WO2004069966A1 - Additives for lubricating oils and fuel oils, lubricating oil compositions, and fuel oil compositions - Google Patents

Abstract

Additives for lubricating oils and fuel oils, which contain as the main component disulfide compounds represented by the general formula (I) or (IV): R1OOC-A1-Sx-A2-COOR2 (I) (wherein R1 and R2 are each independently C1-30 hydrocarbyl which may contain oxygen, sulfur or nitrogen; A1 and A2 are each independently CR3R4 wherein R3 and R4 are each independently hydrogen or C1-20 hydrocarbyl; and x is 2), and R1OOC-A3-Sx-A4-COOR2 (IV) (wherein R1 and R2 are as defined above; A3 and A4 are each independently CR5R6-CR7R8 wherein R5 to R8 are each independently hydrogen or C1-20 hydrocarbyl; and x is 2). The additives exhibit excellent functions as extreme -pressure additive or anti-wear additive and little corrode nonferrous metals, thus being useful as sulfur-containing extreme-pressure additives suitable for lubricating oils and fuel oils.

Description

 Description Lubricating oil and fuel oil additives, lubricating oil compositions and fuel oil compositions

 The present invention relates to a lubricating oil and fuel oil additive, and a lubricating oil composition and a fuel oil composition. More specifically, the present invention relates to a friction modifier, particularly an extreme pressure additive, which is used for lubricating oils and fuel oils containing as a main component a disulfide compound having a specific structure having an excellent function as an antiwear agent. The present invention also relates to a lubricating oil composition and a fuel oil composition each containing the above-mentioned additives. Background art

 Conventionally, lubricating oil has been used in internal combustion engines, drive systems such as automatic transmissions, shock absorbers, and power steering to facilitate their operation. It is well known that lubricating performance is initially insufficient, and the lubricated surface friction and wear occurs, eventually causing seizure. Therefore, lubricating oils containing extreme pressure additives and antiwear agents are used. However, conventional extreme pressure additives are not always satisfactory because they do not exhibit sufficient anti-seizure effects due to interaction with other additives, corrode metals, or have poor abrasion resistance. It was not.

Metal working oils used for metal working such as cutting, grinding or plastic working include mineral oils and synthetic hydrocarbon oils, and alcohols. It is prepared by blending oily agents such as oils, fatty acid esters, and fatty acids and extreme pressure additives, and attempts have been made to improve processability.

 However, for such a metal working oil, a new working oil that can further improve the workability is demanded from the viewpoint of improving productivity and saving energy. At the same time, chlorine-based extreme pressure additives, which have been widely used as extreme pressure additives, do not cause a deterioration in the work environment, such as causing rash on the human body or 鲭 on the target metal. Because 'they tend to refrain from using it.

 As a metalworking oil that meets the above demand, an oil agent obtained by adding an active-containing olefin sulfide and an overbased sulfonate to a base oil is commercially available.

 The above-mentioned commercially available metalworking oils have good resistance to welding and have the ability to prevent abnormal wear (for example, chipping) of tools and peeling of machined surfaces. However, in machining with relatively low load friction, corrosion and wear of the tool due to active erosion progress, shortening the time until tool replacement or re-polishing, often hindering production efficiency. Conversely, metal processing, in which abnormal wear is not a problem from the beginning, often led to a reduction in production efficiency.

 Next, hydraulic oil is a power transmission fluid used for operations such as power transmission, force control, and shock absorption in hydraulic systems such as hydraulic equipment and devices, and also functions to lubricate sliding parts. .

In such a hydraulic oil, it is essential to have excellent anti-seizure properties and abrasion resistance in particular. The above performance is imparted by blending an extreme pressure additive, an antiwear agent, and the like into a base oil such as a synthetic oil. However, conventional extreme pressure additives are not always satisfactory enough, such as insufficient abrasion resistance and corrosive wear, even though the effect of preventing load seizure is sufficient. Was.

 In addition, gear oils, especially gear oils for automobiles, have been subject to abrasion resistance due to the increase in loading capacity in recent years, or the harsh operating conditions such as long-distance transportation due to the development of the expressway network, and the extension of oil renewal intervals. Improving stability and oxidation stability is urgently needed.

 Until now, extreme pressure additives or anti-wear additives such as sulfurized oils and fats, sulfided olefins, phosphoric acid dithiophosphoric acid compounds, and zinc dithiophosphate have been mainly blended with lubricating base oils. However, further reduction in wear resistance, oxidation stability, and wear coefficient ratio (low speed Z high speed) are required.

 On the other hand, it is known that lubricating performance of fuel oils becomes insufficient as it is highly hydrogenated, and it has been pointed out that fuel pumps using highly refined fuels wear out. . Therefore, recent high-performance turbine fuels are required to have high lubrication performance, and are adsorbed on the metal surface of fuel system equipment to form an extreme pressure film, which improves lubricity and reduces wear. High performance fuel oil additives are desired.

Conventionally, sulfur-based extreme pressure additives have been frequently used as extreme pressure additives for lubricating oils. This sulfur-based extreme pressure additive has a sulfur atom in the molecule and is dissolved or uniformly dispersed in the base oil to exert an extreme pressure effect. For example, sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, polysulfides, sulfided olefins, thiocarbamates, thioterpenes, and dialkylthiodipropionates are known. However, these sulfur-based extreme pressure additives corrode metals, do not exhibit sufficient seizure prevention effects due to interaction with other additives, or have insufficient abrasion resistance However, it was not always satisfactory.

