Note: Descriptions are shown in the official language in which they were submitted.
WO 92/22629 1 ~ P~/US92/04go2
LAUNDRY DEl~OEMr OONTAINING ~ POLYHYDROXY FArlTY AMIDE AP~
INSOLUBLE E~XYL,ATED AL~OOHOL
This Application relates to fabric cleaning compositions and more
particularly ~o fabric cleaning compositions capable of providing
grease and oily stain removal.
5 The sur~a tant systems of commercially available fabric cleaning
compositions are designed to remoYe a varie~ of s~il types from the
fabric surface. The majori~ of such systems are based on one or
more anionic surfactants with minor levels of other surfactant types
such as nonionics, ampholytics and cationics. In particular, a
o combination of a major proportion of aIIionic and a minor
propor~ion. of nonionic s~rfa~tant is commonly used to obtain an
~: acceptable ba!ance of particulate soil remoYal and grease and oily
soil removal characteristics. Detergent compositions incorporating
surfactant systems in which the major componerlt is~nonionic are
15 hlO~II in the aIit, e.g. EP-A-0006268 and ~B 2206601 bu~ any
mercial application has tended to be of a specialist na~re. This
~ ~ is because compositions base~ on anionic surfactants provide
: ~ acceptable det~rgèn~y o~r a broader spect~m of soil ~pes, display
ater compatibility with adjuncts such as optical brighteIlers and
20 : fabric softening~ additives and:are also; less aggressive ~owards fabric
: ~ : dyestuf~s and washing machine components.
~ccordingly7 a~need still exists f~r detergent Gompositions displaying
improved grease :and oily soil remoYal without any sacrifice in the` ` 2 5 r ~moval~i~f other soil l;ypes and withou~ impact on the pe*ormance
of othe~de~ergent ingredients. ~ ~
:, :
~ :
WO 92/22629 ~ 2 - PCr/US92/0~902
The present inve~tion provides laundry detergent compositions which
contain nonionic surfactant systems which comprise one ar more
polyhydro~ty &tty acid amides and one or more additional nonionic
surfactants. When included ~n such laundry detergent compositionst
5 these nonionic surfactant system~ une~cpectedly improve the
effectiveness of such compositions agamst greasy/oily stains across a
broad range of laundry conditions.
I he commo~ly assigned copending tJS Application Serial No~
o 07/578760 ~aKarney's docket No. 4265) filed 28 September 1990
discloses nonionic surfactant systems~ compris~ng combinations of
certain polyhydro~cy fatty acid amides and one or more additional
noDionic surfactants. The polyhydro~cy fatty acid amides have the
formula
R
O
R2_c ~ r ~ ~ z
20 wherein Rl is H, a Cl-C4 hydrocarbylt 2-hydro~cyethyl, 2-
- ~ hydro~cypropyl or mi~tures thereof,~R2 is a Cs-C31 hydr~earbyl and
Z ;s a polyhydto~cy~ hydrocarbyl having a li~ear hydrocarbyl chain
with~at least 3 hydro~yl groups directlY connected to the chain, or an
allco~cylatcd denva~o thereof. ~ The ~weight ratio of the polyhydro~cy
~` ~ 25 fatty~acid amide~to the additional nonio~ic surfactaDt can lie in the
raDge from~about 1:5 to`about 5~ O~hcr surfactant ~pes such as
ani~nic,~ca~ioDic, ampholytic,~zwitterionic and semipolar can be
included as optioDal compon~Dts and~ detergent compositions
co~ g ~e su~factant systems~are also disclosed.
l'he ~pplieant;h~s une~cpeetedly~found that~det~rgent eompositions
ineorporatiDg nonionie~ surfaetant systems of this general type
eomprising eertain;~combina~io~s of~polyhydrol~y f~tty aeid amides
and water insoluble ~etho~cylated noluonie surfaetants together with
35 other water soluble surfaeta~ts proYide une~cpeetod oil and greasy
soil rer~oval benefits with:~ no deerease ~in the detergeney performance
on other soil typés.~
(*~;ee pa~e 57~ for Equivalent Applicatioll)
WO 92/22629 2111 ~j 9 2 Pcr/us92~o4go2
- 3 -
BACKGRQ~ ART
A variety of polyhydroxy fatty acid amides have been
¦ 5 described in the art. N~acyl, N~methyl glucamides, for example,
are disclosed by J. ~. Goodby, M. A. Marcus, E. Chin, and P. L.
Finn in '~he Thermotroplc Liqutd-Crystalllne Propert1es of Some
Straight Chain Car~ohydr~te Amph1philes,~ Ltqu1d Crystals, 1988,
Yolum~ 3, Ho. 11, pp 1569-1i81, and by A. Muller-Fahrnow, y
Zabel, M. Steifa, and R. Hllg~nfald 1n ~Molecular and Crystal
Structure of a Hon10n1c Deterg~nt: Hon~noyl~N-methylglllcamite,~
Chem~ Soc. Chem. Commun., 1986, pp 1~73-1574. The use o~ N-alkyl
polyhydroxyam1de s~rfactants has be~n of sub5t~ntial interest
recently for use 1n blochem1stry, for *x~mple 1n th~ d~ssociation
of b~ological ~e~br~nes. See, for ~xampl@, the journ~1 article
~H D-61uco N~methyl-~lkanam1d~ Compounds, a New Class of Non-Ionic
Det~rgents For Membrane ~10chemlstry,~ B~ochem. J. (1982), Vol.
: 207, pp 363-366, by J. E. K. H11dreth.
The use of N-alky1 gluc~mld~s ln detergent compos1t10ns has
also been d1scuss~d. U.S. Patent 2,965,576, 1ssued Dec~mber 2C,
1960 to E. R. ~11son~ and G.B. P~tent ~09,060, pu~l~shed February
18, 1959, ass19ned to: Thomas H~dl@y & Co.l~ Ltt. relate to
; deteryent co~pos1t10ns conta1n1ng ah~ontc surfact~nts and certain
amtd~ surfaet-nts. whteh c~n tnclu~ H-methyl glucam~d~, added,as
2S ~ low t~pe~tur~ suds enh~nc1ng ~2nt. ~h~s~ co~pounds 1nclude
` an N-aeyl ra~1e~1 o~ a h19h~r str~ight cha1n fatty ~acid haY~flg
10-14 c~rbon ato~s:. Thes- co~pos1ttons ~y also conta~n ~x1l1ary
~t~rla~s such as ~lk~lt mot~l phosph~t-s~ aik~ et21 s~llcates,
sulf~t~s, ~nd c~rbon~t-s.: :It 1s ~lso gen~r-lly lndlc~ted th~t
sddttlontl ~const1tuents to~ 1~p~rt d~s~r~ propcrt1es to the
compos1t10n: c~n also b~ 1nclud-d 1n th~ eo~posttlons, Isuch as
fluor~ssent:dyes, bl~ach1ng ~g~nts~ pQr~u~2s 9 ~tc.
U.S, P~tent: 2,703,798~ lssu~d M~rch 8~ 1955 to A. M.
Schwartz, rel~tes to~aqu~ous~detergent compos~t10ns containing ~he
eondens~t10n ~ r~act10n~ product. of N-alkyl gluc~mine and an
phat~ ester of a fatty ac1d. ; Th~ produet o~ this reaction ~s
,
~: :
: ` :
WO 92/22629 PCI/US92/0~902
~111.5!)~
said to be useable in aqueous detergent compositions without
further puri~ication. It is also known to prepare a sulfuric
ester of ~cylat~3d glucamine as disclosed in U.S. Patent 2~717,894,
issued Sept~mber 13, 19S~, to A. M. Schwartz.
PCT Internat10n~1 Applkat10n 11l0 83/04412~ publishQd December
22, 1983, by J. Hlldreth, relates to amph1phil 1c compounds
cont~1n1ng polyhydroxyl ll lphat1c groups s~id to be us~ful for
variety of purposes 1nclud1ng us~ as surfa~t~nts ln cosmet1cs,
drugs, sh~mpoos, totlons, and eye o1ntments. as emuls1fiers and
d1spens~ng agQnts for ~ed1elnes, and ln b10chemtstry for
solub111z~ng ~s~br~n~s, ~hol~ c~lls, or othltr t1ssu~ samples, and
for pr~p~ ng of 11p~s~s~ Incl~ld~d tn th1s d~scl.osure arP
co~pounds of th~ for~ula R'CON(R)CH~R~ and R~CON(R~' wh~rein R 1s
hydrogen or an or~ul1c grouplng, R' ls an ~1tph~t1c hydrocarbon
IS group of at least three carbon atoms, ~nd R~ 1s the residue of an
~1 dose .
Europe7ln P~tsnt 0 285 768, publ1sh~d October 12, 19~8, H.
K~lkenb~ t al ., r~l~t@s to th~ USB of N-pol~hydroxy al kyl
fatty ac1d z~ t~s as thlck~n1ng ag~nts 1n ~qu~ous deterg¢n~
syste~s. Inolud~d ar~ ~ldes of th~ formulæ RlC(O)H(X)R2 whorein
Rl ~5 a Cl-~17 (pr~f~r~bly C7-C17) ~lkyl~ R2 1s hydrogen, a Cl-C18
(pr~fRrabl~ Cl~Cc~ alk~l, or ~n ~lkyl~n~ ox1d~ ~nd % ~s
po~yh~rox~ alk~l h~v1ng four to s~vsn c~rbon ato~s, e~g.,
N-~thyl, coconut f~tt~ ac1~ gluc2~ . Th~ thtek~nlng prop~rtles
of th~ s ar~ 1nd1cat~ct as b~1ng of p~rt1cular ~se 1n 11quld
surfAct~nt $y~t~$ cont~1n1ng paraff1n sul ~n~to, al ~hough the
aquQou~ surfaetant s~s~ c~n collt~ o~h~r snton1c sur~etants,
sllch a~ 1aryl sulfon~t~s, ol~1n sulfon~t~, sulfosucc~n1c; ac1d
~ h~lf est~r s~lts"n~ f~tt~ alcohol Itth~r sulfonat@s, anJ non~on1c
sur~ac~an~s such as fat~ :~leoho~ po~glycol ~th~r, alkylph~no1
poly~ycol ~tAI~r9 fatty ae1d pol~gl~eol est~r, polypropyl~ne
ox~ polyath~l~n- ox1d~ lxa~ pol~rs, ~tc. Paræfftn sulfonat~/
~-~thyl soconut fatt~ ac1~ gluca~1d~/non10n1c sur~aetant sh~mpoo
fo~lfit1ons ~r~ :~x~pl 1f1~d. In addtt10n to th1ckentng
3S attr~but~s, th~t N~polghydroxp ~lkyl fatty ac1d ~a1des ar~ sa1d to
h~ sup~r10r sk1n tol~ranc~ attr1bu~$.
wo g2/2262g 211 1 5 9 2 Pcr/US92/04902
U.S. Patent 2,982.737, issued May 2, I961, to Boettner, et
al., relates to detergent bars containing urea, sodium lauryl
sulfate anionic surfactant, and an N~atkylglucamide nonionic
surfactant wh1ch ls s~l~cted from N-methyl 9N-sorbityl lau~2mide
S and H~mQthyl. N~sorbltyl myrtstamid~.
Oth~r gluc~ide surfact~nts ~r~ dlsc~osed. for ex~mple, 1n UT
2,226,872, publ lsh~d O~ce~b~r 20, 1913, H. W. Eck~rt, et al .,
~h~ch relat~s to w~sh1ng co~pos~tions compr1s1ng one or more
surf~ctants and bu11der salts select~d from pol~mer1e phosphatesl
sequester1ng ag~nts, 3nd w~shtng ~lkal1s, tR~proved by th~ adttt10n
of ;In l~acy1polyhydroxy~l kyl -~r0tn~ ~f the formul a
RlC(û)H(R2~CH2(CH~l)nCH20H, wher-1n R~ 1s a C1-C3 ~lkyl, R2 is a
Clo-C22 alkyl, and n 1s 3 or 4. ~he ~ cylpol~hydroxyalk~ m1ne
ts added ~s a so11 susp~ndlng agent.
IS U.S. P2tent 3~65~,166, 1ssued Apr~l ~, I972, to H. \1. Eckert,
~t al.~ re1~tQs to d~itergent compos1ttons comprtslng at l~!~st on~
surfaetant solected fro~ the ~roup of an10n~c~ zw1tterton1c, and
non10n1c surf~ctants ~nd, ~s a text~le so~t~ner, an N-~eyl,
N-~lkyl polyhytroxylalkyl co~ound of the~for~ RlN(Z)C(O)R2
wh2re1n Rl ts a C~o-c22 allkyl, R2 1s ~ C~-C21 alkyl, Rl ant R2
~ot~l fr~ 23 to 3~ c~rbon ~to~s, ~nd 2 1s a polyhydrs~alkyl
~h1ch c~n b~ -~H2~CHOH)~H2~ ~hl~r~ ~ is 3 or 4.
U.S. ~atent 4,021,53g~ t$su~d Ma~ 3, 1977, to H. M~ller, et
al., rQl~t~s to sktn trll~t1ng cos~tlc so~pos1t10ns conta1n1ng
IN~polyh~droxylalkyl-~ne~ ~hich 1ncludæ e~pounds of th~ formu7a
R1H(R)CH~a~)~2 ~h~1n Rl ls H, lo~r ~llkyl, hydrox low~r
l, or ~no~lkyl~ ~s ~ll ~ h~t~cl1e a~lnoalk~l, R 1s the
S# ax Rl ~ut both cannot~ b~ 11, an~ R2 1s CH20tl or COOtl.
Freneh Pat~nt 1,360,018, Apr111 26, 1963, ~ss1gned to
Co~re~at Sot~nts Corpor~t10n, r~t~s to solut10ns of
for~ld~hyd~ st~blll ~ aga1nst pol~r~2~t10n ~1th the add1t10n
of L~des of th~ lFon~a RCgO)H(R~)6 wh~r~1n R 1s a c~r~ox~llc
ac1d ~unet10n~11ty havin~ at l~ast s~v~n c~rbon atoms, Rl 1s
hydr~og~n or ~ low~r ~lkyl group, and G ls a gl~c1tol radkal with
~t te~st 5 carbon ato~s.
WO 92/22629 PCI'/US92/04~02
2 ~ 2
G~rmall Patent 1,261.861. February 29, 1968~ A- Heins, relates
to glucamine derivativeS useful as wett1ng and dispersing agents
of the formu1~ H~R~(Rl)(R2) wherein R is a sugar residue of
~luc~m~ne, R1 ~s a Clo~c20 alk~l rad1c~ nd R2 is a Cl~C~ acyl
5 radlcal.
G.B. P~tent 745,036, publ1shed F~bruary 15, 1956, ass1~ned to
Atl2s Powde~ Somp~ny, r~lates to het~rocyc1 1c amides and
earboxyllc ~sters th~r~o~ th~t 2r~ sa1d tlJ b~ usefu1 as chemka1
tnte~ed1ates, e~uls1f~ers, s~l~tt1n~ ~nd d1spers~ng agents1
10 dct~rgsnts, text11~ soft~n~rs, l~tc. ~he compound3 are expressed
by the ~or~ N(R) ~Rl)C~)R~ ~h~r~1n R 1s th~ rQStdue of an
~nhydr1z~d hexane pentol or ~I car~oxyl~c ~c1d ~st~r thereof, Rl is
a ~ono~al~nt hydroearbon r~1cal, and -C~O)R2 is th~ aeyl r~dkal
of ~ e~oxyl1c ~c1d h~Y1ng fro~ 2 t~ 25 c~rbsn a1;oms.
1~ U.S. Patent 3,312,627, 1ssued Apr11 ~, 1967 to D. T. Hooker,
d1scloses sol1d toil~t bars that ar~ subst~nt1ally free of anton~c
d~t~ nts and alk~l1n~ bu11d~r ~at2r1~1s,, 4nd ~h1ch ~ontatn
1 tthlu~ soap of eert~1n f~tty act~s, a non10n1c surfactant
s~loct~d fro~ c~rta1n propyl~ns oxld~-eth~l~n~d1a~n~-ethyl~ne
20 ox1d~ cond~ns~tes, propyl~n~ oxld2~propyl~n~ glyeol-ethyl~ne oxide
cond~nsat~s, ~n~ pol~#r1z~d ~th~l~n~ glyc~l, and also contain a
nonlon1c l~th~rtng c~on~nt whgeh can 1nclud~ pol~hydroxy~ of
thQ for~ul~ RC(O)NRl(R2) ~ r~tl~ RC~O~ conta1ns ftORI a~out 10 to
about 14: carbon ato~$~ and Rl ~nd R2 o~ch ~ra H or ~l-C6 alkyl
2~ groups, s~1d ~ l grou~s conta1n1n9 a total number of c~rbon
~t~ of fro~ 2 to ~ t 7 and a tot~l nu~r of subst1 tu~nt
hydroasyl gr~up~ o~ fr~ 2 to ~ut 6~ A substantl~lly s1~11ar
d1~e~o~ro 1s found ln U.S. Pat-nt 3,3l2,62i5, ~150 1ssued Apr11 ~,
1967 to ~. T. Hook~.
3~ us~ :of non~onie ~urf~c~nt~ 1~ d~t~ent compos1tlons is
o~ t~ th~ art. U.S~ P~t-nt 3,6549~66, ~ssuæd Apr11 ~1 1972 to
Eekær~ 2t allo~ d1sclos~ ~ dQt~rgsnt co~pos1t10ns compr1s1ng a
s~l~faetant s~l~ctl~d~fro~ 10n1es, z~1tt~r10n1cs and non10n1cs ~nd
~r, H~alkyl-N-acyl-N-polyh~d~x~:~lkyl c~polmd.
3~ ~
WO 92~22629 2 1~ ~ ~ 9 2 PCr/US~2/0~1902
Another disclosure of the use of nonionic surfactants in detergent
compositions is provided by GB Patent 1241754 which teaches that
ethylene oxide addu~ts of C~-C1s substantially unbranched
monohydric alcohols having an average ethylene oxide content of from
5 10% to 51% by weight can serve as detergency improvers for water
soluble organic anionic or nonionic surfactants. The improvers are
used in a weight ratio of surfactant to improver of from 5:1 to 1:1.
However, the re~erence does not contemp~ate the combinations of the
present invention tha~ employ water insoluble polyhydroxy fatty acid
10 amide surfactants as well as defined water insoluble ethyoxylated
nonionic surfactants
According to the present invention, there is provided a laundry
detergent composition use~ul for cle~ning fabrics in automatic washing
15 machines, said composition comprising one or more water soluble
anionic, cationic, ampholyt}c or zwitterionic detersive surfactants or
mixtures th~reof, and optionally detergent builder compounds, said
composition being characterised in that it comprises" in combination,
(a) at least 1% by weight of the composition of a polyhydroxy fatty
: 20 acid amide having the formula
O E~l
1~1:: 1
~2--C N z -
~ ~
; where Rl: is H, Cl-C4 hydrocarbyl, 2-hydroxyethyl, 2
hydro~ypropyl or a mixture thereof, R2 is Cs-C31 hydrocarbyl
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbon
~:~ 1; . I I chain with at ieast 3 hydro~y gro~ps direc~ly corlnected~ to said
chain, or an~ ally~ylated derivative thereof; and
~:~ (b) at least 1% by weight of the composition of a substantially
:` ~ water-insoluble ethoxylated C11-C1s primary aliphatic
alcohol containing an average of no more than ~lve ethylene
oxide ~ ::
~:
":`~ : :
W0 92/22629 PCI`/US92/04902
~1115~2
~groups per mole and having an ethylene o~ide content of less
tha~ 50% by weight.
