 to 2.5% by mass, still more preferably 0.9 to 2% by mass with respect to the entire composition. It is contained. If it is less than the above lower limit, the shudder prevention property may not be ensured. Above the above upper limit, the viscosity at low temperature may increase.

The mass ratio of the component (C-1) to the component (C-2) is not limited, but is preferably (C-2) / (C-1) = 1-10, more preferably 1.5-8. 2 to 6 are preferable, and 2 to 6 are more preferable. By containing the mixture in a ratio within the above range, it is possible to achieve both a friction coefficient and a shader characteristic. When the amount ratio of (C-2) exceeds the above upper limit value, the amount of the component (C-1) is too small, and the characteristics at low temperature, for example, 40 ° C. are insufficient in the shudder prevention property, and in the durability test, The problem of early manifestation arises. If the amount ratio of (C-2) is less than the above lower limit value, the characteristics at a high temperature, for example, 120 ° C. are insufficient, and there arises a problem that it becomes apparent early in the durability test.

The first and second succinimide compounds in the present invention may be an succinimide compound known as an ashless dispersant or a boring succinimide compound. The boronized succinimide compound includes a succinimide compound having at least one alkyl group or alkenyl group in the molecule, modified (borated) with a boron compound such as boric acid or borate. .. Examples of the alkyl group or alkenyl group include olefins such as propylene, 1-butene and isobutylene, or oligomers thereof, and co-oligomers of ethylene and propylene.

上記式において、Ｒ^１は互いに独立に炭素数４０〜４００のアルキル基またはアルケニル基であり、ｍは１〜２０の整数であり、ｎは０〜２０の整数である。特にはビスタイプのコハク酸イミド化合物が好ましい。コハク酸イミド化合物は、モノタイプ及びビスタイプの併用、２種以上のモノタイプの併用、２種以上のビスタイプの併用であってもよい。 The succinimide compound is, more specifically, a compound in which succinic anhydride is added to a polyamine. There are monotype succinimide compounds and bis-type succinimide compounds, both of which can be used. The monotype succinimide compound can be represented by, for example, the following formula (1). The bis-type succinimide compound can be represented by, for example, the following formula (2).

In the above formula, R ¹ is an alkyl group or an alkenyl group having 40 to 400 carbon atoms independently of each other, m is an integer of 1 to 20, and n is an integer of 0 to 20. In particular, a bis-type succinimide compound is preferable. The succinimide compound may be a combination of a monotype and a bistype, a combination of two or more types of monotypes, and a combination of two or more types of bistypes.

The boronized succinimide compound is a compound obtained by reacting an imide succinimide compound as represented by the above formula with a boron compound. Boron compounds include boric acid, boric anhydride, boric acid ester, boron oxide, and boron halide. The boronized succinimide compound may be used alone or in combination of two or more.

In the lubricating oil composition of the present invention, the first and second succinimide compounds may be part or all of the boronized succinimide compounds. That is, the first and second succinimide compounds in the present invention are independently one or more of the non-borinated succinimide compounds, one or more of the boring succinimide compounds, and the like. And any combination selected from one or more non-borinated succinimide compounds and one or more succinimide compounds boronized. The proportion of the borated succinimide compound in each of the components (C-1) and (C-2) is not particularly limited, but is preferably 5 to 100% by mass, more preferably 20% by mass, based on the mass of each component. It is preferably ~ 100% by mass, more preferably 50-100% by mass.

(C-1) The first succinimide compound has a mass average molecular weight of 4,000 to 7,000. The mass average molecular weight is preferably 5,000 to 7,000, more preferably 5,200 to 6,800. If the molecular weight of the first succinimide compound is less than 4,000, the shader properties deteriorate. In the present invention, the mass average molecular weight of the first succinateimide compound is: solvent: THF (tetrahydrofuran), packed column: styrene / divinylbenzene copolymer, set temperature: 40 ° C., set flow rate 1.0 ml / min. It is a polystyrene-equivalent value measured by an RI (differential refractometer) detector.

