(19)
(11) EP 0 593 068 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication:
20.04.1994 Bulletin 1994/16

(21) Application number: 93116704.3

(22) Date of filing: 15.10.1993
(51) International Patent Classification (IPC)5C10M 141/10, C10M 169/04
// C10N40/06, C10N40/08 ,(C10M141/10, 133:08, 137:02, 137:04)
(84) Designated Contracting States:
DE FR GB

(30) Priority: 15.10.1992 JP 301576/92

(71) Applicant: NIPPON OIL COMPANY, LIMITED
Tokyo (JP)

(72) Inventors:
  • Miyagawa, Toru, c/o Nippon Oil Co., Ltd.
    Naka-ku, Yokohama-shi, Kanagawa (JP)
  • Hirata, Shigeaki, c/o Nippon Oil Co., Ltd.
    Naka-ku, Yokohama-shi, Kanagawa (JP)
  • Okada, Mitsuo, c/o Nippon Oil Co., Ltd.
    Naka-ku, Yokohama-shi, Kanagawa (JP)

(74) Representative: WILHELMS, KILIAN & PARTNER Patentanwälte 
Eduard-Schmid-Strasse 2
81541 München
81541 München (DE)


(56) References cited: : 
   
       


    (54) Hydraulic working oil composition for buffers


    (57) A hydraulic working oil composition for buffers which comprises a lubricating oil as a base oil, (A) a phosphoric acid ester such as dioleyl acid phosphate and/or a phosphorous acid ester such as dioleyl hydrogen phophite, and (B) an adduct of an aliphatic amine such as oleyl amine with an alkylene oxide such as ethylene oxide, the compounds (A) and (B) being the essential components added to said base oil; and, in one embodiment, a process for lubricating buffers which comprises adding said compounds (A) and (B) to said base oil to prepare a hydraulic working oil composition and using the thus prepared oil composition in buffers.


    Description

    BACKGROUND OF THE INVENTION


    1. Field of the Invention



    [0001] This invention relates to hydraulic working oil compositions for use in buffers and more particularly to such oil compositions suitable for car suspension devices such as shock absorbers, active suspensions, stay dampers and engine dampers.

    2. Prior Art



    [0002] As conventional hydraulic working oils which have hitherto been used in car buffer devices such as shock absorbers, active suspensions, stay dampers and engine dampers, there have been known those incorporated with a phosphoric acid ester and/or a phosphorus acid ester to provide them with friction-reducing properties and wear-preventing properties. In addition, there have also widely used such hydraulic working oils in which a fatty acid, aliphatic alcohol, fatty acid ester, aliphatic amine and other oily agents are used to further improve the working oils in friction-reducing properties.

    [0003] Hydraulic working oils are those which are required to be capable of reducing friction at friction surfaces simultaneously with preventing wear of the friction surfaces. Recently, there have been increasingly used bush members impregnated with a Teflon resin in attempts to reduce friction at friction surfaces from the standpoint of material or substance used. Further, particularly gas-sealed type and damping force-variable type buffer have increasingly been used and, therefore, load applied to the friction surfaces of buffers has been increased and conditions under which the buffers are used have come to be severe.

    [0004] With a change in such conditions or circumstances under which hydraulic working oils are used, conventional such oils incorporated only with a phosphoric acid ester and/or a phosphorous acid ester, or those in which a fatty acid, aliphatic alcohol, a fatty acid ester and other oily agents are used, have raised problems that they will allow friction surfaces to be considerably worn with their friction-reducing effects being low and poor. In addition, it has been found that the conventional working oils in which is used a phophoric acid ester and/or a phosphorous acid ester as well as an aliphatic amine which is an oily agent, will exhibit somewhat excellent wear-preventing and friction-reducing effects on the friction surfaces of a suspension device at the initial time when the working oils are used therein but the conventional working oils will raise problems that they cannot keep such effects durably and will greatly increase in frictional coefficient during their use whereupon spherical particles produced by the wear of the friction surfaces are attached to the friction surfaces which are the surfaces of a Teflon resin-impregnated bush member.

