Note: Descriptions are shown in the official language in which they were submitted.
95T,221 CA 022232~6 1997- 12- 18
LUBRICATING OIL COMPOSITION
Field of t}le L.~nLùA
Ihe present ~ OIl relates to a novel hll .. .l ,.t;. ~E~ oil ro~ Qs*~ More
sl,e ;r..~, tAe ~.ent ~ C~ll.;l~ relates to a lubricat~ oil c~ . useful as a
lu~rir~ting oil fnr inten~ ccsnbustion en~nes, ,...(..,.~ . c,..;c,:r~ ...yc,s,
power ~Lc_~r~ and the like, ~arly use~l as~ a 1~ g oil for
intesDal--comhll~ion ~ gin~c, w~h cn~ n has ~-- P~ t .~,.L~.~ pf~ li~e, and
~ri~on-.~luL...g p~es and can 1..~ the fric~ion-~lu~g ~uupc~Les for a
prolonged period of tune w~thout undergomg det~,u.~o.l even in the ar co.~t~ g
.lihubc~ oxides gas.
ra~~~ag oils are used f~r intemal--c~~nhucticn ~r~Dnes~ and for driving units
and gears such as "~ I;r tran~ ;c~ nc, ~ CL~7 and power stee~ gc in order to
en~,ure smooth o~ lio~ there~ In particular, 1~ ,.t;.~g oils for intanal-com~lc*~n
engmes ~t only Illh..r~P ~ranoUs sliding por~c,ns such as a cu~ g surhce ~:L~
a p~ston rmg aTld a cylinde~ lin~, a be~g fiDr a crank snait or a r~ I ;--g rod, a~d a
ve-operating ...er~ .,., ;..rh..li.~ a ~n and a valve lift, but also cool the ~side of
the c~gines, clean and L~.~ ,e c~rnhllcti--n y~ L~, and prevent the rustmg and
C~L~U~71U~1 of the ~ nPc
lbus, 1~ oils for intprn~l-c~ATntnlc~iAn engines have been .e i,~ to
ha~ e a great variety of y~u~S. ~ ., bigher~ n~ hlh.1-~;..g O~s are
now ~e.~ d due to the recent txnd hi~h-p~-,~ce m ;--t~ n~l-ccmhllc~;nn
eilgines such as the tre~d toward lowa rates of ~el c~ , the tre~d toward
bigh-ou~ut and the trend toward severer o~g ccn~i1;onc ~erein. On the other
hand, cQmhtls1ion gas g~-. . "t~ m an inte~ cnmhJc~n engine par~ally leaks
.h a piston and ~rl;.~dcr th~an, and cames into a cranlc case as blowby gac.
Such co~ . gas ~ ;..s ~ uo~ o~des gas in a cnn~d~h1y hi~h c~n~..,t,.~ n
The nitrogen oYides gas d-~t~ t~-~ along with oxygen ~o~t~;n~ in the blowby gas,
CA 02223256 1997-12-18
the lubncating oil used for the intemal-combustion engine. Due to the rece~t trend
toward high-pc~ ce in inte~al-combus~on engines, there is such a tende~cy
~at the con~r~t~t;~ of nihug~l oxides gas which comes into a ~ank case is
illcreased. In ordOE to make h~h~ g oils for internal-combus~on engines meet theabove-described r~ ent~ and undergo no dete,io~l,on even in the ~ir co~ E
nitrogen o~des gas, various addil;~es such as ~li-.~ agents, metallic detEl~,~,
nonash d;a~lts and ~liu. id~t~ are ~ded to them, a~o~ gly.
It is particl~larly i".~ as a~ ~ss~ 1 ;al ~ln~nn of h.~ t; - .~ oils for
internal-c~mbustinn engines that the 1.~ g oils can ensure the smooth o~ lion
of the ellgines under every cnr.Jil ;orl to prevent the ~ear ~d seizure of the en~nes
The lubri~ted parts of the engines _re, for the most part, under the ~uid llll..;.,a;. n
cont~itinn IIo~ ., a ~1alve-opera~ng system, and the top and bottom dead centersof a piston tend to corne under the boundary lubl.~holl cnn~1it;.~.. Antiwe_r properties
shoqn under the bou~ luh~hnn r....,l;l;~n are generally imparted to lul~
oils by the addition of zinc rl;l~;n~h~ h~tP
Energy loss at the f~ctinn~l parts of inter~al-com~ stinn engines which are
]~h~ ted by h~ira*-E oils is so great that a friction .~ el is added to the
lu~c~ti~e oils in order to reduce the fric~ion loss and to deaease the rate of fuel
con~ t;n~l For P~mrlP an organic molybdenum c~,uul.d, a fatty ester, or an
al~ylamine is usually used as the fnction ,l.odi~e~.
Under such ~.u~ ccS, we made ea~nest studies. As a result, it was found
that although such a friction ...~1;r.~. is ~hv~: at the outset of its use, it loses its
effects when under~oes o~bdative dec;~ t;~ by o~ygen cont~ined in the air, in
particular, the effects are ~ cti~lly illly~uci in the pre~ce of ~ ug~ 02~ides gas.
An object of the present invention is th~ to proYide a Illhriratin~ oil c~
which can ,.,~;,.I.;n, for a long period of tune, the e~fect of reduang friction caused in
engines without being adversely a~ected by r~l oxides gas.