When the boronized succinimide compound is used as the first succinimide compound, the boron content in the component (C-1) is not limited, but the boronized succinimide, which is the component (C-1), is used. It is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, further preferably 0.2 to 2% by mass, and particularly 0.2 to 2% by mass, based on the mass of the acidimide compound. 1.5% by mass is preferable. The nitrogen content in the component (C-1) is not limited, but is preferably 0.3 to 10% by mass, more preferably 0.3 to 10% by mass, based on the mass of the imide compound boronized succinate which is the component (C-1). It is preferably 0.5 to 5% by mass, and particularly preferably 0.8 to 2.5% by mass.

The content of the first succinic acid imide compound in the lubricating oil composition is not limited, but is preferably 0.05 to 2% by mass, preferably 0.08 to 1.% by mass, based on the total mass of the lubricating oil composition. 8% by mass is more preferable, and 0.1 to 1.5% by mass is further preferable. If the content is less than the lower limit, sufficient cleanliness may not be ensured, and if the content exceeds the upper limit, sludge may be generated.

(C-2) The second succinimide compound has a mass average molecular weight of more than 7,000 to 10,000. The mass average molecular weight is preferably 7,100 to 9,600, and more preferably 7,500 to 9,200. When the molecular weight of the second succinimide compound exceeds 10,000, the low temperature viscosity deteriorates.
In the present invention, the mass average molecular weight of the second succinateimide compound is: solvent: THF (tetrahydrofuran), packed column: styrene / divinylbenzene copolymer, set temperature: 40 ° C., set flow rate 1.0 ml / min. It is a polystyrene-equivalent value measured by an RI (differential refractometer) detector.

When the boring succinimide compound is used in the second succinimide compound, the boron content in the component (C-2) is not limited, but the succinylated succinic acid which is the component (C-2). The boron content is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, further preferably 0.2 to 2% by mass, and particularly 0, based on the mass of the imide compound. .2 to 1.5% by mass is preferable. The nitrogen content in the component (C-2) is not limited, but is preferably 0.2 to 5% by mass, more preferably 0.2 to 5% by mass, based on the mass of the imide compound boronized succinate which is the component (C-2). It is preferably 0.3 to 2.5% by mass, and particularly preferably 0.5 to 2% by mass.

The content of the second succinimide compound in the lubricating oil composition is not limited, but is preferably 0.05 to 2% by mass, more preferably 0.08 to 1.8% by mass, and 0.1. ~ 1.5% by mass is more preferable. If it is less than the lower limit value, sufficient cleanliness may not be ensured, and if it exceeds the upper limit value, low temperature viscosity is generated.

The lubricant composition of the present invention may further contain another ashless dispersant in combination with the above component (C-1) and the above component (C-2). Other ashless dispersants typically include succinic acid amide compounds.

(D) Phosphorus-based extreme pressure agent The lubricating oil composition of the present invention essentially contains (D) a phosphorus-based extreme pressure agent. The phosphorus-based extreme pressure agent is an extreme pressure agent having phosphorus, and may be a conventionally known one. The content of the phosphorus-based extreme pressure agent in the lubricating oil composition is not limited, but is preferably 0.01 to 2.5% by mass, and 0.02 to 1.5% by mass, based on the total mass of the lubricating oil composition. The mass% is more preferable, and 0.02 to 1.0 mass% is further preferable. The phosphorus-based extreme pressure agent in the present invention may have sulfur, and a phosphorus-sulfur-based extreme pressure agent such as a thiophosphate ester is included in the phosphorus-based extreme pressure agent, and is included in the sulfur-based extreme pressure agent described later. Not done. However, in the present invention, the phosphorus-based extreme pressure agent does not include zinc dithiophosphate. Particularly preferably, the phosphorus-based extreme pressure agent in the present invention does not have a metal element.