Preferably the compositio~ is granular a~d comprises from 3 % to
5 15% by weight of ~ionic surfacta~t, from 1~i to 10% of compoIlent
(a) and from 1~ to lO~i of compo~en~ (b), the weight ratio of
anionic sur~actant to the combined weights of compone~ a) and (b)
lyin& iIl the ra~ge from 1:3 to 3:1. Mo~ prefer~bly the anionic
surfactant comprises a mi~ture oP a major propor~o~ of a water
o soluble C1~-C1s ~llcyl sulfate and ~ or propor~o~ of a C12-C~s
alkyl e~hoxy sulfate co~hirai:~g a~ average of three etho~;y groups per
mole of alkyl etho~cy sulfate.
15 The deterge~t composition of ~he present i~ve~ion compri~e three
essential eomponen~s, viz. a polyhydro~y fatty acid ~mide, a water
insoluble ethylene o~ide adduet of a Cll-C15 alipha~e alcohol and a
water soluble surfactan~ that may be aDio~i~9 catio~c, ampholytic or
zwitterionic.
,
'
- ~ ~
~ . ~
WO 92/226~9
~ 1 1 1 S 9 2 P~/US~2~0~02
~h~ polyhydroxy fatty ac1d a~1d~ surfaet~nl: component of thQ
pr~sant lnv~nt10n co~rtsu ~o~po~lnd~ ~f thQ structura1 formul~:
O Rl
Il I
(I~ R2 ~ C ~ N
~h~r~n: Rl 1s H, Cl C~ hydroc~rbyl, 2 hydrox~ ~thyl, 2-hydroxy
prop~l, or ~ ~1xt~r- tb~r~of~ pr0fl~ra~ty Gl~C~ al kyl, n~r~
pr~for-b1y Cl or C2 alO~ pr~fær~bl~ C~ yl (l.~.,
~th~13; and R2 1~ ~ Cs-C32 h~firoearb~, prl~f~r~bl~ str~1ght ha~n
cl ~.C19 alk~l or alk~n~ pr~f~rab~y stra1ght ch~3n cl ~-c
alkyl on ~lk~nyl. ~o~t pr~f~r~ tra~ght eh~1n Clscl7a~ or
alk~n~l, or ~1xtur~ th~of; a~ Z 1s a polyhydrox~hydrocar~yl
h~Ytn9 a 11n~ar h~droe~ l cha1n ~lth st ~a~t 3 hy~roxyl s
~1r~tl~ coRn~ct~d to th~ eha1~, or ~s all~ox~l~t~ ~r~v~lt1v~
pra~rll~ly ~thox~l~ts~ or ~ropo~lat~) th~ o Z pr~f~r~bly
~11 ~ d~r1v~ fr~ a r~1n~ r t~l ~ r~ct1v~ a~1n~t10n
r~ale~10n; ~ors pr~f~r~ Z 1~ e1ty~. Su1t~blo r~ c1ng
~ug~n ~ncl~- glllco$~ ~eto~ov ~alto~ cto$~ lAeso$~,
x~ls~. A~: r~ ~t~r1æl~, hlgh Joatt~o~e eor~ 'syrup,
h1~h fructo~ corls $~Uel~ a~ h1~h 0a~t~ co~ rup c~n b~
utgl t2d ~ ~oll a$ th~ U~ r~ t~ abo~ h~SQ
2S eo~ ~ ~ y1~ r c~oll~nt~ for Z. It should
5ill tt9111g !t 1~ 1a81~B 1ntu~o xclud~ oth~r
~gta~ ~ ~ts~al~., t p~r~l~ et~ f~ th~
gro~ eo~ t1ng Q~ -CH2-(C~H)nCH~,
~r(c~N~ag~ h~ro
391 ea t~ ~A tl~to~or~ 3 t o 5, 1t~ 1w~15 H ol~ ~ cycl1c or
: al l~h~ic ~aeeh~ lko~l~ clsr1~a~1v~ thor~g~f .
P~o$t pP~ ar~ ~lye1tyl~ n t~ ~, pi~rt1c~
~H2~gH~)4~
Fo~la: (~:,: RI c~ b~" ~r ~ ll ~th~ th~l,
~ p~pgl, ~ o~ropgl,:N~but~ o2-h~dro~ ~th~l, or N-2-hydrox~
P~g~
W~ 92/22629PCr/U~i92~0q902
5 ~ 2
~o
R2-CO^U~ can be, for example, cocamide, stearamide, oleamide~
lallramide, ~yristam~de. capricamide, palmitamide, tallowamide~
etc.
Z can be l-deoxyglucttyl, 2-deoxyfrlJct1tyl, l-deox~rmaltltyl,
l-deoxylact1tyl ~ l-d~oxy~zlact~tyl, l-d~ox~m~nn1t~ deoxymalto~
tr~o~1tyl, e~c~
The most pr~ferred polyhydroxy f~tty ac~d ~m~de has ~he
gQneral for~
O CH3
1011 1 ,,
R~ ~ C - N - CH2 - (CHOHJ~CH20~
~here1n R2 ls a cll-cl9 str~lght~ch~1n alkyl or ~lkenyl group.
M~thods for ~k1n~ polyhydr~xy f~tty ~c1dl ;Im1de$ ar~ known in
the ~rt. In g~n~r~1, they c~n b~ ~d~ by react1ng 2n ~lkyl ~m~ne
lS~1th a r~duc1ng sugar ln a r0duct1v~ a~1nat13n r~ct1sn to form a
corr~spond1ng N-al~ polyhydroxy~1n~. ~nd then react1flg the
lkyl po!~hydrox~r~1no w1th a fatty al 1phat~c ~ster or
ts~lglgcoer1d~ 1n ~ cond~3sat10n~1dat10n st~p to form thQ H-~lkyl,
N~polyhydrox~ fatty ~c1d a~1d~ product O Proeoss~s for mAkl ng
20compos1t~ons collt~1nlng po1yhyJroxy f~tty 2c1d a~1des are
~1sc10~7 for ~x~pl~, 1n C.8. P~tant Sp~c1flc~t10n 809,0607
publ1she~ f~bru~ary 1~, ~959, b~ Th~s H~dl@~ ~ Co., Ltd~, ll.S.
P~t~nt 2,965,576, 1$SU~ OI~Cltlllb~ 20~ 1960 to E. R. ~11 son, ~nd
U~S. Pat~nt 2,703,79~9 ~ntho~ M. Seh~rtz9 1ssu~d Mareh ~, 1955,
25~nd U.S.~ ~ P-t~nt 1,985,q24~ 1ssll~d hc~ r 2S, 1934 to P1gg4tt,
~ch o~ ~1ch 1~ 1ncor~or~to~ h~rstn b~ f~r~ne~
In ~ pr~f~ pPoe~s~ ~or produc~ng N-alkyl or
~I-hy~roxgalbl, N~d~ox~glye1t~1 f~ttr ~cid ~d~s ~h~r~n th~
ct~ co~on~nt ts d~r1v~d fr~a glucos~ and th~ lkyl or
30~-h~dPox~ furleg10nallt~ ls ~N-~th,~ N~ hyl, N-propyl~
but~19 Nhydrox~-t1~1~ or` ~h~rox3p~pyl,l th~ produtt ls ~aade
by r~act1ng N~ or :N~hydrox~Qlk~l-glue~nl~ w~th a fatty
~t~r s~l~ctQd fro~ f~tt~ ~th~ t~rs, f~tty ~thyl ~st~rs, ~nd
f~t~ t~gl~c~r1d~s ~n th~ pr~s~ne~ of a catalyst selected frsm
35th~ group sonst$tlng of tr111th1~g phosph~t~, trlsod1um phosphate,
tr1potasslu~ pbospha~t~, totr~ssdt~ pyrophosphat~, p~ntapotllss1u~
.
W o 9~/~2629 2 1 1 1 ~ 9 2 PCT/Us92/04go2
11 -
tripolyphosphate, 1 ithium h~droxide, sod~um hydroxide, potassium
hydrox1de, calc1um hydroxide, l~thiu~ carbonate. sodium carbonate,
potass1um carbon~te, disodium t~rtrate, dipot2ssium tartrate,
sod1u~ potass1um tartr~te, tr~sod~um c1trate, tr1potass1um
c1trate, sod1un~ bastc s111c~tes, pot~sstunl bas1c s11~cates, sod1um
baslc alum1nos111c~tes. ~nd potas~1u~`b~s1c ~lum1nos111c~tes, and
~t%tur~s thereof. ~h~ a~o~mt of cat~1yst 1s pr~ferably from ~bout
0.5 ~ole X to ~ballt 50 ~ %, ~or- pr~f~r~bly fro~ ~bout 2.û ~ole
X to about 10 mol~ %, on ~n ll~alk~l nr H-hydroxyalkyl-sluc~m1ne
~olar basts. ~he: re-cl:10n ls pref~rably carr1ed out at froQI a~out
138^C to about ~70~C for typ1catly fro~ t 20 to about 90
~nut~s. When tr1g1yc~r1des :~r~ utll1zed 1n the re~ct10n ~txt~re
~s the fatty ester source, th~ r~act10n 1s a1so preferabty c~rr1ed
out us1ng from about 1 to about 10 w~1ght X of a ph~se transfer
; ~ 15 agent, ~1eut~ted on ~ we1ght p-rc-nt b~s1s of total react10n
ixture, selecte~ fro~ saturatad fatty alcohol polyethoxylates,
alkylpolyglycos1des, l~ne~r glyc-~d~ surf~et~nt, ~nd ~1xtur~s
; ther~of. ~: ;
; Pref2r~1y, th1s proe~ss 1s ~arr1~d out ~s follows:
~) ;préhe~t1ng the f~tty est~r ~o ~bout 138~C to about
170~
(b) tdd1ng :th~ N-a1kyl or N-hy~r~xy~lk~l glucaa1nQ to the
:heat~d f~tty:~c1~ ~st-r an~ ~1x1ng to th~-ext~nt n~ded
to for~ two~phas~ 11quid/11qu1d ~x~ure;
2S (c) ~1x1ng th~ c~t~lyst~1nto th~ rQact1on ~1xtur~; ~nd
~:~` (d)~ stlrr1ng for th~sp~c1fi~d r*act10n t1~.
Al~so~ pr~ferablr,~f ~ : ~bout~ ~X t~ ~bout 20~ of pr~for~d
11n~r ~ l bl/N-h~drox~-l bl,~H~11n-~r glucosyl f~tt~ ~c1d ~1d~
p ~ uet ~1s~ -dd~ to ~th : r~ct10n ~1xtur~, by ~ lght of th~
: 30 :r~act~nt~ s th~pha~s~ tr~nsf~r ~g~nt 1f th~ fatty ~st-r ~s ~
trlgl~c~r1d~ Th1s ~s-~ds~ th~ r~ct10n, thor~by ~ner~s1ng
reae~10n~::`rat~ A deta1t~d `~xp~ ent~1 proc~dur~ 1s prov1~d
~:~ : : b~lo~ tn~th--~Exp~r1~ent~
Th~ polyhydroxy ~atty:ac1:d~ ~u~1te ~t~r1~1s used h~re1n ~lso
off~r th~::adv~ntag~s:to th~ d~t~gent for~ulætor th~t they can be
~: :pr~p~r~d.~hol~ or; prl o r11y~fro~natura~, r n~bl~, non-p~tro-
WO ~2/22629 ~ 5 g 2 PCI/US92/~)4902
-- 12 --
chemical feedstoclcs and are degradable. They also exhibit low
toxici~ to aquatic li~e.
In one particularly preferred embodiment of the in~ention the
5 polyhydro~y fatty a~id amide materials are sourced from tallow
~t such that R2 is a C1s-(: 17 straight chain alkyl group.
It should be recognized that along wi~h the polyhydroxy fatty
acid amides of Formula (I), the processes used to produce them
will also typically produce quantities of nonvolatile by-product
10 such as este~amides and c~clic polyhydroxy fatty acid amide.
The level of these by-products will vary depending upon the
particular reactants and process conditions. Preferably, the
polyhydro~y fatty acid amide incorporated into the detergent
compositions hereof will be provided in a form such that the ~
15 polyhydroxy fatty acid amide-containing compositions added to
the detergent contains less than about 10%, preferably less than
about 4%, o~ ~clic polyhydroxy ~atty aci~ amide. The
preferred processes described above are advantageous in that
they can yield rather low levels of by-products, including such
20 cyclic amide by~product. ` ~ ;
The polyhydroxy fatty acid amide component is present at a
level of at leas~ 1.% by weight of the composi~ion, more
preferably at a ~level of from 1% to 10% by weight and most
25 preferably at:a level of from 2% to 6% by weight.
NonioniSurfactants
Laundry detergent compositions of the present invention
comprise~ addiSion to the polyhydroxy fatty ac;d amide
30 component, one or more of the nonionic surfactants describ~d
herein~ Ihe nonionic su~f~ctants described herein will
hereinafter by: re~erred to as "additional nonionic sur~actants."
Nonionic compounds other than these additioIlal nonionic
surfactants may:be optionally included in the nonionic
~: ~ 35 surfactaIlt system of:the~present:invention. These other,
op~ional donionic compounds~will~hereinafter be referred to as
opeional nonionics." Without` intending to be limited thereby,
; ~ ~
WC) 92~;!26~9 2 1 1 1 ~ ~ 2 P~/U592/04902
-- 13 --
it is believed that when such optional nonionics are included in
the nonionic surfactant system of the present invention, they do
not provide the unexpected stain-removal benefits already
described herein.
Additional Nonionic Surfactants
Primary Cl 1-Cls aliphatic alcohols condensed with an average
of no more than ~Ive ethylene oxide groups per mole of alcohol
comprise the additional nonionic surfactants useful in
o compositions of the present invention. Such alcohol
ethyoxylates should have an ethylene oxide content of less than
50% by weight and should be water insoluble.
A preferred aliphatic alcohol etho~ylate is a linear or
15 substantially linear aliphatic alcohol containing an average of
12-15 carbon atoms in the a~ chain, ethoxylated with an
average of three ethoxy groups per mole of alcohol.
The additional nonionic surfactant is present at a level of at
20 least 1~, preferably from 1% to 10% and more preferably from
;~ ~ 1% to 6% by weight of the composition.
The third essential component o~ laundry detergen~ -
compositions in ac~ordance with the invention is one or more
` 25 water soluble surfactants selected from anionic, cationic,
ampholytic and zwitterioniG surfactants.
`: : : :: ::
:
wo 92/226~9 Pcr~US92/0~902
æ~ 592 _ i4_
~QQi~-ctants
The laundry detergent co~pos1t10~s of th~ pr~sent 1nvention
can conta1n, 1n add1tton to the non10n~c surf~ctant sys~e~ of the
present 1nvent10n, on~ or more ~n10ntc surfactants as descr1bed
5 below.
Alkyl ester sulfon~t~ surf~ctants hereof lnclude l~near
est~rs of C~C20 carboxyl1c ~c1ds (t.e., f~tty ~1ds) wh k h ~re
sulfonat~d w1th g~s~ous S03 ~ccord1ng to ~Th~ Journal of the
A~r1~n 011 Ch~1sts Soc1~ty,~ 52 (1975), pp. 323~329. Su1t~ble
start1ng ~ter1~1s would 1nclud~ n~tur~l f~tt~ subst~nces ~s
der1ved fro~ t~llow, p~l~ otl, etc.
.The pref~rred ~lkyl ~stor su?fon~tQ surfAct~nt, espect~lly
for laundry ~ppl1c~t10ns, co~pr1s- ~lkyt ester sulfon~te
15 surf~ct~nts of ~he struetur~l for~u1~:
o
R3 - CN - C - OR~
I
S03M
20 ~h~re1n R3 1s ~ C8-C20 hgdroc~rbyl, pr~fer~bl~ ~n ~lkyl, or
coeb1nat10n th~r~of, R4 1s a Cl-C6 h~drsc~rb~ ref~r~bly ~n
~lkyl, or co~b~natton ther~of, and M ~s ~ cat10n wh1ch fon~s ~
~at~r solubl~ salt ~1th th~ ~lkyl ester sulfon~t~. Su1t~ble
s~lt~ h re1ng c~t10n~ 1nclud~ ~et~ls s~eh as sodt~v, potass~u~, and
2s 11thtuu, ~nd subst1tut~ or unsubst1tut~d ~4n~u~ c~t10ns, such
as ~ono~thuno1~n~n , d1-th~nol~1n~, and tr1eth~nola~1n~.
: : Pr~for~bl~, R3~ t~o~tl6~ ~lbl, ~nB ~ ts ~athyl, ethyl or
t soprop~ Esp-ct ~1 ly preferr~d ar- th~ ~eth~l ester sul fonates
:: ~her~1n R3 1s~CIo-CI6 21kyl.: ~
.
30 ~1~ ~
All~l,sul:,fat- surface~nts hereof ar~ ~ter soluble salts or
tctts of th~ fo~llla ROS03M ~here1n R pr-f~rably ~s ~ Clo-C24
hydroc-rbyl, pr~f-r~bly ~n~lkyl or hydroxyalk~l havtng a Clo-C20
~ alkyl eo~ponent, ~or- pr~f~r~bly Cl2-Clg alkyl or hydroxy~lkyl~
;:: 35 ~nd M 1s H or ~ ~c-tlon, ~.9., ~n alk~ t~l cat10n (e.g.,
: sod1u~, pot-sslu~, lith1ur), or a~Qntu~ or subst1tut~d ammon1um
: : ~e.g., ~ath~ th~ nd tr1~eth~1 a~on1u~ c~t10ns and
:: :
:: :
Wo 92/22629 2 1 1 1 ~ ~ 2 PC~/US92/0~902
quatern~ry a~non1um cat10ns such as tetra~ethyl-an~nium and
d1msthyl ptperd1n~um cat10ns and quaternary amnon1um cations
derived frcm alkylamines such as ethylamine, diethylamine,
triethylamine, ~nd mixtures thereof, and the ltke)~
A1kyl chains of 12-16 carbo~ atoms, more preferably 1~15 carbo~
atoms are preferred.
Alkyl ~l~koxyl~ted sulfate surf~ct~nts hereof are water
soluble salts er ~c1ds of the for~ula RO(A)mS03M ~herein R is an
o unsubst1tuted CIo~c2~ Alk~l or hydroxy-lkyl grc~p hav1ng ~ Clo-Cz
~lkyl co~Ponent, preferably ~ C12-C2~ ~lkyl or hydroxY~lkyl~ more
preferably an a~kyl group hav~g fro m 12 to 18 carbon a~Dnos~
especially ~rom 12 to 15 carbon atoms.
: ~ A 1s ~n ethoxy or
propoxy un1t, ~ 1s greater than ~ero, typ1cally betw~en ~bout 0.5
~nd ~bout 6, ~ore pref~rably ~etw~en ~bout O.S ~nd ~bout 3 " nd M
ts H or ~ e~t10n ~h1eh ean be, for exa~ple, ~ ~etal eat10n (e.g.,
sod1u~, pot~ss~um, 11th1u~, eale~u~,:magn~s1u~. ete~ ontum or
20 subst.tuted~mon~um e~t10n. Alkyl ethoxylated su1f~tes as well
: as alkyl propoxyl~ted sulf~tes ~re: eonte~plat-d here1n. Spée1fic
ex~ples of :subst1tuted:~ a~4n1u~ e~t10ns : 1nclude ~ethyi-,
di~ethyl-,~ tr1~ethyl-u~4n~u~ cat10ns ~nd qu~tern~ry a~onium
e~t10ns such as tetra~ethyl-a~on1~u~ and d1~thyl p1perd1n~um
e~t10ns ~nd:~:thos~ d~r1ved fro~ ~}k~ 1n~s sueh ~s e~hylamine,
: d1~thyl~tne,~ tr1ethylu~1ne,~ ~ixtures th~reof. and the llke,
: Prefe~d e3~amples~0f:aLkyl aDcoxyl~ sulfate surfacta~ts are the
C12~Cig~ a~ eth~cy sulf~tes cont ~i~ing all a~rerage of up to three
e~o~y groups~per mole of al~l etho~cy sulfate.