We have made earnest studies in order to develop a lubrica~ng oil co~osition
having ~e above-desrrihed ad~antageous ~ es, and, as a result, found that the
CA 02223256 1997-12-18
above o~Diect o~ the ."v~uhon c~n be at~ined by a crmpoctnon which is obtained by
bl-n~ ng, w~h a lubnrating base oil, an oxymol~ie--u~ sulfide .l~inc~ ,ate having a
sp~ifi~ aikyl group, a zinc dialkyl .l;lh;~)~hrs~ate havi~g a spe~fi~ al~yl group, a
a~ sulfur cu..,~u~d, a specific metallic d.~ ~t and a boron--rr l,lA; ~
compou~d, each in a p~dct~ d amount The ~esent h.~,h~n h~s been
ar~ iched on ~e basis of this finding.
Namely, the present ~"~c..hl~n ~u~,~es (1) a lub.~h~g oil ~ oa;~ n
rl....~..;~;.~g a l~ A~ r b~se oil and the follû~mg c~ L~
(A~ an UAr,..ol~ ,.~ sulfide rll1h~ AlL~ldte ,h ~g an alkyl g~oup cl~rlA;; g
8 to 18 arbon atoms,
(B) a zinc dialkyl ~ ;n~hosphate having a psimar~ a~yl group rnntAinir~e 1 to 18carbon ato~s,
(C) one or more su~ur co~ m~ selected from t_e group concicti~ of z~c
dialkyl ~ AI ~ q copper dialkyl di~ c~; ~ l l lAt~ s or nickel dialkyl
d-~h;~ _- L~L~s ~ g an alkyl group ~ Il~A;ll;l~g 2 to 18 carbon atoms,
tetraal~ l.;..A.. ~ fites halring an ancyl group ~ A;~ g 2 to 18 carhon atoms,
diS~llMps ha~ring an a~l group co~tA;~ g 2 to 18 carhoD atoms, ~;~u~ hav~g an
aryl, alkyl aryl or aryl al~yl group co~ltA~ g 6 to 18 carbon atoms, ~;A~l;A~ e
w~l~O~da ha~g a 5~h,l1~ ..t which cont~uns 3 to 24 carbon atoms and sulfur, olefin
sulfiden" sulfites of fish oil and sulfides of whale oil,
(D) one or more me~ic det~-~ , selP~ed ~om the group co~ g of
calcium ~l;~ e,;~.. salicylate, calcium ~..lF..r.,~.- rn~lD~--m s~ rut~ and
cakilml ph~n~
(E) a 'ooron-co,~tA;~ g co~p~ cd ~ that the amou~t of
molybdenum d~i~Ted fmm the o~ymoly~d~.,~ sulfide ~ e is from 200 to
2,000 ppm (w~ ht basis) af the to~l weight of the ~O~ ;t;~
the amou~t of pk~ ho~us daived from the z~c dial}nrl rl;th;~p~lO~ e is from
0.02 to 0.15~o by weight of the total weight of the c.. ~L~o~
the amount of sulfur derrYed from the sul~r ~o...t~ d(s) is from 0.02 to 0.30%
CA 02223256 1997-12-18
by weight of the to~l ~eig~t of tke C<llllpO'~;t;OI~
t'ne amo~mt of the metallic deter~ent(s) is fro~ 1 to 10% D'j ~eight of the total
weight of the c~ oi,, and
the amo~mt cf boron derived from the boro~--c~ t~ lg cuiu~ul,d is from 0.005
to 0.06% by ~eight of the total w~ght of the COl~ait~
~ur~er, t'nere can be .. ~ nPd the followulg lubricaong oil c~ s as
preferred ~bGA;~ P~ ofthe~x~ent ~ hO~
t2) a l~ t o~ c~ ,c;~ as set forth isl the above i~ n (1), whc.~ (A)
the oxymol~ d~.~ sulfide ~ ;O~ has an a~l group c~ t 8 to L3
rbon atoms, (B) t~e D~C d~l LlLo~.hoslll~te has a ~primary a'kyl group ~U~It~Lllg
3 to 12 carbon at~s, and (C) the baros~--rrnt~ning co"l~ d is boro~--cGn~ g
surci~imide and
(3) a lu~ica~g oil co~ ;on as set forth in the above i~n (1) or (2), wherein
the amount of molybdenum derived from the osymol~le~ su~hde ~ith~ dte is
from 300 to 800 ppm (~veight basi~s) of the total weight of the CO.~ 5;~ \ the amount
of ~hssyh-l~ls derived from the zinc dial~yl rlithir~Fhosrh~tp is ~om 0.04 to 0.12% by
weight of the totll weight of the co .~sh~ and the amount of boron derived ~om the
b~ron--c~,t~ ~ un~ is from 0.01 to 0.04~o by weight of the total weight of t-h~ecomposition.
The present u~h~u will ~lOW be ~ ;... A in detaiL
There is no ~cul~ l;...it,~l ;on v~ the l~ ting base oil for use in the
hricatir~ n.~ n of the pre~sent u~ ;VLI, and any base oil, such as any of
mineral oils ~d synthetic oils, ~hich is co~ ly used f~r the co,~ L.ondl luL~u.gV~9 can be use~
F ~ ,lf s of the mine~al o~s include jArr ~ s obtamed by su~ ~ raw
~natf~ fOr ~ A~llg oils to s!ol~t refin~ng which ~s effected by using arl ~u,~c
r ~ l;on solYe~l~ such as phenol or ~lrf ~~1~ ~y~lLu~ated oils ob~ined by s~lhjectin~
raw m~t~nals for ~ rirat~ng oils to hylLu~ iu~ t which is ca~ied out by
us~ng a hr~l~u~ catalyst such _s cobalt or mOI3~bdrILI~I supporte~ on a
CA 02223256 1997-12-18
-- 5
s~ica--a~ canner. a~d l-lb~ g oil ~innc obt~ined by ~e j5~ of
~axes, such as 60 ~eutral oil, 100 neutral oil, 150 neuml oiL 300 neu~l oil, 500
neut~al o~ and bnght ~tocks.