    [0005] There have been eagerly desired the developments of novel hydraulic working oils for a buffer which meet new requirements such as excellent applicability to Teflon resin-impregnated bush members and excellent durablity (little degradation during the use) of friction-reducing and wear-preventing effects, in addition to the conventional requirements, since said new requirements have come to be made much of.

    SUMMARY OF THE INVENTION



    [0006] The primary object of this invention is to provide hydraulic working oil compositions for a buffer which are excellent in applicability to Teflon resin-impregnated bush members as well as durability (little degradation with the time of use) of friction-reducing and wear-preventing effects.

    [0007] The present inventors made intensive studies to achieve the object of this invention and, as the result of their studies, found that the combined use of (A) a phosphoric acid ester and/or a phosphorous acid ester and (B) an alkylane oxide of an aliphatic amine in a lubricating oil as a base oil will exert their synergistic effect thereby to obtain a new hydraulic working oil exhibiting excellent performances when used, thus completing this invention.

    [0008] The primary object of this invention is achieved by providing a hydraulic working oil composition prepared by adding to a lubricating oil as a base oil the following ingredients as essential components

    (A) a phosphoric acid ester and/or a phosphorous acid ester and

    (B) an alkylene oxide adduct of an aliphatic amine.



    [0009] This invention will be explained below in more detail.

    [0010] The lubricating oils used as a base oil in this invention are not particularly limited, and both mineral oils and synthetic oils which are usually used as a base oil for lubricating oils may be used as the base oil in this invention.

    [0011] The mineral oil-type lubricating oils which may be used as a base oil, include paraffinic and naphthenic oils obtained by refining, for example, lubricating oil fractions obtained by the atmospheric and reduced-pressure distillation of a crude oil, by means of a suitable combination of solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, and the like.

    [0012] The synthetic oil-type lubricating oils which may be used as a base oil, include poly α-olefins (polybutene, 1-octene oligomers, 1-decene oligomers, etc.), alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane caprylate, trimethylolpropane peralgonate, pentaerithritol 2-ethyl hexanoate, pentaerithritol peralgonate, etc.), polyoxyalkylene glycol, polyphenyl ethers, silicone oil and perfluoroalkyl ethers.

    [0013] The lubricating oils used as a base oil are hereinafter sometimes referred to as "base lubricating oils" for simplicity.

    [0014] The base lubricating oils may be used singly or jointly, but the mineral oil-type base lubricating oils are preferably used from the standpoint of their adaptability to, or compatibility with, gum sealants in this invention.

    [0015] The base lubricating oils used in this invention are optional in viscosity, but those having a viscosity of 8 - 60 cSt, preferably 10 - 40 cSt, at 40°C are usually used from necessity for their applicability to damping force required in general buffers.

    [0016] The component (A) which is an essential additive to be added to a base lubricating oil according to this invention is a phosphoric acid ester and/or a phosphorous acid ester.

    [0017] The phosphoric acid ester defined here is a compound represented by the following formula (1)


    and the phosphorous acid ester defined here is a compound represented by the following formula (2)


    In these formulae (1) and (2), R¹ and R⁴ are each a straight-chain or branched-chain alkyl or alkenyl group having 4 - 22 carbon atoms, or are each an aryl group, or an alkylaryl or arylalkyl group having a straight-chain or branched-chain alkyl group, the aryl, alkylaryl and arylalkyl groups each having 6 - 22 carbon atoms; R² and R³, and R⁵ and R⁶ may be identical with, or different from, each other, respectively, and these R², R³, R⁵ and R⁶ are each a straight-chain or branched-chain alkyl or alkenyl group having 1 - 22 carbon atoms, or are each an aryl group or an alkylaryl or arylalkyl group having 6 - 22 carbon atoms, the alkyl group in these alkylaryl and arylalkyl groups being a straight-chain or branched-chain alkyl group.

