JP4768234B2 - Automotive driveline lubricant composition - Google Patents

Description

  The present invention relates to an automotive driveline lubricating oil composition, and more particularly to an automotive gear oil composition, particularly a manual transmission lubricating oil composition.

In recent years, the promotion of various environmental conservation measures, including global warming countermeasures, has become an inevitable issue for the modernized society, and as part of this, the demand for the development of environmentally-friendly lubricants has increased remarkably. As an environmentally friendly lubricating oil used for automobiles and the like, a lubricating oil excellent in fuel efficiency improvement effect is required in order to reduce discharge of carbon dioxide gas from an internal combustion engine or the like. In order to enhance the fuel efficiency improvement effect of the lubricating oil, two methods by reducing friction at the sliding portion and lowering the viscosity of the lubricating oil itself have been studied.
Regarding the former friction reduction, for example, a gear oil composition using a friction reducing agent such as molybdenum dithiophosphate (Patent Document 1 (Japanese Patent Publication No. 6-33390) in order to enhance the energy saving effect of gear oil used in a power transmission system. In addition, a lubricating oil composition that can maintain a low coefficient of friction even after oxidative degradation by using a specific polymethacrylate viscosity index improver in combination with a molybdenum friction reducer. (See Patent Document 2 (Japanese Patent No. 2906024)).

However, a manual transmission of an automobile incorporates a synchronizer using friction between metals, and it is not preferable to reduce the friction coefficient for smooth operation of the synchronizer. For this reason, for the manual transmission oil, there is a great expectation for improving the fuel efficiency by lowering the viscosity of the latter, but there is a problem that the oil film becomes thin and easily wears by simply lowering the viscosity. In particular, aluminum members, which are being adopted to reduce the weight of drive trains, are easily worn out of steel, and may be easily affected by low viscosity. Most transmission oils have a kinematic viscosity at 40 ° C. (hereinafter, sometimes referred to as “40 ° C. kinematic viscosity”) of 40 mm ² / s or more. It has not reached the practical stage.

Under such circumstances, development of a lubricating oil composition for a manual transmission that utilizes fuel efficiency improvement technology by lowering the viscosity of the lubricating oil itself has been eagerly desired.
Japanese Patent Publication No. 6-33390 Japanese Patent No. 2906024

  Therefore, in view of the development status of the low fuel consumption technology as described above, the object of the present invention is to improve the fuel efficiency by reducing the viscosity of the lubricating oil and to maintain the durability with respect to the wear resistance. In particular, it is to provide a manual transmission oil composition.

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have a kinematic viscosity at 40 ° C. of 40 mm ² by blending an organic acid alkaline earth metal salt and zinc dithiophosphate in a specific ratio. Even if it has a low viscosity of less than / s, it is equivalent to or better than the wear resistance of the current commercial oil with a kinematic viscosity at 40 ° C of 76 mm ² / s for aluminum members that are particularly easily worn among general steel materials The present inventors have found a lubricating oil composition having high wear resistance and have completed the present invention based on these findings.

That is, according to the present invention,
(A) at least one organic acid alkaline earth metal salt selected from the group consisting of alkaline earth metal salts of sulfonate, salicylate, and phenate blended in the base oil; and (b) zinc dithiophosphate A lubricating oil composition for a manual transmission comprising:
The kinematic viscosity at 40 ° C. of the lubricating oil composition is 40 mm ² / s or less,
The content of the organic acid alkaline earth metal salt based on the total weight of the lubricating oil composition is 0.1% by mass or more as the amount of alkaline earth metal element in the oil,
And the following formula:

（ただし、式中、油中亜鉛元素量は、前記ジチオリン酸亜鉛から由来し、前記油中アルカリ土類金属元素量は、前記有機酸アルカリ土類金属塩から由来したものである。）
を満たすことを特徴とする手動変速機用潤滑油組成物
が提供される。

(However, in the formula, the amount of zinc element in oil is derived from the zinc dithiophosphate, and the amount of alkaline earth metal element in oil is derived from the organic acid alkaline earth metal salt.)
A lubricating oil composition for a manual transmission is provided.