On the other hand, ~mrl~s of the synthetic oils iDchlde poly( ~ --olefin)
oligomers, polybute~e, alkylhPn~e, polyol cster.s, polyglycol este~s, esters of dibasic
auds, Fh~SF~nr esters and silicone oil. Thoee base o~s cas~ be uscd either singly or
in cQIT hin~tin~ of two or more. Fusther, a ~T~re of mineral oil and s~n~etic oil can
also be used in the present u.~
'Ihose oils whose y;~r~cil ~c at 100-C are in the range of 3 to 20 mm21s are
preferable as ~he base oils for use in the lubrj g o~ co,~ o~;~,o,. of the present
inve~on. Of these, I.Jl,~cke~ oils and wax--ieom~ed oils wnich contain 3% by
weight or less of ~UI~ 5, 50 ppsn or less of sulfur and 50 ppm or less of ~i~ug~ are
pamcularly ,.,t:f~
A co~ u~ GIJr~3c.,lcd by the fo~o~ing ge~e~al formul~ ~1] is used as the
oxymolybdenum sul~ide ~ o~u~,at~ to be L~aco~ dt~li into the IUL;-_d~ g oil
r~ o~ n of the pre_e~til~
N-C-S-~o \llo-S-C-N \ [ I ]
wherein Rl, R2, R3 and R4, ~hich may be the same or dif~ere~t, ea~h r~Gsl,l~ an
aL~cyl group ha~g 8 to 18 carbon at~ms, and X is sulfur or o~
The alkyl group ha~nng 8 to 18 c~rbon atoms, re~-~s~t~ by Rl, R2, R3 or R4 ~
the ge~eral f~rmula n] can be eith~ ~near or ~ h~ In the l~ r~*ng oil
~o-~ ;t;~.. of the prese~t ~Oll. it is particularly preferable tht the alkyl group
rc~s~le1 ~ Rl, ~ R3 or R4 has 8 to 13 carbon atnms.
Specific e ~'ES of the al~yl group r.p.~s~,ted by R1, R2, R3 or R4 include
octyl, nonyl, decyL undeql, dodecyl, tridency!, tetradecyL pvn~yl, he~a~ecyl,
h~dc.yl and o~ade~l groups.
CA 02223256 1997-12-18
In the lub~ *ng oi~ ~ n~n of the present LllY~I~Oll. eithe- ore ~- two or
more o~ oly~d~u,ll sul~de dithio~l-~A~s ~. ~e used. F~he~, the
oxymoly~n~Tn s~lfide ~itni~ is L~.}~ ted L~IO the co..~l~u~n;l~ so that theamount of moly~ u~. deriYed from ~hc oxymolybd~n-lm sulfide dilh~c.~u:~ e Gm
be from 200 to 2,000 ppm ~wught ba~is), ~,~ably ~om 300 to 800 ppm ~weight ba~s)of the total weight o' the ~~~ Wh~ the UA)'l~O]~ sulfide
.1;~.;...~. L~.ld~ is ~eo.~ ted isto the C~ such an amou~lt t~t the amount
of mol~ derived from the o~ymol~u... sulfide ~lnniG - I.w~te is less t~n
200 ppm (wei~t basis) of the total weight of the ~4~ , the effec, of i,--~u~
frir~n~ pe~Lcs (fnc~ior~ cmg p-oy~l;cs) ~nnot be fully obta~ned On the
oth~ h~nd, when the o,.~Luol~ ~ienur,n sul~de ~ e is Ll~o~Juldll~ int~ the
o~;t;ol~ ~3 such an a~Dun: ~hat the amou~t of molybd0um denYcd from the
osymoly~ 1 ~ sulfide ~3ithlo~ e is ~ e~ ess of 2,000 ppm (Welg,~tbaSiS) of '~he
total weight of the ~ oc;t;~ the effect cannot bc ~hanced in y.u~.hon to such anu~e~ amount of ~e u,~, ~lybd~- sulfide ~ ~u~e, and slud~ges or t~e
like tesld to be formed
A c~.u~olh.d ~c~ Atl!;~ by the fDII~ gcneral formula [2] is used as the zi~c
dia~yl ~-ith;o~hosphat~ to be ~co.~o~ed into the 1~ oil ~ ;r;~" of the
present i~ U~I:
S S
R5 ~\l 1/~ R7
P-S-Zn-S-P [2]
R6 o/ b R8
wherein R5, R6, R7 _nd R8, w}~ch 31ay be the same or ~ c~-~t a pri~nary
all~yl ~oup ha~n~ 1 to 18 GlrDO3 atoms
The ~ al~ ~t~d by R5, R6, R6 or R7 i~ the gC3CIal fo~mula
~] can be eithe~ ea or bP~r~ F~ PS of such a prm~ry a~ roup include
methyl, ethyl, propyl, buryl, pe3~L he~yl heptyl, octyl, ~onyl~ dec~L unde~L dode~yl
CA 02223256 1997-12-18
tndecyl, ~etradecyl, pentad~cSrl, h~de~r~ he~J~de~l and ocl~de.~-l ~oups. It is
par~cularly ~ ble to use. in the lubncating oil f~ ~c;hull of the present i ~ liol~
a z~nc diall~l dilhlo~ho.~,}~hstp ha~nng a p~ alkyl group co..t~ g 3 to 12 carbon
atoms.
