JP2000510498A - Improvement of oily composition containing active sulfur - Google Patents

Abstract

  (57) [Summary] The compatibility of a lubricating composition containing an active sulfur-containing additive with a nitrile elastomer seal is such that the additive or a concentrate containing the same or the composition is treated with one or more olefinically unsaturated compounds selected from the following compounds: Enhanced by treating: (a) an acyclic compound having at least two double bonds in which adjacent double bonds are separated by two saturated carbon atoms; (b) at least eight carbon atoms; A compound comprising an alicyclic ring having at least two double bonds, wherein each double bond is separated from the nearest neighboring double bond by two saturated carbon atoms; and (c) a saturated alicyclic ring; A compound having at least one exocyclic double bond.

Description

DETAILED DESCRIPTION OF THE INVENTION                     Improvement of oily composition containing active sulfurTechnical field   The present invention relates to improving the long-term reliability of elastomer seals, and in particular, to engine seals. The need for nitrile seals arises from the latest engine design and operating conditions; It relates to making it possible to fulfill environmental considerations.Background art   Transmission mechanisms, such as those in motor vehicles, prevent lubricant from leaking and A shaft and a bearing seal are required to prevent intrusion. The life of the seal, especially The suitability of the seal for use, the degree of care used to install the seal, The temperature to which the seal is exposed during use, the type of lubricant that the seal contacts, and the Depends on the condition of the surface that the tool contacts. Seal breakage is almost always Leads to lubricant spills and is deemed increasingly unacceptable and no longer intended Seals that cannot perform a function usually must be replaced. Follow Therefore, it is required that the life of the seal is extended as long as possible.   International Application No. 85/04896 does not mention the unstable sulfur-free additives of lubricants. Add stable sulfur-containing additives to copper or other substances reactive with copper and labile sulfur or Are olefins, especially α-olefins, preferably 4 to 30 carbon atoms, especially carbon What can be obtained by treating with an α-olefin having 10 to 20 atoms It is shown. The olefins described in the examples are all C_15-18Or C_16-18α- It is an olefin.   C_15-18Alpha-olefins can also be used in the process described in U.S. Pat.No. 4,228,022. Preferred compounds to use. Generally, the olefin is preferably Having 10 to 30 carbon atoms, especially 15 to 20 carbon atoms, and is straight-chain or branched It is shown that there may be.   EP-A-151 581 B states that lubricants, including additives, are non-static on copper and similar substances. Has a sufficiently low level of active sulfur to make it non-corrosive and non-corrosive It relates to the preparation of lubricating oil additives. Olefinically unsaturated with 8 to 36 carbon atoms Compounds have been used. The olefinically unsaturated compound comprises one or more non-aromatic diamines. It is a compound having a heavy bond and may be linear or alicyclic. α-olefin , Especially C_16-18Alpha-olefins are preferred, but other types of olefinically unsaturated Compounds are also mentioned.   U.S. Pat. No. 4,147,640 protects copper-lead bearings from corrosion without metal and phosphorus The preparation of lubricating oil antioxidants with the ability to It is disclosed to react with the fins to reduce the corrosiveness of the product. Use me The fin has about 6 to 18 carbon atoms and 1 to 3 olefinic double bonds. Good Preferred compounds are cyclopentadiene dimer and allocymene.   Other specifications specifically disclosing lubricating oil compositions containing oil-soluble sulfur-containing organic compounds Nos. WO 86/04601, WO 86/04602, WO 86/03772 and WO 86/026 No. 38 and U.S. Pat. No. 4,664,825. All of these five statements are By treating a compound with an alkali metal sulfide, the active or unreacted Mentions the possibility of reducing the au content. Nitrile sea of the disclosed composition Good compatibility is also shown.   The Applicant has found that the lubricating composition in contact with the seal contains active sulfur. If the composition contains a specific olefinically unsaturated compound, the nitrile It has been discovered that the life of the lastmer seal is significantly increased. With "active" sulfur Means sulfur containing the elemental sulfur that erodes the nitrile elastomer.   