  As described above, according to the present invention, a specific amount of an organic acid alkaline earth metal salt, particularly magnesium sulfonate, is blended with a low-viscosity base oil, and the organic acid alkaline earth metal salt and zinc dithiophosphate are specified. By blending in this ratio, it is possible to provide a manual transmission oil that exhibits remarkable wear resistance with respect to an aluminum sliding member as well as a steel material while having a low viscosity, and has an excellent fuel efficiency improvement effect.

As described above, the present invention provides an automobile gear oil composition, particularly a manual transmission oil composition, comprising a low-viscosity base oil, a specific ratio of an organic acid alkaline earth metal salt and a zinc dialkyldithiophosphate. However, the following 1) to 5) are included as further preferred embodiments.
1) The lubricating oil composition for manual transmission, wherein the kinematic viscosity at 40 ° C. is 30 mm ² / s or less.
2) The lubricating oil composition for a manual transmission, wherein the organic acid alkaline earth metal salt is an alkaline earth metal salt of sulfonate.
3) The lubricating oil composition for a manual transmission, wherein the organic acid alkaline earth metal salt is magnesium sulfonate.
4) The lubricating oil composition for manual transmission, wherein the total base number of the organic acid alkaline earth metal salt is 200 mgKOH / g or more.
5) A lubricating oil composition for a manual transmission comprising a base oil, magnesium sulfonate and zinc dithiophosphate blended in the base oil,
The kinematic viscosity at 40 ° C. of the lubricating oil composition is 30 mm ² / s or less,
The content of the organic acid alkaline earth metal salt based on the total weight of the lubricating oil composition is 0.1 mass% or more as the amount of alkaline earth metal element in the oil,
And the following formula:

（ただし、式中、油中亜鉛元素量は、前記ジチオリン酸亜鉛から由来し、前記油中アルカリ土類金属元素量は、前記有機酸アルカリ土類金属塩から由来したものである。）
を満たすことを特徴とする手動変速機用潤滑油組成物。

(However, in the formula, the amount of zinc element in oil is derived from the zinc dithiophosphate, and the amount of alkaline earth metal element in oil is derived from the organic acid alkaline earth metal salt.)
A lubricating oil composition for a manual transmission, characterized in that:

6) at least one organic acid alkaline earth metal salt selected from the group consisting of a base oil and (a) alkaline earth metal salts of sulfonate, salicylate and phenate blended in the base oil, and (b) dithiophosphoric acid A lubricating oil composition for a manual transmission containing zinc,
The kinematic viscosity at 40 ° C. of the lubricating oil composition is 40 mm ² / s or less,
The content of the organic acid alkaline earth metal salt based on the total weight of the lubricating oil composition is 0.1% by mass or more as the amount of the alkaline earth metal element in the oil,
And the following formula:

（ただし、式中、油中亜鉛元素量は、前記ジチオリン酸亜鉛から由来し、前記油中アルカリ土類金属元素量は、前記有機酸アルカリ土類金属塩から由来したものである。）
を満たす手動変速機用潤滑油組成物であり、アルミ摺動部材を有する手動変速機の潤滑に適した手動変速機用潤滑油組成物。

(However, in the formula, the amount of zinc element in oil is derived from the zinc dithiophosphate, and the amount of alkaline earth metal element in oil is derived from the organic acid alkaline earth metal salt.)
A lubricating oil composition for a manual transmission that satisfies the above requirements and is suitable for lubricating a manual transmission having an aluminum sliding member.

  Hereinafter, the components of the lubricating oil composition for manual transmission according to the present invention will be described in more detail. The lubricating oil composition for a manual transmission is used for other transmissions that maintain a base oil, an organic acid alkaline earth metal salt contained in the base oil, zinc dithiophosphate, and other extreme pressure performances. Contains an additive as a constituent.