In the llthrtr~ oil co...~;l;nn of the present u~ .h~ the zmc dialkyl
dithlu~,ho~ate is u~cu~u~dL~d so that the amount of phospho~us deri~ed from the z2nc
dialkyl ~;lh;~hoslth~tP Gm be from 0.02 to 0.15% by weight, prefP ably ~m 0.04 to
0.12% by waght of the tot~l weight of the a~ Oail;Oll. When the zinc dialkyl
d~thio~h~ is ~cO~u~aL_d into the c~ t in such an amount that the amountof Ilh9s~h~"~a demed from the zinc dialkyl ~ h;~ h9a~ate is less than 0.02% by
we~ght of the total weight cf the c~ the resulting c~,..poa~ion is poor in.~r p,o~,c.t~cs, and, in q~ n ra~not show a ~ticf~r~rily lo~ co~r;~ .t of
friction u~der the o~ ,~t;~ cC~ ;t;l~c Of high oil t~ L~cs ~d low ~o~lional
speeds. On the other hand. whe~ the 2inc dialkyl ditL;ophos~hate is il~c~ ted into
the c~ in such an amount that the amount of rhl~s~hsrus deri~red f~om the zinc
dialkyl ~lil.L;uyh~)hate is iIl e~cess of 0.15% by weight of the total weight of the
CO~ Oc~ , the effect G~not b~ ~nhanred in }.,o~ u,~on to such an i~cre~sed amount of
the z~c dial}~ h~9Fh9a~ P
A co,..},u~nd r~l~r~.lted by the following general fc~ a [3~ is used as the
dialkyl ~l;lh;~ .l~.ate to be u-cu"~ ~d into the h~h~ic~ting oil P~ ;ti.~ of the
present ~ iùn:
\N-C-S-M-S-C!N / [3]
Rl~ Rl2
wherein M is zinc, copper or nickel, and R9. R10, R11 ;~nd R1~, which may be t_e same
or different, Iepres~,~ an alkyl group having 2 to la carbon atoms.
The alkyl group hanng 2 to 18 carhon atoms, ~et~,es ~te~l ~ry R9, R10, R11 or
R12 in the gene~l formu~a [3] can be eithE~ linear ur bran~he~ npl~s of such _n
CA 02223256 1997-12-18
alkyl group include e.thyl. propyl, butyl, pe~tyl, hexSl, heptyl, ocryl, nony!, decyl,
undecyl, dodecyl, tndecyl. ~e~adecyl, p~ e~yl~ hexadec~l, heptadeql anà octadecyl
groups.
A C~ ~UIId repre~ed by the followin~ ge~e~l formula ~4j is used as the
te~aal~lll.;...,.,.. ~islllfirle ~o be ~.,cu~ ed mto the lubri:a~g oil C~ pO5il~01~ of the
N-C-S-S-C!N [4]
Rl~ \RI6
wherein R13, R14, R15 a~t R16. w~ch may be the sa~ne or different, re~.~.t an aL~cyl
group ha~ing 2 to 18 carba~ at~r.ns.
The alkyl group ha~ing 2 to 18 carbon atoms, .ep~t s~ ed by R13, R14, RlS or
R16 in the general formu~a t4] can be eith~ linear or bra~ched. Fy~rl~s of such an
alkyl group in~lude ethyl propyl, butyl, pentyl, hexyL heptyL octyl, nonyl, decyl,
u~decyl, dodecyl, tndecyl, ~e1~ad~1, p ~ C~YI~ hc~adecyl 11~ dC~I and oc~decgl
groups.
A co~ represOEted by the foLlo~ng general formula [5~ is used as the
fide to be u~ ted into the It~hri~ ng oil compoeihon of the presen~ ~V~15~u:
R17 - S - S--R18 ~S]
wnerein R17 and R18, which may be the same or different. represe~t an a~l gs~up
ha~nng 2 to 18 carbon atoms, or an aryL
The aIl~yl gmup ha~g 2 ~ 18 carbon atoms, ~e,~es_,lted by R17 or R18 ~3 the
general formula ~j c~n ~c eithc linear or ~ e~l. F~ .lrs af such an alkyl group
include ethyl, propyl, butyL pcntyl, he~l, hcptyl, octyl. nonyl, decyl, undecyL dodecyl,
hidecyl, tc~d~l, pentadecyl, h~de~l, heptadecyl and octadeql groups. Fur~her,
~-..rles of the aIyi alkyl ~gl or as5d a~yl group ha~nng 6 to 18 carbo:l atoms,
rep~cs~ed by R17 or R18 include phe~y~ benz~l, phenethyl, ~ethylben~l and
d~ph~lyk~lhyl groups.
CA 02223256 1997-12-18
A c~lll.u~,d reuies~ed by the fo~owing general formuld [6~ is used as the
th;~ coTnl~olln~ ha~ g a subs~stuent wn~n c ~n~inc sulfur, to be ,.~d~ed int~
Lhe hlhri~ing oil ~nmpoqh~n of the present i~ L;u~.