The issues of seal compatibility and copper corrosivity are addressed in the prior art for sulfur-containing additives. Has been assembled but is still an improved or alternative product or elastomer with such additives There is a need for a method of improving compatibility with seals, especially nitrile seals. Shi The challenge of tool compatibility is the problem of sulfur content in lubricating oil compositions in contact with nitrile seals. Fatally impairing the utility of the additive.Disclosure of the invention   Applicants have surprisingly discovered that active sulfur-containing lubricating oil additives, concentrates or compositions. The use of certain olefinically unsaturated compounds selected to treat Found to provide a particularly significant extension of the life of the rill elastomer seal . The present invention is directed to heavy duty diesel engines that typically contain relatively high levels of sulfur-containing materials. Particularly effective for lubricants such as engine lubricants.   The present invention also provides a lubricating composition obtained by mixing the following components: It is. (1) a large proportion of lubricating oil; (2) an active sulfur-containing oil-soluble additive; and (3) an oil-soluble olefinically unsaturated compound selected from the following compounds:   (A) at least two adjacent double bonds separated by two saturated carbon atoms         An acyclic compound having a double bond of   (B) at least eight carbon atoms and each double bond is two saturated carbon atoms;         At least two that are separated from the closest double bond         A compound containing an alicyclic ring having a double bond; and   (C) Compounds having a saturated alicyclic ring and at least one exocyclic double bond.   The present invention also provides an active sulfur-containing lubricating oil additive, concentrate or composition as described in the preceding paragraph. To provide a treatment method characterized by treating with a specified olefinically unsaturated compound. Things.   The invention further relates to sulfur and / or sulfur which have a deleterious effect on the elastomer. To improve the compatibility of lubricating compositions containing nitrile elastomers with nitrile elastomers Olefinic unsaturated compound selected from the above (a), (b) and (c) used The use of goods is provided. For example, select from the above (a), (b) and (c) The olefinically unsaturated compounds that can be used include nitrile elastomers containing sulfur and / or Used to reduce the tendency to be degraded by lubricating compositions containing sulfur-containing compounds To extend the life of engine seals in contact with such compositions. Used.   Antioxidants, extreme pressure additives and antiwear additives and / or load bearing in lubricating compositions Sulfur-containing additives such as water-soluble additives are widely used and commonly used species. One class of sulfur-containing additives is sulfurized phenols, sulfurized olefins and phosphorus and / or sulfur. Salts of au-containing acids, such as phosphorodithioic and dithiocarbamic acids, The invention is not limited to these individual types of additives. Such additives include various Lubricants, including functional fluids, such as hydraulic fluids, automatic transmission fluids, and heat transfer fluids, such as Used for crankcase lubricating oil, gear lubricant and metal working oil.   As the sulfurized phenol, phenol or alkylphenol mono, di and Includes polysulfides, their salts and their overbased salts. Alkyl phenols are The aromatic ring can include one or more alkyl groups. As a lubricant additive Typical sulfurized alkylphenols used are represented by the following formula: In the formula, R represents an alkyl group, n is 0 or an integer of 1-4, and p is an integer of 1-3. X is an integer from 1 to 4, and the average number of carbon atoms of the alkyl group is appropriate in the oil. The number is enough to perform sufficient dissolution. Each group represented by R is typically a carbon It has 5 to 40 atoms, preferably 8 to 20 atoms. The metal salt of sulfurized phenol is Alkylphenol sulfide and a sufficient amount of metal-containing materials, such as metal oxides or Is reacted with hydroxide to produce neutral or overbased sulfurized metal phenate if desired Is obtained. Methods for preparing overbased metal phenates are well known in the art. And are well known and need not be described here.   Examples of sulfurized olefins and other unsaturated compounds used in lubricating compositions are described herein. Prior art cited earlier in this document, for example, WO 86/04601 and WO 86/02638 And U.S. Pat. No. 4,664,825.   