Note: Descriptions are shown in the official language in which they were submitted.
Wo95~19132 F~~
2~80716 ~
DIACYL & TETRAACYL PEROXIDES TO INHIBIT TRANSFER OF BLEACHABLE FOOD
SOIL IN MACHINE DISHWASHING
r
Technical Field
The present invention relates to the use of diacyl and tetraacyl
peroxide bl~ species for ;,.1,;1;~;"~ the transfer of t' ~ 'le
food soils in a li,l.~ i lg method. A further aspect of the invention
relates to the use of said b' ~ ~ ' E, species to enhance the removal of
b' ~ f' food soils from a plastic substrate in a di~ .~l .g
method.
Background of the T ..
A well lr~c~ problem arising during modern fabric l~.,.,fl. . ;"~
O~.aLi~JIIS iS the tendency of some coloured fabrics to release dye into the
laundry wash solution. The dye is then hal~f~,.l.,d onto other fabrics
being washed therewith.
In di;,h~. ' g especially machine ~ ,h~lihlg, methods there exists a
related problem, which is however, not widely 1~ ~ ,;, d in the art.
Coloured/l-l~ A~ e food soils, c-~ natural dyestuffs, may be
removed from soiled articles into the wash solution, and then may be
p,,~;t, d from the wash solution onto other articles in the wash or onto
the interior of the .li~ .a~llillg machine.
The problem is particularly llu~ when the washload includes
articles soiled by foods naturally c--"~ gi~ifi~ t levels of coloured
dyestuff~ 'e~, including for example tomato sauce and curry.
_ _ _ _ _ _ _ _ _ _ _ _ . .
WO gS/19132 P~~
2~07~6
The Applicant has found that plastic articles in the wash, and areas of the
interior of the dishwashing machine which are made of plastic material,
are particularly susceptible to the ~Pp..~ific.n of coloured food soils from
the wash liquor. Said soils can interact with the surface of such plastic
substrates producing staining which can be very difficult to remove.
A solution to the problem of dye transfer in li~ulld~hlg opFr~til n~ is to
bleach the fugitive dyes washed out of dyed fabrics before they have the
u~lJvl ~LI,liLy to become attached to other articles in the wash.
A number of the Applicant's copFn~lin~ European Patent -~MI irAtione
have disclosed that certain of the solutions proposed to mitigate dye
transfer in la~ulJ~ ~Ig operations may also be applied to solve the
problem of coloured food dyestuff~Ppl ~iti-n in a machine ~ L~.a;l~ g
method.
For example, copPn~iinp European Patent ~rpli'`Ati~l~ 93870066.3 filed
April 9, 1993, provides an efficient dye transfer inhibiting c.,."~
for use in a machine .li~ .a~llillg method. The c~ c~ an
C~ a ic system capable of ~ dLillg hydrogen peroxide in
C{""l,;,.A~;l-n with certain metallo catdlysts.
The Applicant has now found that diacyl arldtor tetrdacyl peroxide
hlFA~hin~ species may be used to inhibit the transfer of
coloured/t~ '^ food soils when c .II~lu~ in a d; Ill~.ailPillg,
especially machine .li~ illg, method. The use of a diacyl and/or
tetraacyl peroxide blPA~hinp species for this purpose has not been
disclosed in any of the arul- .". ,li~nPd prior art do~iu-.. .I~
The Applicant has also found that diacyl arld/or tetradcyl peroxide
bleaching species may be used to enhance the rer~val of ~' ' ~I~le soils
from a plastic substrate when employed in a d;~ .~Lil~g, especially
machine d; ,II~.a~Lillg, method.
Whilst the utility of diacyl and/or tetraacyl peroxide hlP-Arhin~ species to
enhance ~' ' ' 'e stain removal has been previously .~i~o~,i,~d in the
WO 95tl9132 ~ ~1l-1... _ . /1
218~71~ ;~
art, including for example PCT Application No. WO 93/07086, the
specific utility of such bleaching species in the clean up of stained plastic
articles has not previously been recognized. As previously noted, the
soiling and related staining of plastic is a particular problem in the
di ,llw~l~ g art.