:: A par~icularly preferred~suffaclant is C12-C1s al~yl
polyetho~ylate (3.0) sulfà~o (Cl2-Cls E(3.~)M). C)ther e~cemplary
surfacta~s~ include C12:~ g all~yl poly~o~sylate (1.0) sulfate
(C12~l8 E(l-O)~M), ~l2-cl8 alkyl polyetho~cyla~e (2.25)
WO 92/22629 PCI /US92/0~902
2111~92
-- 16 --
sul~ate (C12-ClgE(2.25)M). C~2 Clg alkyl poly~thoxylat~ (3.0)
sulfa~e (C12~1gE(3 O~M), and C12-C1g alkyl poly~thoxylate (4 ût
~ulfat~ (C12-C18E(4.0)M), wherein M ~s canveniently selected froo~
sodtum and potass1um.
S 9 =,~5~
Oth~r anionic surfactants us~ful for d~t~rs1~e ~tlrposes can
als~ be ~ncluded 1n th~ l~undry dete~gent co~npos1t~ons of the
pressnt lnv~llt~on. ThesQ e~n 1nclud~ salts (1ncludtng, for
ex~ple, sod1u~ potasslum, anmon~u~, and subst1tuted an~non1um
salts such as ~ono~, d1~ and tr~ethanola~ln~ s~lts) of soap,
Cg~C20 1 lnear al kyl benz~neslll fonat~s, C~C22 pr1m~ry or secondary
~1 k~nesul fonates, C8~C24 ol ~fl nsul fon~tes, sul fonated
polyc~rboxyl lc ac1ds pr~p~r~d by sulfonat~on of the pyrolyzed
prod~lct of alk~llnQ e~rth ~tal c1tr~tes. ~9., ~s descr~d ~n
Br1 t1 sh p~tent spec1 f t cat1 on No . 1, 082 ~179, Cg-C24
alkylpolyglycol@thersulfates (cont~ln1ng up to. 10 mol~s of
~th!~len- ~ox1d~ lkyl glyc~rol sul~n~t~s, fatty acyl glyc~rol
- S~ll fOll~tGS ~ fatty ol eyl 91yc~rol sul f~t~s, al kyl phensl ethyl ene
ox~d~ eth~r slul~tes, p~rafftn sulfonat~s, alkyl phosph~tes,
20 1s~thlonates such as th~ acrl 1s~th10nates, H-scyl t~ur~tes~ alkyl
s~lcc1n~at~s ~nd sulfosuce~nat~s, ~sno~sSers of sulfosucc1n~tes
(~sp~ct ~l ~y saturat-d ~nd uns~turated Cl2-Clg monoest~rs )~ and
d~st~rs of sulfo~ucc1n~to~ (ssp~c1~ s~tur~t~ and uns~tur~lt~d
~6~S12 d1-st-rs), ac~l s~r~os~n~t~s, sulf~t~s of alk~lpol~s~cch~r-
25 1i~s such as tho sulf~ of alkylpolyglllcos1d~ (th- nontontc
non$ul~t~ eo~oun~ b~ng d~sr1b~ low), branch~ prtm~r~
ul fat~ 9 ~ and al k~l polyothox~ c~r~xyl at~ sueh as thoss ~f
th~ foraul~ CH2CH20)kC112tOO~ r~n R 1s a C8~C22 a1kylg k
t~ a~i~ 1nt~g~r fro~ O to lO, a~ ts a soluble s~lt-fomtng
30 : e~t~on. Res~n; ae~ds ~nd hyd~nat~ r~s1n ~c1ds ~r~ ~lso
su1t~bl~, sueh ~ ros~ h~ nat-d ro~1n, ~ s1n ~etds ~nd
~: : h~dro~nat~d~ r~s~n aet~s pr~nt 1n or do~1v~d fr~ tall o1~.
Fur~h~r ~ ~xa~l~ ar~ d~scr1b~ 1n Surfaee Aet1~R Ag~nts ~nd
t~ nts- (Vol~ nd~ II b~ Seh~ P~rry and B~rch). A
3S ~arl~t~ of such:sur~ct~nts:~rs ilso g~n~r~tly d1sclssed 1n U.S.
P~nt 3,929,6~8, 1ssu~ c~r 30, 1975 to L~ughl~n~ et al. at
:: :
WO 92/22629 , PC~/US92/0~1902
~1115g~
Colu~ 23, 11n- S~l thnu~h ~ol~_ 29, ltn 23 (h~r~t~ lncorpor~ted
by r~ nc~)~
Preferred a~omc sl~lcta~t systems employed i~ thc law~ry
de~ge~t composi~o~g Qf the iDve~on are frec of al~yl be~ene
s sulfonate salts. A highly preferred system comprises a m~xture of a
major proportion of a water-soluble C14-C15 alkyl sulfate and a ~or
propor~on of a C12~1s ~1 etho~ysul&tc co~ g an avera~c of
three etho~y ~roups por mole of allcyl ctho~y sulfato~ Thc laundry
detcrgene composi~o~ of the prese~t ~vcn~o~ typically eomprise
o from about 1% to ab~ut 20%, preferably from about 3ga to ab~ue
15% aDd ~ost prefc~bly fr~m 5% to 10% by weight of an~onic
s~.
Qth~r ~
~h- l~untry d~t~r~nt e ~ ~t10n~ ~ th~ pr s-nt ~nv~nt10n
~ lso cont~tn c~t10n1c, a-pholr~1e, z~1tt~rton1c, ~nt
: s~ pol~r ~urf~ct~nts
C~tton1c d~tart1 w surf~ct~nt~ su1t~bt~ for us~ ~n th~
t~undrr d~t~rg-nt e ~ ~1t10n~:o~ th- pr~-nt 1nv~t10n ~r- thos~
~ h~v1n~ on~ long~cb-1~ hydroc~rby7 g n up. xa pl~ of such
: ~ ~ 20 c~t10n1c surftct~nts 1nclud~ th~ surf~ct~nts such as
a1k~1d1~th~l u ~ontun h~logon1d~ nd tho~ surf~ct~nts h~v1ng
th- fornul~:
[R2~3)~ tOR~ 2R5 ~
:~h~ro1n R2 ~ n ~lk~l or ~lbl b~flz~ grou~ h-v1ng fro~ ~bout 8
t~ ~bout l~ ea~ ~to~ 1n tb ~lk~l eh~ ch R3 i~ s~l~ct~d
~group con-t~tl~ o~ ~CH2C~2-. -CH2CH(CH3)-,
-~N2tH(CN20~ CH2CN2~#2-, ~und ~1xtur ~ tho~of; ~ch R~ 1s
s~locS~ fr~ th group consl~t1~ o- Ct~C4 1k~19 Cl-C4 h~drox~-
lb~,~ b nR~l :rt~ structur ~ ~or ~d b~ ot~ g th- t~o k4 groups9
N a~N2~ h~xo~- or h~xo~o
polp~ h~ cul~r ~ght l~ th~ ~ t 100~, and
hyoroo~ ;not~ 0; R5, t~ th s~_ a~ ~ or 15 ~n ~11~1
ch~ hcr~n~th~:to~l ndor o~ car~ ~to~ of R2 plus RS 1s
not ~ th~ out 18;:-ach r~1- fro~ to ~ lO ~n~ th~ 5U~
o~ th~ lu~ fro~ a~ to~:~bout 15; a~d X 1~ an~ co~p~t~blQ
WO 92/22629 PCI /lUS92/0~902
. .
-- 18 --
Other cationic surfactants useful herein are also described
in U.S. Patent 4,228,044, Cambre, issued October 14, 1980,
tncorpcrated herein by reference.
b~hen 1nc1uded theretn9 the 1aundry detergent compositions of
the present inventlon typic~lly compr1se from 0% to about 25%,
preferably fro~ ~bout 3~ to ~bollt 15% by w~t~ht of such cat~onic
surf~etants.
Rmpholyt1e surf~ct~nts are ~lso su1table for use in the
1 aundry d~t~r~ent eompos1ttons of the pr~sent tnv~ntlon. These
surfae~nts can b~ broadly descrlb~d ~s aï 1ph~t1c d~rivat1ws of
s~eondary or tert1~ry ~n~1n~s~ asn ~ltphatte d~r~YattY~s of
het~roeyel1e s~con~ary and tert1ar~ a~1n~s ~n ~h1ch the ~llphat1e
radt~al ean be stra1ght- or ~anch~d-ehaln. One of the ~11ph~t1c
su~stttuents eont~ns at l~ast about 8 e~rbon ~toms~ typically
1~ frOffl 2t~0ut R t5~ ~bout 18 earbon ~tOMsl and at le~st one eont~1ns
an an10n~e ~ter~solubll lzlng gro~p, ~.9 ~, e~rboxy, s~l fon~te,
sulfate. Se~ U.S. Pat~nt Ho. 3,929,67~ to Laughlln ~t al., issued
û~ee~ 30, 1975 at eolu~ l9, 11n~s 18-35 (her~1n 1neorpor~ted
by r~ferenc~) for ex~mpl~s G~ ~pholyt1c surf~ct~nts.
~h~n 1nclucled thQr~ th~ l~undr~ detergent composit10ns of
the present 1nvent10n typlc~ co~pr1s~ fro~ OX to about, 15%,
pr~ferabl~ fro~ about 1% to a~out lOX b~ ~ight of such ~mpholyt1e
surfAet~nt~;.
1tter10ntc surf~ct~llts ~r~ also su1table for ~se 1n lwndry
d~t~ nt coapos1t10ns. Th~s~ sur~ct2nts can b~ broadly
dl~scr1b~d as der~va~1v~s of s~eondary nd tcrt1~ry a~tnes,
d~r1~t1v~s of h~t~roe~el 1e $~on~ry and tert1;~ amtn~s1 or
r~ t1v~s of ~qu~t~ar~ u~on~, q~l~t@rn~r~ phosphon1u~ or
t~rt1ar~sr sulfon~llQ eo~pounds. SQ~ U.S. P~t~l)t HO. 3,929,G7~ tO
:: : 30 Laugb~ t ~l., tssu~ c~r 30, l975 at eolu~ 19, 11ne 38
through eolu~ 2~, 11n~ ~8 ~h~r~1n 1neo~por~tQ~ by r~f~renee) for
~xa~ s o~ tt~r~on1e ~urf~ct~nts.
~h~n ~nelud~d ther~ln,: th~ l~undry d~t~ n~ compos1ttons ~f
the~pr~sent~ 1nvent~on ~ypteall~ eo~r1s~ f70fll 0% to about 15X,
~s pr~f~rab1~ fro~ ~bout 1%; to Ibout lOZ by w~1ght of such
2~t~t~r10~s1c surf~c~ants.
WO 92/22629 2 1 1 1 9 2 PCT/US92/04902
-- 19 --
Semi-polar nonionic surfactants are a special category of
non1 oni c surfactants whi ch i ncl ude wate7~- sol ubl e ami ne ox i des
containing one al ky1 motety of from about lO to about 18 carbcn
~toms ~nd 2 moiettes selscted from the ~roup consisting of alkyl
5 gro~ps ~nd hydroxy~lkyl groups conta~n~ng from about 1 to about 3
car~on atoms; wat~r-solub1e phosphlne oxldQs containing one alkyl
~oi~ty of from about lO to about 18 c~rbon atolns and 2 moieties
selected from the group cons~st1n9 of alkyl groups and
hydroxyalkyl grolJps cont~n1ng fro~ ~bout 1 to about 3 carbon
10 ~toms; and w~ter-soluble sulfox1d~s conta1n1ng one ~lltyl mo1ety of
from about 10 to ~bout 18 cArbon atoms and a ~1ety s~lect~d from
the group constst1ng of 21kyl ~nd hydroxyalk~l mo1et1es of from
~bout l to about 3 carb~ ato~s.
Semt-polar non10nic deterg~nt surfactants include the amine
lS ox1de surfactants hav1ng th~ formul~
o
R3(oR~)xN(R5)2
~here1 n R3 i s an al ky.l, hydroxyat kyl, or al kyl phenyl group or
~o m1xtur~s thereof cont~1n1n~ fro~R about 8 to about 22 c~rbon ato0s;
R~ is ~n ~lkyl~næ or hy~rox~alkyl~n~ group conta~n1ng from about 2
to ~h~Jt 3 c~rbon ato~s or ~xt~lr~s th~ sf; x ~s fro~ O to a~o~t
3; ar.d Qach RS 1s an albl or hydrox~alkyl group conta1n1ng from
about 1 ~to about 3 c~rbon ate~s or 2 polyethyl~ne oxtde group
cDnt~n1ng fr~ a~out 1 to about 3 ~thyl~nlt ox~d~ grollps. Th~ 1~5
groups c~n ~ ~tt~eh-d to ~ach othQr~ ., through ~n oxyg~n or
nltrog~n at~, to fQ~ ~ r1Rg structur~.
h~s~ 1no ox1de surf~ct~nts 1n p~rt1cul~r ~nclude C~o-Clg
a~k~rl d1~thrl ~1n~ ox1d~ and C~-C12 alkoxy ethyl d1hydroxy
~thyl ~1n~ ox~des.
~hQn ~nsludl!d th~retn, th~ ~aundr~ d~t~rgent eo~pos1t10sls of
~` th~ presont tnventton typ1cll11y c~pr1s~ fro0~ ~X to about 15%,
pr@~-rably fro~ ~bout:lX to abo~t lOX by ~e~ght of suoh sem1~polar
non10n1c sur~ctants.
3S
wo 92/22629PCr/US9~/04gO~
'~1 1 15~2
-- 20 --
~lg~ .
~h~ 1aundr~ deterg~nt compos1t10ns of th~ present invention
c~n comprts~ lnorg~niC or org~n1c daterg~nt bllilders to ~ssist in
~1n~ral har~n~s contro~.
5Th~ l~v~l of bu11d~r oan v~ry ~1d~ty dep~nd1ng upon th- ~nd
us~ of th~ co~pos1t10n and 1ts ~1r~d physlc~l fon~. L1qu~d
for~u1attons typ1c~ c~r1s- at to~st lbout 1X, ~or~ typlcally
fro~ ~bout 5X to ~b~ut 50X, pr-f r~bly ~bout 5X to ~bout 30%, ~y
~lght of d~t~r~ont bu11d~r., Br~nul~r for~ t10ns typ1c~11y
10co~pr1s- ~t l~st ~out lX, ~or~ typ1c~11y fro~ ~bout lOX to ~bout
80X, p f~r-bl~ fro~ ~out 15S t~ ~ut ~0% ~ ~1sht o~ the
~t4rg~nt bu11~r. L~r ~r h1ghor l~wl~ of bu11d-r, hs~oY~r,
~r~ n~t ~nt to b xclut~.
Inorg~n1c d~targ~nt ~u1td-r~ 1nelud~, but ~r~ not 11~1t~d to,
th- ~lk~11 ;~t~l, ~on~ anolu~ s~lts of poly~
phosphatos~ x- pl1f1-d by tho tr1pol~pho~ph-t~, p~rophosph~t~,
nd gl~ssy pol~r1c~t-~phosph~t-~, pho~phon~t~, phyt1e ~c1d,
s1t1cat~. c~hon~ta~ ~ ~1ncluding b1c~on~t~s ~nd s-squt~
carb~n~u), su~f~ and~ 1no~11tcat~. V~rat-bu11d~rs, ~s
20~1 ~s bu~ldors conta1n1ng b~r~t~-for~ng ~t-r1~1s th-t c~n
prod~ bor~t~ ~ unt~r d~targ~t storag- ol ~sh cond1t10ns
ab~t SO-C,~ e~i~lb; ~e~ t~ ab~ 4~G Pre~ ed buildé~
o 1~ of
. ~
25EJUUIj1 Ot ~111c~1~n~ro tho alkat1 ~t~t ~11c~t~,
n~ p~rt1e~:~rl~ tho~ h-Y1ng~ - 5102~ 20 r~10 11l th- r~ 1.6:1 to
: ~ ~ I.2~ c~t~s, Juch ~ th~ d sod1u~ s1l1e~tQs.
~;
`: :
~ ~ .
::. : :: :
wo 92/~262~ i 9 2 PCr/USg~/0~902
-- 21 --
Preferred crystalline layered sodium silica~es have the ge~eral
formula
NaMSixC)2x~l YH20
s
wherein M is sodium or hydro~e~, x is a number from 1.9 to 4
and y is a number from 0 to 20. Crystalline layered sc3dium
silicates of this ~pe are disclosed in l~P-A-0164514 and methods
for their preparati~n are disclosed in DE~-A-3417649 and DE-A-
~o 3742~43, irlcorporated herein:by reference. For the purposes ofthe present i~ventisn, x i~ the general ~ormula aboYe has a value
of 2, 3 or 4 and is preferably 2. More preferably M is sodium
and y is 0 and preferred examples of this ~ormula comprise the
~ -, B - ~ - and ~ - forms of NazSi2C)s. These materials
lS are available from ~Ioechst AG ~G as respecti~ely ~aSKS-5,
NaSKS-7, NaSKS-11 a~d NaSKS-6. The most preferred material
is ~ -Na~Si2Os, NaSKS~6.
20 Other silicates may also be useful such as fo~ example magnesium
silicate, w~ich can senre as a crispe~ing agent in gra~ular
formulations, as a stabilizirlg age~t for o~yge~ bleac~es, and as a
compo~e~t of suds control systemis.
:
;~5 E~amples of carbonate buildors are the alkali~e earth and alkali
mstal carbonates, includ~ng s~dium ~arboaate and sesqui-
1 ~
:: ::
:
`: ` :
~, ~
W(:) 92/2262g PCI~/~lS9~/04902
2111S~2
-- 22 --
carbonate and mixtures thereof with ultra-fine calcium carbonate
as disclosed in German Patent Appl~catlon No. 2,321,001 published
on November 15. 1973, the dlsclosure of which is 1ncorporate~
herein by reference.
Aluminosil1eat~ bu11d~rs are ~spectally useful in the present
~nYent10n. Aluminosil k~t~ ~uilde~s are o~ 9reat importance in
~ost curr¢ntly ~r~et~d h~vy duty ~r~nul ar detergent
compostt10ns " nd c~n also b~ a s1gn1f1cant builder ~ngr~dient in
llqutd detergent formulat10ns. A1u~1nos~1~cate builders include
thos~ hav1ng th~ ~mp1r1cal formula:
MZ(~1O2~YS~O2~
~h~r~in M 1s sodlum, potass1u~, ~m~on~ or subst1tuted ammonium,
z 1s fro~ about 0.5 ~o about 2; ~nd y 1s 1; thts mater1al having a
~a~nestu~ 10n exch~ng~ capae1ty of at l~ast ~bout S0 milligr~m
1~ ~q~lvalents of CaC03 har~n~ss p~r gr~m of ~nhydrous alumino-
s1tlc~te. Pr~f~rred~alu~1nos111eates ar~ zeolltQ bui1ders wh1ch
: h~v~ the for~ula: :
Naz~Alo2)z(slo2)yl-~H2o
: : ~h~rein z and ~ ar~ tnt~g~r~ of ~t l~st ~, the mo1~r rat10 of z
to y ts in the rang~ ~rom 1.0 to about 0.5, ~nd x ~s an in~eger
. froQ ~out l5 to about 2649
Us~f~l alU~RoS~11C~t~ 1On exch~nge mater1ak are
~ eo~m~rc1~ Y~11ab1~. Th~s~ ~lu~1noxl~1cat2~ c~n b~ crystall1ne
: ` or a~orphous 1n struetur~ and~can b~ natura~ly-occurr~ng ~lumino~
: 25 : s11~c~t-s or~ ~ynth~t1c~ d-rtv~d. A m~thod for produe1ng
1u~tRos11~eat- 1On;~xcha~g~ ~tQr1~ls ts d1sclos~d 1n U.S. P~tent
3,9~,66~ Kru ~9 ~t~ 1ssucd ~stobær l2, 197$, 1ncorporated
:h~ M~n ~ ~r~oer~nco~. : Pr~farr~d synth~t1e c~st~ll1ne ~l~miRo-
tleat2 1On~ èxehan~ ~at~r1~1s usaful h~r~tn Are avail~blè under
:: ` 30 ~ th~d~s~gnat1Ons Z~oiit-~A, 2~ol1t~ )t ~nd Z~ol1te X. In ~n
ssp~ pr~f~rr~d~ ~nbod~nt, th~ eryst~lline alum~nosll k~te
on oxehanga Mat~r1~1 has tb~ for~ula:
N~l2lg~ 2ts1o2)~2}-xH2o
: ~h~re1n x 1s::fro~ about ~O to:about 30~ espgc1all~ about 27. Th~s
~ateria1~ 1s kno m~ as~eo1ttQ A. ~ref~rabl~, the aluminosil~cate
has ~ p~rt1c1~ s1ze of~ou~t Q.l-lO ~crons 1n d1~meter.