Examples of phosphorodithioic acid salts include dihydrocarbyl dithiophosphate metal salts, for example, Examples include zinc dihydrocarbyl dithiophosphate (ZDDP). For oily compositions A particularly preferred ZDDP used is of the formula Zn [SP (S) (OR¹) (OR^Two)]_Two(In the formula , R¹And R^TwoHas 1 to 18, preferably 2 to 12, carbon atoms. R¹as well as R^TwoIs particularly preferably an alkyl group having 2 to 8 carbon atoms. R¹And R^TwoBut Examples of groups represented are ethyl, n-propyl, i-propyl, n-butyl. Butyl, i-butyl, sec-butyl, amyl, n-hexyl, i- Xyl, n-heptyl, n-octyl, decyl, dodecyl, octade Silyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl And a methylcyclopentyl group, a propenyl group and a butenyl group.   The salt of dithiocarbamic acid is typically of the formula [RR'NC (S) S]_nM (where , R and R 'are the same having 1 to 18, preferably 2 to 12, carbon atoms or Different hydrocarbyl groups, for example alkyl, alkenyl, aryl, a Aralkyl, alkaryl or cycloalkyl). M is appropriate Metals such as molybdenum, zinc or copper. Used in lubricating oil compositions More preferred dithiocarbamates are those having 2 to 12 carbon atoms.   The sulfur-containing lubricant additives described above and many other sulfur-containing lubricant additives are Typically, the starting compound is combined with a sulfur and / or a sulfur-containing compound, such as hydrogen sulfide. Or by reacting with a sulfur monohalide or dihalide. Made. Sulfurization products, usually containing a mixture of different compounds, are typically free Containing at least some sulfur that is or is only loosely bound, Its sulfur is effective in eroding nitrile elastomers: as shown earlier In addition, sulfur that erodes nitrile elastomers is referred to herein as "active sulfur". Devour.   Lubricants for heavy duty diesel engines are typically alkyl phenol sulfides. 0 to 3% by mass of a sulfur-containing compound such as sulfur.   According to the present invention, an active sulfur-containing additive for a lubricating composition, the composition itself or a preferred additive. Alternatively, a concentrate for producing a lubricating composition containing such an additive may comprise the following compound: Treated with an oil-soluble olefinically unsaturated compound selected from the group consisting of: (A) at least two adjacent double bonds separated by two saturated carbon atoms       An acyclic compound having a double bond; (B) at least eight carbon atoms and each double bond is composed of two saturated carbon atoms;       At least two doubles separated from the closest double bond       A compound containing an alicyclic ring having a bond; and (C) Compounds having a saturated alicyclic ring and at least one exocyclic double bond.   If desired, more than one selected from (a), (b) and (c) above Of course, olefinically unsaturated compounds are used. Two or more If compounds are used, make sure they are from the same group. do not need. Therefore, for example, the compound selected from (a) is (b) or (c) Used with compounds selected from   Preferred compounds of group (a) are unsubstituted or substituted linear terpenes. Book The unsubstituted linear terpene used in the present invention has the formula (C)₆H₈)_n(Where n is at least 2), that is, a terpene having only carbon and hydrogen atoms. The present invention The preferred unsubstituted linear terpene used for is squalene (n in the above formula is 6 There is). Possible substituents on the linear terpene to be used in the present invention are, for example, , A hydroxyl group.   Preferred substituted terpenes include geraniol and farnesol .   A preferred group (b) compound having only two double bonds is 1,5-cyclothio Kutadiene. If desired, the compound of group (b) can be at least It contains three double bonds, each end of each double bond being two saturated carbon atoms at each adjacent two Separated from heavy bonds. Preferred group (b) having three double bonds The compound is 1,5,9-cyclododecatriene.   Compounds of group (c) are preferably a saturated alicyclic ring and at least one exocyclic double bond Is a compound having Advantageously, one of the exocyclic double bonds is a carbon in the alicyclic ring Bond the atom to the exocyclic carbon atom. The alicyclic ring in the group (c) compound is preferably Contains at least 6 carbon atoms, and advantageously has 3 ring carbon atoms and a 4 membered ring. Substituted with the forming methylene bridging group. The methylene carbon atom of such a bridging group is preferably Preferably, it may be substituted with two methyl groups. Particularly preferred group (c) The compound is β-pinene.   Additive wherein the aliphatic double bond in the compound used in the present invention is treated with the compound Reacts with active sulfur in a concentrate or oily composition to convert the sulfur to a nitrile seal It is considered "fixed" in a form that has no detrimental effect, but is not The invention should not be construed as limiting.   