    [0018] The R¹ and R⁴ each include an alkyl group such as butyl groups (including all isomeric groups), pentyl groups (including all isomeric groups), hexyl groups (including all isomeric groups), heptyl groups (including all isomeric groups), octyl groups (including all isomeric groups), nonyl groups (including all isomeric groups), decyl groups (including all isomeric groups), undecyl groups (including all isomeric groups), dodecyl groups (including all isomeric groups), tridecyl groups (including all isomeric groups), tetradecyl groups (including all isomeric groups), pentadecyl groups (including all isomeric groups), hexadecyl groups (including all isomeric groups), heptadecyl groups (including all isomeric groups), octadecyl groups (including all isomeric groups), nonadecyl groups (including all isomeric groups), eicosyl groups (including all isomeric groups), heneicosyl groups (including all isomeric groups) and docosyl groups (including all isomeric groups); an alkenyl group such as butenyl groups (including all isomeric groups), pantenyl groups (including all isomeric groups), hexenyl groups (including all isomeric groups), heptenyl groups (including all isomeric groups), octenyl groups (including all isomeric groups), nonenyl groups (including all isomeric groups), decenyl groups (including all isomeric groups), undecenyl groups (including all isomeric groups), dodecenyl groups (including all isomeric groups), tridecenyl groups (including all isomeric groups), tetradecenyl groups (including all isomeric groups), pentadecenyl groups (including all isomeric groups), hexadecenyl groups (including all isomeric groups), heptadecenyl groups (including all isomeric groups), octadecenyl groups (including all isomeric groups), nonadecenyl groups (including all isomeric groups), eicosenyl groups (including all isomeric groups), heneicosenyl groups (including all isomeric groups) and docosenyl groups (including all isomeric groups); an aryl group such as a phenyl group and naphtyl groups (including all isomeric groups); an alkylaryl group such as tolyl groups (including all isomeric groups), ethylphenyl groups (including all isomeric groups), propylphenyl groups (including all isomeric groups), butylphenyl groups (including all isomeric groups), pentylphenyl groups (including all isomeric groups), hexylphenyl groups (including all isomeric groups), heptylphenyl groups (including all isomeric groups), octylphenyl groups (including all isomeric groups), nonylphenyl groups (including all isomeric groups), decylphenyl groups (including all isomeric groups), undecylphenyl groups (including all isomeric groups), dodecylphenyl groups (including all isomeric groups), tridecylphenyl groups (including all isomeric groups), tetradecylphenyl groups (including all isomeric groups), pentadecylphenyl groups (including all isomeric groups), hexadecylphenyl groups (including all isomeric groups), xylyl groups (including all isomeric groups), ethylmethylphenyl groups (including all isomeric groups), diethylphenyl groups (including all isomeric groups), dipropylphenyl groups (including all isomeric groups), dibutylphenyl groups (including all isomeric groups), methylnaphtyl groups (including all isomeric groups), ethylnaphtyl groups (including all isomeric groups), propylnaphtyl groups (including all isomeric groups), butylnaphtyl groups (including all isomeric groups), dimethylnaphtyl groups (including all isomeric groups), ethylmethylnaphtyl groups (including all isomeric groups), diethylnaphtyl groups (including all isomeric groups), dipropylnaphtyl groups (including all isomeric groups) and dibutylnaphtyl groups (including all isomeric groups); an arylalkyl group such as a benzyl group, phenylethyl groups (including all isomeric groups) and phenylpropyl groups (including all isomeric groups).