Slmnm~ry of th~ Tnv~ntion
According to the present invention there is provided the use of a
b' _L' ~ species to inhibit the transfer of a bleachable food soil
from an aqueous wash solution to a substrate in a L~ .~lling
method wherein said bleaching species is selected from diacyl and
tetraacyl peroxide bleaching species and mixtures thereo
According to another aspect of the present invention tlLIere is
provided the use of a LU~ 3 species to enhance the removal of
blea~llt~ble food soils from a plastic substrate in a ~ . ~hing
method employing an aqueous wash solution wherein said ~L- I ' 3
species is selected from diacyl and tetraacyl peroxide blp~chin~
species and mixtures thereof.
n~t~iled n~rr~ti~n of th~o TnvPnti~n
Bl~ h~hle food soil tr~ncfPr inhihiti~ n
According to the present invention the b~ species is used in a
.li~ll.,.. ' ~ method for the pu~pose of ;. .1.;1.;1;..~ the transfer of
bl '- ' ' - food soils from an aqueous wash solution to a substrate
surface.
By bl ~ ' ' le soils it is meant essentially any coloured food soils
which may be rlProl~ ri~Pd by tlLIe action of bleach. The present
invention is most especially co~ with the ~ tiUIl of
transfer of llyd~u~ b' LI2.~l~ food soils, particularly those
having ,~v~.~u ~ ,h.vlllu~llvlci.,, such as beta-carotene, Iycopene.
;1 1 or c ~ . referred to generically as
cd.uL~..vid soils. Carotenoid soils can be derived from carrots and
.... ... . . . . . . . . . .
Wo 95/19132 P~l/~., S.~ /
~18071~ '
tomatoes, and any processed products c~nt~inin~ these Culll~ull~"lL
as well as certain tropical fruits and saffron.
The Applicant has found that the substrate material which is most
prone to receipt of the transfer of bleachable food soils is plastic
material, such as polypropylene, polyethylene, polystyrene
(including alkyl butyl styrene) or PVC. Such plastic substrate
material may interact with any b'---' -' le food soils on the substrate
surface to produce ~ . ,; 7~ staining of the substrate. This stair~ing
is particularly visible on l,, "x~ " plastic material, as is commonly
employed for food storage boxes and tubs.
According to another aspect of the present invention the b~
species can also used in a di ~ a.71lillg method for the purpose of
rnh~nrin~ the removal of bll, ' ' 1~ food soils from a l,.c~ iuu ,Iy
soiled substrate, wherein the substrate is made from plastic material
as II~"~"IIdl~U~C ~l~oyrriherl
ryl ~nrl Tetr~ryl p~roxitito BlP~rhin~ S~ecies
The b' ' ~ species may be selected from essentially any diacyl and
tetraacyl peroxide bleaching species and mixtures tnereof.
The diacyl peroxide b' ' g species is ~lefc.abl~ selected from diacyl
peroxides of the general formula:
O O
Rl-C-OO-C-R2
in which Rl .c~ , an aromatic group or a C6-C1g alkyl, preferably
C6-C12 alkyl group ~r",l:~,";"~ a linear chain of at least 5 carbon atoms
and optionally c-,..l~,~.,;,.~ one or more ~ IY (e.g. -N+ (CH3)3,-
COOH or -CN) and/or one or more illt~.l~tillg moieties
(e.g. -CONH- or -CH=CH-) interpolated between adjacent carbon atoms
of the alkyl radical, and R2 I~ ,.,.,..LX an aliphatic or aromatic group
csmr~fihl~ with a peroxide moiety, such that R1 and R2 together contain
a total of 8 to 30 carbon atoms. In one preferred aspect Rl and R2 are
.. ..