The base oil as a constituent component of the lubricating oil composition for manual transmission is not particularly limited as long as it is used as a normal lubricating base oil and can be used. Mineral oil base oils, GTL (Gas to liquid) base oils, synthetic oil base oils or mixed oil base oils thereof are used.
Mineral oil base oils include solvent refining, hydrocracking, and hydrotreating of the lubricating oil fraction obtained as distillate by vacuum distillation of residual oil from paraffinic, intermediate or naphthenic crude oil distillation equipment. , Mineral oil such as solvent refined mineral oil or hydrotreated oil obtained by arbitrarily selecting and using various refining steps such as hydrorefining, solvent dewaxing, catalytic dewaxing, clay treatment, etc., vacuum distillation residue oil Mineral oil obtained by treating the deoiled oil obtained by the above solvent defoaming treatment by the above-mentioned refining process, mineral oil obtained by isomerization of the wax, or a mixed oil thereof can be used as the base oil base material. . In the above-mentioned solvent purification, aromatic extraction solvents such as phenol, furfural and N-methyl-2-pyrrolidone are used, and liquefied propane, MEK (methyl ethyl ketone) / toluene, etc. are used as solvents for solvent dewaxing. It is done. On the other hand, in catalytic dewaxing, for example, shape selective zeolite or the like is used as a dewaxing catalyst.

  Examples of the refined base oil base material obtained as described above include light neutral oils, medium neutral oils, heavy neutral oils, bright stocks, and the like having different viscosity levels, and these base materials are related to the present invention. A mineral base oil can be produced by appropriately preparing a low-viscosity oil.

  Examples of the GTL base oil include a lubricating oil fraction separated from a liquid product obtained by using a natural gas or the like as a raw material by a GTL process, or a lubricating oil fraction obtained by hydrocracking a produced wax. Can do. Further, a lubricating oil fraction separated from a liquid product oil obtained by an ATL (Asphalt to Liquid) process using a heavy residual oil component such as asphalt as a raw material can be used.

  On the other hand, the synthetic base oil can be selected from the group of compounds listed below so as to meet the viscosity properties of the lubricating oil composition for manual transmission according to the present invention. For example, poly (α-olefin) (eg, poly (1-hexene), poly (1-octene), poly (1-decene), and the like and mixtures thereof); polybutene; ethylene-alkylene copolymer; alkylbenzene (eg, Dodecylbenzene, tetradecylbenzene, di (2-ethylhexyl) benzene, dinonylbenzene, etc.); polyphenyl (eg, biphenyl, alkylated polyphenyl, etc.); alkylated diphenyl ether and alkylated diphenyl sulfide and derivatives thereof; Dibasic acid (for example, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, peric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) and various alcohols (for example, Butyl alcohol, f Ester with sil alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.); monocarboxylic acid having 5 to 18 carbon atoms and polyol (for example, neopentyl glycol, trimethylolpropane, penta) Ester with erythritol, dipentaerythritol, tripentaerythritol, etc.); other examples include polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxyalkylene glycol ether, and phosphate ester.

As described above, the base oil of the lubricating oil composition for manual transmission according to the present invention has a 40 ° C. kinematic viscosity of the lubricating oil composition of 40 mm ² / s or less, preferably 30 mm ² / s or less. These are selected from the above-mentioned various base oil bases and are each singly or in combination of two or more, and have a desired viscosity and other properties necessary as a lubricating oil. Accordingly, the viscosity of the base oil is not particularly limited as long as it can provide the lubricating oil composition according to the present invention, and depending on the additive composition, the viscosity at 40 ° C. is 25 to 40 mm ² / s. Those selected from are preferred.