The compound used in the present invention may be an additive, a concentrate or an oily composition to be treated. Used in proportions of active sulfur in water, and in some cases the most appropriate If this is the case, it can be determined by ordinary experiments. Final lubricating oil composition (with olefinically unsaturated compounds Inclusive), generally from 0.01 to 5% by weight, advantageously from 0.05 to 1% by weight, preferably from 0. The use of from 05 to 0.5% by weight of olefinically unsaturated compounds is suitable, If the product contains a relatively high proportion of active sulfur, a somewhat higher The use of unsaturated compounds is preferred.   As indicated above, olefinically unsaturated compounds are active sulfur-containing lubricating oils. Processing additives or lubricating oil compositions (concentrates or finishing oils) containing such additives Used to However, advantageously, the compound is an active sulfur-containing additive. Oils containing additives and optionally one or more other additives and having a lubricating viscosity; The final lubricating oil composition is optionally mixed with one or more other additive concentrates or additives. Used to process concentrates that can be formed. Lubricating oil compositions, especially Crankcase lubricating oil compositions or additives used to prepare such compositions Other types of additives that can be present in the agent concentrate include ashless dispersants, Includes viscosity index modifiers, detergents, antiwear additives and antioxidants. these Details of the types of additives, concentrates and compositions containing them are given later in this specification. It is.   Reference herein to treating a first substance with a second substance refers to the specificity of the two substances. It should not be understood as indicating a mixing order. Therefore, for example, the first substance May be introduced into a container that already contains the second substance, or vice versa. The quality may be simultaneously introduced into the container.   Olef used in the present invention of active sulfur-containing additive, concentrate or lubricating oil composition The treatment with the unsaturated unsaturated compound is carried out by mixing at ambient temperature, Preferably, it is performed at an elevated temperature. Thus, for example, olefinically unsaturated compounds When the mixture is added to the mixture, the mixture is added to the mixture after adding the olefinically unsaturated compound. It is heated to a temperature of 0-100 ° C, preferably 46-60 ° C, at which temperature a person skilled in the art Advantageously, it is maintained with stirring for an easily determined time.   Lubricating oil additives and additives used or treated as described herein, Olefinic unsaturation used in accordance with the present invention to treat condensates or compositions Is the compound oil-soluble (common with certain other additives mentioned below)? Or a dispersible substance that is soluble or stable in oils with a suitable solvent. Honcho The terms oil-soluble, soluble or stable dispersible as used in the textbook refer to additives and chemicals. Make sure that the compound is soluble, soluble, miscible or suspendable in oil in all proportions. Not shown. However, additives and compounds may be used, for example, in rings where oils are used. Oil soluble or stable dispersible to the extent sufficient to exhibit the intended effect in the precincts It means there is. Further, additional mixing of other additives may be high if desired. It allows for the mixing of levels of individual additives or compounds.   Additives used or treated as described herein can be added to the oil in a convenient manner. Is mixed. That is, at a desired level of concentration, optionally, toluene and cyclohexene. Disperse or dissolve in oil in suitable oils, such as sun or tetrahydrofuran To be added directly to the oil. In some cases the mixing takes place at room temperature, in other cases High temperatures are advantageous for   Base oils in which additives are used include spark ignition and compression ignition internal combustion engines, such as automobiles And crankcase lubrication for truck engines, marine and railway diesel engines Includes those suitable for use as oils.   Synthetic base oils include dicarboxylic acids, polyglycols and alkyls of alcohols. Ester; alkyl-benzene organic of poly-α-olefin, polybutene, phosphoric acid Esters and polysilicone oils are included.   As the natural base oil, for example, paraffin, naphthene, mixed or Is paraffin-naphthene and the method used for its preparation, eg For example, minerals that may vary widely in distillation range such as straight run or decomposition, hydrogenation, solvent extraction, etc. Oil lubricants are included.   