 Recently, as a sulfur-based extreme pressure additive, general formula (VII)

R ⁹ OOC — A ⁵ — S _x — A ⁶ -COOR ¹ . · ·-(VII)

(In the formula, ¹⁹ and ¹ ° are each a hydrocarbon group having 1 to 20 carbon atoms, A ⁵ and A ⁶ are each a hydrocarbon group having 0 to 20 carbon atoms, and X is an integer of 1 to 6. (For example, JP-A-2001-288490).

According to Japanese Patent Application Laid-Open No. 2001-288490, the compound of the general formula (VII) is composed of a chlorinated ester such as a monomethyl acetate and a polysulfide. Since it is produced by reacting with tritium, it is inevitable that the mixture will be a mixture of monosulfide, disulfide, and trisulfide or higher polysulfide. As for the divalent hydrocarbon groups tables in A ⁵及Pi A ^6, Les describes the number of carbon atoms, in Runomi, any description is not made for that structure, any good Una structure It is not entirely clear if one is preferred. Disclosure of the invention

Under these circumstances, the present invention provides a Sulfur-based extreme pressure additives used for lubricating oils and fuel oils, which have excellent load-bearing capacity and wear resistance and low corrosiveness to non-ferrous metals, and lubricating oil compositions containing the additives And a fuel oil composition.

 The present inventors have conducted intensive studies to achieve the above object, and as a result, the object can be achieved by a lubricant and fuel oil additive containing a disulfide compound having a specific structure as a main component. I found that. The present invention has been completed based on such findings.

 That is, the present invention

 1. General formula (I)

R ¹ OOC— A ¹ — S _x — A ² — C〇 OR ² · · (I)

(In the formula, R ¹及Pi R ² each independently represent an oxygen atom, a sulfur atom, or human Dorokarubiru group for the nitrogen atom optionally containing an carbons 1 be ~ 3 0. A ¹ and A ^2, Each is independently a group represented by CR ³ R ⁴ , wherein R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X represents 2.)

2. An additive for lubricating oil comprising a disulfide compound represented by the following formula: 2. General formula (II) and / or general formula (III)

ROC— A ¹ — SH · · · (II)

(Wherein, R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, A ¹ is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.)

R ² OOC -A ² -SH (III) (Wherein, R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, A ² is a group represented by CR ³ R ⁴ , ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.)

A lubricating oil additive comprising a disulfide compound as a main component obtained by oxidatively coupling the mercaptoalkanecarboxylic acid ester represented by

 3. General formula (IV)

R ¹ OOC— A ³ — S _x _ A ⁴ — COOR ² · ·-(IV)

(Wherein, R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom. A ³ and A ⁴ are each And each independently represents a group represented by CR ⁵ R ⁶ —CR ⁷ R ⁸ , wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X represents 2. )

A lubricant additive mainly composed of a disulfide compound represented by

4. General formula (V) and / or general formula (VI)

I ^ OOC—A ³ — SH · ·-(V)

(Wherein, R ¹ is a hydrocarbyl group having ι to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ³ is represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ R ^{5 to} R ^s are each independently hydrogen or a hydrocanoleville group having 1 to 20 carbon atoms.)

R ² OOC -A ⁴ -SH (VI)

(Wherein, R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ⁴ is CR ⁵ R ⁶ — CR ⁷ A group represented by R ⁸ , wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. )

A lubricating oil additive mainly comprising a disulfide compound obtained by oxidizing the mercaptoalcarboxylic acid ester represented by

 5. The content of the above-mentioned item 1, wherein the content of the polysulfide compound in which X in the general formula (I) is 3 or more is 30% by mass or less based on the total amount of the polysulfide compound and the disulfide compound. Lubricating oil additives.

 6. The content of the above-mentioned (3), wherein the content of the polysulfide compound in which X in the general formula (IV) is 3 or more is 30% by mass or less based on the total amount with the disulfide compound. Lubricating oil additives,

7. General formula (I)

I ^ OOC— A ¹ — S _x — A ² — COOR ² · · (I)

(Wherein, R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom.

1 and ² are each independently a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X is 2 Is shown. ) An additive for fuel oil containing a disulfide compound represented by

 8. General formulas (II) and Z or general formula (III)

R i QOC— A ¹ — SH · · · (II)

(Wherein, R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ^! Is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or carbon number 1 to 20 Is a hydrocarbyl group. )

R ² 〇 OC— A ² — SH · · · (III)

(Wherein, R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ² is a group represented by CR ³ R ⁴ , ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.)

A fuel oil additive mainly comprising a disulfide compound obtained by oxidative coupling of a mercaptoalkanecarboxylic acid ester represented by the formula:

 9. General formula (IV)

R ¹ OOC— A ³ _ S _x — A ⁴ — COOR ² · ·-(IV)

(Wherein, R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom. A ³ and A ⁴ are each And each independently represents CR ⁵ R ⁶ —CR ⁷ R ⁸ , wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X represents 2. )

10. A fuel oil additive comprising a disulfide compound represented by the following formula: 10. General formula (V) and / or general formula (VI)

I ^ OOC—A ³ — SH · ·-(V)

(Wherein, R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ³ is represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.)