    [0019] On the other hand, the R² and R³ and also the R⁵ and R⁶ each include hydrogen, an alkyl group such as a methyl group, an ethyl group, propyl groups (including all isomeric groups), butyl groups (including all isomeric groups), pentyl groups (including all isomeric groups), hexyl groups (including all isomeric groups), heptyl groups (including all isomeric groups), octyl groups (including all isomeric groups), nonyl groups (including all isomeric groups), decyl groups (including all isomeric groups), undecyl groups (including all isomeric groups), dodecyl groups (including all isomeric groups), tridecyl groups (including all isomeric groups), tetradecyl groups (including all isomeric groups), pentadecyl groups (including all isomeric groups), hexadecyl groups (including all isomeric groups), heptadecyl groups (including all isomeric groups), octadecyl groups (including all isomeric groups), nonadecyl groups (including all isomeric groups), eicosyl groups (including all isomeric groups), heneicosyl groups (including all isomeric groups) and docosyl groups (including all isomeric groups); an alkenyl group such as butenyl groups (including all isomeric groups), pentenyl groups (including all isomeric groups), hexenyl groups (including all isomeric groups), heptenyl groups (including all isomeric groups), octenyl groups (including all isomeric groups), nonenyl groups (including all isomeric groups), decenyl groups (including all isomeric groups), undecenyl groups (including all isomeric groups), dodecenyl groups (including all isomeric groups), tridecenyl groups (including all isomeric groups), tetradecenyl groups (including all isomeric groups), pentadecenyl groups (including all isomeric groups), hexadecenyl groups (including all isomeric groups), heptadecenyl groups (including all isomeric groups), octadecenyl groups (including all isomeric groups), nonadecenyl groups (including all isomeric groups), eicosenyl groups (including all isomeric groups), heneicosenyl groups (including all isomeric groups) and docosenyl groups (including all isomeric groups); an aryl group such as a phenyl group and naphtyl groups (including all isomeric groups); an alkylaryl group such as tolyl groups (including all isomeric groups), ethylphenyl groups (including all isomeric groups), propylphenyl groups (including all isomeric groups), butylphenyl groups (including all isomeric groups), pentylphenyl groups (including all isomeric groups), hexylphenyl groups (including all isomeric groups), heptylphenyl groups (including all isomeric groups), octylphenyl groups (including all isomeric groups), nonylphenyl groups (including all isomeric groups), decylphenyl groups (including all isomeric groups), undecylphenyl groups (including all isomeric groups), dodecylphenyl groups (including all isomeric groups), tridecylphenyl groups (including all isomeric groups), tetradecylphenyl groups (including all isomeric groups), pentadecylphenyl groups (including all isomeric groups), hexadecylphenyl groups (including all isomeric groups), xylyl groups (including all isomeric groups), ethylmethylphenyl groups (including all isomeric groups), diethylphenyl groups (including all isomeric groups), dipropylphenyl groups (including all isomeric groups), dibutylphenyl groups (including all isomeric groups), methylnaphtyl groups (including all isomeric groups), ethylnaphtyl groups (including all isomeric groups), propylnaphtyl groups (including all isomeric groups), butylnaphtyl groups (including all isomeric groups), dimethylnaphtyl groups (including all isomeric groups), ethylmethylnaphtyl groups (including all isomeric groups), diethylnaphtyl groups (including all isomeric groups), dipropylnaphtyl groups (including all isomeric groups) and dibutylnaphtyl groups (including all isomeric groups); an arylalkyl group such as benzyl groups phenylethyl groups (including all isomeric groups) and phenylpropyl groups (including all isomeric groups).

    [0020] From the standpoint of excellency particularly in wear-preventing and friction-reducing effects, the phosphoric acid ester of the component (A) used in this invention is preferably a compound of the formula (1) wherein R¹ and R² are each a member selected from a straight-chain or branched-chain alkyl or alkenyl group having 8 to 20 carbon atoms and a monoalkylphenyl group having 14 - 20 carbon atoms in which the alkyl is a straight-chain or branched-chain one, and R³ is hydrogen. The phosphoric acid ester is more preferably a compound of the formula (1) wherein R¹ and R² are each a member selected from a straight-chain alkyl or alkenyl group, and R³ is hydrogen.

    [0021] From the standpoint of excellency particularly in wear-preventing and friction-reducing effects in the same manners as in the phosphoric acid ester of the formula (1), the phosphorous acid ester of the component (A) used in this invention is preferably a compound of the formula (2) wherein R⁴ and R⁵ are each a member selected from a straight-chain or branched-chain alkyl or alkenyl group having 8 to 20 carbon atoms and a monoalkylphenyl group having 14 -20 carbon atoms in which the alkyl is a straight-chain or branched-chain one, and R⁶ is hydrogen. The phosphorous acid ester is more preferably a compound of the formula (2) wherein R⁴ and R⁵ are each a straight-chain alkyl or alkenyl group, and R⁶ is hydrogen.