More specifically, the natural lubricating base oil used is a straight lubricating oil or paraffin. Distillate oil obtained from oil, naphthene, asphalt or mixed base crude oil. Wear. Also, if desired, various mixed oils and residual oils, especially asphalt components The one from which the minute has been removed is used. The oil may be prepared in any suitable manner, e.g., acid, alkali. And / or purified using other materials such as clay or aluminum chloride; Uses the oils produced, for example, phenol, sulfur dioxide, furfural, Soluble in solvents such as diethyl ether, nitrobenzene or crotonaldehyde. It is extracted by medium extraction.   The lubricating base oil conveniently has a viscosity of about 2.5 to about 12 cSt or mm at 100 ° C.^Two / Sec, preferably about 3.5 to about 9 cSt or mm^Two/ S.   Additives used or treated as described herein may typically be lubricating oils. Used in lubricating oil compositions containing large amounts and additives, typically small amounts. add to Additives are mixed into the composition to allow to meet individual requirements . Examples of additives included in lubricating oil compositions include viscosity index improvers, corrosion inhibitors, oxidation Inhibitor, friction modifier, dispersant, detergent, metal rust inhibitor, anti-wear additive, Pour point depressants and defoamers.   Viscosity index improvers (or viscosity modifiers) provide lubricating oils with high and low temperature operability. And can remain shear stable at high temperatures and have an acceptable viscosity or flow rate at low temperatures Can also be indicated. Compounds suitable for use as viscosity modifiers are usually It is a high molecular weight hydrocarbon polymer containing ester, and the viscosity index improving dispersant is dispersed Acts as an agent and viscosity index improver. Oil-soluble viscosity adjusting polymers are usually gel Weight average content determined by permeation chromatography or light scattering It has a particle size of about 10,000 to 1,000,000, preferably 20,000 to 500,000.   Corrosion inhibitors, also known as anticorrosives, are used to identify the parts of the metal that the lubricating oil composition contacts. Reduce the solution.   Antioxidants or antioxidants reduce the tendency of mineral oil to deteriorate during operation, Evidence indicates, for example, the formation of varnish deposits and sludge on metal surfaces and increased viscosity. It is. Suitable antioxidants preferably include C_Five~ C₁₂Has an alkyl side chain Alkaline earth metal salts of alkylphenol thioesters such as nonylphen Nylsulfide calcium and octylphenyl sulfide barium; dioctyl Phenylphenylamine; phenyl α-naphthylamine; and phosphosulfurized or sulfurized carbonized Contains hydrogen.   Other antioxidants or antioxidants used in lubricating oil compositions are oil-soluble copper compounds including.   Friction modifiers and fuel economy agents compatible with other components of the final oil are also included. Such thing Examples of qualities are glyceryl monoesters of higher fatty acids, such as glyceryl monooleate. Eat, esters of long-chain polycarboxylic acids and diols, for example, dimerized unsaturated fats Butanediol esters of acids and oxazoline compounds.   Dispersants are used to suspend oil-insoluble substances resulting from oxidation during use in a fluid. Maintain and prevent sludge flocculation and sedimentation or deposition on metal parts . So-called ashless dispersants are effective on combustion in contrast to metal-containing (ash-forming) detergents. Organic substances that do not qualitatively form ash. Suitable dispersants include, for example, long chain Derivatives of hydrocarbons-Substituted carboxyls in which the hydrocarbon radical has 50 to 400 carbon atoms Examples of such derivatives that include acids include the derivation of high molecular weight hydrocarbyl-substituted succinic acids. Body. Such hydrocarbon-substituted carboxylic acids are, for example, nitrogen-containing compounds, advantageously Can be reacted with a polyalkylene polyamine or ester. Such nitrogen Silicon-containing and ester dispersants are well known in the art and will be described here. And do not need. Particularly preferred dispersants are polyalkyleneamine and alkenyl It is a reaction product with succinic anhydride.   As indicated above, the viscosity index improver dispersant is a dual of the viscosity index improver and the dispersant. Act as a person. Examples of suitable viscosity index improving dispersants for use in lubricating compositions In some cases, amines, such as polyamines and hydrocarbyl substituents, add viscosity Hydrocarbyl-substituted mono- or dicals containing chains of sufficient length to provide number enhancement Includes reaction products with boric acid.   Detergents and metal rust inhibitors include sulfonic acids, alkylphenols, Sulfurized alkyl phenols, alkyl salicylates, naphthenates and other oil-soluble And metal salts which may be overbased of dicarboxylic acids. Metal is alkaline Overbased metal sulfonates selected from earth metals and magnesium are used as detergents. Is particularly appropriate. Representative examples of detergents / rust inhibitors and their preparation are described in Europe This is shown in application 208560A.   