R ² OOC -A ⁴ -SH (VI) (In the formula, R ² is a carbon number which may contain an oxygen atom, a sulfur atom, or a nitrogen atom: a hydrocarbyl group of from 30 to 30, and A ⁴ is represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.)

A fuel oil additive mainly composed of a disulfide compound obtained by oxidizing the mercaptoalcarboxylic acid ester represented by

 1 1. The content of the above 7 wherein the content of the polysulfide compound in which X in the general formula (I) is 3 or more is 30% by mass or less based on the total amount with the disulfide compound. The additive for fuel oil as described above.

1 2. The method according to the above item 9, wherein the content of the polysulfide compound in which X in the general formula (IV) is 3 or more is 30% by mass or less based on the total amount of the polysulfide compound and the disulfide compound. Additive for fuel oil.

1 3. A lubricating oil composition comprising: (A) a lubricating base oil; and (B) the lubricating oil additive according to any one of 1 to 6 above.

 14. The lubricating oil composition as described in 13 above, wherein the content of the component (B) is 0.01 to 50% by mass.

 1 5. A fuel oil composition comprising: (X) a fuel oil; and (Y) the fuel oil additive according to any one of the above items 7 to 12.

 1 6. The fuel oil composition according to the above 15, wherein the content of the (Y) component is from 0 · 101 to 1000 mass ppm.

Is provided. BEST MODE FOR CARRYING OUT THE INVENTION

 The compound represented by the general formula (I) used in the lubricating oil and fuel oil additives of the present invention has the following structure

R ¹ OOC— A ¹ — S _x — A ² — COOR ² · · (I)

Is a disulfide compound having the formula:

In the general formula (I), R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, particularly Hydrocarbyl groups having 3 to 18 carbon atoms are preferred. The hydrocarbyl group may be linear, branched, or cyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom. The R ¹ and R ² may be mutually identical, but may be different, for manufacturing reasons, arbitrary preferable to be identical.

Next, A ¹ and A ² are each independently a group represented by CR ³ R ⁴ , and R ³ and R ⁴ are each independently hydrogen represented by a monovalent hydrocarbyl group having 1 to 20 carbon atoms. It is. The hydrocarbyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 8 carbon atoms. A ¹ and A ^2, specifically a methylene group, Echiriden group, propylidene group, and the levator Gerare, among them a methylene group is particularly preferred. Also, may be identical to A ¹及Pi A ² Hata purchase, may be different, for manufacturing reasons, it is preferably identical. X is 2.

In the lubricating oil and fuel oil additives of the present invention, the content of the polysulfide in which X in the general formula (I) is 3 or more is a compound represented by the general formula (I) (X is 2) 30% by mass based on the total amount of The following is preferred. When the content is 30% by mass or less, corrosiveness to nonferrous metals can be sufficiently suppressed. The content of the polysulfide compound having X of 3 or more is more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

 Therefore, in the production of the disulfide compound represented by the general formula (I), it is important to adopt a method in which the by-product amount of the polysulfide compound having X of 3 or more is in the above range. It is. In the present invention, for example, it is preferable to produce according to the following method. That is, as a raw material, general formula (II) and / or general formula (III)

R i OOC— A ¹ — SH · ·-(II)

R ² OOC -A ² -SH (III)

(Wherein, R ¹ and R ² , A ¹ and A ² are the same as described above.)

Oxidative coupling is carried out using the carboxylic acid ester represented by the following formula. According to such a production method, by-products of polysulfide compounds higher than trisulfide are substantially not generated.

Specifically, scale ^1. . . A ¹ — S ₂ — A ² — C〇 OR ² , R ¹ OOC — A ¹ — S s — A ¹ — COOR ^ RSOOC— A ² — S ₂ — A ² — COOR ²

 Examples of the oxidizing agent include oxygen, hydrogen peroxide, halogen (iodine, bromine), hypohalous acid (salt), sulfoxide (dimethylsulfoxide, diisopropylpropylsulfoxide), and manganese oxide (IV). Among these oxidizing agents, oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferable because they are inexpensive and easy to produce disulfide.

As a specific example of the disulfide compound represented by the general formula (I), Is bis (methoxycanoleponylmetinole) disnorefide, bis (ethoxycanolepo-noremetinole) dis / refide, bis (n-propoxy-pote boninoleme chinole) disenoleide, bis (isopropoxycanolenotinole) Dishonolefide, Bis (cyclopropoxy-norreboni ^ / methinole) Dishonolefide, 1, 1-bis (1-methoxycanoleponinoletin) Ethyl sulfide, 1, 1—Bis (1-methoxycarbo-lu n —Propyl) disnolesulfide, 1,1-bis (1 — methoxycarbone-l__p-inole) disulphide, 1,1-bis (1-methoxyethoxy-n-hexynole) disnolesulfide, 1,1 1 bis (1 — methoxy canepo 2-n-octyl) disulfide, 2 '2-bis (2-meth Toxic canoleponinole n-propynole) disanolefide, a, monobis (α-methoxycarbonylbenzyl) disulfide and the like.

 The compound represented by the general formula (IV) used for the lubricating oil and fuel oil additives of the present invention has the following structure:

R ¹ OOC _ A ³ — S _χ — A ⁴ — COOR ² · ·-(IV)

Is a disulfide compound having the formula:

In the general formula (IV), R ¹及Pi R ² are the same as your Keru R ¹ and R ² in the general formula (I). R ¹ and R ² may be the same or different, but are preferably the same for manufacturing reasons.