The lubricating oil composition of the present invention may further contain a sulfur-based extreme pressure agent in addition to the phosphorus-based extreme pressure agent. The sulfur-based extreme pressure agent is an extreme pressure agent having sulfur, and may be a conventionally known one. Further, as described above, the lubricating oil composition of the present invention does not contain zinc dithiophosphate. Therefore, the sulfur-based extreme pressure agent in the present invention does not include zinc dithiophosphate. Particularly preferably, the sulfur-based extreme pressure agent in the present invention does not have a metal element. The content of the sulfur-based extreme pressure agent in the lubricating oil composition of the present invention is 0.1% by mass or less, preferably 0.08% by mass or less, and more preferably 0.06% by mass or less in the lubricating oil composition. Is the amount. If the lubricating oil composition contains a sulfur-based extreme pressure agent in the lubricating oil composition in an amount exceeding the above upper limit value, the shader characteristics deteriorate.

As described above, the lubricating oil composition of the present invention does not contain zinc dithiophosphate. This is because the presence of zinc dithiophosphate in the lubricating oil composition deteriorates the shader properties of the lubricating oil composition.

The phosphorus-based extreme pressure agent preferably includes a phosphoric acid ester, an acidic phosphoric acid ester, a phosphite ester, an acidic phosphite ester, and amine salts, phosphoric acid, and phosphite thereof. These may be one kind alone or a combination of two or more kinds. Particularly preferably, the phosphorus-based extreme pressure agent includes at least one selected from phosphoric acid ester, acidic phosphoric acid ester, phosphite ester, acidic phosphite ester and amine salts thereof, and phosphoric acid and A combination of at least one selected from phosphite. A sulfur-based extreme pressure agent may be contained in addition to these phosphorus-based extreme pressure agents, but the content must satisfy the above-mentioned conditions.

Phosphate esters and acidic phosphoric acid esters are represented by (R ¹ O) _a P (= O) (OH) _3-a . a is 0, 1, 2, or 3. R ¹ is a monovalent hydrocarbon group having 4 to 30 carbon atoms independently of each other. Here, the case where a = 1 or 2 is the acidic phosphoric acid ester.

Phosphite esters and acidic phosphite esters are represented by (R ² O) _b P (= O) (OH) _2-b H. b is 0, 1, or 2. R ² is a monovalent hydrocarbon group having 4 to 30 carbon atoms independently of each other.

The phosphoric acid ester and acidic phosphoric acid ester are preferably, but are not limited to, a phosphoric acid monoalkyl ester, a phosphoric acid dialkyl ester, and a phosphoric acid trialkyl ester.

The phosphite ester and acidic phosphite ester are preferably, but are not limited to, a phosphite monoalkyl ester and a phosphite dialkyl ester.

Further, as a phosphorus-based extreme pressure agent, a compound in which a part of oxygen atoms of the above-mentioned phosphoric acid ester, phosphite ester, acidic phosphoric acid ester or acidic phosphite ester is replaced with a sulfur atom, for example, thiophosphate ester, etc. It also includes thiophosphate ester, acid thiophosphate ester, and acid thiophosphate ester.

More specifically, monooctyl phosphate, dioctyl phosphate, trioctyl phosphate, monooctyl phosphite, dioctyl phosphite, monooctyl thiophosphate, dioctyl thiophosphate, trioctyl thiophosphate, monooctyl thiophosphate, thio Dioctyl Phosphate, Monododecyl Phosphate, Didodecyl Phosphate, Tridodecyl Phosphate, Monododecyl Phosphate, Didodecyl Phosphate, Acidic Phosphate Butyl Estel, Acidic Phosphate Hexyl Estel, Acidic Phosphate Octyl Estel, Acidic Phosphate Dodecyl ester, acidic phosphite butyl ester, acidic phosphite hexyl ester, acidic phosphite octyl ester, acidic phosphite dodecyl ester and the like can be mentioned, but are not limited thereto.

Further, alkylamine salts and alkenylamine salts of the above compounds, which are partially esters, can also be preferably used. That is, an amine salt of an acidic phosphoric acid ester and an amine salt of an acidic subphosphate ester can be used, but the present invention is not limited thereto.