~ WO95/19132 21 8Q 716 r~l~u~ r /1
linear lln~llhstibltPd C6-C 12 alkyl chains. In another preferred aspect R
and R2 are phenyl groups. Most preferably Rl and R2 are identical.
Dibenzoyl peroYide, in which both Rl and R2 are phenyl groups, is
particulArly preferred.
The tetraacyl peroYide hl~A- hin~ species is ~ f~ bly selected from
tetraacyl peroxides of the general formula:
O O
11 o~
R3 -C-OO-C-(CH2)n-C-OO-C-R3
in which R3 ~ lL~ an aromatic group or a Cl-Cg allyl, p~ l~ly
C3 - C7, group and n l~ ,s,~llL~ an integer from 2 to 12, preferably 4 to
10 inclusive
The diacyl and tetraacyl species are most ~l~fi,lably present as
~u~ ; of a detergent c~ n Such species are however
intr~nQi~AIIy unstable above their melting points and are liable to self-
A~`.~ll . ~.1 ;l l~ thermal d~u.--~o ,;lion. To provide storage stability it is
hence n~ a.y to illcullJu.dt~ the diacyl and tetraacyl b' ~ species
as "guest" mr' IP~ in "host-guest c~ I ' " in which the mrl ~
of the b' ' 1~ species are individually separated from each other by
their inclusion in the host receptor sites. The hosts may for e,Y~ample be
inorganic or organic crystals having relatively open :.Llu-,Lull ., which
provide sites that may be occupied by guest -' ' thus forming the
host-guest c , ' FY~F' of suitable hosts include certain
clathrates or inclusion G~ u~ , including the urea clathrates and the
cyclolirY-b ini~ particularly the beta-~ ,lo~ The hosts are most
preferably water soluble, to enable effective release and .l;~l,- , ... of the
1;' ~ ' ~ species on illLludu~ ofthe host-b~ species
c~ into an aqueous media, such as a wash solution. Urea
clathrates of diacyl and tetraacyl ~ species have been disclosed in
PCT Application No. WO 93/07086.
The diacyl and tetraacyl bleaching species in ~ u~ , have been found
to be of particular utility in the b~ of carotenoid soils, _nd in the
WO 95/19132 r~ 5
21 807i6
removal of tea stains. Alt~ . ly, the diacyl and tetraacyl species may
act as bleach actiYator species, arld by in situ reaction with ~.,lllyLu~yl
ions form p~ .u~y~iids which act to bleach a wide range of soil/stain
types. The p.,lllydlu~yl ions may originate from, fûr example, the
inorganic p~lllydlalc salts such as the alkali metal p~ at~ ~ and
p~ u~ t~
The diacyl and tetraacyl b'~s ' E, species are preferably present in the
aqueous wash solution at a total level of from I to 100 ppm, more
preferably from 5 to 50 ppm most preferably from 10 to 40 ppmby
weight of the wash solution.
Dl~ll~A~11;1~ m~thnrl
The d;~ .~Lillg method may be essentially any conventional
~li~ll~llil~g method. ~cf~l~ly the di~l~.~.li.lg method is a machine
.li~ll~._allillg method ~- r ~ d using a diD~ . machine, which may
be selected from any of those commonly available on the market.
The machine di ,l~ illg method typically involves treating soiled
~ c~ such as crockery, ~ , hollowware and cutlery, with
an aqueous wash solution having dissolved or dispersed therein an
effective amo~ t of a detergent comr(~gitir~n The diacyl and
tetraacyl bl~A~,Lil.g species are preferably present as c~ of
said detergent c~Jll~l~u~;l;nn
By an effective amount of detergent cu~"l,~ it is generally
meant from 5g to 60g of detergent c~mr~ ~itiA~n per wagh, dissolved
or dispersed in an aqueous wash solution volume of from 3 to 10
litres, to provide a wash solution c.)~ of the detergent
cc,l.l~o~ilion of from 0.05/O to 2% by weight. The wash t- -..1~- ,-1~ c
may be in the range 40C to 65C as commonly is; , ' ,~_d in such
methods. A rinse aid c~ g~ \ may also be used, if desired.