Next, A ³ and A ⁴ are each independently a group represented by CR ⁵ R ⁶ —CR ⁷ R ⁸ , wherein R ^{5 to} R ⁸ are each independently hydrogen or a group having 1 to 20 carbon atoms. Is a monovalent hydrocarbyl group. As a hydrocarbyl group, Those having carbon numbers of ι to ι 2, and more preferably those having 1 to 8 carbon atoms are preferred. Also, A ³ and A ⁴ may be mutually identical or may be different, for manufacturing reasons, and this is preferably the same. X is 2.

 In the lubricating oil and fuel oil additives of the present invention, the content of the polysulfide in which X is 3 or more in the general formula (IV) is a compound represented by the general formula (IV) (where X is 2). ) Is preferably 30% by mass or less based on the total amount. When the content is 30% by mass or less, corrosiveness to nonferrous metals can be sufficiently suppressed. The content of the polysulfide compound in which X is 3 or more is more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

 Therefore, in the production of the disulfide compound represented by the general formula (IV), it is important to adopt a method such that the by-product amount of the polysulfide compound having X of 3 or more is within the above range. It is. In the present invention, for example, it is preferable to produce according to the following method. That is, as a raw material, general formula (V) and / or general formula (VI)

R i OOC—A ³ — SH · · · (V)

R ² OOC -A ⁴ -SH (VI)

(In the formula, R ¹ and R ² , A ³ and A ⁴ are the same as described above.)

Oxidative coupling is performed using a mercaptan carboxylic acid ester represented by the following formula. According to such a production method, by-products of a polysulfide compound higher than trisulfide are substantially not generated.

^{Specifically, R ^ OOC- A 3 - S} 2 _A 4 - CO OR 2, R 1 OOC -A 3 - S 2 -A 3 - C OOR \ R 2 OOC ~ A 4 - S 2 -A 4 - C _〇〇 R ² is manufactured _ά

 ο; — As the oxidizing agent used to produce the corresponding disulfide by oxidizing the mercaptocarboxylic acid ester, the oxidizing agent used to produce the disulfide from mercaptan can be used. Oxidizing agents include oxygen, hydrogen peroxide, halogens (iodine and bromine), hypohalous acid (salt), sulfoxide (dimethyl sulfoxide, diisopropyl sulfoxide), and manganese oxide (IV). And the like. Of these oxidizing agents, oxygen, hydrogen peroxide, and dimethyl sulfoxide are preferred because of their low cost and easy production of disulfide.

 Specific examples of the disulfide compound represented by the above general formula (IV) include 1,1—bis (2-methoxycanoleponinoleethyl) disulfide and 1,1bis (2—ethoxycanolepo- Nolechinole) disulfide, 1,1bis (2_η-propoxycanolepo-noletinole) disulfide, 1,1bis (2—isopropoxycarboninoleetinole) disnosulfide, 1,1bis (2 —Cyclopropoxycanoleboenolechinole) disulfide, 1,1bis (2—methoxycarburyl η —propyl) disnorefide, 1,1—bis (2—methoxycarboninole η —Petinole) Disulphide, 1,1-bis (2-methoxycanoleponinole η-hexyl) Disulphide, 1,1bis (2—Methoxycarbinole-η—P Pill) disulfide, 2,2—bis (3-methoxyethoxycarbonyl) η—pentyl) disulfide, 1,1—bis (2—methoxycanoleponinole 1 Can be.

These disulfide compounds are load-bearing as sulfur-based extreme pressure additives. It has excellent versatility and abrasion resistance, and is used as an additive for lubricating oil and fuel oil.

 In the lubricating oil and fuel oil additives of the present invention, the general formula

The disulfide compound represented by (I) and / or the disulfide compound represented by the general formula (IV) may contain one kind or two or more kinds.

Then, the lubricating oil composition of the present invention, and (A) a lubricating base oil is one that contains a lubricant additive comprising (B) the aforementioned disulfide compounds _{(Incidentally,} lubrication in the present invention Oil compositions include internal combustion engines, drive systems such as automatic transmissions, shock absorbers, and power steering; automotive lubricating oils used for gears; metal processing such as cutting, grinding, and plastic working. Includes metal working oils used for metalworking, hydraulic fluids used in hydraulic systems such as hydraulic equipment and devices, power control, and hydraulic fluids that are also used as power transmission fluids for damping and other operations.

 In the lubricating oil composition of the present invention, the lubricating oil base oil used as the component (A) is not particularly limited, and may be selected from mineral oils and synthetic oils according to the purpose and conditions of use of the composition. Appropriately selected from among them. Here, as the mineral oil, for example, a distillate obtained by distilling a paraffin-based crude oil, an intermediate-base crude oil or a naphthenic-based crude oil under normal pressure, or a residual oil obtained by distillation under normal pressure under reduced pressure, Or, refined oils obtained by refining them according to a conventional method, specifically, refined oils of solvent, refined hydrogenated oils, dewaxed oils, and clay treated oils may be mentioned.

Examples of synthetic oils include low-molecular-weight polybutene, low-molecular-weight polypropylene, α-olefin oligomers having 8 to 14 carbon atoms, and Esters such as polyol hydrides (such as fatty acid esters of trimethylol pulp and fatty acid esters of pentaerythritol), dibasic acid esters, aromatic polycarboxylic acid esters, and esterol phosphates Examples thereof include alkyl aromatic compounds such as danield products, anolequinolebenzene, and anolequinolenaphthalene, polyglycol oils such as polyalkylene glycol, and silicone oil.