More specifically, monooctyl phosphate amine salt, dioctyl phosphate amine salt, trioctyl phosphate amine salt, dioctyl phosphite amine salt, trioctyl phosphite amine salt, dioctyl thiophosphate amine salt, Amine salt of trioctyl thiophosphate, amine salt of tridodecyl thiophosphate, amine salt of didecyl phosphate, amine salt of didecyl phosphite, amine salt of didodecyl phosphate, amine salt of tridodecyl phosphate, amine salt of didodecyl phosphite , Amine salt of tridodecyl phosphite, amine salt of tridodecyl thiophosphate, amine salt of trihexadodecyl phosphate, amine salt of trihexadodecyl phosphite, amine salt of acidic butyl ester of acid, hexyl ester of acid phosphate Amine salt, acid octyl ester amine salt, acid dodecyl ester amine salt, butyl acid phosphite amine salt, hexyl acid phosphite amine salt, octyl acid phosphite amine Examples thereof include salts and amine salts of acidic phosphite dodecyl ester.

Further, phosphoric acid and phosphorous acid are preferably used as phosphorus-based extreme pressure agents other than the above. Further, but not limited to, at least one selected from acidic phosphoric acid esters, acidic phosphite esters, phosphoric acid esters, phosphite esters, and amine salts thereof, and phosphoric acid and phosphite. It is preferable to use in combination with at least one selected from. The ratio of phosphoric acid and phosphite when used in combination is not particularly limited, but is 0.02 to 0.5% by mass of phosphoric acid and phosphite with respect to the total mass of the phosphorus-based extreme pressure agent. It is preferable to have it.

Further, in particular, a combination of an acidic phosphoric acid ester and one or more selected from phosphoric acid and phosphite is preferable. In particular, as the acidic phosphoric acid ester, one or more selected from acidic phosphoric acid butyl ester, acidic phosphoric acid hexyl ester, acidic phosphoric acid octyl ester, and acidic phosphoric acid dodecyl ester is preferable.

Examples of the sulfur-based extreme pressure agent include olefin sulfide, oil and fat sulfide, sulfide ester, and polysulfide.

Sulfide olefins are compounds obtained by sulfurizing olefins. Sulfide olefins are obtained, for example, by sulfurizing olefins such as polyisobutylenes and terpenes with sulfur or other sulfide agents.

Sulfide fats and oils are reaction products of fats and oils and sulfur. For example, it is obtained by sulfurizing animal and vegetable fats and oils such as lard, beef tallow, whale oil, palm oil, coconut oil and rapeseed oil. The product obtained by the reaction may be a mixture of various substances rather than a single substance species. Therefore, the chemical structure is not always clear.

In addition to the above-mentioned sulfide fats and oils, the sulfide ester is an ester compound obtained by reacting various organic acids (saturated fatty acid, unsaturated fatty acid, dicarboxylic acid, aromatic carboxylic acid, etc.) with various alcohols and sulfided with sulfur or other sulfide agents. The ones that can be obtained are listed. Like sulfide fats and oils, the chemical structure is not always clear.

The lubricating oil composition of the present invention preferably further contains (E) a metal cleaning agent and / or (F) an ether sulfolane compound in addition to the above components (A) to (D).

(E) Metal cleaning agent Examples of the metal cleaning agent include a cleaning agent having an alkali metal or an alkaline earth metal. Examples include, but are not limited to, sulfonates containing alkali metals or alkaline earth metals, salicylates containing alkali metals or alkaline earth metals, and phenates containing alkali metals or alkaline earth metals. Examples of the alkali metal or alkaline earth metal include, but are not limited to, magnesium, barium, sodium, and calcium.

The sulphonate containing an alkali metal or an alkaline earth metal is preferably, but not limited to, calcium sulphonate and magnesium sulphonate.

The salicylate containing an alkali metal or an alkaline earth metal is not limited, but calcium salicylate and magnesium salicylate are preferably used.

The phenate containing an alkali metal or an alkaline earth metal is preferably, but not limited to, calcium phenate and magnesium phenate.