: ~ : : ::
: ~ :
W0~2/22629 2111~ ~ ~ PCI/US9Z/04902
-- 23 --
Specific examples of polyphosphates a~e the alkali metal
tripolyphosphates, sod~um, potassium an4 ammonium pyrophosphate~
sod1um and potasstum 2nd an~nontum pyrophosphate, sodium and
pot~ss1um orthophosphate, sotium polymeta phosphate in wh~ch the
degree of polymer1zatton r~nges from ~bout 6 to about 2~, and
salts o~ phyt~c ~c1d.
Ex~mples of phosphon~t0 bu11der s~lts ~re the w~ter-soluble
s~lts of eth~ne l~hydroxy~l,l-d1phosphonatQ p~rt1cularly the
sod~u~ ~nd pot~sstum s~lts, th~t w~ter-soluble s~lts of methylene
d1phosphon1c ~c1d e.g. th~ tr1:sod1u~ ~nd tr1pot~ssium salts and
the w~ter~so1uble s~lts of subst1tuted mQth~len~ d1phosphon~c
~c1ds, such as the trtsod1um nd tr~pot~ss1um ethyl~dene,
1sopyropyl1dene b0nzylmethylid~ne ~nd h~lo methyltdene
phosphonates. Phosphonatc bullder s~lts uf the aforementloned
types ~re~d1sclosed 1n U.S. P~tent: Nos. 3,159,581 ~nd 3,213,030
; : 1ssued D-cem~er 1, 196~ ~nd Octoh r 19, 1965, to D1ehl; U.S.
;; P~tent Ho. 3,~22~,021 1ssucd J~nu~ry 14, 1969, to Roy; and U.S.
P~tent Nos. 3,400,1~8 ~nd:3~22,137 1ssuQd Sopte~b~r 3, 1968, ant
J~nu~ry 14, 1969 to ~u1~by;,` s~1:d d1sclosure~ betng tnc~rporated
h~re~n by~r~ference. ~
::~ Polyc~rboxyl~t~ ~ bu11der :c~n generally b~ ~dded to the
compostt10n~1n~ac1d for~,~ b~t:c~n:~lso b~dd~d 1n the form of a
neutr~ ed:~s~1t. ~ben ùt111z d~1n:salt for~, ~lkil1 met~ls, such
s~s~od~u~ pot~ss~u~ and~ 1th1~u~;s~1ts, ~spec1ally sodi~um salts~
: 2~ or ~ ~ n~u~and:subst1tuted~a~on1u~ (~.9., ~lkanolammon1um) s~lts
Incl:ud J~a~ong:~the po1yc~r~oxy1~t~ bu11d~rs ~re ~ var1ety of
c~t ~ 1es~of~usefu1 ~atcr1a1s.i Ona tQport2~ c~tegor~ of poly-
cs ~ x~1~t~ u1lders~ neo~p;~s~os th~th~r pol~c~rboxyl~t¢s. A
~ ~nu~r:~o~ether~po1yc~rbox~1~t~s havc b~n d1selosed for us- ~s
;d~terg~nt~:bu11:de~s~ Exa~ples~ of~ us~ful eth~r polycarboxyl~tes
;tnclud~ ~oxy~t~:uec1nat~ s :d1~sclos~ :tn B~rg, U.S. P~tent
3,128:~287,~tssued~Apri;l ~,: 196~ nd L~bert~ ~t ~l., U.S. Paten~
3.63~,83~,~1ssued~January~I8,~1g72, both of wh1ch re 1ncorporated
:: 35 ~here1n by~r~fer~nc~
WO 9~/22629 PCI/U~;92/04902
!3 2
A specific type of ethen polycarboxylates useful as builders
1n the present lnventiOn also include those hav~ng the general
formula:
CH~A~(COOX)'CH(COOX)-a-C~(COOX)~CH~CQOX)(B)
S ~herein A is H or OH; B ts H or -O-CH(CO~X) CH2(COOX); and X is H
or a salt-forming cat10n. For ~xam~ f ln thQ above gensral
formul~ A and B are both H, then th~ comp5und ~s oxyd1ssuccinlc
acid and 1ts w~t~soluble s~lts. If A ls OH and B 1s H, then the
compound 1s tartrat~ ~onosuccln1c ~c1d (TMSJ and 1ts ~lter-soluble
sllts~ If A 1s H ~nd B 1s -~-CH(C~OX)-CHz(COO%~, then the
eompound 1s tartrate dlsucc1n1c acid ~DS) and 1ts w-ter~soluble
salts. Mixtures of thQse bu11ders ~re esp~c~lly pr~ferred for
us~ hereln. Part1cular1y preferred ar~ mixtures of TMS and TDS in
a weight rat1O of TMS to TDS of fro~ about 97:3 to about 20:80.
lS These bu11ders are d1sclosed 1n U.S. P~t~nt 4,663,071, 1ssued to
Bl~sh ~t ~1., on May S; 1987.
Sui tabl e ether pol yearboxyl ~tes ~1 so 1 ncl ude cycl i
cs~po~nds, p~rt1cularly ~11eycllc co~pounds, such as those
deser~b~d tn U.S. Pat~nts 3,923.679; 3,V835~163; ~,158,63S;
4,120,874 and 4,1029903, all of wh~ch ar~ incorp~rated her~in by
r~fer~nc~
Other us~ful det~rg~ncy bu11d2rs include the ~ther
hydroxypolycarboxylates repr~ent~d ~y th~ structure:
HO- tC ~R) (COOM)~-C (R) (COC3M~ ~OJr,-H
~her~1n M ts hydro~n or ~ c~t1On where1n the result~nt salt is
~at~r-sQ~uble, pr~f~r~bl; an alk211 ~t~ ontu~ or subst1tut~d
: a~o~ cat1On, n 1s fro~;a~out 2 to about 15 (preferably n is
fro~ about 2:to about 10, ~or~ pr~f~rably n ~v~rages fro~ abo~t 2
1` ~
to ~bout 4) ~n~ ~ch R 1s th~ s~ or d1ff~r~nt ~nd select~d from
hy~rog~n9 Cl.4 ~ or C~ subst1~uted alkyl (pr~fer~bly R 1s
h~drogen). ~
:: Stlll other ~ther pol~car~ox~l~t~3 lflclud~ copolymers of
~al~1e ~anhydrld- w1th ethyl~n0 or v1nyl ~ethyt ether~ l, 39
S~tr1hydr3xy benzene2, ~, 6-tr1sulfon1c acld~ ~nd carbo%ym~thyl-
oxysucc1n k ac1d.
:
:
WO 92/22629 2 1 1 1 ~ ~ 2 PCI'/U~92/04902
-- _5
Organic polycarboxylate builders also include th~ various
alkal~ metal, anmonium and substltuted an~nonium salts of poly-
acetl ac~ds. Examples of polyacetic acid builder salts are the
sod1um, potasslum, 11th1um, an~onlum and subs~ltuted amnonium
sat ts of ethyl ened1 ~mi ne tetra~c~t1 c aci d and nt tri 1 otri acetk
ae1d ~
Also 1nclud~d ~re polyc~rboxyl~tes such as mellitk ac1d,
succ1n1c ac1d, poly~le1c ac1d, b2nz~ne l,3,$-trtcarboxyllc ~c1d,
ben~zsne pentac-rboxyllc ~1t, ~nd car~oxymethyloxysuc~lntc acld,
1~ ~nd soluble salts thereof.
C~tr1c bu11ders, e.g.~ c1trlc ~c1d ~nd sc1ubl~ salts thereuf,
1s a poly~ar~oxylata bu11der of p~rt1eular 1Fport~nce ~or heavy
duty 11qutd detergent for~ulat10ns, but can also b~ used 1n
granular compos1t10ns. Su1tabl~ s~lts lnc1ude the metal s~lts
15 such as so~1um, 11th~u~"nd pot~ss1u~ sal-s, as well as ~mmonium
~nd substltut~d ae~4n1u~ s~lts.
Oth~r c~rbox~latQ bu11d~rs 1nc1ut~ th~ carboxylated
carbohy~rat~s d1sclos~d 1n~ U.S. P~t~nt 3,723,322, D1ehl 9 1ssued
M~rch 28, .1973, lneorpor~t~d her@1n by ref~renc~.
20 Also: su~table 1n th~ launtry deterg~nt composittons of the
pr~sent 1nwnt1~n ~re th~ 3,3-d1c~rbox~ oxæ~l ,6~h~x~ned10ates
and tha r~lat~d c~unds d1sclos~d 1n U.S. Pat~nt 4,566,98~"
~ush, ~ssued Janu~ry 2~, 1981;, lncorporat~ h~r~n~by refer~nc~.
~ ~ :Us~ful succ1n1c ac1t bu11t~rs tnelu~ th~ Cs~C20 alkyl succ1n1c; ~: 25 ac1~s and:~s~lts th-r~of. ~ part1cul~rly pr~f~rred compound of
th1~s ~ typ~ ~:ts d~c~n~lsucc1n1c ~e1d. Alk3~1 succtn1c ac1ds
c~ ar~ of tb~ g~ r~l for~ula R-CH(COOH)CH2(COOH) 1.~.,
i ~1v~tlv-s o~ succ1n1c:~ac1d, ~h~ R 1s hydroc~r~n, ~.9.,
Clo~C~o albl or lbnyl, pr~f~r~ly C12-ClC or whi~r~n R ~na~ b~
30 subst1tu~ w1th hy~rox~ s~ sulfox3~ or sulfon~ substltuents,
all a~ d@ser1b~ n ~th~ ~hv~nt10n d p~it~its.
h~ ~suee1nat~ bu~ r~ pref~bly us~d 1n th~ for7R of
t h~tr :~at@r-so~ui~ salts, tnelud1ng th6 sod~i~9 pot~sslu~,
iU~ and alkanol~ 1~ s-l~ts.
;~ : 35Sp~et~1e~ :exa~ s of: suee1nlt~ bu~ld~rs ~incluid2: lauryl-
succtnat~t; ~rtstylsuee1tt~t~ p~1~1t~rlsuec1nat~, 2idodi~c~nyl-
. ! . ` ;J . ~, C " t ~
WO g2/2262~ , . PCr/USg2/04902
2111~'qi~ ,
- 2~ -
succlnate (preferred), 2-pentadecenylsuccinate. and the like
Laurylsucc1nates are the preferred builders of this sroupl and are
describ~d in European PatPnt Appl1cat~Qn 862006gO.5/0,200,263,
publlshed November 5, 1986.
Examples of u~eful builders also ~nclude 50d1um and potassium
carboxymethyloxymalonate, c~rboxymethylox~succinate, cis-cyclo-
h~xaneh~x~carboxylate, c1s cyclop~nt~n~-t~tracarboxylate, water-
solubl~ polyacryl~t~s (these poly~cryl~tes hav1ng molecular
~1ghts to ~bo~e ~bout 2,000 c~n ~lso b~ effect1~ely ut11 k ed as
d1spers~nts), ~nd the copo~ymers of ~ate1c anhydr1de w~th vinyl
~ethyl ether or ethylen~.
Other su1ttble po1yc~rboxyl~t~s ar~ the poly~cet~l carboxy-
l~tes d1sc1Os~d tn U.S. P~t~nt ~ ,226, 0rutchflelt et al.,
1ssued March 13, 1979, 1ncorpor~ted h-re1n by reference. These
polyacet~l carboxylates c2n h prep~r~d by brtngtng together,
under polym~r1z~tton~eond1t1Ons, ~n est~r of glyoxyl1c ac1d and a
polymer1z~tton 1n1t1~tor. ~he result1ng polyacet~ carboxylate
~ster .~s then ~ttach~d ~to che~lc~lly stabl~ 2nd groups to
~: stab11tze th0 poly~c~tal c~rboxyl~te ~9~1nst rapidd~polymer1z~t1On 1n ~lk-lin- solut1On, converted to the
corr~spond1ng s~lt, ~nd addQd t~ - surfactant.
Polyc~rboxyl~t~ bu11d~rs ~r- also dlscloscd 1n U.S. Patent
. 3,308,067, O~hl, ~1ssud M~rch 7, 1967f 1ncorpor~ted h~rein by
r~f~rence.: Such ~t~r1a1s 1nclud~ th~ w~ter-soluble s~l~s of
ho~o- an~d~copoly~r~of:~l1phat1c carboxyl~c ac1ds ~uch ~s m~le1c
ac1d, 1t~con~c ~c1d, ~ ~con1c ~e1~, ~u~r1e ~c1t, aeon1t1c ae1t,
: : c1tracon1c acl~and ~thyl~ne~alonlc ac1tO
th~r org~n1c:~bu1lders ~honfi ln the ~rt c~n also b~ used.
For exa~plo,~ ~4noc~rbox~11c: ac1ds~ and solubl~ salts thereof,
0 :hav1ng lon~ oh~1n :h~ roc~rb~ls c~n b~ ut111z2d. these would
ncl`ud~ ~ater1~1s g~n~r~ r~ferr~d to as ~so~ps.~ Cha~n lengths
of ~lo-c2o ~-r~ typ1~cally ut111z~d. The hydroo2rbyls can be
s~t~rat~d or~:unsatur~t~
: 35 : D~t~rs1~ve enzymes~ ean b~tnclud~d 1n the l~undry detergent
: : co~po~1t10ns of th~ pres~nt~ nY~nt1on for a var1ety of reasons
W~ 92/22629 2 1 1 1 ~ g ~ PCr/U~92,04902
-- ~7 --
~ncluding removal of prot~in-based, carbohydrate-based, or
trtglyceride-based sta~ns, for examp1e, and prevent~on of refugee
dye trinsfer. The enzymes to be lncorporated ~nclude proteases,
amylases, l~pases, cellul~ses, and perox1dases, as well as
mixtures thereof. They may be of any su~table or19~n, such as
vegetable, an1mal, b~cter1al, fungal and yeast or1g1n. However,
the~r cho1ce 1s go~erned by sev~r~l f2ctors such as pH~ct1vity
and/or stab111ty npt1ma7 ther~ostablltty, stab111ty versus act~ve
det2rgents, ~u11d~rs and so on. In th1s respect bactert~l or
fung~l enzymes arQ pr~ferred, such as bacter1~1 amylases and
prote~s@s, 2nd fun~al ce11ulas~s.
Su1t~bl~ ~xampl¢s of prot~s~s ~r~ tho subt111s1ns wh1ch are
obt~1ned from part1cul~r str~1n5 of t.subt111s ~nd 8.11ch~ntforms.
Ano~her su1t~ble protease ls obt~1ned fro~ ~ stra1n of 8ac111us,
hav~ng ~x1~ ct1v1~y throughout th- pH r-n~ nf 8-12, dev~lop~d
and sold b~ Hovo Industr1~s A/S und~r th~ re~ster~d tr~de n~m~
Esp~rase. ~h~ prepar~t10n of thls ~nzym* and an~logous enzymes
~s deser~bed 1n ~r1t1sh pat~nt sp~c1f1cat10n No. 1,2~3,784 o~
Hovo. Prot~olyt1c ~nz ~ s su1t~bl~ h r r~oYlng prota1n-bas~d
statns that ar~ com~rc1~11y ava11abl~ :1nclud~ thos~ sold undQr
th~ traden ~ s ALCALASETM and ~AVINASETM by ~ovo Industrl~s A/S
(D~ ark) and HAXA~ASETM by ~nt~rn~t10nal 810-Synth2tlcs, Inc.
;~ (Th~ Noth~rlan~s).
Of tnter~st 1n th~ cat~gor~ of prot~olyt1c ~nzym~s,
.~,
gspae1ally~for llqu1d d~t~rgont eo~0o~1t~ons, ~r~ enzy~es r~f~rr~d
: to h~r~1n~:as ~rDt-as~ A and Prot~s~ ~. Pr~t-as~ A ~nd ~thodsfor 1ts p~par~t10n ~r dj~cr1~d 1n Europ~n P~t~nt Appl1c~t10n
: 130,7S6, publ1sh~d J~n~r~: 9, I985,~ tneorpo~atQd h~reln by
` r~f~r~nc~.: Prot-~s~ ~ 1s ~ prot~olyt1c ~nzg~ wh1ch ~1ffers fro~
,
~: 3~ Prot~s~ A tn that lt h~$ ~ l~uc1n~ subst1tut~d for tyros1ne ln
pos1tion 217 ln 1ts a~1no:acid s-~u~nc~. Prot~asæ B 1s d~ser~b~d
1n Europ~-n Pat@nt Appl1c~t10n S~rtal N~. 873~3761.8, f~led April
~: Z8, l987,; ~1ncorpor-t~ h~r-1n by r~ren~. Methods for
prepir~t10n o$ Prot~as~ ~ ar~ also;d1sclosed 1n Europe~n Patent
Appllcatlan 130,7S6, Bott et :al., ~ubl~sh~d January 9~ 1985,
;~ tncorporated~:hære1R by re~r~nc~.
(*see page ~7~ for Equivalent Application)
WO 92/22629 PCI/U~i92/04gO2
2~ r~ 28
Amyl~ses lnclude, for ~x~mple, ~-amyl~ses obtained from a
spectal str~n of B.llchentforms, d~scrlbed ~n more detail in
Br1t~sh patent spec~f~ca~10n No. 1,2967839 (N9vo), preYiously
tncorpor~ted here~n by reference. Anylolyt~c prote1ns ~nclude,
5 for exampls, RAPIDASETM, Intern-t~on~l B10-Synthetks, Inc. and
TERMAMYLTM, Novo Iodustr1es.
~ he cellulas~s usabl~ tn th~ pr~sent 1nv~lltlon lnclude both
bact~r1~1 or fungal cellulas~. Pr~f~rably, they wlll h~v~ a pH
opt1~u~ of b~tw~en 5 and 9.5. Sutt~bt- c~llul~s~s ar2 d1sclosed
~n U.S. Pat~nt 4~435,30t, ~lrbltsgo~rd et ~1., 1~sued March 6,
1984, 1ncorpor~ted hcr~tn by r~ r~nc~ whleh d1sclos~s fungal
cellulas~ produced f~o~ Hu~co1a 1nsol~ns. Su1t~bl~ c~l 1 ul ases
ar~ also d1sclos~ ln G~A~2.07S.428; G8~A~2.095.275 and
DE-OS~2 . 247.~32 .
Exal~ 5 of such c~llulaso~ i~ c-llula~cs produe~d by a
straln o~ Hu~1cola 1nso1~ns (H~1eo~l grts-~ var. ther~otde~),
p~rt1cularly th~ H~1cola str~1n O~M lgGO, ~ c~llul~ses produc~d
by a f~ngus of ~c111~s N or z e-llulas~ 2l2-produc1ng ~ngus
b~long~ng: to th- g-nus A-~n~ nd c~ las~ ~xtr~ctlt~ fro~ thc
h~pa~op~ncr~a~ of a ~r~n~ ~ollusc (Oolahlla Aur1cul~ Solimd~r).