 One of these base oils may be used, or two or more of them may be used in an appropriate combination.

 The content of the lubricating oil additive of the component (B) in the lubricating oil composition of the present invention is appropriately selected according to the purpose and conditions of use of the composition. The range is 0% by mass. In the case of automotive lubricating oils and hydraulic oils, it is usually in the range of 0.01 to 30% by mass, and preferably in the range of 0.01 to 10% by mass. In the case of metal working oils, the additive alone may be used. Although it can be used, it is usually selected in the range of 0.1 to 60% by mass, preferably 0.1 to 50% by mass.

 In the lubricating oil composition of the present invention, depending on the intended use, various additives, for example, other friction modifiers (oiliness agents, other extreme pressure additives) 摩 耗 antiwear agents, ashless dispersants, metal cleaning agents , A viscosity index improver, a pour point depressant, an antioxidant, a metal corrosion inhibitor, an antifoaming agent, a surfactant, an antioxidant, and the like.

Other friction modifiers and antiwear agents include, for example, sulfur-based compounds such as olefin sulfide, dialkyl alkyl polysulfide, dialkyl alkyl polyphenol, and diaryl polysulfide, phosphoric acid esters, and sulfide. Acid ester, estenol phosphite, alkylhydrogenphos Phosphorus compounds such as phyto, phosphoric acid ester amine salts, phosphorous acid ester amine salts, chlorinated fats and oils, chlorinated paraffins, chlorinated fatty acid esters, chlorinated fatty acid esters and other alkyl compounds Or ester compounds such as alkyl or alkenyl succinic acid ester, or organic compounds such as alkyl or alkenyl succinic acid, alkyl or alkenyl succinic acid, naphthenate, Organic compounds such as zinc dithiophosphate (Zn DTP), zinc dithiophosphate zinc zinc (Zn DTC), oxymolybdenum sulphide, organodiphospho-dithioate (Mo DTP), oxymolybdenum pudendithiocarbamate (Mo DTC) Metallic compounds and the like can be mentioned. Typical examples of ashless dispersants include succinic imids, boron-containing succinic imids, benzylamines, boron-containing benzylamines, succinic esters, fatty acids and succinic acid. Examples of the metal-based detergent include neutral metal sulfonates, neutral metal phosphates, neutral metal salicylates, and the like. Neutral metal phosphonates, basic sulfonates, basic phenates, basic salicylates, basic phosphonates, overbased sulfonates, overbased phenates, overbased salicylates, overbased phosphonates And the like.

Examples of the viscosity index improver include polymethacrylate, dispersed polymethacrylate, an olefin copolymer (for example, an ethylene-propylene copolymer, etc.), and a dispersed olefin copolymer. Polymers, styrene-based copolymers (eg, styrene-gen hydrogenated copolymers), etc., and pour point depressants include, for example, polymethacrylate. I can do it.

 For example, alkenyl succinic acid or its partial ester may be used as an antioxidant, and benzotriazole, benzimidazonole, benzothiazonole, thiadiazole, etc. may be used as metal corrosion inhibitor, for example. However, as the defoaming agent, for example, dimethylpolysiloxane, polyacrylate and the like are used, and as the surfactant, for example, polyoxyethylene alkylphenyl ether and the like are used.

 Examples of the antioxidant include an amine antioxidant such as alkylated diphenylamine, phenyl-1-a-naphthylamine, and alkylated naphthinoreamin; 2,6-di-tert-butylcresol; Examples include phenolic antioxidants such as 4, -methylenebis (2,6-di-t-butylphenol).

 The lubricating oil composition of the present invention can be used for, for example, automotive lubricating oils used in internal combustion engines, drive systems such as automatic transmissions, shock absorbers, power steering, gears, etc., such as cutting, grinding, and plastic working. Metalworking oil used for metalworking, power transmission in hydraulic systems such as hydraulic equipment and devices, power control used for actuation of damping, etc. Used as hydraulic fluid.

 On the other hand, the fuel oil composition of the present invention contains (X) a fuel oil and (Y) a fuel oil additive containing the above-mentioned disulfide compound. In the fuel oil composition of the present invention, a highly hydrorefined fuel oil, for example, a high-performance turbine fuel oil, is preferably used as the component (X).

The fuel oil composition of the present invention contains the fuel oil additive (Y). The weight is usually in the range from 0.01 to 100 mass 111, preferably from 0.01 to 100 mass ppm.

 In the fuel oil composition of the present invention, various additives can be appropriately compounded as necessary. Examples of such additives include antioxidants such as phenylenediamine, diphenylamine, alkylphenol, and amidephenol, and detergents such as polyetheramine and polyalkylamine. Metal deactivators such as Schiff-type compounds and thioamide-type compounds; surface ignition inhibitors such as organic phosphorus compounds; anti-freezing agents such as polyhydric alcohols and ethers; Antioxidants such as earth metal salts, sulfuric acid esters of higher alcohols, such as sulfuric acid esters of higher alcohols, aionic surfactants, cationic surfactants, amphoteric surfactants, etc .; Known fuel oil additives such as discriminants such as quinizarin and coumarin, odorants such as natural essential oils and synthetic flavors, and coloring agents such as azo dyes. . . Example

 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

 The coefficient of friction, wear scar diameter, and corrosiveness of the lubricating oil composition were determined according to the methods described below.