The amount of the alkali metal or alkaline earth metal contained in the metal cleaning agent is not limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and 1.0 to 15%. Mass% is more preferred.

The metal cleaning agent preferably has a total base value of 10 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g, and even more preferably 150 to 400 mgKOH / g. In particular, when it is 200 to 400 mgKOH / g, more preferably 300 to 400 mgKOH / g, and most preferably 310 to 400 mgKOH / g, the cleaning effect is high and the generation of sludge is suppressed. Most preferable because it is possible.

The metal cleaning agent may be contained in the lubricating oil composition in an arbitrary ratio. For example, it is 0 to 5% by mass, more preferably 0.1 to 2% by mass, and even more preferably 0.2 to 1% by mass.

As the metal cleaning agent, one type may be used alone, or two or more types may be used in combination. The type is not limited even when used in combination, for example, sulfonate compounds and salicylate compounds, and phenate compounds may be used, but a combination of sulfonate compound and salicylate compound, sulfonate compound and phenate compound, and salicylate compound and phenate compound may be used. ..

上記式において、Ｒは炭素数１〜２０のアルキル基であり、好ましくは炭素数８〜１６のアルキル基である。 (F) Ether Sulfolane Compound The lubricating oil composition of the present invention can further secure an appropriate seal rubber swelling property by containing the ether sulfolane compound. The ether sulfolane compound is the following compound.

In the above formula, R is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 8 to 16 carbon atoms.

The blending amount of the ether sulfolane compound is preferably 0 to 5% by mass, more preferably 0.1 to 2% by mass, and even more preferably 0.2 to 1% by mass in the lubricating oil composition.

The lubricating oil composition of the present invention may further contain other additives other than the above (B) to (F). For example, oil-based agents, anti-wear agents, extreme pressure agents other than phosphorus-based and sulfur-based extreme pressure agents, rust inhibitors, friction modifiers, antioxidants, corrosion inhibitors, metal inactivating agents, flow point lowering agents, etc. Examples include defoaming agents, colorants, and package additives for automatic transmission fluids. Various packaging additives for lubricating oils containing at least one of these can also be added.

Kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention, but are not limited, it is preferably from 3 to 10 mm ² / s, more preferably 3 to 8 mm ² / s, 4 further preferably ~7.5mm ² / s, and still more preferably from 4 to 6 mm ² / s. If the kinematic viscosity of the lubricating oil composition at 100 ° C. is less than the above lower limit value, it may not be possible to sufficiently secure the friction coefficient. Further, if it exceeds the above upper limit value, the shadder characteristics may deteriorate.

The viscosity index of the lubricating oil composition of the present invention is not limited, but is preferably 150 or more, and more preferably 160 or more. If the viscosity index of the lubricating oil composition is less than the above lower limit, it may not be possible to sufficiently secure the low temperature characteristics. The upper limit is not limited, but is preferably 250.

Although the lubricating oil composition of the present invention has a low viscosity, it has an effect that it has a sufficiently large coefficient of friction between metals and can secure shadder characteristics. Further, as described above, the shear stability can be ensured by further specifying the composition of the base oil and the viscosity index improver according to the present invention. Furthermore, by containing the ether sulfolane compound, it is possible to secure an appropriate seal rubber swelling property. Furthermore, it is preferable to use a metal cleaning agent having a total base value of 200 to 400 mgKOH / g because it is possible to suppress the generation of sludge while ensuring cleanliness. The lubricating oil composition of the present invention can be suitably used for continuously variable transmissions.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Each component used in Examples and Comparative Examples is as follows. Each component shown below was mixed with the composition shown in Table 1 or Table 2 to prepare a lubricating oil composition. In the following, KV100 means kinematic viscosity at 100 ° C., VI means viscosity index, and PMA means polymethacrylate.
(A) Lubricating oil base oil / mineral oil 1: Highly hydrorefined paraffin-based base oil (KV100 = 3.1 mm ² / s, VI = 112)
-Mineral oil 2: Highly hydrorefined paraffin-based base oil (KV100 = 4.2 mm ² / s, VI = 122)
-Mineral oil 3: Highly hydrorefined paraffin-based base oil (KV100 = 4.2 mm ² / s, VI = 134)
-Mineral oil 4: Hydrorefined paraffin-based base oil (KV100 = 2.2 mm ² / s, VI = 109)
-Mineral oil 5: Hydrorefined paraffin-based base oil (KV100 = 2.5 mm ² / s, VI = 99)
-Synthetic base oil 1: Poly-α-olefin (KV100 = 10 mm ² / s, VI = 137)
-Synthetic base oil 2: Poly-α-olefin (KV100 = 40 mm ² / s, VI = 147)
-Synthetic base oil 3: Ethylene-α-olefin copolymer (KV100 = 10 mm ² / s, VI = 150)
-Synthetic base oil 4: Ethylene-α-olefin copolymer (KV100 = 40 mm ² / s, VI = 155)