Antiwear additives, as the name implies, reduce the wear of metal parts. Dihydro Zinc carbyl dithiophosphate, such as those described above, are widely used as antiwear additives. Used.   A pour point depressant, also known as a lube oil flow improver, is the temperature at which the fluid flows or Reduce the temperature at which it can flow. Such additives are well-known. Fluid Typical additives that improve cold flow are C₈~ C₁₈Dialkyl fumarate / Vinyl acetate copolymer, polymethacrylate and wax naphthalene. Foaming Is a foam of a polysiloxane-based, for example, silicone oil or polydimethylsiloxane. Controlled by the eraser.   Some of the above additives can provide multiple effects, and thus, for example, A single additive can act as a dispersant-antioxidant. This method is And is not required to be elaborated herein.   Where the lubricating composition includes one or more of the above additives, each additive typically comprises It is mixed with the base oil in an amount that allows it to provide the desired effect. For crankcase When included, typical effective amounts of such additives are as follows. Additive active ingredient mass%^*  Active ingredient mass%^*                                         (Normal) (preferred) Viscosity modifier 0.01-6 0.01-4 Corrosion inhibitor 0.01-5 0.01-1.5 Antioxidant 0.01-5 0.01-1.5 Friction modifier 0.01-5 0.01-1.5 Dispersant 0.1-20 0.1-8 Detergent / anti-rust additive⁺                  0.01-6 0.01-3 Anti-wear additive 0.01-6 0.01-4 Pour point depressant 0.01-5 0.01-1.5 Defoamer 0.001-3 0.001-0.15 Mineral oil or synthetic base oil^* Active ingredient mass% based on the final oil.⁺ For marine applications, relatively large amounts are usually used, for example at least 10% by weight. .   If more than one additive is used, one or more additive concentrates containing the additives (concentrated The product is often referred to herein as an additive package) to prepare several additives. It is desirable, but not essential, that the agent be added to the base oil at the same time to form a lubricating oil composition. Absent. The dissolution of the additive concentrate in the lubricating oil is mixed with the solvent and with gentle heating. This is facilitated, but not required. Concentrate or additive package Page typically occurs when the additive package is mixed with a predetermined amount of base lubricant. Is formulated to include the additives in the appropriate amount to give the desired concentration in the final formulation. You. That is, one or more additives treated in accordance with the present invention may comprise a small amount of base oil or other Add the active ingredient to a compatible solvent with the other desired additives to For example, about 2.5 to about 90% by mass, preferably about 5 to about 75% by mass, Most preferably an additive comprising about 8 to about 50% by weight / weight of the appropriate proportion of additives. An agent package can be formed, the remainder being base oil. Also shown above As such, olefinically unsaturated compounds can be added to additive packs containing active sulfur-containing compounds. Used to process cages (concentrate).   The final formulation can typically use about 10% by weight of the additive package. , The rest being base oil.   The following examples illustrate the invention.   Reducing the adverse effects of active sulfur-containing lubricating oil additives on nitrile seals The ability of the refining unsaturated compound to determine whether the nitrile elastomer sample contains active sulfur Immersion in lubricating oil composition containing additives and compounds to be tested, break after immersion Compare the elongation at break (EAB) and / or the tensile strength (TS) with the corresponding numbers before immersion. By testing. The most effective compounds have elongation at break and / or tensile strength. It shows the minimum% reduction. Test methods DIN 53521 and DIN 53 504 was used.Example 1   A large number of olefinically unsaturated compounds are converted to 0.72% by mass of nonylphenol (NPS) and tested in lubricating oil compositions containing dispersants, detergents and antioxidants , The elastomer is an acrylonitrile-butadiene rubber known as NBR28 did. Reduction of elongation at break (EAB) when using a non-olefinically unsaturated compound % And 0.1% and 0.25% by weight of each of the test compounds are shown in Table 1. % Is Based on the total weight of the lubricating oil composition containing the compound. Contains nonylphenol sulfide The% reduction in EAB for the base formulation containing no and nonylphenol sulfide is 31% and 54% respectively.   