N N
\SY [6]
wherem R19 and R2~. wnich may be the same or ~I;Ll~-t. r~ a mono~ralent
gmup L'"'~ g 3 to 24 G~bon atoms aD~ one or more sulfur atoms.
F.~ yl~s of t.he mono~1alent E~oup c~ 3 to 24 carb~n atDms and one or
more sulfur atoms, .~"L~ted by Rl9 or R20 ~ t~e general formula t6] include
5--tl,~G..~I, 2,5--~lithi~hP~yl~ 3,4--r~it~i~hP~yl, 4,5--~lithi7h~ 3,4,5--tr~thiahept~l,
3,4,5,6-~e~ t~ 1, S-thia-2--heptenyl 4-Lh~y~lohexy~ 1,4-~hl~ h~hyl,
5-(me~lyllh;o~octyl~ 4-tet}lyllh;o)-2-pentenyl, 4-(m~ o)~y lo~eJ,~l,
4-Lu~ henyl, 4-(me~ l.lù)phenyi 2snd 4-(he~thio)ben2yl groups. Of these,
pam~ularly preferable groups are those in w~ch 2 tD 4 sulfur atoms are se~u ..~;~ny
combinp~l ~ ~e chain, for ;~ nr~ 3,4--~lithi~hp~yl group rc?~ the formula
r71, 4,5--lithi~h~ glOup r-~"esc.ltcd by the formula [5], 3,4,5-tTith~ Prtyl group
Le~s~..txl by the formula [9]. and 3,4,5,6--~d~hid~Lyl ~roup re~,~se~u~ by the
formula[10]:
CH3CH2-S-S-CH2CH2- [~
CH3-S-S-C~ CH2- [8]
CH3CH2-S-S-S-CH2CH~- ~9]
Cn~n~-S-S-S-S-CH2CH2- ~0]
The olefm sulfide to be ~oL~u.dt~d into the I~ u-t;~ oil ~..,.,I.,c;t;.~,l of the
pre~sent .u~ Lio.. is an ole~ sulfide C~ .;.,.e 25 to 40% by weight of su~fur, obtaned
by .s~ ln7ir~g a polymer of isoL~lL~l~cor the like. The s~e of fish oil or whale oil
to be inccu~dted into the lul,.~d~u~g oil cu---~ of the present iLl~ lLiUl~ iS one
obtai~ed by likewise ~llhm~ fish o~ or whale oil.
In the lubricdtiDg oil c~u~ u~ of the presen~ L~ lltiU~l, ~e dialk~l
CA 02223256 1997-12-18
-- 10 --
dithio~L~.ates repres~nted by the ge~e~al fo~mula [3], the te~ thim~m riiclllfi~es
se~,es~ed by the gene~al formula [4~. the tlicl-lfirles l~,res~l~ed by ~e general
formula t51, the ~h;~ ole cu",yu~.ds re~iesent~d by the general formula [61, theo~ef~ sulfides, the suliides of fish oil and the sulhtes of whale oil Gn be used either
singly or in comhin~tio~ of two or more. These sulfur compoullds are inco,~dtad i~to
the ~!ll~jt;~ 50 that t~e amount of sulhrr derived from the sulh~r c.. ~ c can be
~om 0.02 to 0.30% by we~ht of the total wei~ht of the c~ n When t_e sulfur
compounds are incu.t,u~dt~d into the c~ n m such an amount that the amount of
sulhr derived from the sulfur co..,~o~ds is less than 0.02% by weight of the total
weight of the Co~ û9~ l the resu~ng cu~ osi~ûn cannot ful}y m~inhin the
fri~tio~-reducing ~lu~hes for a long penod of time On the other han~, when the
sulflL- cnlnro~ln~c are ,,.cu,~u,~,Led mto the c,l l~ci~ n in such a~ amount that the
amount of sulfur de~ived from the su~ur c~npo~lnds is in excess of 0.30~O by weight of
the total weight of the culul~o~,Lio~, ~e efÇect cannot be Pn~nrPcl in l.lopu~L~n to such
an ~I~Gased asnount of the sulfur ccu,.~uuds.
One, or two or more metallic de~.,~ sPlPe~ from the group cor,~.~L~g of
calciurn sali.yhte, .~ s;,.ll~ salicylate, calcium stlK~n~tr 1~ -11 phos~te and
calcium phenate are u wllJo~d~d into the Illhri~tinE oil ~n, po~ n of ~e presentu~ ,on These metanic d~terE,c.l~ are Lllco~uL.~Led into the ~ " ~ ;nn in an
amolLnt of 1 to 10% by weight of the total weight of the c~ When the
amount of the metallic det~ rgents is less t~an 1% by weight of the tota~ weight of the
cnm~ n, Clpanir~ effect cannot be fully obtained On the other har~ wben ~e
amount of the metallic det~l5,~ts is in e~cess of 10% by weight of the total weight of
the t~ the effect r~nnrt be r l~t~r~ in ~u~Lon to such a~ ased
amount of tbe metalhc tet~;~, and, i~stead, the ash content is i~crease~
In ~e IIlhricating oil c~ n of the present "l~l;on, the total base number
of the c-.l ~l~o~ n is a~justed to ~erab}y 3 to 10, more preferably 4 to 7 The total
base number of the c~ l~oc;t;~-n can be det~nin~d in accul~ce with ~IIS K2501 The
total base number of the c~ ~o~ Qn be suitably atju~t by sdecting metallic
CA 02223256 1997-12-18
det~~ t~ na~ng pro?es base numbe~.