(B) Viscosity index improver / PMA-based viscosity index improver 1 (Mw = 30,000)

(C) Borylated succinimide compound (C-1)
Borylated succinimide compound 1 (Mw = 5,600, B: 0.34 wt%, N = 1.58 wt%, in formula (2) above, R ¹ is a mixture of polyisobutenyl groups, n = 4-12)
Borylated succinimide compound 3 (Mw = 4,600, B: 1.8 wt%, N = 2.35 wt%, in formula (2) above, R ¹ is a mixture of polyisobutenyl groups, n = 4-12)
(C-2)
Borylated succinimide compound 2 (Mw = 8,500, B: 0.23 wt%, N = 0.88 wt%, in formula (2) above, R ¹ is a mixture of polyisobutenyl groups, n = 4-12)

(D) Extreme pressure agent (D-1) Phosphoric acid (D-2) Phosphoric acid (D-3) Acidic phosphoric acid butyl ester (D-4) Amine salt of acidic phosphoric acid butyl ester (D-5) Acidic Phosphoric acid hexyl ester (D-6) Acid phosphite butyl ester (D-7) Olefin sulfide (D-8) Zinc dialkylthiophosphate (primary alkyl group with 6 carbon atoms)

(E) Metal detergent / Ca sulfonate (total base value 350 mgKOH / g)

(F) Ether sulfolane compound-LUBRIZOL 730 (in the following formula, R ¹ = C ₁₀ H ₂₁ compound)

(G) Other additives
Anti-wear agents, friction modifiers, antioxidants, defoamers, metal deactivators, and colorants

Various properties of each lubricating oil composition were measured according to the following method. The results are shown in Tables 4-6. (1) Dynamic viscosity at 100 ° C. (KV100) Test method: Measured according to ASTM D445.
(2) Viscosity index test method: Measured according to ASTM D2270.
(3) Shear stability test method: According to JASO M347-2014, the viscosity at 100 ° C. after 10 hours was measured, and the rate of change from the viscosity before the start of the test was determined.
(4) Shadder prevention life test method: One of dμ / dv (average at 1.0 to 2.0 m / s) evaluated at 40 ° C., 60 ° C., 80 ° C., and 120 ° C. according to JASO M349-2012. -2x10 below the ^-3 was determined the time.
(5) Coefficient of friction (comparison with commercial products): Using an SRV friction and wear tester manufactured by Optimol, using the SUJ ball (diameter 10 mm) and SUJ disc (diameter 24 mm x height 6.9 mm, wrapping treatment) manufactured by the same company. The test was carried out with a load of 100 N, a temperature of 100 ° C., a frequency of 50 Hz, and an amplitude of 0.5 mm, and the average value of the friction coefficient after 30 minutes was obtained. The ratio was determined by setting the friction coefficient of the commercially available oil (Comparative Example 5) to 1.0.
(6) Rubber swellability test method: Using ASTM D471 with C type dumbbell-shaped ACM rubber (T945 manufactured by NOK), the sample oil was immersed at 150 ° C., and the volume change rate after 70 hours was determined.

In Comparative Example 5, a commercially available lubricating oil composition for a transmission was evaluated.