 (1) Friction coefficient and wear scar diameter

 The Soda four-ball test was performed under the following conditions.

At a rotational speed of 500 rpm and an oil temperature of 80 ° C, each hydraulic load [0.5, 0. 7, 0. 9, 1. 1 , 1. 3, 1. 5 kgf / cm 2 (XO. 0 9 8 0 7 MP a) while holding] 1 8 0 seconds, will stepwise raised load The test was performed for 180 seconds, the friction coefficient under each load was determined, and the diameter of the friction scar was measured according to the test termination law.

 (2) Corrosive

 JISK—2 5 1 3 In accordance with “Petroleum Product Copper Plate Corrosion Test Method”, conduct a corrosivity test at a test temperature of 100 ° C, a test time of 3 hours, and a test tube method. The state was observed, and the corrosiveness was evaluated with subdivision symbols 1a to 4c. The smaller the subdivision number, the lower the corrosiveness, and the greater the corrosiveness in alphabetical order. Production Example 1 Production of bis (ethoxycarbonylmethyl) disulfide Bis (ethoxycarbonylmethyl) disulfide was produced by oxidizing ethyl mercaptoacetate with dimethyl sulfoxide according to the following method. No polysulfide higher than trisulfide was found in this compound.

In a 10 O ml eggplant-shaped flask, 20.9 g of methyl menolecaptoacetate and 30.8 g of dimethyl sulfoxide were put, and heated in an oil bath at 120 ° C. for 8 hours. After cooling, the residue was dissolved in 100 ml of toluene and washed 10 times with water to remove unreacted dimethyl sulfoxide. The toluene was distilled off under reduced pressure to obtain 16.0 g of bis (ethoxycarbonylmethyl) disulfide. Production Example 2 Bis (n-butoxycarbonylmethyl) disulfide was oxidized in the same manner as in Production Example 1 except that n-butyl mercaptoacetate of bis (1-butoxycarbolmethyl) disulfide was used to produce bis (n-butoxycarbonylmethyl) disulfide. did. No trisulfide or higher polysulfide was found in this compound. Production Example 3 Production of bis (n-octoxycarbonylmethyl) disulfide

 Oxidation was carried out in the same manner as in Production Example 1 except that 11-octyl mercaptoacetate was used to produce bis (n-octoxycarbonylmethyl) disulfide. No trisulfide or higher polysulfide was found in this compound. Production Example 4 Production of bis (2-ethylhexoxycarbonylmethyl) disulfide

 Oxidation was carried out in the same manner as in Production Example 1 except that 2-ethylhexyl mercaptoacetate was used, to produce bis (2-ethylhexoxycarbonylmethyl) disulfide. In this compound, no polysulfide higher than trisulfide was found. Production Example 5 Production of bis (isooctoxycarbonylmethyl) disulfide

The same procedure as in Production Example 1 was carried out except that isocaptyl mercaptoacetate was used. And oxidized to produce bis (isootatooxycarbonylmethyl) disulfide. No trisulfide or higher polysulfide was found in this compound. Production Example 6 Production of bis (n-stearooxycarbonylmethyl) disulfide

 Stearyl mercaptoacetate was oxidized in the same manner as in Production Example 1 to produce bis (stearyloxycarbonylmethyl) disulfide. No polysulfide higher than trisulfide was found in this compound. Production Example 7 Production of 1, 1-bis (1-ethoxycarbonylethyl) disulfide

 Oxidation was carried out in the same manner as in Production Example 1 except that ethyl α-mercaptopropionate was used to produce 1,1-bis (1-ethoxycarbonylethyl) disulphide. In this compound, no polysulfide higher than trisulfide was found. Comparative Production Example 1 Production of bis (η-butoxycarbonylmethyl) polysulfide

Bis (η-butoxycarbonylmethyl) polysulfide was produced by producing sodium and sodium polysulfides from sodium sulfide and sulfur, and then reacting with sodium η-butyl acetate. At this time, for the purpose of comparison with the disulfide of the present invention, the sulfur flatness of sodium polysulfide (Na ₂ S x) was used. The molar ratio between sodium sulfide and sulfur was adjusted so that the average number (x) was 2. Also, sodium polysulfide was used in an excess of 5% so that n-butyl acetate was not remained. Specifically, the reaction was carried out according to the following method to produce bis (n-butoxycarboermethyl) polysulfide. That is, in a 500 m1 glass four-necked flask equipped with a stirrer and a heating reflux condenser, 26.4 g of sodium sulfide 9-hydrate, 3.52 g of sulfur, and 95% ethanol 15 After adding 0 ml, the mixture was heated and stirred in an oil bath at 80 ° C for 5 hours. After cooling to room temperature, n-butyl acetate 0.12 g was added little by little, and the mixture was stirred at room temperature for 2 hours. The reaction solution was transferred to a separating funnel, dissolved in 500 ml of toluene, and washed 10 times with water. The toluene was distilled off under reduced pressure to obtain 26.5 g of bis (n-butoxycarbonylmethyl) polysulfide.