~ per;fir ~y~mrles of the boron--co~ g cu~ 1 fnr use L'l the lubrl~g oil
composTtton of the presen i,~ L,on s:clude boron-~onm;ll;llg ~.lri ;";",;.ies and
boro~-c~ -g ~lc~ ;-.a~c ~ . '~s of ~~le boron--cor.t~;..;"g Stlc. ;-~ rS L~ Ude
hose ~Ac w~ich are ~ se"t~i b~ ~. e follo~nng ge~eral formula ~11] or
R2 1--CH--C
~R22~ H [Il]
CH2 o z
O O
R2 1--CH--C ~C--CH--R2 1
o Z l [l2l
wneren R21 is a l.y~o~bon group ha~ 1 to 50 c;~bon atoms, R22 is ar, alkyieDe
group na~ng 2 to 5 c~bon atoms, n is a numbcr of l ~o lO; tw~ R21s in the co"-p ~ds
of the gene~al formula [12) may be the same or diffe~alt and R22s in ~e number of ~n"
in the general formula nl~ or of "n+l" in the gulcral forrnula n2] snay be ~he same or
, and Z is a boron--~n~ining ~b,u~ .t h~mg such as the fo~owing
stn~ure:
OH
/OH O--B
B--O B or~/ b
\OH \O B/
OH
r~ny~ nECA 5025n (J-~ l ed by E~xon ~h~mi~l CO., LtIL)I
"LliBRIZOL 935~ f- I~,~l by T~ LU~RIZOL CORP.) and the like c~ be
~1111111. . A~.,A
F~thcr, ~ k5 of ~e boron-c~ g SUCJ ;~'A1~5 indude those csl-l~ds
whi~h are ~ ~e follD~g gene~al fo~nula n3]:
~13]
CA 02223256 1997-12-18
CH; CH3 CH3 O
CH3 - C ' CH~ - C~n CH_- CH { H~ - CH - C - O _
CH3 CH3 CH~ C - O ~
o
wherei~ 3 is a ~umb~s of 1 to 20; R23 is a lm~ or 1~ hyllL~I101~ group ha~g
2 to 18 c~bon ato~s, whic~ c~n con~ thcre n aa a~ c or double bond; and Y and
2 a~e boron-c~ sub,~ ~, at least one of thesl ballg coor~ esl to the
S~IC~ t.o by cculcl~t~ boDd.
Sp.~nfir~lly, "LIJ~OL 936" (.~ d by ln~ LIJ'BR~ZOL CORP.) and thc
1i3~e Qn be ~IIIIIIIr .AtlA
Of the xson--~o,~ ;"g cQsT~ro~n~e. the boron-ccn~.g ~u~ 5 are
~d. Furthc, the ~om~i~nnn use of the bo~--co~t~ <~ and a
c which will be desaibed hter is also a useful means. The borort--c< It~
C~ u!l l is i~~,~,.~Lcd mto the co~ ;I;o.l in such a3 amoumt that boron de~ive~
fr~l the boron-~ can be from 0.005 t~ 0.06% by wei~ht, ".i~..bl~
~m 0.01 to 0.04~ by wciE~t of t~e total weight of the ~ c~ ~hcn the
b~n-~ol.tA;.I;~.g ci...pu~u~d is ~u~yO-~U~ i3~0 ~e r~....~.o~ in ~t an amou~t
t~at the anolmt of boron d~ from t~e bc~ ~ I~ cc.~ is less thar~
0.005% by weig,'~t of the TDbl wcight of the c~ ,o~ the rP~ cv~
canno: ha~e, rr-; ..~ y.u.~d fri~c~l p.uyC,~CS (fric~ion--~cd~ y~JC~IiCS).
On the othes haDd, wha~ thc bon~n-c~ g ~ 1 is ih~u~u~tLd into the
c~ ;An i~ such as~ amount that the amount of boron desivcd from the
bom:l c~ A;ll;l~ ...A is m e~cess of ~.Q65~a by weight of t~e tota~ ~ht of the
o~;~;o~ t~e e~fe~ c~ot be ~nh~nr~d ~ ~uyu~ tD such an ~.~;c~ ~ou~t of
the boron co~l; .; .g c~ ~A
Yarious ~Lh~.s which are usually i~u~uu~ to the cu,.~ ;n~ -l lu~.~l.,~g
Oila~ SUC~l as o~er fric5ion ...n.1-~ oth~ 3Pt~ c dct~ a, other ~uh-.~ agents.
oth~ nDnas- d;.spe~ aCGa~ d~ ~y~u~ , pour -yOiUt
d.J~Sa~La, a~ fo~in~ agents. rus~ iJrt~_J1~cs a~c c~a~ nhi~tnrs, cal be
added, if n~c~sc~ t~ the l.lb~.~h~ oil ~.,"~.~ n of the ~rese~t inY~ltion Wit~
CA 02223256 1997-12-18
such a l~it that they do ~ot disturb the ~ It of ~e object of ~e present
~v~Ld~
F , ' of other fnc~on ,..~l;r.. . a include par~ally-estPri~Pd polylly~ic
:~k~nhnlc, amines. amid~c and sul~te est~
Examplcs of other me~allic de~l;~ include basium ~lf~ and barium
Fh~ In gene~al, thq are added to the a~ rJ~ in asl amount of 0.1 to 5~o by
wcig~
Esamples of other ~h.. ~ agents ~ de meta~ic sal~s of th~oph~s}~k~
su~r ~ ....A~, phos~.J.i~ ~rs aud ~hO~k~tu~ ester.s. In g~n~ they are
added to the ~ n;-~n in a~ amount of 0.05 to 5.09i by weigh~
E~amplec of other ~ona~h dia~J.,~,~s i~c~ude t~ose of 5l1~ ;Q;~ e type,
~UC~ AII~ t~ ~L~e type and cster type. ~ generaL thery are added to the
c~ - m z ;~nount of 0.5 to 7% by wei~ht.