Next, the organic acid alkaline earth metal salt is selected from the group consisting of the respective alkaline earth metal salts of sulfonate, phenate and salicylate.
Alkaline earth metal sulfonate is petroleum sulfonic acid or alkaline earth metal salt of long-chain alkylbenzene sulfonic acid and alkyl naphthalene sulfonic acid. As a component of the composition for manual transmission according to the present invention, as a typical example, Formula (1);

The thing represented by is included. In the formula, M is an alkaline earth metal, and examples thereof include magnesium, calcium, and barium, and magnesium is particularly preferable. R ¹ and R ² are hydrocarbon groups having 1 to 30 carbon atoms, and may be the same or different. However, at least one of the hydrocarbon groups is an alkyl group having 6 or more carbon atoms. Preferred hydrocarbon groups include a linear or branched alkyl group having 1 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 6 to 30 carbon atoms; -18 aryl groups and the like can be mentioned. The aryl group may have an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms as a substituent. Particularly preferred hydrocarbon groups are linear or branched alkyl groups having 6 to 18 carbon atoms.

  In the lubricating oil composition for a manual transmission according to the present invention, the sulfonate is preferably an overbased salt, but a normal salt or a basic salt can also be used. The overbased salt is a colloidal dispersion of excess hydroxide or carbonate in sulfonate, and preferably has a total base number of 200 mgKOH / g or more.

  Alkaline earth metal sulfonate is blended at a ratio of 0.1% by mass or more, preferably 0.15 to 0.6% by mass as the amount of alkaline earth metal in the oil based on the total weight of the composition, with respect to the base oil. Is done. A particularly preferable blending amount is 0.15 to 0.3% by mass.

  As the alkaline earth metal sulfonate, magnesium sulfonate is particularly suitable, and in combination with zinc dithiophosphate in a low-viscosity state, it exhibits excellent wear resistance in a manual transmission equipped with an aluminum sliding member.

  The alkaline earth metal phenate is represented by the general formula (2) represented by the alkaline earth metal salt of sulfurized alkylphenol;

で表わされるものを包含する。式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ炭素数１〜３０の炭化水素基であり、それぞれ互いに同一でもまたは異なるものでもよい。ただし、炭化水素基の少なくとも一つは炭素数６以上のアルキル基である。好ましい炭化水素基としては、炭素数１〜１８の直鎖状または分岐状アルキル基；炭素数２〜１８の直鎖状または分岐状アルケニル基；炭素数６〜３０のシクロアルキル基；炭素数６〜１８のアリール基等を挙げることができる。アリール基は、置換基として炭素数１〜１２のアルキル基または炭素数２〜１２のアルケニル基を有するものであってもよい。特に好ましい炭化水素基は、炭素数６〜１８の直鎖状または分岐状アルキル基である。また、ｘは１〜３の整数である。Ｍはマグネシウム、カルシウムまたはバリウムであり、特にマグネシウムが好ましい。

The thing represented by is included. In the formula, R ¹ , R ² , R ³ and R ⁴ are each a hydrocarbon group having 1 to 30 carbon atoms, and may be the same or different from each other. However, at least one of the hydrocarbon groups is an alkyl group having 6 or more carbon atoms. Preferred hydrocarbon groups include a linear or branched alkyl group having 1 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 6 to 30 carbon atoms; -18 aryl groups and the like can be mentioned. The aryl group may have an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms as a substituent. Particularly preferred hydrocarbon groups are linear or branched alkyl groups having 6 to 18 carbon atoms. Moreover, x is an integer of 1-3. M is magnesium, calcium or barium, and magnesium is particularly preferable.

Similar to sulfonate, a phenate overbased salt is a colloidal dispersion of hydroxide or carbonate on phenate. The total base number is preferably 200 mgKOH / g or more, but both normal salt and basic salt can be used.
Alkaline earth metal phenate is blended at a ratio of 0.1% by mass or more, preferably 0.15 to 0.6% by mass as the amount of alkaline earth metal in the oil based on the total weight of the composition, with respect to the base oil. Is done.