 The compound was analyzed by high-performance liquid chromatography [column: ODS, solvent: acetonitrile, detector: refractive index (RI) detector]. As a result, the monosulfide compound: 21%, disulphide Body: 40%, Trisulfide body: 20%, Tetrasnolefide body: 12%, Pentathnolide body: 4%. Each value represents% by mass. Comparative Production Example 2 Production of bis (2-ethylhexyloxycarbonylmethyl) snoresulfide

2,2'-Thiodiglycolic acid 45,5 lg, 2-Ethynolehexanol 110-1.6 g, p-Tonolene in a 500 m1 glass eggplant-shaped flask equipped with Dean-Stark dehydrator 2. O g of sulfonic acid monohydrate was added, and the mixture was heated and refluxed for 5 hours. After cooling, separate the reaction mixture onto a separatory funnel. And washed twice with an aqueous solution of sodium hydrogencarbonate and then five times with water. Toluene was distilled off under reduced pressure to obtain 12.0 g of bis (2-ethylhexyloxyboninolemethynole) snoresulfide. Example 1

Was obtained in Preparation Example 1 Bis (E butoxycarbonyl methyl) Jisurufu Lee de, 5 0 0 mineral P 5 of the neutral fraction 0 0 N (1 0 0 ° C kinematic viscosity of 1 0. 9 mm ² / s, % CA 0.1 or less) to prepare a lubricating oil composition by adding 1% by mass based on the total amount of the composition to evaluate its performance. The results are shown in Table 1. Examples 2 to 7

 As shown in Table 1, the additives obtained in Production Examples 2 to 7 were added to 500 N neutral fraction mineral oil P500N so as to be 1% by mass based on the total amount of the composition. Then, a lubricating oil composition was prepared and its performance was evaluated. The results are shown in Table 1. Comparative Example 1

 Example 1 was carried out in the same manner as in Example 1 except that the bis (2-ethylhexyloxycarbonylmethyl) sulfide obtained in Comparative Production Example 1 was used. The results are shown in Table 1. Comparative Example 2

In Example 1, the bis (n-ptoxica) obtained in Comparative Production Example 2 was used. (Rubonylmethylene) The procedure was the same as in Example 1, except that polysulfide was used. The results are shown in Table 1. Comparative Example 3

 The evaluation was performed in the same manner as in Example 1 without adding any additives to | 500-Eutral fraction | oil P50ON. The results are shown in Table 1. 1 — 丄

Fruit 1 Table 1 2

製造例 8 1 ， 1 _ビス （ 2 —エ トキシカルボニルェチル） ジスル フィ ドの製造

Production Example 8 Production of 1,1-bis (2-ethoxycarbonylethyl) disulfide

 a-Ethyl mercaptopropionate was oxidized with dimethyl sulfoxide according to the method shown below to produce 1,1-bis (2-ethoxycarbonylylethyl) disulfide. No polysulfide higher than trisulfide was found in this compound.

A 100 ml eggplant-shaped flask was charged with 20.9 g of ethyl mercaptopropionate and 30.8 g of dimethinoresnorreoxide, and heated in a 120 oil bath for 8 hours. After cooling, it was dissolved in 100 ml of toluene and washed with water 10 times to remove unreacted dimethyl sulfoxide. The toluene was distilled off under reduced pressure to obtain 16.0 g of 1,1-bis (2-ethoxycarboninoleethyl) disulphide. Production Example 9 Production of 1, 1 _bis (2-2-ethylhexoxycarboninoleethyl) disulfide

 2-Ethylhexyl mercaptoacetate was oxidized in the same manner as in Production Example 1 to produce 1,1-bis (2-2-ethylhexoxycarpo-norethyl) disulphide. No trisulfide or higher polysulfide was found in this compound. Example 8

The 1,1-bis (2-ethoxycarbonyldiethyl) disulfide obtained in Production Example 8 was combined with a mineral oil P 500 ON of a 500 neutral fraction (100 ° C. kinematic viscosity of 10.9 ° C.). mm ² / s,% CA 0.1 or less) to prepare a lubricating oil composition by adding 1% by mass based on the total amount of the composition, and evaluated the performance. The results are shown in Table 1. Example 9

Example 8 was carried out in the same manner as in Example 8, except that 1,1-bis (2-2-ethylhexoxycarbonylethyl) disulfide obtained in Production Example 9 was used. The results are shown in Table 2.

Table 2

 As is clear from the above Examples and Comparative Examples, it can be seen that the lubricating oil composition using the additive of the present invention has a small wear scar diameter and extremely high load resistance and wear resistance. In addition, in comparison with Comparative Example 1, when a lubricant additive having a high content of a polysulfide compound in which X in the general formula (I) and the general formula (IV) is 3 or more is used, a non-ferrous metal is used. It shows that the lubricating oil composition of the present invention has a low corrosiveness to non-ferrous metals, and is very good, whereas the lubricating oil composition of the present invention has a low corrosiveness. Industrial potential

 ADVANTAGE OF THE INVENTION According to this invention, compared with the conventional sulfur type extreme pressure additive, it has excellent load-bearing performance and abrasion resistance, and has a low corrosiveness to non-ferrous metals. It is possible to provide a sulfur-based extreme pressure additive to be used, and a lubricating oil composition and a fuel oil composition containing the additive.