Wo95119132 r~ .. ,5'~ ~/1
218û716
)PtP~ent Compl eitionc
rhe detergent composition may also contain various other
C~ including aulr~,LhuLa~ detergent builders, alkalinity
sources, other bleaching agents, lime soap dia~ aailLa, organic
polymeric c~ yuullds including polymeric dye transfer inhibiting
agents, crystal growth inhibitors, heavy metal ion se~luci,L,~ulLa,
enzymes and enzyme stabilizers, cûrrosion inhibitors, suds
au~ ,.,Sula, solvents, and lly~LuL up~ ~. rrhe diacyl and tetraacyl.
bleaching species are preferably present as cu~ Jull~ b of a
detergent culll~ua;Lion.
Surf~rt~nt systPnn
A highly preferred Collll ol."llL of the detergent c~-."1~ ionc herein
is a aulr;-~;L~IL system cu."l" ;~;"~ ,", r~- ~ .I selected from anionic,
cationic, nonionic ampholytic and ~Wil~,l;UiliC a~l~ r~ ; and
mixtures thereof. The a~ r . 1~.ll system is typically present at a level
of from 0.5% to 40% by weight, more ~l~f~ldl~l~ 1% to 30% by
weight, most ~ f~ bly from 1.5% to 20% by weight of the
culll~uailions.
In one preferred PYPc~tion the au~r~iLiull system consists of low
foaming nonionic 5~rf~-~t~nt, ~1~ r~ilc.bly selected from ethoxylated
and/or propoxylated nonionic aul r~L~lL~ more preferably selected
from nûnionic ~ vAylat~ d/propoxylated fatty alcohol ~.,. r~ ."~
In an alternative preferred eYPc--tion the a~r~;L~ull system c~.",l" ;~high foaming anionic aulra~;L~Il, particularly alkyl ethoxysulfate
a~l~ rP" ~"I in cambination with a suds au~ aulg system.
.
.Anionic C.ll r~
FccPnti~lly any anionic aulr~;L IlL~ useful for detersive purposes can be
included in the C~",l,Oc;l;,~ These can include salts (in-~l--rlin~, for
example, sodium, pul~;""" ~"""~",;."", and ~ ~ ~ "",U"i1~l" salts
WO 95/19132 P~
218~71~ '
such as mono-, di- and trir~ n~ salts) of the anionic sulfate,
sulfonate, ~,~u~u~yl and ~u.,~ surfactanb.
Other anionic surfactants include the isethionates such as the acyl
thil ~ N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfnc~ , of ~ulru~ ' (especially
saturated and u~ Luldl~d C12-C18 mon~-Prt~rC) diesters of sulfosuccinate
(especially saturated and Ul~dlUI_ ' C6-C14 diesters), N-acyl ~U~,U~illal~s.
Resin acids and llydlu6~ ' resin acids are also suitable, such as rosin,
lly-l-u, ' rosin, and resin acids and lly~ , 1 resin acids present in
or derived from tallow oil.
Aninni~ 5111f:1tl'. sllrf~r~n~
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary alkyl sulfates, alkyl ethu~y. Ir , fatty oleyl glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(CI-
C4 alkyl) and -N-(CI-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkyl~vl~ such as the sulfates of alkylpoly,~lucoside (the nonionic
being described herein).
Alkyl ethoxysulfate sulr~ lb are preferably selected from the group
consisting of the C6-CIg alkyl sulfates which have been ethoxylafed with
from about 0.5 to about 20 moles of ethylene oxide per molecule. More
preferably, the alkyl elllu~ r surfactant is a C6-CIg alkyl sulfate which
has been ulllu~y~ I with from about 0.5 to about 20, ,ul~f~.~ly from about
0.5 to about 5, moles of ethylene oxide per molecule.