で表わされる化合物で代表される。式中、Ｍはアルカリ土類金属であり、マグネシウム、カルシウムまたはバリウムであり、特にマグネシウムが好ましい。Ｒ^１およびＲ^２は、炭素数１〜３０の炭化水素基であり、互いに同一であってもまたは異なるものでもよい。ただし、炭化水素基の少なくとも一つは炭素数６以上のアルキル基である。好ましい炭化水素基としては、炭素数１〜１８の直鎖状または分岐状アルキル基；炭素数２〜１８の直鎖状または分岐状アルケニル基；炭素数６〜３０のシクロアルキル基；炭素数６〜１８のアリール基等を挙げることができる。アリール基は、置換基として炭素数１〜１２のアルキル基または炭素数２〜１２のアルケニル基を有するものであってもよい。特に好ましい炭化水素基は、炭素数６〜１８の直鎖状または分岐状アルキル基である。 The alkaline earth metal salicylate has the general formula (3):

It is represented by the compound represented by. In the formula, M is an alkaline earth metal, and is magnesium, calcium or barium, and magnesium is particularly preferable. R ¹ and R ² are hydrocarbon groups having 1 to 30 carbon atoms and may be the same or different from each other. However, at least one of the hydrocarbon groups is an alkyl group having 6 or more carbon atoms. Preferred hydrocarbon groups include a linear or branched alkyl group having 1 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms; a cycloalkyl group having 6 to 30 carbon atoms; -18 aryl groups and the like can be mentioned. The aryl group may have an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms as a substituent. Particularly preferred hydrocarbon groups are linear or branched alkyl groups having 6 to 18 carbon atoms.

For the lubricating oil composition for a manual transmission according to the present invention, an overbased salicylate is suitable, but in addition to the normal salt, a basic salt can also be used. An overbased salt is prepared by colloidally dispersing carbonate in salicylate.
The alkaline earth metal salicylate is blended in an amount of 0.1% by mass or more, preferably 0.15 to 0.6% by mass as the amount of the alkaline earth metal in the oil based on the total weight of the composition with respect to the base oil. Is done.

  As described above, examples of the component of the lubricating oil composition for manual transmission according to the present invention include alkaline earth metal salts of the sulfonate, phenate, or salicylate. Among these, alkaline earth metal salts of sulfonate are particularly preferable. Are preferred, and magnesium sulfonate is more preferred.

Next, zinc dithiophosphate as a component of the lubricating oil composition for manual transmission of the present invention will be described.
As zinc dithiophosphate, the following general formula (4):

で表される化合物を挙げることができる。一般式（４）において、Ｒ₁ 、Ｒ₂ は炭素数１〜２０の炭化水素基であり、各々、同一でも異なるものでもよい。炭化水素基としては、炭素数１〜２０のアルキル基；炭素数２〜２０のアルケニル基；炭素数６〜２０のシクロアルキル基、アリール基、アルキルアリール基、アリールアルキル基等を挙げることができ、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ステアリル基、オレイル基、ブチルフェニル基、ノニルフェニル基等およびこれらの分岐状アルキル基等を挙げることができる。好ましい炭化水素基は、炭素数３〜１８のアルキル基である。アルキル基としては第１級および第２級アルキル基のいずれでもよい。具体的にはイソプロピル基、イソブチル基、第２級ブチル基、ペンチル基、ヘキシル基、４−メチル−２−ペンチル基、オクチル基、２−エチルヘキシル基、ノニル基、デシル基のほか、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等のアルキル基を有する化合物を用いることが好ましい。

The compound represented by these can be mentioned. In the general formula _{(4), R 1, R} 2 is a hydrocarbon group having 1 to 20 carbon atoms, each of which may be the same or different. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; a cycloalkyl group having 6 to 20 carbon atoms, an aryl group, an alkylaryl group, and an arylalkyl group. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a stearyl group, an oleyl group, a butylphenyl group, and a nonylphenyl group, and branched alkyl groups thereof. A preferred hydrocarbon group is an alkyl group having 3 to 18 carbon atoms. The alkyl group may be either a primary or secondary alkyl group. Specifically, in addition to isopropyl group, isobutyl group, secondary butyl group, pentyl group, hexyl group, 4-methyl-2-pentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, It is preferable to use a compound having an alkyl group such as a tridecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group.