From Table 1 where the additives used in the present invention are indicated by *, 0.1% squalene ( Group (a) compounds) containing nonylphenol sulfide The decrease in elongation at break shows a very remarkable decrease as compared with the letter (54%). It can be seen that the improvement was obtained even with the use of 0.25%. In addition, 1,5,9-cyclododeca Triene and group (b) compounds also have exocyclic double bonds at both 0.1% and 0.25% levels. And other cyclic compounds containing α-pinene and limonene (one ring double bond ), 1,3 and 1,1,5-cycloheptatriene (two in-ring double bonds having two (Not separated at both ends by two saturated carbon atoms) and acenaphthylene (aliphatic But not aromatic, containing double bonds). About group (c) Β-pinene, methylenecyclopentane and methylenecyclohexane are It showed better results than limonene in which the formula ring was not saturated.Example 2   Olefinically unsaturated compounds are compared to concentrates without olefinically unsaturated compounds. And added to the additive concentrate containing 6.76% by mass of nonylphenol sulfide. Described in Example 1 except that the experiment is performed on another batch of NBR28 nitrile seal The general procedure was repeated. Concentrate also contains dispersants, detergents and antioxidants Was. Next, the concentrates in each case were diluted with oil and lubricated containing 0.72% by weight of the finished oil. An oil composition was obtained. 0.1% by mass or 0.2% by mass of compound in finishing oil (including compound) Was added to the concentrate in such a ratio as to obtain the compound of the formula (1). Addition of compound to concentrate is 6 Performed at 0 ° C. Table 2 shows the obtained results. Contains nonylphenol sulfide EAB reduction for base formulations containing no and nonylphenol sulfide The percentages were 31% and 42%, respectively. Nonylphenyl in Examples 1 and 2 Differences between the results obtained from the base formulation containing sulfide Results and the performance of the test methods used there were.  From Table 2 where the additives used in the present invention are indicated by *, the group (a) compound Squalene, geraniol and farnesol are suitable for use in the present invention. It showed significantly better results than uncut Decene 50, Decene Mix and Nonene. I understand. Furthermore, 1,5-cyclooctadiene (group (b) compound) is Monene (having only one ring double bond), methylcyclopentadiene (testing The compound is a dimer and has no two intracyclic double bonds in the same ring) and Clohexadiene (the two ring double bonds are not separated by two saturated carbon atoms) I) showed significantly better results. Further, β-pinene (group (c) compound ) Showed significantly better results than limonene (alicyclic rings are not saturated). The compounds to be used in the present invention are all methylcyclopentadiene Dimer, better than most effective compound not suitable for use in the present invention in Table 2 Good results were shown.Example 3   Lubricating oil composition containing 0.72% by mass of nonylphenol sulfide based on finishing oil Compounds to be tested added to finishing oils (including olefinically unsaturated compounds) Used at a ratio of 0.05% by mass, 0.1% by mass and 0.3% by mass with respect to Is the acrylonitrile-butadiene known as NBR34 The general procedure described in was repeated. Finishing oils are dispersants, detergents and antioxidants Was also contained. Table 3 shows the obtained results. Veins containing nonylphenol sulfide The percent reduction in EAB for the base formulation was 47%.   From FIG. 3 where the additives used in the present invention are indicated by *, the treatment level is 0.3 mass % Squalene and β-pinene (the compound used in the present invention) are α-pine Significantly better results than cyclopentadiene and dipentene and cyclopentadiene dimer (same fat) Having no two double bonds in the cyclic ring) and 1,5,9-cyclododecatriene It can be seen that good results were shown.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10N 40:02 (81) Designated country EP (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), AM, AT, AU, BB, BG, BR, BY, CA, CH, CN, CZ, DE, DK, EE, ES, FI , GB, GE, HU, IS, JP, KE, KG, KP, KR, KZ, LK, LR, LT, LU, LV, MD, MG, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, TJ, TM, TT, UA, US, UZ, VN (72) Inventor Dilworth Brid UK Daylesford Shah O X 2 9 Bieru Oxford Botley Orchard Road 17 (72) inventor Thornhill Michael Ann United Kingdom Oxfordshire O X 11 7 speedy Didokotto Castle Walk 14

Claims (1)