Aninnir 5111f~n f~ su~
Anionic sulfonate surfactanb suitable for use herein include the salts of Cs-
C20 linear alk~l~.,l~....~, ..,lr. , alkyl ester sulfonates, C6-C22 primary
or secondary alkane ~ulr~ , C6-C24 olefin ~ulr~ , sulfonated
poly~ubu~ylic acids, alkyl glycerol ~ulr~ , fatty acyl glycerol
sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
SUB~TITUTE SHEET (RULE 26)
WO 95/19132 , ~, 1111..~5,'~ / I
~1807~6
Arliollic ~rboxyl~tp sllrf~rf~nt
Anionic carboxylate ~-1 r~ suitable for use herein include the alkyl
ethoxy carboxylates, the alkyl polyethoxy pOly-,~bo~ylaL~ ~ulra.;~l~ and
the soaps ('alkyl carboxyls'), especially certain secondary soaps as
described herein.
Preferred alkyl ethoxy ~albvl~yl.lt~,~ for use herein include those with the
formula RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to Clg aLlcyl
group, x ranges from O to 10, and the ethoxylate distribution is ~uch that,
on a weight basis, the amount of material where x is 0 is less tharl about 20
%, and the amount of material where x is greater than 7, is less than about
25 %, the average x is from about 2 to 4 when the average R is C13 or
less, and the average x is from about 3 to 10 when the average R is greater
tharl C13, and M is a cation, ~ .ably chosen from alkali metal, alkaline
earth metal, ~rnmonillm, mono-, di-, andtri-ethanol---,.",. ~ -", most
r~.a~ly from sodium, pVL~:tiUII~, ~'1l1ll`~ll;ll'll andmixtures thereofwith
".~.,~ .;"." ions. The prefer~ed alkyl ethoxy carboxylates are those where
R is a C12 to Clg alkyl group.
Alkyl polyethoxy poly~ albv~yldt~ ~ ra~ ~.~ suitable for use herein
include those having the formula RO-(CHRI-CHR2-O)-R3 wherein R is a
C6 to C18 alkyl group, x is from I to 25, Rl and R2 are selected from the
group c~ 1 ;"~ of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, wherein at least one
Rl or R2 is a succinic acid radical or II~J~u~u-,~,il-lc acid radical, and R3
is selected from the group co~ of hydrogen, ~ d or
.,I;llit~d llyd~u~ lull having between I and 8 carbon atoms, and
mixtures thereo
Preferred soap ~-,- r~ ".."~ are s~olld~y soap i, ~ rA~ which contain a
carboxyl unit c~"~ to a SC~COlld~LIy carbon. The ~,culldcu,y carbon can
be in a ring structure, e.g. as irl p-octyl benzoic acid, or as in alkyl-
cyclohexyl albu~yl~ . The se~ulldal ~ soap ~." r.. ,~
should preferably contain no ether linkages, no ester lirlkages and no
hydroxyl groups. There should preferably be no nitrogen atoms in the
head-group ( mrhirhilir portion). The s~colld~y soap sllrf~rt~ntc usually
..
WO 95/1913Z 2 i ~ 0 7 1 6
` 10
contain 11-13 total carbon atoms, although slightly more (e.g., up to 16)
can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred
s~ daly soap ~
A. A hignly preferred class of S~OII~CU,Y soaps c~,., .I.. ;g~ the secondary
carboY~yl materials of the formula ~3 CH(R4)CooM, wherein R3 is
CH3(CH2)x and R4 is CH3(CH2)y, wherein y can be O or an integer from
I to 4, x is an irlteger from 4 to 10 and the sum of (x + y) is 6-lQ
preferably 7-9, most preferably 8.
B. Another preferred class of secondary soaps c- ~ those
carboxyl c~ wherein the carboYyl . -I-.I;I--- .l is on a ring
lly~ ub.yl unit, i.e., S~UII~L,Y soaps ofthe formula RS-R6-COOM
whe}ein R5 is c7-cl0, ~l~f~ .~ly C8-C9, alkyl or alkenyl and R6 is a ~ing
structure, such a3 benzene, cyclopentane and cycl~h~ Y~n~ (Note: R5 can
be in the ortho, meta or para position relative to the carboY~yl on the ring.)