Su1tabl~ ~îpas~ l~nz~ for d~tgrg~nt us~g~ 1nclud~ tho~e
produe~ teroorgan1s~ of tb- ~s~ onas group, sueh ~s
~s~ on~ ~tlltz2r1 A~CC 19.154, ~ d1sclos~d 1n Br1t1sh P~tent
No. 1~3?2,034, tlleorporat~d h~r~1n ~ r-f r~ne-. Su1t~bl~ l~pas~s
2S 1nclud-~thosQ ~ h s~0~4 a pos~t1v~ nolog1e~1 cross~r~et10n
~11th th~ 1body o~ th~ , pro~ue~ br th~ ~1croorg~n~s~
P~N~ooq7~ or~Jc~n* 1~ 1057. fh1~ ltp~s~ and ~ m~thod for
1t$ p~r1fteat10n h~vo b~on d~er1b~ 1n Jap~nas~ Pat~nt
~pplteat10n No~ 53~2045~ op~n to p~l1e 1nsp~ct10n on
Fabr~lar~ ~ :24, 1978.:: Th1~ llp~sa 1~ ~v~11abl~ fro~ ~no
har~aeulttc~l Co. Ltd., Hago~ J~p~n, u~d~r th~ tr~d~l n~e
L1p~s~ ~ano, ~ h~ n~ft~r r~f~m~ to at ~A~no-P. " Such
:~ 1:1pa~ o~ thl~ pr~s~nt 1nv~ 10ll should shs~ a pos1~1Ye
~_~olo~1cal cros~:r~ct1Qn ~1th th~ ~o-~ ant1body, us1ng th~
s~ a~d and ~ll-kno~ 1ffu~ton proc~durs~ accord1ng to
,
: Oucht~rlon~ ~Act~ d. Scan., 133, pa~ 76~79 (1950)), Th~s~
:-
Wo 92/22629 29 PCr/VSs2/04so2
3 2
llpas~, an~ a m~thnd for th~ir tn~nolos~c~l cross^r~ctton with
Amano-P, ar~ also dQscribed in U.S. Patent 4,707,291. Tho~ et al.,
lssued November 17. 1987, incorpor~ted here1n by referenc~.
Typic~l examples the~eof ~re th~ no~P l ~pase. the 1 ~p~se ~x
S Ps~udoloon~s fr~gl FERM P 13~9 ( ~va11 abl ~ und~r the tr~d~ name
Am~no~B), 11pas~ ¢x psu~doD~onts nitror-duc~ns Yar. 7 ipo~ cvn
FERM P 1338 ~v~11ab1~ undl~r th~ tr~ na~ ~ano-C~S), 1~pas~s ex
Chro~b~lcter Y15COSUII~, .9. ~ro~4~ct~r viscosu~ var. 11'po1yticu~
H~L~ 3673, c~rc1ally ~va~labl~ fro~ toyo Jozo Co., Tagah,
10 J~p~n; and furthcr Chr~b-ct~r ~lscogu~ 1 lp~s~s fro~ U.S .
B10ch~1c~1 Corp., U.S.A. and D1so~rn~h co~, ~h~ N~th~rlands, and
lipases ex Pseudomo~as gladioli. ~ especially pre~rred lipase
enzyme is manufactured and sold by Novo Irldustri A/~ Denmar~,
15 under the trade ~ame Lipolase (13iotechnology Newswatch, 7
March 1988, page 6) and men~ioned, along with other suitable
lipases, in EP O 258 068 (Novo), incorporated herein by
reference.
Perox1~as~ enz~ ~r~ us~ tn c~btn-t10n ~1th ox~g~n
- sourc~ Oq~, psrearbonat~, p~borat~ rsulf~t~, hytrog~n
p~rox1d~, ~tc. Th-~ ~rR us~d for ~solut10~ bl~ach1ng,~ . to
pr nnt transf-r of d~ or p1g~t~ r~v~ fro~ substratQs
dur1ng wash op-rat~on~ to otb-r sub~trat-~ 1n th- ~sh solut1~n.
~ ~ P~rox~as~ ~nz~ ar~ n 1n th~ srt, Afl~ tnclud~$ for ex~p1~
25 hors~ra~tsh p~rOX~l~a3~ gfl1na~ a0~ hatop~rox1~as~ sla~h ~s
chloro~ b~o-p~rox1das-. P~roxt~ c~nt~1n1ng d~torg~nt
eo~o~1t10Q~ a~ ~1~elo~d. for x~l~, ln P~T Int~rnat10n~1
Appl~ca~lon ~10 a9~0991~13, p~ h~ ~to~ 19, 1~a9, by 00 K~r~,
~t~gn~d to ~ovo In~u~tr~$~S9 lncorporat~ h~ b~ r~f~r~ne~.
30J~ t rang~ of ~ t~r121~ n~ for th~1r
1t,eo~por~t10r~ to: ~nth~1e~t~ nt ~r~n~ '18 ~t~o d1~clo~d
în U.,S. ~a~n~ 3,5S3,l3~, t~ J~u~ S, 1971 to ~cS~rt~ ~t ~1.
~neortor~t~ h~ b~ nhr~ ar~ furth~r ~t~el~
~: 1n VO~ Pa~ar~ Ns.~ ~,101,457, Pl~c~ ~t al.~ 1ssu~d July 1~, 197~,
2~A ln U.S0 ~at~nt 4,50~,Zl~, HIlgh~ u~ l~a~h 26, 198S, both
~nco~r~d h~ n ~r: ro1'~ . E~ ~a~sr1al~ u~ful ~or
l t~u1~ t~rgont fo~l~10r~ h0tr 1neor~orat10n 1nto such
` fo~ul~t10n~, ar~dl~elo~ U.S. P~ llt~ 8, Hora~ta~.,
~S3Ui~ Aprll ~l~, l9U~ so ~neo~nt~ har~ by r~f~r~nc~0
~ a~ ~ 1neo ~ l~v~t~ suff1c1-nt to
pro~1~ up to:::abou~ 5 ~ ~ ~ t~1eally about O~OS ~g
:
to ~ut 3 ~, of aetîv~ ~n~ p~ ~ra~ o~ ~h* eo~ tlon.
W O ~2/z2629 2 1 1 1 ~ '3 2 PCT/US~2/~4902
For granular detergents, the ~nzymes are preferably Coated or
prilled wtth additives inert toward the enzymes to minimize dust
formation and improve storage stabilitY- Techni~ues for
accompltshing thts are ~ell known in the art. In tiquid
c formul~t10ns, an enzyme stabilization system is preferably
uttlized. Enzyme stAb~llzat1on technt~uss for aqueous detergent
compostt10ns ~re we71 known in the art. For ex~mple, one
t~chnlque for anzy~e stabll1zatlon 1n aqu~ous so~utions involves
the us~ of free c~lc1u~ 10ns fro~ sourc~s such ~s calc1um ~cet~te,
c~lc1u~ formtte " nd c~lctum prop1On~t~. C~lctum 10ns can be used
1n co~bln~t1On w1th short ch~tn c~rboxyl1c ~e1d salts, preferably
fon~atos. See, for ex~mple, U.S. P-t~nt ~.3I8.818. Letton, et
al., 1ssued M~rch 9, 1982, 1ncorpor~ted heretn by reference. It
h~s ~lso been propos~d to us~ pol~ols 11ke glyc~rol and sorbttol.
: 15 Alkoxy~alc~hols~ dt~1kylglycoethers. mixtures of poly~ nt
~lcohols ~1th polyfunct10n~ ph~t1c ~m1nes (c~g., ~lk~nol~mines
: sueh ~s dtcth~nol-MIne, trleth~nol~m1ne. d1-1sopropanolamine,
etc~, and bor1c ~c1d or :~lkal1 m~t~l borate. Enzyme
st~btliz~t1On techntqu~s ar- ~dd1t1Onally ttsclosed and
ex~mpltf1ed 1n U.S. P~tent ~,261,~68, tssued Apr11 14, l9Bl to
Horn, et:-l., U. S. P-t~nt 3,600.319, tssued August 17, 1971 to
~: 6edge, et al., ~oth tncortorat~ here~1n by referenc~, and EuropQan
P~ttnt~ App11cat10n Publtcat1On Ho 0 l99 ~Q5, App11sat10n Ho
86200586~5, publ1shed October 2~, l9 6, V~neg~s Hon~borjc ~cid
~nd ~r-to ;st~111z~r~ ~r~ ~ pr~f~. Enz~e st~bll1~at10n
syst~ ~ ar also~ de~cr1~ed, for ~x~ll~, tn U S Pat~nts
"261,8a, 3,600,319, ~ ~n~ 3,519,570
Tk~ taundry~d~t~ nt co~pos1t10ns of th~ present lnvent10n
30 ~ ~r conta1n ble~ch1~ng ~ag~nts~or ~bl~ach1ng co~pos1t10ns conta1nlng
blcachtng ~g~nt ~and on~ or nor~ ~1Q~Ch ~et1~ators ~en ~nc~luded,
pr~s~nt blc~chin~ co~pounds ~111 typ1Gally co~pr1se f~om ~bou~ 1%
to ~ t 20. ~or~typ1c~ froo~about~ lX to abou~ 10%, of cuch
undry ~detergent co~pos~t10n In g~n~ral, ble~ch~n~ compounds
r~ opt10n~1~ compon~nts 1n n~n-llqu1d formul~t10ns, e g, granular
d~terg~nts If ~ pre;s~nt, ~the ~ount of bl e~ch ~ct i v~tors ~i l l
: : :
W0 92/22629 2 1 1 1 ~ 9 2 P(~/USg~/04902
-- 31 -- ,
typ1calty be fro~ ~bout O.lX to about 60%, ~ore typically trom
~bout 0.5X to ~bou~ ~0% of ~he ~le~eh1ng c~mposttton.
The ble~ch1ng ~gents us~d her~1n c~n b~ an~ of th~ bleaching
ag~nts us~ful for det0rg~nt co~positloFIs ln t~x~ cteaning, h~rd
5 . surf~c~ cl~an1ng, or oth~n el-~n1nq purpas~ th~t are no~ known or
b~co~ kno~n.
On~ e~t~or~ o~ ch1ng ~g~nt th-t e~ b~ u~ nco~ s~s
p~ar~o~l1e ~ctd bl-~eh1ng a~-nt~ alt~ th~r~of~ Su1tabl~
~x~1~5 a~ th;1~ ela~ Of n~nt~ 1nc1udl- ~gn-s1t~ ~no~roxy~
phth~lat~ hoxah~r~t~, ~ th~ aA9~s1u~ s~lt of ~t~chloro
p~rbcnzo1e ae1d, ~n~l~rl~lno~ xop~rox~ut~r1e ~c1t ant
d1p~nx~ c~n~d101c acj~. Su~ch bl~ a9~nt~ ar~ d1sclos~t
1n U.S. P~t~nt 4,~U,781, H~ su~d N4v~r 20, lg8~, U.S.
Pat~n~ A~pl1cat10n 7~ U* turn~ ~t al~, ~'11~ Jun~ 3, 198S,
Eunpa~n P~t-nt ~ppl1cat10n 0~133.3~ t a~., pu~11sh~
f~ruu~ 20, l98~. an~ U.S~ P~t-nt ~,~12,g3~, ehuns t a1., 1ssu~
~sv~r l, 19~, all of ~h1ch ar~ 1ncor~orat~ b~ r~f~r~nc~
hcrotn. 111ghl~ p~f~ bl~ch1ni~ ~g~nt~ algo 1nelu~ non~l
~1no6Joxop~ox~c~pn1e ~et~ u t--cr1~ 1n U.S~ P~t~n~
~,63~,S51~ su~ J~nu~ , l9~7 to Burn~"t ~ fleorpor~t~d
h~ro1n ~ f~r~nc~
The lauDdry detergent compositio~s of thc p~esent i~ention will
geae~ally ~clu~e:a peroxygcn bleaching age~t, usually a~
inorga~ic perh~idrate ~bloach, no~rmally in the form of thç sodium
25 salt.
Suitable~perhydrate ~leaches~;may be ~ of ~he inorganic salts
such ~as. perborate, percarbonate,: perphosphatc ~d peFsilica~e salts
but is co~re~tionally~ a~ all~ali:~metal~normally s~dium, pe~borate
30 ~ or: pe~carl bonate. Sodium pe~borate~ ca~ be iD the fo~m of the
monohydra~e ~of no~~ al formula; NaBOzH202 or the tetrahydrate
2H2~ 3~20 ~
Sodium percarbona~e, which ~is~ the preferred pe~hyd~a~e, is an
35 addition compound~ having~ a: formula correspond~g to
'Na2C~3^3~ d Is avallabb::;commercially as a crystalline
solid.: Mose commercia31y~available:material il~ludes a low level
of a heavy m*al sequestra~ such as EDTA~ l-hy~ro~sycthylide~e~
(*see page 57~ for Equivàlent ~Application)
:
wo 92/22629 2111 j 9 2 -32- PClr/US92/04902
1, l~iphosphonic acid ~HEDP) or aII a~phospho~ate, that lS
incorporated into detergent compositions during the manufacnuring
process. Although the percarbonate can be incorporated into
detergent compositions without additional protection, preferred
executions of such compositions utilise a coated form of the
material A variety of coat~ngs can be used. but the most
economical is sodium silicate of SiO~:Na2O ratio from 1.6:1 to
3.4:1, preferably 2~8:1, applied as an aqueous solution to give a
}evel of from 2% to 10%, (normally from 3% to S%) of silicate
o solids by weight of the percarbonate. Magnesium silicate can also
be included in the coatmg.
Pero~tygen bleaching agents are prcfcrably combu~ed wath bleach
ac~ivators, which lead to the L~ situ p~atuc~on in aqueous soluuo~
(i.e., duling the washing praccss) af thc pero~y acid corrcsponding
to the bleach acti~,rator.
,
A wide rangc of blcach ac~rators ca~ be us~d, e%ample~ be~ng
disclosed in Spadini et al USP 41793~. Preferr~t bleach acuvators
i~clute the ~ raacetyl alkylenç diami~es, pardcularly te~a~cetyl
ethyle~c diamine ~AED):and =c~yl glyc~uril (TAGU).
:
R - C - L ~,
h~r~1n R ts ~n alk~l group cont-1ntng f~oo ~bout 1 to ~bout 18
c~r~on ~toos ~h~r-1n th-~long~st t1n--r ~lkyl ch~1n ~xtend1ng f~om
nd 1~cluding~th- oarbonrl c ub~n:cont~1n- fron ~o~t 6 to ~bout
10 c~r~on~to s ~nd L:1s a 1~av1ng ~ ~ up, th- con~u~ate acld of
nh~ch h~ pK~ 1n th~r~ngo of~fr~ about 4 tD ~bout 13. Thcst
~ bl~ch~aet1v~tors~ ~ n :g-scrt~4J~1n U.S. PAt~nt ~,9lS,85~, tssuqd
:: ~pr11 10,~ 1990 to M-o, ~t al., 1ncorpor~t-d hQ ~ t~ b~ ref~renc~
U.S.~ t~nt~4,412,93~ h1 d ~ u pro~outl~ tncorpor~eJ
h~ n1n by r~f r nc~
; 0t~ehtnQ aj~ntx oth-r than oxyg~n ~ ch1ng g~nts ar~ ~ls3
bn~n :1n~th~rt ~nd~c~n;~ut111z-~h-~ 1n. On~ type of non-
oxr~ bl~a d ing~ g-nt of p~rt1cu1-r 1nt?~re~t 1ncludes photo-
a~t1vat d:~bl~sh1~9 ~gant~ :s ~ ~ th- sulfonat~d z1nc andtor
al~-1nu ~phth~oey~n1:n~ Tbos~ t~r1als a n ba depos1tcd upon
~ t?ha s~b~tr~tc~dur1ng th~ w~h~n~ proc-gs~ Upon 1rrad1at10n ~1th
11ght, 1n~:th~pr~s~nc~ of ~G~r9~n, sueh as b~ h-ng1ng cloth?~s out
t~ d~ 1n th~t~yl1gbt, th~:~sulfon~t~d z1ne phthalocyan~n~ ~s
~ct1~tcd ~n~ con~*qu~t1~, tha sub~tr~t?a t~ bl ~ - ?Ch~ . Pref~rr~d
.
W ~ 92/22629 2 1 1 1 5 9 ~ PCT/US92/04~02
ztnc phtha1Ocyanine and a photoactivated bleaching process are
described ln U.S. Patent 4,033,718. issued July 5, 1977 to
Holcomb~ et al., incorpor~ted herein by reference. Typically,
d~tergent composit1Ons will conta~n about 0.025% to about 1.25%,
by ~eight, 9f sulfonat~d xlnc phthalocyanine.
Po1vmeriç ~Qil Rels~s~ Aaen~
Any po1ymer1c so~1 r~1eas~ agents known to those sk111ed in
the ~rt can b~ e~ployed ln th~ l~undry detergent compos1t1Ons of
the present 1nv~nt10n. Polym~rtc soil rele-se agents are
charact~r12ed by ha~1ng both hydroph111c segments, to hydrophiltze
the surf~c~ of h~drophob1c f~bers, such ~s polyest~r ~nd nylon,
and hydrophob1c seg~ents, to depos1t upon hydr9phob k f~bers and
r~aln ~dhered thereto through comp1et1On of ~sh1ng and rinsing
cycles ~nd, thus, serYQ as an anchor for the hydroph~11c segments.
I~ Th1s can ~nabl2 sta1ns oceurrlng su~sequent to tre~tm~nt w1th the
: so11 rel~as~:agent t~ b~ ~ore eas11y cl~ned 1n 1ater wash~ng
proc~dures.
Poly~er1c so11 rel~s~ ~g~nts 1nclud~ c~llulostc d~r1 Yat1 ves
su~h ~s hydroxyether cellulos1e polym~rs~ copol ~ rlc blocks of
2~ ethylene terephthal~te ~ or propyl~ne t~rephth~l~te ~ith
polyethylen- oxtd~ or polypropylen~ ox1d¢ t~rephth~late, and the
11k~
.. C~ 10s1c dertvat1v~ :th-t ar~ funct1On~1 ~s so~1 r~ se
agents ~r- com~erc1~11y~ av~ bl~ and lnclud~ hydroxyethers of
~ : 25 cellulos~ such ~s M~thoc~lR (Oo~.
: : CQllul~os1e so~t~ r~ s~ ~ag~nts ~lso ~nclude thos~ s01ect~d
ro~ t~ group co~s1st1ng oP CI~C4 ~lkyl ~nd ~4 hydroxy~lkyl
: : c~11ulos~su~lh ~ thy1c~11ulos~ th~1c~11ulss~, hydroxypropyl
hjlc~lt~los~, ~n~ hyd~oxybutyl ;~th~lc~llulos~. A v~r1~ty of
call~l~se~ rtv~ttv~s~ ~u~s~f~l a~ so11 r~l~as~ p91ym~rS are
~ d1~selosed 1n U.S. P~t~nt ~,~oo,on. lssu~ Oecember 28, 1976 ~
N1~col, Qt:al~,:1ncorpor~t~d h~rsin by r~r~ncQ.
So11 ~:r~leas~ ag~nts ch~r~ctor12~d by poly(v1nyl ester)
hydrophob~:seg N nts~1nclud~ gr~ft~Gopoly~rs of poly~vlny1 ester),
: : 35 e.g., CI-C6~v:~nyl::esters, pr~r~bly pDly(v~nyl acetate) grafted
onto poly~l bl~n~ ox1d~ b~ck~on~s~ such as polyethylene oxtde
WO g2/22629 PCII/US92/04902
2 ~
- 34 -
bac~bones. Such materials are known in the art and are described
in European Patent Application 0 219 ~48, publlshed April 22, 1987
by Kud, et al. Suitable cor~nercially available soil release
agents of this k1nd ~nclude thQ SokalanTM type of material, e.g.,
S Sok~l~nTM HP~22, avail~ble from BASF (llQst Germ~ny).