As shown in Examples 1 to 15 shown in Tables 4 and 5, the lubricating oil composition of the present invention is prepared at 100 ° C. by combining two types of succinimides and containing a phosphorus-based extreme pressure agent. Despite its low kinematic viscosity, the shade prevention life can be extended without lowering the coefficient of friction between metals. As shown in Comparative Example 1, if the component (C-2) is not contained, the shader characteristics deteriorate. Further, as shown in Comparative Example 4, if zinc dithiophosphate is contained, the shader characteristics are deteriorated. Furthermore, if a sulfur-based extreme pressure agent is contained above the upper limit of the present invention, the shader characteristics will deteriorate.
Further, as can be seen from the comparison between Examples 1 and 8, by specifying the composition of the component (A) and further containing (F) ether sulfolane, the seal rubber swelling property is further improved in addition to the above effects. can do.

The lubricating oil composition of the present invention can be particularly suitably used for an automobile transmission, particularly for a continuously variable transmission.

Claims (13)

(A) Lubricating oil base oil,
(C) (C-1) Succinimide compound or borated succinimide compound having a mass average molecular weight of 4,000 to 7,000,
(C-2) A lubricating oil composition comprising (C-2) a succinate imide compound or a boring succinate imide compound having a mass average molecular weight of more than 7,000 to 10,000, and (D) a phosphorus-based extreme pressure agent. Therefore, the lubricating oil composition does not contain zinc dithiophosphate and may optionally contain a sulfur-based extreme pressure agent, except that the content of the sulfur-based extreme pressure agent is 0.1 in the lubricating oil composition. The lubricating oil composition which is not more than mass%. A poly-α-olefin or α-olefin copolymer having a ^{kinematic viscosity of 6 to 80 mm 2} / s at 100 ° C. as a part or all of the component (A) was added to the total weight of the lubricating oil composition. The lubricating oil composition according to claim 1, further comprising a polymethacrylate containing up to 30% by mass and (B) having a mass average molecular weight of 15,000 to 40,000. The lubricating oil composition according to claim 1 or 2, wherein the component (C-1) and a part or all of the component (C-2) are borated succinimide compounds. Any of claims 1 to 3, wherein the content of boron in each of the component (C-1) or the component (C-2) is 0.1 to 3% by mass with respect to the mass of the boronized succinimide compound. The lubricating oil composition according to item 1. The lubrication according to any one of claims 1 to 4, wherein the mass ratio of the component (C-1) to the component (C-2) is (C-2) / (C-1) = 1-10. Oil composition. The lubricating oil composition according to any one of claims 1 to 5, wherein the succinimide compound is represented by the following formula (1) or (2).

In the above formula, R ¹ is an alkyl group or an alkenyl group having 40 to 400 carbon atoms independently of each other, m is an integer of 1 to 20, and n is an integer of 0 to 20. The lubricating oil composition according to any one of claims 1 to 6, which has a kinematic viscosity of 3 to 10 mm ^{2 / s at 100 ° C.} The lubricating oil composition according to any one of claims 1 to 7, which has a viscosity index of 150 or more. (D) At least one phosphorus-based extreme pressure agent selected from acidic phosphoric acid ester, acidic phosphite ester, phosphoric acid ester, sulphate ester, and amine salts, phosphoric acid, and succinic acid thereof. The lubricating oil composition according to any one of claims 1 to 8. (D) The phosphorus-based extreme pressure agent is at least one selected from acidic phosphoric acid ester, acidic phosphoric acid ester, phosphoric acid ester, phosphoric acid ester, and amine salts thereof, and phosphoric acid and sub. The lubricating oil composition according to claim 9, which is a combination with at least one selected from phosphoric acid. The lubricating oil composition according to any one of claims 1 to 10, further comprising (E) a metal cleaning agent. The lubricating oil composition according to any one of claims 1 to 11, further containing (F) an ether sulfolane compound. The lubricating oil composition according to any one of claims 1 to 12, which is used for a continuously variable transmission.