    [0022] The phosphoric acid ester which is among the components (A) used in this invention includes dioctyl acid phosphate (dicapryl acid phosphate), didecyl acid phosphate, didodecyl acid phosphate (dilauril acid phosphate), ditetradecyl acid phosphate (dimyristyl acid phosphate), dihexadecyl acid phosphate (dipalmityl acid phosphate), dioctadecyl acid phosphate (distearyl acid phosphate) and di-9-octadecenyl acid phosphate (dioleyl phosphate). The phosphorous acid ester which is among the components (A), includes dioctyl hydrogen phosphite (dicapryl hydrogen phosphite), didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauril hydrogen phosphite), ditetradecyl hydrogen phosphite (dimyristyl hydrogen phosphite), dihexadecyl hydrogen phosphite (dipalmityl hydrogen phosphite), dioctadecyl hydrogen phosphite (distearyl hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite) and a mixture thereof.

    [0023] In the hydraulic working oil composition for buffers of this invention, the amount of the phosphoric acid ester and/or phosphorous acid ester added may be arbitrary, but it is an amount of preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition.

    [0024] Further, the component (B) which is another essential component used in this invention is an adduct of an aliphatic amine with an alkylene oxide. The alkylene oxide adduct of an aliphatic amine defined in this invention means a compound represeted by the following general formula (3)


       wherein R⁷ represents a straight-chain or branched-chain alkyl or alkenyl group having 8 - 22 carbon atoms, R⁸ and R⁹ may be identical with, or different from, each other and are each a straight-chain or branched-chain alkylene group having 2 - 4 carbon atoms; and m and n may be identical with, or different from, each other and are each an integer of 0-10 with the proviso that m plus n equals 1-10, prefereably 1-5.

    [0025] The R⁷ is exemplified by an alkyl group such as octyl groups (including all isomeric groups), nonyl groups (including all isomeric groups), decyl groups (including all isomeric groups), undecyl groups (including all isomeric groups), dodecyl groups (including all isomeric groups), tridecyl groups (including all isomeric groups), tetradecyl groups (including all isomeric groups), pentadecyl groups (including all isomeric groups), hexadecyl groups (including all isomeric groups), heptadecyl groups (including all isomeric groups), octadecyl groups (including all isomeric groups), nonadecyl groups (including all isomeric groups), eicosyl groups (including all isomeric groups), heneicosyl groups (including all isomeric groups) and docosyl groups (including all isomeric groups); and an alkenyl group such as octenyl groups (including all isomeric groups), nonenyl groups (including all isomeric groups), decenyl groups (including all isomeric groups), undecenyl groups (including all isomeric groups), docenyl groups (including all isomeric groups), tridecenyl groups (including all isomeric groups), tetradecenyl groups (including all isomeric groups), pentadecenyl groups (including all isomeric groups), hexadecenyl groups (including all isomeric groups), peptadecenyl groups (including all isomeric groups), octadecenyl groups (including all isomeric groups), nonadecenyl groups (including all isomeric groups), eicosenyl groups (including all isomeric groups), heneicosenyl groups (including all isomeric groups) and docosenyl groups (including all isomeric groups). The R⁸ and R⁹ include an ethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, 1-ethylethylene group, 2-ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group and 2,2-dimethylethylene group.

    [0026] The alkylene oxide adduct of an aliphatic amine, which is represented by formula (3) and is the component (B) used in this invention, is preferably a compound of the formula (3) in which R⁷ is a straight-chain alkyl or alkenyl group, and R⁸ and R⁹ are each an ethylene group, in view of excellent wear-reducing effects.

    [0027] The particularly preferable alkylene oxide adducts of an aliphatic amine, which are the component (B) used in this invention, include ethylene oxide adducts of an aliphatic amine and a mixture of the adducts, and more particularly they are alkylene oxide adducts of an aliphatic amine such as octyl amine (capryl amine), decyl amine, dodecyl amine (lauril amine), tetradecyl amine (mylystyl amine), hexadecyl amine (palmitil amine), octadecyl amine (stearyl amine) or 9-octadecenyl amine (oleyl amine).

    [0028] In the hydraulic working oil composition for buffers of this invention, the amount added of the alkylene oxide adduct of an aliphatic amine, which is the component (B), may be arbitrary, but it is desirable to add the adduct in an amount of preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition.