One type of preferr~d s~il rel~ase a~ent is a copolyner
h~ving r~ndom blocks of ethylQn~ tQrephth~late and polyethylene
ox~de (PE0) terephth~t~te. Mor~ sp~cif~cally. these polymers are
campr1sed of repe~t1ng un1ts of ~thylen~ terephthalate and PE0
terephthal2t~ ~n a mole r~t10 of ~thyl~n~ t~r~phthalate units ts
PE0 terephthalate units of from ~bout 25:75 to about 35:6~, said
PE0 terephthalate un1ts contaln1ng polyethylQne oxite h~Ying
~olecular weights of from about 300 to ~bo~t 2000. ~he ~olecular
we19ht of th~s polymer1c so11 rel~as~ agent ls in the range of
fro~ about 25,000 to ~bout 55,aoo. Se~ U.S. Patent 3.959,230 to
~ys, tssued May 25, 1976, ~Ih1ch ~s 1ncorporat0d by referenoe.
Se~ also U.S. Patent 3,8g3,929 to Bas~dllr 1ssu~d July 8, 1975
(1ncorpor~t~d b~ refl!ranc~ ~hlch d1sclos~s s~11ar copolynwrs.
Another preferred po1~mertc soll rel~s~y ~gent ls a polyest~r
w~th repeat un1ts of ~thylen~ ter~phth~ te un1ts containing
10~15% by we1~ht of ~thylen~ t~rephthalat~ un1ts togethe~ wi~h
90-80X by we~ght of pol~oxyel~hyl~ t~r~phthalat~ un1ts, deriYed
fro~ a pol~roxyethyl~n~ glgco1 of averag~ ~olec~ r ~eight
300-5,,000, and th~ r~t1O of ~th~l~ne tQr~phthal~te un1ts to
2S polyoxy~th~ n~ t~rsphthal~t~ un1ts ln ths pol~r1c eompound i s
b~tw~n 2~ nd 6:1. x~1~s of th1s po~ r include the
: eo~Qre1~11y ava~la~ at~r1al Z~lconR 5126 (fro~ D~pont3 and
~11aas~R T ~fro~ ICI). ~h~s~ pol~rs and m~thods a f their
pr~p~r~t1On ar~ full~ d~scrtb~d ln ~.S. Pat~nt 4~702,8577
~ssu~d Octob~r 27~ 19~7 to 6OssQ11nk, ~1eh 1s 1ncorporated herein
by r~r~nc~. ~
Another preferr~d pol~r1e so11 r~lease ag@nt i c a
~sulfon~t~ product of: ~ subst~nt1ally 11near es~er oligomer
conpr1sed of an oligo~rtc ~s-~r b~ckbon~ of terephthaloyl and
oxyalkyl~neoxy re~e~t un~ts ~nd ter~1nal mo1~t1es covalently
~tt~ch~d to th~ b~cl~bon~f s~1d so~ BS~ ~gent b~1ng der1ved
:
W O 92/22629 PC~r/~lS92/04902
from allyl alcohol ethoxylate t dimethylterePhthalate. and l.2
propylene diol, ~herein the terminal moieties of each oligomer
have, on average, a total of from about 1 to about 4 sulfonate
groups. These soil releas~ agents are described fully in U.S.
Patent Sg684~l~ 1ss~ed 6 ~nvemberl9~0 to J. J. Schei~el and
E. P. Gossel1nk, U.S. Ser1~l No. 07/47~,709, f~led January 29,
1990, 1ncorporated here1n b~ ref~rencR.
Oth~r suitable polymeric so~l r~lease ~gents include the
ethyl- or methyl-capped 1,2-pr4pyl~ne ter~phthalate-polyoxy-
ethylene terephthalate polyQsters of U.S. Pat~nt ~,711,730, issued
D~c~mber 89 1987 to Goss~11nk et al., the ~n10n1c end-capped
c11gomerlc esters of U.S. P~tent q,721,5tO, 1ssued J~nu~ry 26,
1988 to Gossel1nk, ~he~1n the an~on1c end-caps compr1se
sulfo-polyethoxy groups der1v~d from polyethylan~ glycol (PEG),
the block polyester ol1gom~r1e co~puunds of U.S. Pat~nt ~,7G2,857,
1ssued OctaDer 27, 1987 to 60sselgnk, h~v~ng poly~thox~ end-caps
of th2 for~ul~ X-(OCH2CH2)n- whereln n 1s fro~ 12 to ~bout 43 and
X 1s a Cl-C~ alkyl, or pref~rably ~thyl, all o~ these pat~nts
be1ng 1ncorporated here1n by refer~nce.
2~ Addlt10nal soil rale~s~ pol ~ rs 1nclud~ the so11 r~l~ase
polymers of U.S. Patent 4,877,896, lssu~d October 31, 198~ to
~1~1da~lado ~t al., ~h~eh d1selos~s an~onte, 2spoe1~ sulfo~royl,
: ~ ~nd~e~ppe~ ter~phth~latQ est~rs, s~1d pat~nt b~1ng 1neorpor~ted
hel~e1n b~ refer~ne2. Th~ ter~phthal~t@ esters conta~n
uns~netr1eall~ su~stltute~ ox~1,2 alk~leneoxy un1ts.
I~ ut111zed~ sotl r~ * ~g~nt~ nsr~lly eompr1se fro~
~bout 0.01X to ~bout 10.0~9 pr~f~rab1~ fro~ about 0. lX to ~bout
5.0X,~ pref~rably ~ro~ 0.2gC to a~out 3.0% by we19ht of
th~ l~undr~yd-tergent eo~pos1:t10ns of th~ pr~s~nt lnvent10n.
: 30 L~=L~L~
Th~ ndry~ d~t~ nt eo~postg10ns of th~ pr~s-nt 1nvent10n
lso :optlon~l~y eonta1n on- o~ mor~ 1ron ~nd mang~n~s~
ehoe1~t~ng agents ~s ~ blltlder: ad~unet ~i~t~r1al. Sueh ch~lat1ng
ag~s cæn b~ se1ected fr~ ;thl~ group cofls1stlng of am~no
c~r~oxy1;1t~s, ~no phosphonate$~ polyfuncl;10n~l1y-su~stttuted
tc ~h~l~t1ng ~gents and ~1xtur~g th~r~of, all as h~retn~ft~r
WO 9~/22~29 P~/US9~/0490~
2 1 1 ~ 2
- 36 - !
defined~ ~ithout intending to ba bound by theory, it is belie~ed
that the benefit of these materiats is due ;n part to their ex-
eeptional abiltty to remove iron and m~nganese ions from washing
solut10ns by formation of soluble che1ates.
Amino cArboxylates ~seful as optional chelating agents in
compositions of the invent~on can have one or more, preferably a~
least two, un1ts of the substructure
.. CH2
\
10 H ~ (C~2)x ~ C~-
/
~here1n M ls hydrogen, ~lk~lt m~t~1, ammon1u~ or substttuted
ammon1um (~.9. eth~no1a~n~) ~nd x ls fro~ 1 to about 3, pref-
~rably 1. Pr~fer~bly, th~s~ a~no c~rboxylates do not contain
1~ alkyl or ~1kenyl grw ps ~tth mor~ than ~bout 6 carbon atoms.
Oper~ble ~1ne carboxylat~s 1nclude ethy1en~d1am1n~tetr~acet~tes,
N-hydroxyQthylethylened1u~tnetr~cetates, n1tr11ntriace~2tes,
ethylened1a~1ne tetr~propr~onates, trtethy1~netetraaminehQ%a~
ac~t~s, d1 ~thyl en~tr1 a~i n~p~ntaacet-tes, and eth~nol dt gl yct nes,
20 ~lka,t ~tal, a~on1u~, and subst1tut~d a~ontum salts thereof ~nd
~1xtures the~of.
Am1no phosphon~t~s ~r~ also su1tabl~ for use as chelat1ng
~g~nts tn th~ laundry ~t~r0ont eo~postt10ns of the pres~n~
~nven~10n ~m~n at l~ast low 1~v~1s of total ~hosphorus' ar~
2~ p~r~a1tt~ 1n d~t~ nt c~pos1t10n~. Co~ounds ~1th one or nor~,
prefl~r~bl~5 ~t l~ast two, un1ts of th~ substructure
- ~H2
\
N - (cH2)x ~ ~03M2-
ther~1n M 1~s hydrogen,l~ ~lk~ t~1, an~Ron1u~ or substlt`u~ed
a~ on1u~ ~nd x 1s fro~ l to ~bout 3, pr~f~r~bly l, are useful and
lncl~de eth~l~ned1~netatrakts (m~th~lenephosphonates),
:~ n~trllotrls (methy?~nephosphon~t~s) ~nd dlethylenetr1a~nep~ntak1s
(~ethglenephosphonates). Pre~erably, these ~1no phosphonates do
WO 92~22~ PCr/l~S92/04902
2111~2
- 37 - I
not contain alkyl or alkenyl groups with more than about 6 carbon
atoms. Alkylene groups can ~e shared by swbstructures.
Polyfunctionally-substitut~d aromatic chelating agents are
also useful in the compos1tions herein. These materials can
S comprise compounts having th~ gQneral formula
O~
R ~ R
I0 R
~h~r~1n ~t le~st nne R is -S03H or -C~OH or soluble salts ther~of
and m1xtur~s thereof. U~S. P3tent 3,812,044, issued May 21, 1974,
to Connor et ~1., 1ncorpor~t~d her~n by r~ference, dtscloses
polyfunct10n~11y - substttutQd aro~t1G chel~t1ng ~nd sequestering
1~ ~g~nts. Pref~rred compounds of thls type ln acid form are
d1hydroxyd1sulfob~nzenes such as l,2-d1hydroxy-3.~-d1sulfob~nzene.
Alkallne deterg~nt compos1t10n~ can eontain these materials ln the
form o~ alk~1~ mætal, amm~nlu~ or subst1tuted ammonium (e.g.
~ono-or tr~thanol-a~n~) 521~s.
If ut11:1z~t~ these ch~lattng agents ~11 gen~r~lly eomprise
fro~ about 0.1% to ~bout 1~ by w~ght of the laundry det~rg~nt
compos1t~ons of th~ pr~s2nt 1nw nt10n. Hore preferably chelattng
ag~nt~ ~ r1s~ ~ro~ ~bo~5 O.l~ to about 3~g by ~e1ght of
- such compos1t1~ns. :
~ ~ 25 ~ ~
~la~ so~l r~oYal/~nt~r~J~pos1t1On agents useful ln ~he
laundry::det~rgent compos1t1~n~ o~ th~ present 1nvent~on ~nclute
pol:r~thyl~n- gl~eols and ~t~r-solubl~ ~thoxy1ated a~nas h~ving
cl~y sol1~:re~ov~1 and ant~:-r~d~pos1t1On propert1es.
3~ Pol:y~thyl~n~:glycol co~poun~s us~f~l ~n th~ l~undry det~rg~nt
compos~t~ons of th~ pr@~nt lnYsnt1on typ1cally hav~a mol~cular
~ Qh~ the r~ng~ o~r~ about ~00 t~ ~bout 100,000, pr~f~rab1y
;; ~ fro~ about l,000 to about 20,000, ~ r~ pref2rabl~ from about 2~00
; to ~bout 12,000,~most pr~er~bly fra~ ~bout 4,000 to about 8,000.
~: `3i Such eompounds are~comm~re1~11y ~v~labl~ and are sold as
;` ~: : : ~
Wo g2/22629 Pcr/uss2/04so2
2111~ 38-
Carbowax~, whieh is availabl~ from Union Carbide, located in
Danbury ~ Conn .
The water-soluble ethoxyltted amines are preferably selectea
from the group consisting of:
(1) ethoxyl~ted monoamines having the formula:
(X-L-) ~H-(R~)2
(2) ethoxylat~d dialaines h~vlng the formula:
R2-N-Rl ~.R2 ~R2)~tl-Rl-N- ~R2)2
L L L
X X X
or
(X-L-)z-~-Rl-H-(R2)2
(3) ethoxyl~ted poly~m1nss h~ving the formula:
R~
1~ R3-~(Al)q-(R~ N-L~%]p
(4) ethoxylated ~m1n~ polymers h~v~ng the general formula:
R2
: ~(R2~2-N~w~Rl-N3x~Rl N~y~Rl-N-L-X)z
X
~Rt
(5) ~ixtures thQr~of; wh~r~n Al 1s ~-
O O O O p
-~c-, -qco-, -NCy-, -CN-, -OCN-,
R R R R R ~ R
.
:0 ~ O O O
I I " I I ~ 1 1
-CO-, -OCO-, OC , ~CNC-,
: R
30 o~ -0~; R ts H or Cl~4 albl or hydroxy~lkyl; R1 ts C2-C12
n~, `hydroxyalk~ n~, alk~n~ler-, ~r~ n~ or alkarylen~ or a
C2-C3 oxy~lkyl~tn¢ ~o~@ty hilY~7l9 fro~ 2 to about 20 oxyalkylene
un1t3 pro~1d~d that no 0-N bonds ~rQ forlMd; esch R2 ls Cl~C4 or
hyd~xy~lk~yl, th~ t~ -L-X, or t~o R~ t~9ether form th~ mo~ety
3~ -(CH2)r9 -A2-(CH2)s-~ ~h~1n A2 1s -0- or -CH2-, r ts 1 or 2, s
ls l ~r 2, ~nd r + s 1s 3 o- 4; X ls ~ nonlon1c group, an anionic
wo g2J22629 2 1 1 1 5 9 2 PCT/~Sg2/04~02
- 39 -
group or mixture thereof; R3 is a substituted C3-C12 alkyl
hydroxyal kyl, al kenyl, ~ryl, or al karyl group havi ng substi tuti on
s1tes; R4 is Cl C12 alkylene, hydroxyalkylene. alkenylene, aryl~ne
or alkarylene, or a Cz-C3 oxyalkylene moiety having from 2 to
5 about 20 oxyalkylene un~ts provided th~t no 0-0 or 0-N bonds are
formed; L is a hydrophll~c cha1n wh1ch contains the
po1 yoxyal kyl ene mo i ety - ~ ( R50 )m( CH2CH2a) n 1-, ~here i n R~ i s C3 -C~~lkylene or hydroxya1kylen~ ~nd m and n ;Ire numbers such that the
~noiety -~CH~C~120)n- compr1s~s ~t le~st about S&~ b~ w~1sh~ of said
polyoxyalky1ene moiety; for s~1d monoam1nes, m 1s from 0 to about
~, and n l~ at least ~bout 12; for s~l1d d1amlnes7 m ts from 0 to
about 3, and n ls at least about 6 when R~ 1s C2-C3 alkylen~,
hydroxyalkyl~ne, or alkenylen~, ~nd ~It least about 3 when Rl is
other than C2-C3 alkylene, hydroxy~lkyl~ne or alk~nylene; for satd
polyamines and amin~ pol~rs, m ls from 0 to ~bout lD and n is at
l east about 3; p 1 s from 3 to 8; q 1 s 1 or 0; t 1 s 1 or 0,
provtded that t ~s 1 wh~n q ls 1; w is 1 or 0; x ~ y ~ z is at
least 2; and y ~ z 1s at least 2. The most pr~f~rr~d so1t rele~se
~nd ~ntt-redapos~t10n ~g~nt 1s ethoxyl~ted tetra~thylenepentam1ne.
: 20 Exempl~ry ethoxylated ~nes ~r~ further tescr1bed 1n U.S. Pat~nt
~:~ 4,597,898, Vand~rMeer, 1ss~d July 1, 1986~ 1ncorporAted here1n by
::~ reference. Another group of pr~ferred clay so11 removal/antl-
redepos1t~on agents sr~ th~ cat10n1c compounds d1sclos~d tn
: Europsan P3t-nt Appl~e~t10n 111,965, Oh and 60ssel1nk, publ1shed
~: 2~ Jun~ 2?, 198q9 lncorpor~t~d h~r~1n by refcrænc~. Ot~er cl~y so~l
re~ov~llantl-reds~os1t10n ag~n~s ~h1ch e~n b~ us~d 1ncl~de the
~ ~ ethoxyl~t~d ~a~ne polym~rs disclos~d 1n European P~tent
: ~ Appl~cat~on 11l,98~, :Coss~ltnk, publ1sh~d Jun~ 27, 1984; the
z~ltt~rton~c polym~rs :d1sclos~ ~n Europ~n Pat~nt Appl~cat10n
112,592, Gos:sellnk, publ1shæd July: ~, 1984; ~nd th~ am1n~ oxidies
dlsclosed:1n U.S. Pat~nt ~,s~a~744, Connsr, lssu~d Qctober 22,
~ : 1985, all of:~h1ch ~r~:1`ncorporat~ h~r~in by ref~r~nca.
; ~ The most:pre~erred so11~r@1:~s~ ~nd ~nt1-redepos1tton agents
~: are e~hoxyl~ted: t~tra~thylenæpent~1n~ ~nd the polyeth~lene
: 3~ gly~ols h~v1ng;a~molecular w~1ght 1n the r~ng~ of from about 4,0ao to ~bout 8,000.
WO g2/226~g PCr/USgZ/049~2
2111S9'2
- 40 -
Granular detergent compositions which contain such compounds
typically contain from about 0.01% to about 10.~% by weight of the
clay removal agent; l~quid detergent compositions typically
contain from about 0.01% to about 5.0% by weight.
s e~
Polymer1c polycarboxyl~te d~spers1ng agents can
advant~geo~sly b~ ut~l1zed ln the laundry detergent c~mpos1t~onS
o~ the present lnvent1On. These m~tert~ls c~n atd 1n calc1u~ and
m~gn~s1u~ h~rdness control. In add~tlon to acttng as a butlder
I0 ~d~unct ~n~logously to the polycarboxyl~te desertbed ~bove in the
Butlder descriptton. ~t ~s belteved, though lt 1s not ~ntended to
be ltm1ted by theory, th~t th~se h19her ~olecul~r weight
d1spers1ng 2gents c~n further enh~nce ov~rall detergent bu11ter
p~rform~nce by tnhtbtt1ng crystal growth of tnorgantcs, by
p~rt1cul~t~ sot1 pepttzat1On, ~nd~by ~nt1r~d~pos1t1Ons, when used
1n comblnat1On w1th other b~11ders tncludln~ lower molecul~r
~e1ght polyc~rboxyl~t~s.
The polyc~rboxyl~t~ m~tert~ls whtch can ~e employ~d as the
poly~er~c:po1yc~rboxyl~t~ dtspsrs1ng ~gcnt are th~se po1ymers or
copolymers;wh1ch cont~1n ~t 1-~st ~bout S~ by we1ght of segments
w~th the g~ner~l for~ul~ ~
~ _ _
X Z . ~ .
I 1
--_ t - C--_
_ Y: ~ tO~M ~ ~ :
~: : nh6r~in X,:~Y, ~nd Z ~r~:~ach s~l~ct~d:fro~:th~ group conststtng of
h~drog~n, ~ 4th~ : c~rboxy, ~ ~c~r~ox~th~1, hydroxy ~nd hydroxy~
r,eth~ a~s~lt-fo~tng cat10n nd~;n 1s fr~ ~bout 30 ~o about ~00.
; Pl~f~r~b1y, X ~s hydrogen or hydrox~, Y ts hydrog~n or car~oxy, Z
s :~hydrog~n and ;M t~s hydrog4n, ~lkal1 m~tal, a~wnta or
:subst1tutedn~non1u~
Poly~ertc polycarboxyl-te~ t-r1als of thts type can be
:: :: 35:::~pr~p~r~d~by: polrmertz1ng: or copolym~lz1ng su1t~ble unsatur~t@d
~ono~ers, prefer~bly 1n th~t~r::~c1d fon~. Uns~tur~ted mono~ric
..... . . .. . . . . . .. . ....
wo g2/22~2~ 2 1 1 1 5 9 2 ~ US92/Q4902
~1
ac1ds ~hat ~an b~ pol~merized to for~ suitable polymeric poly-
carbnxyl ates 1ncl ude acryl ic ~c1d, mal ei c acid (or mal ei c
anhydr1d~), fumaric acid, 1taconic acid, acanit~ acid, mesacon jc
a~ld, citr~conk ac1d and m2thyl~nemalon1c aeid. The presence in
the polymer1c polyc~r~3xylates herotn o~ monomeric segments,
cont~1n1ng no carboxylat~ rad1cals such as vtnylmethyl 2ther,
styrone, ~thyl~n~, ~tc. ls su1t~bl~ prnv1d~d th~t such s~ nts do
not const1tut~ ~or0 than about ~ by ~lqht.