Accordingly, typical examples of zinc dithiophosphate include, for example, zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc disecondary butyldithiophosphate, zinc di (n-pentyl) dithiophosphate, zinc di (n-hexyl) dithiophosphate. , Zinc di (4-methyl-2-pentyl) dithiophosphate, zinc di (n-octyl) dithiophosphate, zinc di (2-ethylhexyl) dithiophosphate, zinc di (n-nonyl) dithiophosphate, di (n-decyl) ) Zinc dithiophosphate, zinc di (n-dodecyl) dithiophosphate, zinc di (n-tridecyl) dithiophosphate, zinc di (n-tetradecyl) dithiophosphate, zinc di (n-hexadecyl) dithiophosphate, di (n-octadecyl) ) Zinc dithiophosphate and the like. For the lubricating oil composition for manual transmission according to the present invention, zinc dithiophosphates containing primary and secondary alkyl groups are suitable. For example, zinc dithiophosphate having a primary alkyl group as the main component and zinc dithiophosphate The proportion of the primary or secondary alkyl group content can be adjusted by appropriately mixing zinc dithiophosphate having a secondary alkyl group as a main component.
The compounding quantity with respect to the lubricating oil composition of the said zinc dithiophosphate is 0.05-0.5 mass% as an amount of zinc elements in oil, Preferably it is 0.1-0.2 mass%.

  In the lubricating oil composition for a manual transmission according to the present invention, the organic acid alkaline earth metal salt is 0.1% by mass or more as an alkaline earth metal element amount in oil, and the zinc dithiophosphate is in oil. The amount of zinc element is 0.05 to 0.5% by mass, and the following formula:

(ただし、式中、油中亜鉛元素量は、前記ジチオリン酸亜鉛から由来し、前記油中アルカリ土類金属元素量は、前記有機酸アルカリ土類金属塩から由来したものである。)
を満たすように配合されたものである。

(However, in the formula, the amount of zinc element in oil is derived from the zinc dithiophosphate, and the amount of alkaline earth metal element in oil is derived from the organic acid alkaline earth metal salt.)
It is blended so as to satisfy.

を満たす範囲に包含されるものである。 A particularly preferred ratio of the amount of zinc element in oil and the amount of alkaline earth metal element in oil is:

It is included in the range satisfying.

  In the lubricating oil composition for a manual transmission according to the present invention, when the ratio of the amount of zinc element in oil to the amount of alkaline earth metal element in oil exceeds 1, the wear resistance is reduced to 0.2. If not, there is a problem that the wear resistance is further deteriorated.

Next, other additives used in addition to the essential additives will be described.
In the lubricating oil composition for manual transmission of the present invention, an extreme pressure agent is used in order to maintain extreme pressure performance, and if necessary, an ashless dispersant, a friction modifier, an antifoaming agent, a solubilizer, a rubber Antioxidants such as swelling agents and pour point depressants can be used as appropriate, and other additives can be blended as desired.

  Examples of extreme pressure agents include sulfur-based olefin polysulfides, sulfurized fats and oils, dialkyl polysulfides, etc .; alkyl and allyl phosphate esters, alkyl and allyl phosphite esters, phosphorus phosphates such as amine phosphates; and chlorinated paraffins such as chlorinated paraffins. A composite type containing two or more types can also be used. A combination of sulfur and phosphorus is used, and examples thereof include a combination of a sulfurized olefin and an alkyl phosphate ester. As a compounding quantity, it is normally used in the ratio of 0.05-3 mass%.

  Ashless dispersants include, for example, polybutenyl succinimide-based, polybutenyl succinamide-based, benzylamine-based, succinic ester-based succinic acid-acid-based agents, and these are usually 0.05 Used in a proportion of ˜7% by weight.