Eamplcs of the .~"l;...;A~r.t~ lude a~Dme At~ A~t~ such as allcylated
diphc~L~4 phc~yl- a--naphlll~l~c and aIL~l~cd a -~l~e, a~d
p~rnr~lir ~ ;Q--~15 such as 2,6--di--t--butyl--4---u~ l~ol a~d 4,4--....lh~l~c
~is(2,6-di-t-b~ ; ril). In gcncraL thcy are attet to the c~ tn ~n
amount of 0.05 to 4~o by weight.
F~Amples of the y CCû~Ly inde~ .u ~ ~.s ~dude those of polY. - I h~ ~ vhte typc,poly~so~utylcne ~pe, eLh~l~e prop~lesle copol~me~ type and s~rene-bu~i~c
h~Luh~t~i copolymes tg~ In gcrle~, thcy are addcd ~o ~e ~ pO~ m
amoul~t of 0.5 to 35~ ~y weig~t.
E~mples of tbe po~ po~t d~.css~t~ include polyalk~ Y]de,
rt~loJ;~t~ a~--Da~thalelne~~~~ s~ " ~ulu~andalk~ated~oly~~
Es~mples of the asti- ~ age~ts include l~ LYI E~ r and
polyaaylic acid.
Esamples of the ~ust ~ ~.Li~_s tn~lude fatty acids, par~a~y--~st~fi~d a~enyl
~---r; ~t~c. f;~ty a~d soaps, a~yl s~ ty polyh~rdric alcohol ~sters, fat~y
amines, para~ o~des and a~ UA~CL~Y1~C e~hers.
CA 02223256 l997-l2-l8
- 14 -
F.-~mrles of the cu~uslùn inhibitors iuclude ~zv~ole and i:if ~r;~ olP.
The present ~vention ~ill now be e~plained ~re spu~fir~lly by referring t~ the
following F..~".~ s. ITo~.c~, the present irlv~Q~dn is not limited by ~ese PYamples
in any way.
The cor~...; ,.~ of friction of the hlhrir~ing oil o~lu?o~ n~ were detf~ninpd bya re~iproca~ng sliding ~riction tester [SRV F~i~on Tester~ under the cQ.-.tit;.~ of a a
~equency of 50 Hz, an ~mplit~ f of 3 mm, a load of 25 N, a tr".~ e of 80 ~C and a
test ~me of 25 rnimlte~
Further~ the test for U~ t~J~ by the air co~ rutlo,~-ll o~ddes gas was
camed out by ~o~ng, for 8 hours, 150 ml of a sample oil to the air of 130 ~C,
containing 1 Yolume% of nitrogen oxides (NOx), flown at a rate of 2 liter/hour.
F.~.,.rles 1 to 10 & ~ ive F , le3 1 and 2
Lubncatmg oil co~5ill0ns of E~Gples 1 to 10 are those which contain (A) an
oxymolybdenum sulfide ~litl~;fil~ uudte~ (B) a zinc dialkyl dithior~ss~k~le (C) 2inc
dsmyl ~l;lh;~ .L~uate, copper dibutyl rl;Ll.~ .b"~, te~ab,l~yllh;.l,~ icu1fidP
~benzyl ~is.lfi~ or ~ o~onyl)~h;'~ o!F~ ~) c~cium. s~ic~te, and ~)
boron-co~t~;,.;..g s~ e Lubricating oil comp~it~nns of C~ulp~ .lve F..,.~.,plrs
1 and 2 are those wh~ch con~in the (A), (B), (D) a~d (E) cnmr~n~ntC but doec notcontain the comron~nt (C).