P~rt1c~ rly su1t~b1Q pol~r1c polyc~rboxylatBs can be
dertv~d from acr~l1c ac1d. Such ~cryl1c ~ctt~based polylMrs which
are us~ful h~r~1n ~r~ th~ ~st~r~s~lub1- ~lts of polymer1zed
acryl1c ~c1d. Tha av~ga ~olocular ~ 1ght of such pol~rs in
tho ~e1d for~ r~ngQs fro~ a~ut 2,000 to 10,000. mor~ pref~r~bly
fro~ ~bou~ ~,000 to 7,1100 and ~ost pr~f~ably ~ro~ about ~,000 l:o
5,000. ~at2r-solubl~ salts of sueh 2cr~11c ac1d h~polymers ca~
1ncludo, for ~xalnpls, th~ ~lk~ 1, u~on1u~ and subst1tuted
a~on1~ s~lts. Sol~ pol~r~ of th1s typ~ ~re kno~n
~t~ tals. Us~ of poly~er~1~t~ of th1s typ~ tn d~t~rgent
c~pos1t1Ons has ~Qn d1sclos~, for ~x~pl~, 1n Dlehl, U.S.
Pa~nt No. 3,308,n67, 1ssll~ March 7~ 1~67. Th1s p~tent 1s
1ncorpor~t~d hær~n by r~f~r~ne~.
Acr~t 1e/oal~1c-b~~d copol~r~ ~r ~l so b~ use~ ~s a
pr~ r~ co~pon~nt of ths d1sp~rs1ng ~ont. 5uch m~t~r1als
1nel~a th~ ~at2r solubl~ s~lt$ o~ c~pol~rs of acryl1c ac,1d ~nd
~1~1e ~e~d. fh~ av-rag~ cul~r ~1ght o~ such eo~ol~rs ~n
th~ aetd for~ ra~s f~ ah~t 5,000 to 100,000, pr~f~r~ frs~
~t 6,01Na to ~0,000, ~r~ pr~f~bly fro~ abo~lt 7,~00 ~o 60,0ao.
~h~ rat1O o~ acr)~lat~ to ~ t~ S~l~t~ 1n such cspol~Qn
g~n~r~llr r~n~gS~fro~ ~bout 30:1 to a~ut 1:1, ~r~ pre~r~bl~ fro~
~ut 10:1 to 2~ at~r-~olublo s~lts of saleh ~er~11e ae1d/
late ae~d eopo~n e~n 1nelu~, fol~ ~x~pl~, th~i alk~
~n~ n~ s~bst1tut~ ~ $o Solubl~ ~erylate/~al~e
eopo~ o~ th1~ typ~ a~ kno~ ~t~rt~ h1eh ar~ d~scr1bQ~ ln
Eur3po~n P~t~rt Applie~t10n Ho. 6691S, publ1sh~ Dec~mb~r 15,
3~ 19~2. ~btch publ1c~t10n t~ 1ncorporat~d h~1n by r~f~renc~.
:
;:
W o 92/2~629 PCT/USs2/04so2
~ 42 -
If utlllzedt the polymer k d~sp~rsing agents will generally
comprise from about 0.2% to about l0%, pr2ferably from ~bout 1% to
~bout 5X by weight of the laundry detergent composit~ons.
Briqhtsn~r
S Opt1cal br19hteners or other brtghten1ng or whitening agen~s
known to those sk111ed ln the art can be tncorporated lnto th~
laundry detergent composit1cns o~ the present lnventton. ~oweYer,
th~ cho1ce of br1ghtener w111 depond upon ~ number of f~ctors,
such ~s the type of det~rgent, the n~ture of other components
present ln thc tstergent:compos1t10n, the ~e~peratures of w~sh
water, the degree of ~g1t~t10n, and th~ r~tto of the material
w~shed to t~b s1ze.
The br1ghtener select10n 1s also depentent upon the type of
~ter1~1 to be e1eaned, ~.g., cottons, synth~tlcs, ete. S1nce
1~ most l~undry det~rge~t products ar~ used to cle~n a v~rtety of
f~br1cs, the d-t~rgent co~pos1t10ns should cont~1n a m1xture of
br1ghteners~hlch w1ll be ~ffeet1ve for a v~r1ety of f~br1cs. It
ts of course necessary th~t the 1nd1Yidu~l components of such a
br19htener~1xture;be~co~p~t1ble. ~
Co~merc1~1 opt1c~1; br1ghtencrs can be cl~ss1f1ed .nto
subgroups ~h1ch :1ncludc, but are not necessar11y 11m1ted to,
dertvat1~es~of st11bene, p~razol1no, cvu~rin, carbox~ltc ~ctd,
th1n-cyanln-s, d1be~zoth1phen~5,5-dtox~d~, azoles, 5- and
6- _ r:d~r1ng ~het~rocycl~s,~::and~ other m1sc~ neous ag~nts.
: ~: 25 Exu~pl-s:o~;such~brtght-ners :ar dtsclos~d 1n ~h- ~roductton~and
: ~ App11c~t1~on~i of;: Fluor~séent: Br1ghten1ng Ag~nts~, ~. Z~hr~dn1k,
Publ1sh~d~y~John ~11ey~ Sons, NH~ York (1982), the:dlsc~osure of
~: ~ nh1;eh 1s 1~ncorpor~tad~h~ ~n~ b~ r~f~r~nco.
St11 hn~ der1vit1 n s~`1nclud~ but ~r~ n~t nec~ssar11y 11m1ted
: to,~ ter~v~t1ves of : b1~s(tr1~az1n~ tno-st~l h n~; ~1s~cyla~1no
' d~r1vat1v~s~ of st~11b~n~ tr1az~1~ d~r1v~t1v~s of istll~ne;
oxad1~zol~ d~r~v~t1Ye~ :o~ stilb~n~; ox~zole der1vatives of
st~1b~ne;~ nd styryl; der~vat1ves:of st11ben~.
Cert~`n~ d~r1v-t1v~s~:of~`~b1s(tr1~%1nyl~umtnostillbene ~y be
pr~par~d fro~ d1:a~1:ne^stllb~n~-2,2'-d~sul~onlc acid~
: ~
~ ;: : : : : : :
WO 92/2262'9 2 1 1 1 ~ 9 2 Pcr/US92~4902
- h3 -
Coumarin derivatives include, but are not necess~rily l imit~d
to, derivatives substituted in the 3-position. in the 7-pOSition,
and in the 3- and 7-positions.
Carbox~yl1c aetd derivatives include. but are not necessarily
l~mited to, fumaric ac1d derivat1ves; benzoic acid deriYatives;
p-phen~lene-bis-acryl1c ae1d dertvatlves; naphth~lenedicarboxylic
ac1d deriv~t1ves; heterocyclic acid deri~at1ves; and c1nnamic acid
der~v~t1 VQS .
C1nnamtc ac1d derlY2tlves c~n be f~rth~r subcl~ss1fted lnto
groups ~htch include, but are not nec~ss~r11y l~m1ted to, clnn~mic
ac1d der1vat1ves~ styrylazo~ @5, S~y~y~ benzofurans,
styr~1oxadtazole~, styry~t~1~zoles, and styrylpo1yphenyls, as
t1sclosed on p~ge 77 of the Zahradn1k r~fer~nc2~
The styrylazoles c~n b@ further subcl~ss1f1ed 1nto styryl-
benzoxazoles, styryl1m1dazoles ~nd sty~ylth1azol~s. as d1scloset
on p~g~ 78 of the ~ahradn1k refQr~nce~ It ~tll b~ und2rstood that
these thr~e 1dent1f1ed subcl~sses ~y not nec~ss~r11y reflect an
exhaust1ve 11st of subgroups 1nto whlch styrylazoles may be
subclass1f1ed.
Other optlcal brtgh~en~rs ~re th~ der1vat1v~s of
d1~enzoth10phenQ-595~dtox1de dtsclos~d at pag~ 7~-749 of Th~
, Volu~ 3, pages
~37-750 (John ~11e~ & Son, Inc., 196Z3, th~ d1sclosur~ of ~hlch 1s
tncorpor~ted here1n by r~f2r~nce9 and include
3,7-d1~n~d1b~nzothtoph~ 2~B-dtsulfo~1c ac1d 5~5 d10xt~e.
~th2r opt1c~1 ~r1ght~n~r~ ~r~ a~olQs~ ~h1ch are d~r1vatlv~s
of 5~ tsr~d r1ng h~t~rocyc~s. ~h~sa can b~ further
subea~ego~1zed tnto ~o~o~ol e5 ~nd b1sazoles. Examples of
:~ ~ono~zo1~s and b1sa~ol~s ~r~ d1sclos~ 1n the Ylr$:Q~h~
ref~renc~.
~ St111 other optlcal br~ght~n~r~ ~r~ thc dertvat1ves of
: 6-memb~red-r~ng heterocycles d1sclo$ed tn the ~llk Q3h~L
referenc~. Exampl~s of such eo~pounds 1nclu~ br19hten~rs d~r1ved
fro~rpyPaz1ne ~nd br~gh~ene~s deFtv~d fro~ 4-~m~nsnaphthalamtd~.
3~ In ~dd1t~on t~ the br~ghten~rs ~lready descr~bed,
~1sc~ n us ~g~nts ~y ~lso b~ us~ful ~s br1ghteners. Ex~mples
:
WO 92/22629 PCI/US9~/~4902
r~ 9 2
44
of such miscellaneolJs agents are disclosed at pages 93-9S of the
Zahradn1k reference, and include l-hydroxy-3~6~8-pyrenetri~
sulfoflic acid; 2~ dtmethoxy-l~3~s~trtazin-6-yl-pyr¢ne; 4,5 di-
phenyllmidatoloned1sulfonic acid; and d~rivattves of pyrazoline-
quino1tne.
Other spe~1f~c ex~mples of opt kal brlghteners ~r~ those
ldent1f1ed tn U.S. P~tent ~,790,8S6, lssued ~o ~txon on December
13, l9B8, the t1solosure of wh1ch is lncorporated herein by
reference. These brtght~nors tnclude the Phorwh1teTM se~ies of
brtghteners ~rom V~ron~. :Othe~: br1ghteners d1sclosed 1n thts
refercnce 1nclude: T1nop~1 UHP~, T1nop-1 C8S ~nd T1nopal 58M;
~v~ ble from ~lb~Ge1gy; Arct1c ~h1te CC and Art1c ~htte C~D,
~v~t1~b1e from H11ton-Dav1s~ locat~d 1n It~ly; the 2 (~-styryl-
phenyl)-2H-n~phthol~1,2-d~tr1azol~s; ~ b1s-(l,2,3ltr1~zol~2-
~ stilbenes; 4,~'-b1s(styryl)b1sphenyls; and the y-am1no-
cou~rtns. Spec1f1c ex~mples~ of theso br19hteners lnc1ude
ethyl-7-dteth~lu~1no cou~ar1n; 1,2-b1s(-ben~1m1d~zol-2~yl)-
eth~lene;: :l,3-d1pheny1phr~zol~nes; 2,5-b1s~benzox~zo1-2-y1)-
th10phen~::; 2-styr~l-n~phth-[i~2-d]-ox~zolR; and 2-(st11bene-~yl)-
2H-n~phtho[1,2-d]tri~zole.
St11~ other opt1c~1 br1ghten~rs 1nclud~ those d1sclosed in A~
U.S. P~te~nt 3,6~6,01S, 1ssue~ Febru~ry 29~ 1972 to Hu~11ton', the
d1sclosure~of ~h1ch~1s 1ncorpor~ttd~her~1n by ref~rence.
; If:ut111z~d, th~ opt1c~1 br1ght-n~rs ~11 gener~lly compr1se
fro~:~bout;~O.OSX~ to :~bout 2~.0%, pref~r~bly fro~ ~bout 0.1% to
bout~ OX~b~ lght:~of th~ undr~ dct~rgsnt compos1t10ns.
; :~ S d~ SUODr~;;Ir5: ~
mc u = ~ ~no~ ;or ~wh1ch~ hco~k kno~n, for reduc~ng or
suppr~ss1:ng~:-th~for~at10n;~of suds c-n b~ ~neorpor~ted tn~o the
l~un0~ d~t~rg~nt:co~poslt10ns ~of thQ pr~s~nt 1nvent13n. The
ncorporttton of such~ Rt~r1als~ h~r-1naft~r ~suds suppressorst~
::`can : b~ d~s1r!b~ c~us~ th~ polyhydroxy f~tty ~c1d ~tde
surf~ct~nts hc of: can~lncr~sc~ suds st~bllity of th~ deterg¢nt
;co~os1t1~ons. Suds~:suppress10n~ean b~ of part~cutar import2nce
~hen~:the:~detergent:~co-pos1~t:10ns:1~nclude: ~ rel2tlveiy high sudsing
sur~act~nt ~n~:co~b1natton wtth:::t:h- polyhydroxy f~tty acid ~1de
WO g2/22629 PCI`/US92/049~2
2111~92
- 4j -
surfactant. Suds suppression is particulàrty desirable for
compositions intended for use in front loading automatic washin9
machines . These machines are typically characterized by having
drums, f~r containing the laundry and wash water, which have a
hortzontal axis and rotary action about the axis. This type of
agltation can result 1n hlgh suds formation and, consequently, in
reduced c1e~ning perfon~nc~. The use of suds suppressors can
~lso be of p~rt1cul~r 1mportAnce under hot water washing
cond1t10ns ~nd under h19h surf~ct~nt concentr~t10n condttions.
A w1d¢ v~r1ety of ~ater1als m~y be used ~s suds suppressors.
Suds suppressors ~re we11 known to those sk~lled 1n the art. They
~re gen~r~11y descrtbed, for ~x~mplo, 1n K1rk Othmer Encyclopedia
of Chem1c~1 Technology, Th1rd Ed1tlon, Volume 7, p~ges ~30-447
(John ~11ey ~ Sons~ Inc., 197~). One c~te90ry o~ suds suppressor
1~ f part1cul~r 1nterest encomp~ss~s ~4noc~rboxyl1c f~tty ~c1ds ~nd
soluble salts thereof. These m~ter1als ~re dlscussed 1n U.S.
P~tent 2,95~,3~7, 1ssued September Z7, 1960 to ~yne St. John,
~: s~1d p~t~nt betng 1ncorpor-ted here1n by refer~nce. ~he
monoe-r~oxy11c f~tty ~c1ds, ~nd~s~lts thereof~ for use ~s suds
suppressor typ1cally h~v~ hydroc~rbyl ch~1ns of 10 to ~bout 24
c~rbon ~toms, prcfer~bly 12 to 18 e-rbon atoms. Suttable s~lts
tnclude the alka11 ~tt~1 s~lts such ~s sod1u~, ?ot~ss1u~, ~nd
th1u~ s~lts, and ~ ~ n1u~ ~nd ~lk~nol~00n1u~ s~lts. These
m~ter1~1s are ~ pref-rret c~tegor~ of suds suppressor $or
2S detergent co~pos1t10ns~
: ~he l~undr~ doter~nt eo~pos1t10ns of th~ present 1nvent10n
o~ ~lso cont-1n~ non-surf~-ctant suds suppressors. ~hese ~nclude,
for Y~pl-,~h1g~h ~olecul~r ~41sht:hydroc~rbons sueh ~s p~r~ff1n~
:~ :: f~tty ~c1d ~est~rs (;~.g.,~fatty~:~c1d tr1glycer1des), f~tty actd
~ste:rs cf ~onov~l-nt~ ~!cohols,~ ~11ph~t1c ~18-C~o k~tones (e.~.
ste-ron~ etc. Oth-r:suds ~nh1bltors 1ncluJe N~lkyl-ted amino
~r1a2tnes ~:~such ~s;~trl to ~hexa-alkyl~um1nes or d~- to
t~tr--~lkrld~ ne;chlortr1-z1n-s; for~ as produets of cyanur1e
chlor~de w1th~:t~o ~or thre~ al~s of ~ pr~m~ry or second~ry ~m~ne
3S ~contatning 1 to 24~c~rbon~-toms.~propylene ox~de, and monostearyl
phosphat~s such~ ~as mQnoste~ryl 21 cohol phosph~te ester ~nd
W~ g2/22629 PCI/US92/0'1902
5g'~
- 46 -
monnstearyl di-alkall metal (e.g., sodium. potassium, lithium)
phosphates and phosphate est~rs. The hydrocar~ons, such as
paraff1n and h~loparaffin, can be util ked in liquid form~ The
liquid hydrocarbons w~ll be 11quid at rcom temperature and
atmosphertc pressure, and ~ill h~ve a pour po1nt ~n the rang¢ of
about -40-C ~nd about 5-C, and ~ ~nimum bo~lln9 po1nt not less
th~n ~bout 110-~ (atmospher~c pr~ssur~). It is also known to
ut111z~ waxy hydroc3rbons, prefe~b1y hav1ng a ~lt1n~ paint below
~bsut 100-C. ~he h~droc~r~ons eonstttute a preferred category of
suds suppressor f~r tatergent compos1t10ns. Hydroc~rbon suds
suppressors ~re descr1b~d, for ex~mp1e, 1n U~S. P~t~nt 4,26~,779,
tssued May S, 1381 to 6andolfo, et al., tncorporated herein by
referenc~. The hytroc~rbons, thus, 1nclud~ ~11phat1c, alieycl1c,
~ro~at1c, and het~rocycl1e s~turated or unsatur~ted hydrocarbons
g havtng from ~bout 12 to about 70 car~on atoms. The term
p~raff1n,- ~s used.. 1n th1s suds suppressor d1scuss~on, is
1ntend~d to 1ncluto ~1xtur~s of tru~ p~raff1ns ~nd cyclic
hydrocarbons.
Anoth~r preferr~d e~togor~ of non-surfactant suds comprises
~: 2~ s111cone suds suppressors~ Th1s categor~ ~neludes the use of
polyorg~n~s110xan~ o11s, such as pol~dl~ thyls110x~ne, d1spersions
or e~u1s10ns of pol~org~nos110xan~ slls or restns, ~ ~nd
co~b~nat10n~ of polyo~ano~110xan~ wlth s~l1ca p~rt1cles w~ler~1n
th~ pol~organos1lcxan~ ~s ch~1sor~d of fused onto th~ stl ~ca.
5111con~ su~s suppre3sors ~ ll kno~n 1n th~ art ant ar~, for
~xa~plæ,~ dlsclos~d 1n U.. P~nt ~,265,779, 1ssued M2y 5, 1981 to
6~ntolfo: ;~t ~1. and Ellrop~n P~t~nt Appl1cat10n No. ~9307851.9,
pU~l~sh~d F~bru~rr 7, l~90, by Starch, M. S., both ~ncorpor~ted
h~r~tnl: by -re~r~nc~. I
: Oth~r si t 1 cone su~s suppr~ssors ~r~ ~ d1 scl os~d 1 n u . S . Pat~nt
: 3,45~,83g ~ whlch rel~t~ to co~os1t10ns ~nd proeess~s for
d~foa~1n~ aqll~ous :solut10ns b~ ~ncorporat~ng th~retn small amounts
of polyd1~ethyl s11 ox~n~ fl u1ds ~
Mlxtures of s~llcon~ and s~ nated s111ca are descr1bed, for
:1nstance, ~n: Ger~an P~ent Appllcat10n ~OS 2,124,526. S~l~cone
d~foa~rs and suds controli1ng ag~nts ~n gr~nular detergent
w o 92/22629 21115 9 2 RcT/us92/~4so2
co~pos~tions are disclosed in U.S. Patent 3,933,672. Bartolotta et
al., and in U.S. Patent 4,652,392~ Baginski et al., issued March
24, 19~7.