  Examples of the friction modifier include organic molybdenum compounds, fatty acids, higher alcohols, fatty acid esters, oils and fats, amines, polyamides, sulfurized esters, phosphate esters, acidic phosphate esters, phosphite esters, phosphate ester amine salts. Etc. These are usually used in a proportion of 0.05 to 5% by mass.

  Examples of the antifoaming agent include dimethylpolysiloxane, polyacrylate and the like, and these may be mixed in a small amount as appropriate.

  Examples of the pour point depressant include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene, etc. Usually, it is used in a proportion of 0.1% by mass to 10% by mass.

  In addition, when an antioxidant is used, for example, an amine-based antioxidant such as alkylated diphenylamine, phenyl-α-naphthylamine, alkylated-α-naphthylamine, 2,6-di-tert-butylphenol, 4,4 Examples include phenolic antioxidants such as' -methylenebis- (2,6-di-tert-butylphenol), and zinc dithiophosphate. These are usually in a ratio of 0.05% by mass to 5% by mass. Used in.

Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples.
In addition, quality evaluation was performed by the following measuring method, and the following base oil and additives were used.

Wear Resistance Evaluation Method For each sample oil, the wear width generated on the block under the following materials and conditions was measured using an LFW-1 tester (ASTM D2714).
・ Test ring: S-10 (FALEX Test Ring H60)
・ Block: Aluminum sliding member ・ Test condition: Load: 5N
Speed: 2m / s
Temperature: 100 ° C
Time: 1 hr

Base oil refined mineral oil; 40 ° C. kinematic viscosity 25-26 mm ² / s
Additive zinc dithiophosphate (ZnDTP); mixed with primary / secondary alkyl groups
Combined type Magnesium sulfonate; Overbased salt with total base number 400mgKOH / g Extreme pressure agent, etc .; In addition to sulfur and phosphorus extreme pressure agents, ashless dispersant, friction modifier, antifoam
Sulfur-Phosphorus Package containing Agent

[Example 1]
The refined mineral oil is used as a base oil, and 0.15% by mass of magnesium sulfonate as the amount of Mg element in the oil and 0.1% by mass of zinc dithiophosphate as the amount of Zn element in the oil are blended. The Mg element amount ratio in the oil was adjusted to 0.67. Furthermore, 7.1% by mass of a sulfur-phosphorous (SP) package corresponding to GL-4 was blended as another additive to prepare a trial oil A having a kinematic viscosity of 30 mm ² / s at 40 ° C.
The wear width of the trial oil A measured by the wear resistance evaluation method was 0.74 mm.

[Example 2]
0.3% by mass of magnesium sulfonate as the amount of Mg element in oil and 0.2% by mass of zinc dithiophosphate as the amount of Zn element in oil are blended, and the ratio of Zn element in oil / Mg element in oil is 0.67. Except that, a trial oil B having a kinematic viscosity of 40 ° C. and 30 mm ² / s was prepared in the same manner as in Example 1.
The wear width of the prototype oil B measured by the wear resistance evaluation method was 0.80 mm.

[Example 3]
Magnesium sulfonate is added in an amount of 0.3% by mass as the amount of Mg element in the oil, and zinc dithiophosphate is added in an amount of 0.1% by mass as the amount of Zn element in the oil. Except that, a trial oil C having a kinematic viscosity of 40 ° C. and 30 mm ² / s was prepared in the same manner as in Example 1.
The wear width of the trial oil C measured by the wear resistance evaluation method was 0.80 mm.

[Comparative Example 1-1]
When a commercial manual transmission oil having a kinematic viscosity at 40 ° C. of 76 mm ² / s (a ratio of Zn element in oil / amount of Ca element in oil 5.00) was subjected to the wear resistance evaluation test, the wear width was 0.83 mm. The result was obtained.

[Comparative Example 1-2]
A trial oil a having a kinematic viscosity of 40 mm and a viscosity of 30 mm ² / s was prepared using a refined mineral oil having a low viscosity. The ratio of the amount of Zn element in oil / the amount of Ca element in oil was set to 5.00, which is the same as the commercially available product of Comparative Example 1-1. The wear width measured by the wear resistance evaluation method of the prototype oil a was 1.05 mm.