Claims

The scope of the claims 1. General formula (I) R ¹ OOC _ A ¹ — S _x — A ² — C〇 OR ² · · (I) (Wherein R ¹ and R ² each independently represent a hydrocarbyl group A ¹ and A ² having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, A group independently represented by CR ³ R ⁴ , wherein R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X represents 2.) An additive for lubricating oil containing a disulfide compound as a main component. 2. General formula (II) and / or general formula (III)  R 'O O C-A'-S H (In the formula, R ¹ is a hydrogenated noreville group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and Α ′ is a group represented by CR ³ R ^4. R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.) R ² OOC-A ² -SH (III) (In the formula, R ² is a hydrocanolevir group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom; A ² is a group represented by CR ³ R ⁴ ; ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.) An additive for a lubricating oil containing a disulfide compound as a main component, which is obtained by oxidizing a mercaptoalcarboxylic acid ester represented by the following formula: 3. General formula (IV) R ¹ O〇 C— A ³ — S _x — A ⁴ — COOR ² · ·-(IV) (Wherein, R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom. A ³ and A ⁴ are each X is independently a group represented by CR ⁵ R ⁶ —CR ⁷ R ⁸ , wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms. ) An additive for lubricating oil containing a disulfide compound as a main component.  4. General formula (V) and Z or general formula (VI)  R 'O O C -A'-S H... (V) (In the formula, R ¹ is a hydroforce group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ³ is represented by CR ⁵ R ⁶ _ CR ⁷ R ⁸ . R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms.) R ² OOC -A-SH (VI) (Wherein, R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ⁴ is a group represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ Wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbinol group having 1 to 20 carbon atoms.) An additive for a lubricating oil containing a disulfide compound as a main component, which is obtained by oxidizing the mercaptoalkanecarboxylic acid ester represented by the following formula. 5. The content of the polysulfide compound in which X in the general formula (I) is 3 or more is 3.0 mass based on the total amount with the disulfide compound. amount. 2. The additive for lubricating oil according to claim 1, wherein the additive is not more than / ₀ .  6. The content of the polysulfide compound in which X in the general formula (IV) is 3 or more, based on the total amount of the polysulfide compound and the disulfide compound, is 30 mass% or less. 3. The additive for lubricating oil according to item 3. 7. General formula (I) R ¹ OOC— A ¹ — S _x — A ² — COOR ² · · (I) (In the formula, R ¹ and R ² are each independently a hydrocarbyl group A ¹ and A ² having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom. A group independently represented by CR ³ R ⁴ , wherein R ³ and R ⁴ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X represents 2.) An additive for fuel oil containing a disulfide compound as a main component. 8. — General formula (II) and Z or general formula (III)  R ^ OC -A ^ SH (II) (Wherein, R ¹ is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, A ¹ is a group represented by CR ³ R ⁴ , R ³ and R ⁴ are each independently hydrogen or a hydryl group having 1 to 20 carbon atoms.) R ² OOC— A ² — SH '· · (III) (Wherein, R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, A ² is a group represented by CR ³ R ⁴ , ³ and R ⁴ are each independently hydrogen or carbon number 1-2 It is a hydrocarbyl group of 0. ) An additive for fuel oil containing a disulfide compound as a main component, which is obtained by oxidizing the mercaptoalcarboxylic acid ester represented by the following formula.  9: General formula (IV) R ¹ OOC— A ³ — S _x — A ⁴ — COOR ² ·-(IV) (Wherein, R ¹ and R ² are each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom. A ³ and A ⁴ are Each independently represents a group represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ , wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and X represents 2. .) An additive for fuel oil containing a disulfide compound as a main component.  1 0. —General formula (V) and / or general formula (VI) R i OOC— A ³ — SH · ·-(V) (Wherein, R ¹ is a carbon number which may contain an oxygen atom, a sulfur atom, or a nitrogen atom: a hydrocarbyl group of ~ 30, and A ³ is represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ Wherein R ^{5 to} R ⁸ are each independently hydrogen or a hydrocanolevir group having from 2 to 20 carbon atoms.) · R ² OOC— A ⁴ — SH · · · (VI) (Wherein, R ² is a hydrocarbyl group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom, or a nitrogen atom, and A ⁴ is a group represented by CR ⁵ R ⁶ — CR ⁷ R ⁸ Wherein R ⁵ to R ⁸ are each independently hydrogen or a hydrocarbinole group having 1 to 20 carbon atoms.) Oxidized mercaptoalkane carboxylate represented by An additive for fuel oils containing a disulfide compound as a main component, which is obtained by carrying out the process.  11. The content of the polysulfide compound in which X in the general formula (I) is 3 or more is 30% by mass or less based on the total amount of the polysulfide compound and the disulfide compound. 8. The additive for fuel oil according to item 7 in the scope.  1 2. The content of the polysulfide compound having an X force S of 3 or more in the general formula (IV) is not more than 30% by mass based on the total amount of the polysulfide compound and the disulfide compound. Item 10. The additive for fuel oil according to Item 9, wherein 1 3. (A) and lubricating base oil, (B) a lubricating oil composition comprising a lubricating oil additive according to either the claims the items 1 to 6, wherein ₍ 1 4. The content of the component (B) is from 0.01 to 50 mass%. /. The lubricating oil composition according to claim 13, which is:  1 5. A fuel oil composition comprising: (X) a fuel oil; and (Y) the fuel oil additive according to any one of claims 7 to 12. 16. The fuel oil composition according to claim 15, wherein the content of the (Y) component is from 0.01 to 100 mass 1.1.