An ex@mplary sil1cone based suds suppressor for use her~in is
5a sud~ suppressing amount of a suds controll~ng a9ent consisting
essent1ally of:
(1) polydlm~th~ls114xan~ flu~d h~Y1ng a v~scoslty of from
about 20 cs. to a~out 150Q cs. ~t 2S-C;
(11) from about S t~ about 50 p~rts per 100 parts by weight
of
(1) of siloxanQ res1n composed of (CH~)3 S~O~ units of
S102 un1ts 1n a rat10 of fro~ (CH3J3 S10l/~ un.its tnd to
S~2 unlts of from about 0.6:1 to absut ~.2:1;; and
(~11) fro~ ~bout 1 to about 20 parts per 100 parts by weight
: 15 of
~: (t) of ~ sol~d s111c~ ge1;
Suds suppr~ssors, wh~n ut11~zed, ar- present in a ~suds
suppr~ss1ng a~ounS.a 8y ~suds suppress1ng ~ount~ 1s me~nt that
the formulator of the compos1t10n cAn s~l~ct an amount of thts
20suds controll1ng ag~nt that~will control the suds to the extent
stred,~ Tha ~ unt of suds control w~ll v~ry ~th the deterg~nt
,
surfacta~t:s~l~et~d. for ~x~pl~ w1th htgh suds1ng surf~ctants,
r~lat1 nly~ ~or~ of th~; suds controll1ng ag~nt 1s ~s~d to ~ch1~ve
: ~ th~ ~stred s~ds control th~n ~1th loY:fouJ~ng surfact~nts.
25Th~ und~r~ det~rgent eo~po~t10ns of th~ pr~sent inv~nt10n
~111 g~rally c W rls~ ;fr~ O~ to about 5X of su~s ~uppr~ssor.
h~fl utll::t~ed as su~ds~s:uppr~ssors, ~onoearboxyl1e f~tty ~c~ds, ~nd
ther~of, ~111 b~pr~s~t typ1e~11y 1n ~ounts up to aboug
SX, b~ ~a1ght, of: th~ d~t~rg~nt eba4ostt10n. Pref~rabl~, from
30:~about 0.5S to:a h ut 3% of fatt~onoe~rhox~l~t~ SU~5 suppr~ssor 1s
:: ~ u~111z~t.`~;~ S111con@ suds suppr~ssor~ ar~ t~plcally ut111zed 1n
: : : : aæounts:u~to about 2.0X, b~w~1ght, of th- d~t-r~ent compos1tlon,
1though~ hlgh~r ~ ouhts ~a~ b~ :us~d. :Th1s upper 11mtt is
prac~1e~ n nature,~du~:p~ r~1~ to cone~rn ~1th keep~ng cosgs
n1~1zed~ nd~:effectlveoess. of lower ~unts for eff~ct1vely
: : eoatr~ tng suds1ng. ~Pr~:fQr~bl~ fro~ abaut O.OlX to ~bout lX of
WO 92/2262~ PCr/US92/04902
,~ 1 1 1 5 4 8 -- !
silicone suds supp~essor is used, more preferably fro~ about 0.25X
to about 0.5%. As us~d herein, these ~ei9ht percentage values
lnclude any sil ka th~t may be utilized ln combination With
polyorganosiloxane. as wel1 as any ad~unct materials that may be
utll ked. Monostearyl phosphates are generall~ uttlized in
~aunts ranging from about 0.1% to ~bouk 2% by weight of the
co~pos~ttons.
Hydroc~rbon suds suppressors are typio~1ty ut111zed in
a~cunts r~ngtng from ~bout O.OlX to about 5~0%, ~lthough hi~her
IO levels can be used.
Other Ins~ L~
A w1de v~rtety of other 1ngred1ents whloh o~n be ihcluded in
the l~undry: detergent cGmpostt1ons of the present inventton
1nclude other act1Y~ 1ngred1~nts, c~rr1ers, hydrotropes,
process1ng ~ds, dy¢s or ptgm~nts, solv-nts for llqutd
~: formulattons, ~tc.
L1qu1d deterg~nt: compos1t10ns c~n con~a1n w~ter ~nd other
solvents ~s carr1~rs. :Low w!ecular ~e19ht pr~m~ry or s0cond~ry
lcohols exe~pl1ft-d ty m~th-nol, ~thanol, prop~nol, ~nd ~so-
prop~nol~ are su1t-bl~ Msnohxtr1c ~lc9hols ~r~ preferred for
,
solub111ztng surfactant, b~t~p~yo1s sueh 15 those contain~ng from
` about 2 to ~bout 6 c~rbon -to~s ~nd fro~ about 2 to about 6
. h~droxy: groups : (e.g.,~: pr~pylen~ glyeol, ethylen~ glycol,
; glycer1n~ nd l,3-propan~d101):can atso bo used.
: 25 ~h~ undry ~t~rgent;~co~pos1t~ons of th~ present invent10n
tl~pr~fer~bl~ b~ -fo~ulat~d;~such th~t dur1ng use 1n ~qu~ous
c1~an1ng~op-r~t10ns,~;th-~ n sh~ ~t~r ~111 h~ve ~ pH of b~twecn
bout 6;.5~nd ~ut ~ pr~-r-bly:b~tw~n ~bout 7.5 nd ~bout
I9~5.~ Ltqu~d produ~t :for~u1~t10n~ pr~rabty h~v~ a pH bet~n
~bout 7~.5~ ~nd~;about;~9~.5,~or- pr~ferabl~ bet~n ~bo~t 7.5: ~nd
outl 9Ø~::Technlqu-s~ or~controll1ng p~ at r~comRend~d lusage
v~1s 1nclud~:~;thé~ us~ of:~buffe~rs~ alkal1, ~c1~s 9 etc., and are
w~l known~to`~thos~:sk111ed 1n~th~ a~t.
Tht~s~tnv~ntion~ furth~r:~;prov1des ~ m~thod for cleaning
:35:~ substr~tes, such ~s~f1bers, f~r1cs,:h~rd surf~c~s, sk1n, ~tc., by
cont~t1ng s~td~substratc~w1th~ deterg~nt compos1t~on con~ining
wo 92/2262g Pcr/uss2/o4so2
_ 49 _ 21 1 1 5 9 2
the nonionic surfactant system of the present invention, where;n
the weisht ratio of polyhydroxy fatty acid amide to additional
surfactant in the nonionic sur~actant syste~n is in the range of
fro~ about 1:5 to about 5:1, tn the presence of a s~lvent such as
water or a w~ter-miscible solvent (e.s., primary and secondary
alcohols). Agit~t10n 1s pref~r~bly prov1ded for enhancing
cle~n1ng. Su1tab1s ~ans for provld1n~ ~g1tat10n include rubbtng
by h~nd pref~r-bly w~th the a~d of ~ ~rush, or other cle;lnin~
d~v1ce"utomat1c laundry wash1ng Mach1nes"utom~tic d1shwashers,
etc.
~e~L
This exempl tf1es a process for mak1ng a N-meth~ deoxy-
glucttyl lauramld~ surfactant for use horein. Although a sk111ed
che~1st can ~ar~ appa~tl~s conf1gllrat10n, one suitabl~ apparatus
I~ for us~ here~n comprtses a thr~ l 1ter ~our-n~cked fl ask f~tted
~1th a motor~tr1vQn paddlQ st1rr~r and ~ th~meter of length
suff1cient to ~ontact thl~ re~ct10n:mcd1~ he other two nec~s of
the flask are fltted qttth ~ n1trog-n sweep and a w1de-bore sid~-
am~ ~cautton: ~ w~d~bor~ std~ar~ ls 1mport~nt in c~se of v~ry
r~ptd 0ethanol eYolutton) to whlch 1s conneGt~d an efftciant
collect1ng condenser and v~cu~ utl~t. Th~ l~tter ts connect~d
to a n~trog~n bleed and v~cuu~: gauge, th~n to~ an ~spir~tor and a
trap. A~ 500 ~att h~t1ng ~antl~ ~1th ~ var1~ble transformer
~ t~p~ratur~ controll~r (~Yar1~c-) us~d ta he~t the reaction ls so
: 2S pl~ced on~ ac~ tha~ y ~Q r~a~11y ratseg or lower~d to: fu~th~r con~rol t~0~r~tur~ of th~ r~ct1On.
e~h~lgluea~1n- (195~ 9., l.0 m~le, Aldrtch, M4700~0~ and
~ Qth~l laur~t~ ~Proct~r ~ 6asbl~ CE l270~ 220~9 g., I.0 ~ole) ~re
-~ pl~eed 1:n ~ flask~ Tha ~ol1d/liq~1d m1xtur~ ts h~-ted ~t~h
st1rr1ng ~und~r ~ n1trogefl sw~ep ~o fon~ a ~e1t (approx1mately 2~
1n~tes). ! ~h~n th2 m~lt: te0p~ratur~ r~aches 1~9 C~l c~talyst
,
~: (anhydrous po~dered sod1~ carbonat~, 10~5 9., 0.1 mol~, J. T.
8ak~r) ls~:~dded. The n1trogQn:s~p 1s shut off and the asp~r~tor
an~ ~1trog~n~ ble~d are ad~ustod to:g1Y~ S tnches (5/31 atm.) Hg.
.~ 3S vacuu~. Frola th1s~po1~nt on, the; re~ct10n temperature is held at
:: :
: :: : :
1'~
: :
:
W~ 92/22629 P~r/US92/o4~02
'Z11 lS~3~ 50 -
150- C by adJustlng the Variac and/or by raising or lowering the
~antl e .
~ lithin 7 minlJtes, first methanol bubbles are sighted at the
meniscus of the react10n m1xture. A vigorous reaction soon
S fol l ows . Methanol i s d1 stll 1 ed over unt~ 1 ~ ts rate subsi des . The
v~cuum 1s ad~ust~d to give about 10 tnches Hg. (10/31 atm. )
Y~CUU~. The vacuu~ 1s 1ncreased ~pprox1m~tely ~s follows (in
~nch~s Hg. ~t m1nutes): lO ~t 3, 20 at 7, 25 at 10. 11 mtnutes
from th~ onset of ~th~nol evolutlon, heat~ng And ~tlnrtng are
d1scont1nued co-1nc1dent ~th so~ fo~m1ng. The product is cooled
and scl 1 d1 f 1 es .
Th~ follow~ng examples ar~ m~ant to exempl1fy eomposit1Qns of
the present lnvent1On, b~Jt ar~ not n~cessartly meant to 11~it or
oth~r~1s~ ds~f1nl~ th~ scopo of th~ 1nvent1On, s~1d scope belng
1~ det~1ned aeeord1ng to cla1~s :wh1ch foll~w.
The invention is illustrated in the following e~amples in which all
amounts are by weight unless otherwise specified.
.
:
WO 92~2262~ PC~/iJS92/04902
2 1 i 1 5 9 2
-- 51 --
In the Examples, the abbre-~iated compone~t identifications ha~e the
following mea~ings:
C12LAS : Sodium linear C12 alkyl be~ene
sulfonate
TGA : Glucityl tallow ~atty acid amide
TAS : Sodiumtallowaleohol sulfate
C14/15~S : Sodium C14-C1s alkyl ~ulfate
C12/15A~3S : Sodillm Cl2-cls allcyl ether sulfate
co~ g an average of three moles
of ethyle~ o~ide per mole of alkyl
sulfate
TA~Il : Tallow alco~ol etho~ylated with n
moles of et~ylene o~ide per mole of
alcohol.
45E7 : A C~ 5 predom~na~tly lL~ear
primary alco~ol conde~sed with ~
average of 7 males o eth3rlene oxide.
` ~ 25E3 : AC12-C15pdmaryalcohol
~o~de~sed with a~ a~erage of 3 moles
of ethyl~ne oxide.
TAE~D : Te~raace~lethylc~ediamine
~: Silicate r ; Amo~hous Sa~m Silic~te
(SiO2:Na20 ratio ~or~lly follows).
25 Ca~ ~ : Anhydroussodi mcarbonate
Sodium carbo~ymethyl cellulose
Zeolite A~ : Hydra~ed Sodium Aluminosilicate of
~or~ula ~Ia1~(A102SiO~ .27H20
havi~ a pn~ particle si~ ~he
range~ from 1 to lQ micrometers
Citrate ~ : Tri-s~ m ci~b dihydrate
~;: MA/A.A : ~ ~ Co~olymerof l:4maleic
anhydride/acrylic acid, average
molecular weigha about 80,0~.
:
WO 92/2262g PCI /US92/04902
52 -
Perborate : Anhydrous sodiumperborate
Monohydrate bleach empirical formula
NaB02.~Z02
Enzyme : Mia~ed proteolytic and amyloytiG
enzyme sold by No~ro Industries AS.
}3rightener: : Disodium 4,4'-bis(2-morpholi~o~
s~tria~in~ylamino)stilbene-
2:2'~disulphonate.
PMP : Diethyle~e tria~e penta (Methylen~
phosphnnic acid), ~rke~ by
Mo~o uIlde~ e T~e ~ame
Dequest 2060
su~s : 2Sb p~ wa~ Mpt SO~C, 17%
Suppressor hydrophobic siliea, 58~i paraffi~ oil.
~' .
:~ :
:
~: ;
,
::
,
~ ,
:: :
: , ~
.
WO 92/2262g PCI`/US92/04902
_ 53 _ ~ i9 2
EY~ample I
The following pa~iculate detergent compositions were
prepared:
A B C
TAS 2.43
Cl4/lsAs 5.4
C12/lSAE3 S 1,5
TGA 3.5 6.5
25E3 3.0 - 6.5
Zeolite A 15.0
Citrate 6.5
Silicate (2.0 ratio) 3.5
Carbonate 13.6
MA/AA ~.~5
DETPMP 0.38
; :: CMC 0.48
TAEI:) 5.0
Perborate 16.0
En~me ~ 1.4
13rightener 0.19
Suds Suppressor 3.0
The Performance of the three compositions was compared in
bo~h Tergotometer Tes~s and in full scale washing machine
tests. i ~
`~ 25 Teryo~o~eterTests:
6 x 2 litre metal~ pots were filled with water of 12 Clark Hardness
(Ca:Mg ~- ~4~ and heated to 60C. 14g of product was added to
each pot and dissol:ed/dispersed ~to give a product weight
concentration of 0.7%. Stained 7.5 cm x 7.5 CZIl cotton and
30 polycotton ~abric swatches were made by applying separate stripes
~; of arti~ cial sebum, shoe polish and:~d~ motor oil (D~O)
;: uniformly on to each fab~ic swatch. ~A swatch of each fabric type
was then attached to the paddle of each pot and the paddles were
then~àgita~ed in the pots ~or 4~ minutes~ The total number of
35 r~plicates for each product~was 6.~ I~e swatches were ~hen rinsed
:~ ~ in cold:~water, dried:o~ernight and then assessed by an expert
panel using a five poine Schefe~ scale. ~
WO 92/22~29 PCI`/US92/04902
21'1.1~9''~ ,
-- 54 --
Washin~
AEG Lavamat 980 automatic washing machines were used to carry
out a similar comparison of the products. A 45 minute main wash
cycle at 60C was selected and a product ~oncentration of 0.7% in
5 12 Clark Hardness water ~Ca:Mg = 4:1) was used. Sî~lc replicates
for each product were carried out. I~ach wash load compr~sed 3kg
of realistically soiled ballast fabrics composed of cotton sbeets and
towels together with polycoKon items to give a cotton:pvlycotton
weight ratio of appro~cimately 3:1, together with sets of stained
o swatches.
The stam sets comprised:
.
2 greasy stains on cott~n (lipstick, DMO).
2 greasy stai~s on polyester (make up, polish).
15 After rinsing wîth cold water, each swatch was dried and then
assessed by an e~cpert~ panel using a five point Scheff6 scale.
The results of both test techniques are set out below.
,
~: ~
:~ 20 The LH column shows the advantage for~ Compositi~n Av over
Composition B while the RH column~shows ~e a~ntage for
Composition A over~Com~sition C. t
:
. ' ~ : : :
: .: . ~ :: : :
~`: ~: .
. :` ~ : :
WO 92/22629 P~/~ 2/04gO2
i g 2
-- 55 --
Tergotometer A/B A/C
Cotton
- sebum -0.3 -0.3
- polish +0.6 +0.2
- DMO ~1~1(s) ~0.8
Polycotton
-sebum ~0.2 +0.4
- polish +0.8 +0.5
o - DMO + l.5(s) ~0.5
Washing Machi~e
Lipstiek/Cotton ~ l.5(s) ~0.2
DMO/eotton + 1.2 ~0.5
15 Makeup/polyester ~1.0 +0.3
Polish/polyester ~1.4(s3 +l.l(s)
(s) ~ statistieally sig~ificant at 95 % eo~fide~ce level.
20 Produet C represents a prior art eomposi~ion alld the eomparison
A/C shows that eompositio~ ~, in aeeordaneé wi~h the Y
inventio~,provides stain remo~ral be~efits relative to Composition C
over a wide spe~trum~ of soil types a~d fabnes. The eomparison of
eomposi~io~ A~shows the sufpriæL~ be~efit provided by the use
~: 25 of a combi~ io~ i~ accordaDce with the hve~tio~ relative to that
provided by use~of a higher level of the polyhydrs~y fatty acid am~de
: alone. ~; ~
:; ~
~: .
. :
,
; ~ : . :
WO ')2J22629 PCI`/US92/04902
'~1115~32
- ~6 -
~am~
Composition A of E~cample I was eompared to a commercially
available detergent cvmposition (D) which differed from
Composition A only in that the 45AS, 25A1~3S, TC;A and 25E3
s components were replaced by 7.6~ C12 LAS, 3% 45E7 and 1.1%
TA~ll. The comparison was carr~ed out ~n A~G Lavamat 980
washing machines using the wash conditions and procedure of
E~cample 1 and a variety of sta~ns on coKon, polycoKon a~d polyester
fab~ic swatches. Assessme~t of the washed fabr~c swatches by an
o e~pe~ panel us~ng a five point Scheff6 scale showed that
Composition A provided a stai~ removal benefit over Composition D
of
> 2 psu on polish fro~ polyester
~ 1 psu on DMO from polycotton
> 1.5 pSU on make up from cotton
,~;`, : : ~
:,
WO 92/22629 PCI/US92/04902
_ 57 ~ 9 2
Example III
The performance of Co~position A of Example I was compared
to that of two further detergent Compositions D and E which
5 differed from A only in that the 25E3 componeIlt w~s replaced by
68E3 and 6~E5 respectively, where 68E3 and 68E5 are C16-C1g
predominantly linear primary alcohols condensed with an average
of three and ~lve moles of ethylene oxide respectively~ The
performance comparisons were made using the conditions and
lO procedure of the tergotometer test of Example I.
Assessment of the washed fabric swatches by an expert panel
using a ~lve point Scheffe scale showed that ~amposition A, in
accordan e with the invention~ provided~significant stain removal
15 bene~lts over both compositions D and E, neither of which is a
composition in accord with the invention.
The results of the comparisons are set out below.
: ,
2~ The LH column shows the advantage for Compositi~on A over
~: Composition D while the RH column shows the advantage for
Composition A over Composition E.
:~ ~ A/D:: A/E ~
2s Polycotton
- Sebum ~ +0.8s ~0.3
- polish ~ -0.3 -0.6
- DMO . + 1.8s + 2.0s
: : 30
Polyester
~; -sebum +2.6s +2.7s
- polish ~ +1.6s ~0.5
~: 35 - DMO +0.8s + 1.5s
:: ~
s= sta~istically significant at 95% confidenoe level
.
W O 92/22629 PCT/U~92/04902
2111~9% S7/1
(*Equivalent ~pplications:)
~SSN 07/578,760 ~ PCT/US91/06980 published as W092/06160
European ~pplication No. 87303761.8 ~ ~urope~n Patent 0,251,446,
published 7 January 1988
~SSN 740,446 ~ European Patent 0~170,386
.
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