    [0029] As described above, although the hydraulic working oil composition for buffers of this invention having excellent performances can be obtained by only adding to the base lubricating oil the phosphoric ester and/or phosphorous ester which is the component (A), and the alkylene oxide adduct of an aliphatic amine, which is the component (B), into the base lubricating oil. To further enhance the thus obtained hydraulic working oil composition in such performances, heretofore known additives for lubricating oils may be used singly or jointly.

    [0030] These additives include friction-reducing agents other than the components of the oil composition of this invention, such as an aliphatic alcohol, aliphatic acid, aliphatic amine and aliphatic amide; antioxidants such as phenol-, amine-, sulphur-, zinc dithiophosphate- and phenothiazine-based compounds; extreme-pressure agents such as sulfurized fats and oils, sulfides and zinc dithiophosphate; rust preventives such as petroleum sulfonates and dinonylnaphthalene sulfonate; metal deactivators such as benzotriazole and thiadiazole; metallic detergents such as alkaline earth metal sulfonates, alkaline earth metal phenates, alkaline earth metal salicylates and alkaline earth metal phosphonates; ashless dispersants such as succinic imide, succinic esters and benzyl amine; antifoaming agents such as methylsilicone and fluorosilicone; viscosity index improvers such as polymethacrylate, polyisobutylene and polystyrene; and pour point depressants.

    [0031] Although the amount of these additives added may be arbitrary, the contents of the antifoaming agent, the viscosity index improver, the metal inactivator and each of the other additives in the oil composition are ordinarily 0.0005 - 1% by weight, 1 - 30% by weight, 0.005 - 1% by weight and 0.1 - 15% by weight in this order, based on the total amount of the oil composition, respectively.

    [0032] The process for preparing the hydraulic working oil compositions of this invention is not particularly limited. This process, however, may usually comprise mixing a base lubricating oil and additives including the essential components (A) and (B) together, heating the resulting mixture to 30 - 100°C and then maintaining it at this temperature under agitation for 20 minutes to 5 hours, or may comprise separately heating all the additives (solid additives having beforehand been solved in a small amount of the base lubricating oil) to 30 - 100°C, mixing these additives in portions or in full into the base lubricating oil heated to 20 - 80°C and then maintaining the resulting mixture at 30 - 100°C under agitation for 20 minutes to 5 hours.

    DISCRIPTION OF PREFERRED EMBODIMENTS



    [0033] This invention will be better understood by the non-limitative Examples and Comparative Examples.

    Examples 1 - 3 and Comparative Examples 1 - 4



    [0034] In each of the Examples, the ingredients shown in Table 1 were mixed together and the resulting mixture was heated to 50°C under stirring for two hours thereby to prepare a hydraulic working oil composition of this invention (Examples 1 - 3). The oil compositions of this invention so prepared were subjected to a duration test using an actual device to evaluate them for their friction-reducing effects and wear-preventing effects.

    [0035] Comparative hydraulic working oil compositions were prepared by following the procedure of the above Examples except that the component (A) was used singly (Comp. Example 1), except that the component (B) was used singly (Comp. Example 2), except that an aliphatic amine was substituted for the component (B) (Comp. Example 3) or except that a fatty acid was substituted for the component (A) (Comp. Example 4).

    [0036] The comparative oil compositions so prepared were subjected to the same duration test as above.

    Duration Test Using Actual Device



    [0037] Using two commercially available strut-type shock absorbers, duration tests were made under the following conditions until the end of two million frequency of oscillation application.
    Temperature of a test oil 80°C
    Amount of a test oil used 330 ml/one shock absorber
    Lateral load 200 kgf
    Entire amplitude of oscillation applied 50 mm
    Velocity of oscillation applied 0.5 m/s

    (1) Friction-reducing effects



    [0038] The shock absorbers were measured for their frictional coefficients at their surfaces at the time of oscillation application frequency of zero (at the initial stage of the duration test) and at the time of oscillation application frequency of two millions (at the time of completion of the duration test), respectively. The frictional coefficients so measured are as shown in Table 1.