[Claims] 1． A lubricating composition obtained by mixing the following components.   (1) a large proportion of lubricating oil;   (2) an active sulfur-containing oil-soluble additive; and   (3) an oil-soluble olefinically unsaturated compound selected from the following compounds:     (A) at least two in which adjacent double bonds are separated by two saturated carbon atoms           An acyclic compound having two double bonds;     (B) at least eight carbon atoms and each double bond is two saturated carbon atoms           Thus, at least two that are separated from the closest adjacent double bond           A compound comprising an alicyclic ring having two double bonds; and     (C) Compounds having a saturated alicyclic ring and at least one exocyclic double bond. 2． The sulfur-containing additive is a sulfurized phenol, a sulfurized olefin, a phosphorodithioe.   The composition according to claim 1, wherein the composition is selected from a salt and a dithiocarbamate. 3． The olefinically unsaturated compound is as defined in claim 1 (a),   3. The composition according to claim 1, wherein the composition is a terpene. Four. The terpene is squalene, geraniol or farnesol.   Composition. Five. The olefinically unsaturated compound is as described in claim 1 (b),   3. The composition according to claim 1, which comprises only nitrogen and carbon atoms. 6． The method according to claim 1, wherein the olefinically unsaturated compound is 1,5-cyclooctadiene.   Is the composition according to 2. 7． The olefinically unsaturated compound is as described in claim 1 (b),   The alicyclic ring has at least three double bonds, and each end of each double bond is two saturated.   3. A compound as claimed in claim 1, wherein each adjacent double bond is separated by a sum carbon atom.   Composition. 8． The olefinically unsaturated compound is 1,5,9-cyclododecatriene.   7. The composition according to 7. 9． The olefinically unsaturated compound is as described in claim 1 (c),   One of the exocyclic double bonds is between a carbon atom in the alicyclic ring and an exocyclic carbon atom   The composition according to claim 1. Ten. The olefinically unsaturated compound is as described in claim 1 (c),   3. The composition according to claim 1, wherein the cycloaliphatic ring has at least 6 carbon atoms. 11． The alicyclic ring is substituted with a bridging group forming a four-membered ring containing three ring carbon atoms   The composition according to any one of claims 1, 2, 9 and 10, wherein 12． Excluding the crosslinking group (if present) and the side chain having the exocyclic double bond,   12. The method according to claim 1, wherein the carbon atom of the cyclic ring is unsubstituted.   Composition. 13. 3. The composition according to claim 1, wherein the olefinically unsaturated compound is β-pinene.   object. 14. 14. The composition according to claim 1, wherein component (1) comprises a crankcase lubricating oil.   Composition. 15． In addition, ashless dispersants, viscosity index adjusters, detergents, antiwear additives and antioxidants   The composition according to any one of claims 1 to 13, comprising one or more additives selected from agents.   Composition. 16． A contract substantially as described in any one of Examples 1-3 herein.   The composition of claim 1. 17． One or more oil-soluble sulfur-containing additives for oils having lubricating viscosity and the following compounds   By dissolving one or more oil-soluble olefinically unsaturated compounds selected from   The resulting concentrate.   (A) at least two adjacent double bonds separated by two saturated carbon atoms         An acyclic compound having a double bond of   (B) at least eight carbon atoms and each double bond is two saturated carbon atoms;         At least two that are separated from the closest double bond         A compound containing an alicyclic ring having a double bond; and   (C) Compounds having a saturated alicyclic ring and at least one exocyclic double bond. 18． An active sulfur-containing lubricating oil additive, concentrate or composition according to any of the preceding claims.   A treatment method characterized by treating with the olefinically unsaturated compound according to claim 1. 19. Substantially performed as described in any one of Examples 1-3 herein.   19. The method according to claim 18. 20. Contains sulfur and / or sulfur-containing compounds that have deleterious effects on elastomers   Used to improve the nitrile elastomer compatibility of lubricating compositions   Use of an olefinically unsaturated compound selected from the above compounds.   (A) at least two adjacent double bonds separated by two saturated carbon atoms         An acyclic compound having a double bond of   (B) at least eight carbon atoms and each double bond is two saturated carbon atoms;         At least two that are separated from the closest double bond         A compound containing an alicyclic ring having a double bond; and   (C) Compounds having a saturated alicyclic ring and at least one exocyclic double bond. twenty one. A new feature described herein or a new set of features described herein.   Fit.