F ch of the above l~hnr~tin~ o~ c~ ;nnS was blended ~i~ a hse oil tlOO
neutral o~ having a Y~osity at 100~C of 4.4 msn2/s), thereby ob~g lubricating oil
cunl~siLu~ls ha~ing the fnr~ntlhtinn~ sho~n m Table 1 The cu~ ,t of fric~on of
each c~ . thus obt~ Pd was d~tP ,..;~.ed right after the c..,..~s~...~ was
prepared, and af~er the cuu~ oll ~as ..~ d by bemg preserved at 130 ~C for 8
hours in the ~,L~sence of nitlug~ o~des gas. The results are sho~m in Table 1
CA 02223256 1997-12-18
All of the hlnric~n~e oil co npositions of E~nples 1 to 10 according to the
present invenion have ]ow coefficients of f~ctior. and eYceller.t fric~onal proper~es, and
there is a~nos~ no change in the coef~cien-s of ~iction e~er. af.er the compositions are
heated at 130 ~'~ for 8 hours and o~dized. It is thus known that the Inhnr~rin~ oil
Co~ oc;l;nns of the ~.Ycl~L~on have rYcr~ nt resis~ce to oYirli7~tinn Ir. contrast to
this, al~hough t~e lubnr~*n~ oil cnm~ositions of C~.llp~live Examples 1 ard 2,
cunt~ ;ng no sulfur cos:lpound, the col~pone.lt (C), have low co~ffiri~nt~ of ~iction nght
a~ter the ~ ctinn thereof, they have inaease~ co~ri~n~C of friction after t~ey are
~eated at 130 ~, for 8 houss and nYirii7el It is ~us k~o~n that the c~ll.~,dt;.,~
lubricating oil co...yosihd~s ase poor in r~ ,.,fe to o~ ,St;nn
Effects of the Invention
The lubrica~ing oil com~ci~ons of the present inven~30n are prep~cd by ble3ding
a base oil with z~n o~nolybdemL~n sul~de dithiocd b~-ate hanr.g a specific st~ucture, a
z~c dialkyl dithiop~osphate, a sulfur colllpo~d, a metalIic detergent 2rld a
boron--cu~ g co~p.\u~,d. Thexfore, they not only haYe ~ycl~llpnt ~t-iw~
p~up~t ~s, but also exhhit high resistance to ~A;.~ e~en at high t~.,pc,dtlres in
the presence of nitrogen o~ades gas, thereby l~lLl~g ~oYr~ nt fric~onal ~rop~ties
(friction--redl~nng properties) for a prolonged pe~iod of ~sne. The lubncatin~ oil
cornpos *~C of the present i~ lo~ are thus useful as lubricating oils for
intemal--combus~on engines, a.~(~."~t;c t~nc.,.;c~ n gearboxes, d~l.l.er~, powerste~ing~; and the like; thcy are par~icularly usefill as I~ ng oil5 for
internal--combus~on engines.
Q~AMP~
2 3 4 5 6
Anlolln1 ot u.~ In C8-MotJTC (ppm) ~n 6U0 400 Gno C00
Am~llllt ~~ ~"olyb.h.. - . In C18-MoitlC ~m) ~i
Anlounl d ,)h- J~h u~ In C8-ZnDll'l~ vtX) 0.10 U.10 0.10 n.10 O.OG
Amamt Or rllifur în C~Zni~C IwV6) 0.16 0.05 0.10 0.10 0.10
Amount d sulfur In C4~ul~C ~
~nounl ol ~uî~ur in h~ ' dlsulnd~ (~ O
Amolln~ lhlr In dlben~î ,~,m~
Amount ol 6ulrur In 2,5-dl~,~dllh~ ."1)1,3,4-lh' " I ~wtX) ~.,
C~lclwn salicybte (wl%) 3.5 i.5 3.5 3.5 3.5 3.5 1 ~,
Alno~lnt af horon ln boron . ~ 1n~ _ ~u ~ I .5 ,'1e (~vlX) 0.03 0 n3 0.03 0.03 0.03 O.U3
Coefllclent d frlcllon Riahl aller ~ , .J~' r 0.057O.Oli70.090 O.O9oo.U~5~0.094
Alior ~ lOt~X81~ours) 0.0900.091O.O9~i o.ng~umi7 o.ln
('8-M<)~C ~ n~ ... suln(le-N,N~iloctY~ ltii~ te
C13 Momc: ~ ulyw~lum sulfldc-N,N~llîrlll~cyl-dllt h
C8-Znl~lP~prlrnnry): ~inc dl-2~thyll...~ l,d 1(j l)h(~a
C5-i'lll) l~ lc dl~nyl dllhb t~..filc
('A-Cul~TC: copper dlbutyl dllhlc I '~
I~XAMPLE CO~IPRAllVE I~XMlPLe
7 8 9 10 1 2
Anlo~mt of l.. olyb~i-.. ~..In C8~ wr~ G00 fiO0 noo Gao finn
~nounl d n l~LJeu~un In C13-Mol~l~ t~n) Gao
~nlount(t~ uslnC8-ZnD'l~rl y)twt~10 0.10 0.10 0.10 0.10 0.10 0.10
~nount d sulfur In C~Zn~C (wtX) D~nounl d culfur In C4~u~ a ~A,mounl af ullfur In teb~ ~t~ ~ dhul0de (wl~la 0.10
Amount d ~ulfur In dlben~gl tulltde ~wtXl 0~0 0.05
Amount d culf~u In 2,5-dl(4,5~tll'J ~1)1,3,~wt%) 0.10
('~Iclum s~Ucybtc twtX~ 3.5 3.5 3.S 3.5 3.!; 3.5
~nc~unl of boron ln bo.~ - ' n ~ ~ n~ie (wt%) 0.03 0.03 0.03 0.03 0.03 O.U3
Coeftlden~ ct frtcllon R4ht afler ~c ~ u 0.092O.OR50.086 0.090 O.ORG o.oa
Afl~ NO~ ' ' '130'CXaholln)0.095O.OR7 0.094O.O9G0.167 0.17
C8-MoDTC: r ,,..~ 1enum sullld~N,N~lloctyl~,"lll~ rbl~mllte
C13-MoDTC ~ lyl,del~um sulflde-N,N~lllrldec~l dlthloalrban~tc
C8-ZnDTl'(prtmary) : zlnc dl-2 e~hfll~ldlthl~l~svhah
CS-ZnDTC: zlnc dlamyl dllhbcerb~nale
C4{~uDl'C: a)pper dlbutyl dlthlocarban~te