    (2) Wear-preventing effects



    [0039] After the completion of the duration test, the shock absorbers were disossembled to visually evaluate the surface state of their friction surfaces (cylinders, pistons, rods and oil seals of the shock absorbers) with the results being as shown in Table 1. The degrees of the wear-preventing effects are represented in terms of six numerals 0 - 5 (numeral 5 being the best).

    [0040] As is apparent from the results of the Examples, the hydraulic working oil compositions (Examples 1 - 3) are excellent in friction-reducing effects at the initial stage of the duration test and exhibit less degradation of their friction-reducing performances with the lapse of time. In addition, they exhibit less wear at the friction surfaces even at the time of end of the duration test whereby they are also excellent in wear-preventing effects.

    [0041] The comparative hydraulic working oil compositions (Comp. Examples 1 - 4), on the other hand, are excellent in friction-reducing effects at the initial stage of the duration test but they exhibit much more degradation of their friction-reducing performances with the lapse of time. In addition, they are very also inferior in wear-preventing effects to those of this invention.

    Effects of this Invention



    [0042] As is apparent from the foregoing, the hydraulic working oil compositions of this invention are excellent not only in applicability to Teflon resin-impregnated bush members but also in durability (less degradation with the time) of friction-reducing effects and wear-preventing effects.




    Claims

    1. A hydraulic working oil composition for buffers which comprises a lubricating oil as a base oil, (A) at least one ester selected from a phosphoric acid ester and a phosphorous acid ester and (B) an adduct of an aliphatic amine with an alkylene oxide, the compounds (A) and (B) being the essential components added to said base oil.
     
    2. A hydraulic working oil composition for buffers according to claim 1, wherein the phosphoric acid ester, the phosphorous acid ester and the adduct of an aliphatic amine with an alkylene oxide, are represented respectively by the following formulae (1), (2) and (3)

    and

    wherein R¹ and R⁴ are each a straight-chain or branched-chain alkyl or alkenyl group having 4 - 22 carbon atoms, or are each an aryl group, or an alkylaryl or arylalkyl group having a straight-chain or branched-chain alkyl group, the aryl, alkylaryl and arylalkyl groups each having 6 - 22 carbon atoms; R² and R³, and R⁵ and R⁶ may be identical with, or different from, each other, respectively, and these R², R³, R⁵ and R⁶ are each a straight-chain or branched-chain alkyl or alkenyl group having 1 - 22 carbon atoms, or are each an aryl group or an alkylaryl or arylalkyl group having 6 - 22 carbon atoms, the alkyl group in these alkylaryl and arylalkyl groups being a straight-chain or branched-chain alkyl group; R⁷ is a straight-chain or branched-chain alkyl or alkenyl group having 8 - 22 carbon atoms, R⁸ and R⁹ may be identical with, or different from, each other and they are each a straight-chain or branched-chain alkylene group having 2 - 4 carbon atoms; m and n may be identical with, or different from, each other and they are each an integer of 0-10 with the proviso that m plus n equals 1-10.
     
    3. A hydraulic working oil composition for buffers according to claim 2, wherein the m plus n equals 1 - 5.
     
    4. A hydraulic working oil composition for buffers according to claim 2 or 3, wherein in the formula (1) the R¹ and R² are each a straight-chain or branched-chain alkyl or alkenyl group having 8 - 20 carbon atoms or a monoalkylphenyl group having 14 - 20 carbon atoms in which the alkyl is a straight-chain or branched-chain one, and R³ is hydrogen; in the formula (2) the R⁴ and R⁵ are each a straight-chain or branched-chain alkyl or alkenyl group having 8 - 20 carbon atoms or a monoalkylphenyl group having 14 - 20 carbon atoms in which the alkyl is a straight-chain or branched-chain one, and the R⁶ is hydrogen; and in the formula (3) the R⁷ is a straight-chain alkyl or alkenyl group having 12 - 18 carbon atoms, and the R⁸ and R⁹ are each an ethylene group.
     
    5. A hydraulic working oil composition for buffers according to claim 4, wherein the R⁴ and R⁵ are each a straight-chain alkyl or alkenyl group having 12 - 18 carbon atoms.
     