[Comparative Examples 2-1 to 2-6]
Using the refined mineral oil as a base oil, magnesium sulfonate and zinc dithiophosphate are blended in the proportions shown in Table 1, and 7.1 mass% of a GL-4 equivalent SP package is blended as another additive. Oils b to g were obtained.
Table 1 shows the properties of the prototypes A to C and the commercial products, the properties of the prototype oils a to g, and the wear resistance measured by the wear resistance evaluation method.

From the results of the wear width shown in Table 1, a low-viscosity oil having a 40 ° C. kinematic viscosity of 30 mm ² / s excellent in fuel efficiency and having a specific content of Mg element in the oil and Zn in the oil It can be seen that the trial oil in which the ratio of element amount / Mg element amount in oil is set to a specific range of 0.2 to 1 has a remarkable effect. In the comparison between Example 1 and Comparative Example 2-3, the amount of Mg element in oil is the same. In Example 1, the ratio of Zn element in oil / Mg element in oil is 0.67, which is included in the specific range. On the other hand, in Comparative Example 2-3, the ratio of the amount of Zn element in oil / the amount of Mg element in oil is 1.33, which is outside the specific range, indicating that the wear resistance is remarkably reduced. ing.

  FIG. 1 shows the amount of Mg element in the oil derived from Mg sulfonate of each prototype oil prepared in Examples and Comparative Examples on the X axis, the amount of Zn element in the oil derived from ZnDTP on the Y axis, and the wear width on the Z axis. The relationship is displayed in three dimensions. Z axis compared to the trial oil according to the comparative example in which the ratio of Zn element in oil / Mg element in oil falls within the range of 0.2 to 1 (Examples 1 to 3). It has been shown that the position representing the wear width is extremely low, and the wear resistance is remarkably remarkable.

  The lubricating oil composition for a manual transmission according to the present invention is configured as described above, and as a driving system lubricating oil for an automobile, in addition to a manual transmission (MT), a manual transaxle (MTX), a transfer, and a differential (diff) Therefore, it can be used for common lubrication such as MT, MTX and differential for FF vehicles and the like.

  The lubricating oil composition for a manual transmission according to the present invention can contribute to environmental conservation as an environmentally friendly lubricating oil by achieving low viscosity, and as a manual transmission oil, a manual transmission, a manual transaxle, etc. As a drive system lubricating oil for automobiles, it has high quality, and there are some that contribute greatly to the petroleum / automotive industry and the like in terms of production and use by practical use.

It is a relationship figure of the amount of Mg element in oil derived from Mg sulfonate of each trial manufacture oil concerning this invention and comparative invention, the amount of Zn element in oil derived from ZnDTP, and the wear width of an aluminum member.

Claims (3)

A base oil, (a) a sulfonate magnesium salt , (b) zinc dithiophosphate, (c) a sulfur-based and phosphorus-based extreme pressure agent,
Containing
A lubricating oil composition for a manual transmission that does not contain a viscosity index improver ,
The kinematic viscosity at 40 ° C. of the lubricating oil composition is 40 mm ² / _S or less,
The content of magnesium salt of the sulfonate based on the total weight of the lubricating oil composition is 0.1% by mass or more as the amount of magnesium element in the oil ,
And the following formula:

(However, in the formula, the amount of zinc element in oil is derived from the zinc dithiophosphate, and the amount of magnesium element in oil is derived from the magnesium salt of the sulfonate.)
A lubricating oil composition for a manual transmission provided with an aluminum sliding member . The lubricating oil composition for manual transmission according to claim 1, wherein the lubricating oil composition has a kinematic viscosity at 40 ° C. of 30 mm ² / _S or less. The viscosity of the base oil is 25 to 40 mm at 40 ° C. ² / _S The lubricating oil composition for manual transmission according to claim 1, wherein the lubricating oil composition is selected from the range of

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