    6. A hydraulic working oil composition for buffers according to claim 4 or 5, wherein the phosphoric acid ester is dioctyl acid phosphate (dicapryl acid phosphate), didecyl acid phosphate, didodecyl acid phosphate (dilauril acid phosphate), ditetradecyl acid phosphate (dimyristyl acid phosphate), dihexadecyl acid phosphate (dipalmityl acid phosphate), dioctadecyl acid phosphate (distearyl acid phosphate), di-9-octadecenyl acid phosphate (dioleyl phosphate) or a mixture thereof; the phosphorous acid ester is dioctyl hydrogen phosphite (dicapryl hydrogen phosphite), didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauril hydrogen phosphite), ditetradecyl hydrogen phosphite (dimyristyl hydrogen phosphite), dihexadecyl hydrogen phosphite (dipalmityl hydrogen phosphite), dioctadecyl hydrogen phosphite (distearyl hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite) or a mixture thereof; and the alkylene oxide adduct of an aliphatic amine is an ethylene oxide adduct of octyl amine (capryl amine), decyl amine, dodecyl amine (lauril amine), tetradecyl amine (mylystyl amine), hexadecyl amine (palmitil amine), octadecyl amine (stearyl amine) or 9-octadecenyl amine (oleyl amine).
     
    7. A hydraulic working oil composition for buffers according to claim 1 or 6, wherein the base oil is a paraffinic or naphthenic oil refined by subjecting lubricating oil fractions produced by the atmospheric and reduced-pressure distillation of a crude oil to refining steps selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric washing and clay treatment, or is a synthetic oil selected from polybutene, 1-octene oligomers, 1-decene oligomers, alkylbenzenes, alkylnaphthalenes, tridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, trimethylolpropane caprylate, trimethylolpropane peralgonate, pentaerithritol 2-ethyl hexanoate, pentaerithritol peralgonate, polyoxyalkylene glycol, polyphenyl ethers, silicone oil and perfluoroalkyl ethers.
     
    8. A hydraulic working oil composition for buffers according to claim 6, wherein the base oil has a viscosity of 8 - 60 cSt at 40°C.
     
    9. A hydraulic working oil composition for buffers according to claim 1 or 6, wherein the phosphoric acid ester and/or phosphorous acid ester is added to the base oil in an amount of 0.05 - 10% by weight of the total amount of the oil composition, and the alkylene oxide adduct of an aliphatic amine is added to the base oil in an amount of 0.05 - 10% by weight of the total amount of the oil composition.
     
    10. A process for lubricating buffers which comprises adding to a lubricating oil as a base oil (A) a phosphoric acid ester and/or a phosphorous acid ester and (B) an adduct of an aliphatic amine with an alkylene oxide as essential components to prepare a hydraulic working oil composition and using the thus prepared hydraulic working oil composition in buffers.
     
    11. A process for lubricating buffers according to claim 10, wherein the phosphoric acid ester is dioctyl acid phosphate (dicapryl acid phosphate), didecyl acid phosphate, didodecyl acid phosphate (dilauril acid phosphate), ditetradecyl acid phosphate (dimyristyl acid phosphate), dihexadecyl acid phosphate (dipalmityl acid phosphate), dioctadecyl acid phosphate (distearyl acid phosphate), di-9-octadecenyl acid phosphate (dioleyl phosphate) or a mixture thereof; the phosphorous acid ester is dioctyl hydrogen phosphite (dicapryl hydrogen phosphite), didecyl hydrogen phosphite, didodecyl hydrogen phosphite (dilauril hydrogen phosphite), ditetradecyl hydrogen phosphite (dimyristyl hydrogen phosphite), dihexadecyl hydrogen phosphite (dipalmityl hydrogen phosphite), dioctadecyl hydrogen phosphite (distearyl hydrogen phosphite), di-9-octadecenyl hydrogen phosphite (dioleyl hydrogen phosphite) or a mixture thereof; and the alkylene oxide adduct of an aliphatic amine is an ethylene oxide adduct of octyl amine (capryl amine), decyl amine, dodecyl amine (lauril amine), tetradecyl amine (mylystyl amine), hexadecyl amine (palmitil amine), octadecyl amine (stearyl amine) or 9-octadecenyl amine (oleyl amine).
     





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