C. Still another preferred class of 3c~o~ld~u.y soaps c-,..,l.. ;~- ~ secondary
carboxyl COIII~ IS of the formula
CH3(CHR)k(CH2)m-(CHR)n-CH(COOM)(C~R)o-(CH2)p-(CHR)q-
CH3, wherein each R is C l-C4 alkyl, wherein k, n, o, q are integers in the
range of 0-8, provided that the total number of carbon atoms (including the
CaIbUAYI-~) is in the rarlge of 10 to 18.
In each ûf the above formulas A, B and C, the species M can be any
suitable,especiallywater-s~ hiii7infr cv~-~t ;---.
Especially preferred 5~CUIId~Y soap . - r~ for use herein are water-
soluble member3 selected from the group c~ of the water-soluble
salts of 2-methyl-1-1 d ~ - acid, 2-ethyl-l-decanoic acid, 2-propyl-1-
nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
~ W095119132 218~716 ~ sr ll
11
~Ik~li mPtrAl ~rcosin~tP sllrf~rtAnt
Other suitable anionic vulr~ LY are the alkali metal sdl.,o~illdca of
formula R-CON (R1 ) CH2 COOM, wherein R is a Cs-C 1 7 linear or
branched alkyl or alkenyl group, Rl is a Cl-C4 alkyl group and M is an
alkali metal ion. Preferred examples are the myristyl and oleyl methyl
s~ o~ t~v in the form of their sodium salts.
Noni-)nic sllrf~t~nt
FYYPntiAlly any anionic Y~I~ r~ Y useful for detersive purposes can be
included in the c~ ailions. Exemplary, non-limiting classes of useful
nonionic ,. .. r . l~. . I Y are listed below.
Noninnic po~ -u~ fAtty 'ACi~l Anni~lp s.ll r~ L
PIYIIYdLU~Y fatty acid arnides suitable for use herein are those having the
structural formula R2CONRIZ wherein: Rl is H, C l-C4 lly~Loca.l, ~1, 2-
hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, ~lef~lab'- Cl-C4
alkyl, more preferably Cl or C2 alkyl, most prefe}ably Cl alkyl (i.e.,
methyl), and R2 is a Cs-C3 1 lly~ f~ ldl)ly straight-chain Cs-
Clg alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or
alkenyl, most ~ Iy straight-chain C 1 I-C 17 alkyl or aLlcenyl, or
mixture thereof; and Z is a polyl-~ld~v..~l.y~u~ l having a linear
llydl~ ubyl chain with at least 3 llyd~uAyl~ directly c~ d to the chain,
or an aLkuhyld~ d~ dLi~ ,C~,ldbly e;llu~l..~l or ~lV~U~ yl..~
thereû Z ~Ic~.dbly will be derived from a reducing sugar in a reductive
~lll;llA1;~.l. reaction; more pl-,f~ bly Z is â glycityl.
N~nionic cul~ t~ ~ of AlkYI phPnf-lY
The polyethylene, polypropylene, and polybuLyl~ oxide c..~ A~ Of
alkyl phenols are suitable for use herein. In general, the polyethylene
oxide cond~nY~t~Y are preferred. These ~u..,l.v~ include the
cnntlPnyAtir~n products of alkyl phenols having dn alkyl group c. .. ,l S.i ,~; "~
.
Wo95/1913Z 2L8~71~ J s~
` 12
from about 6 to about 18 carbon atoms in either a straight chain or branched
chain configuration with the alkylene oxide.
Nonionic ~thr)~y~ 1 alcr)hol cllrf~rt~nt
The alkyl ethoxylate ~ n products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide are suitable for use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or secondary, and generally contains from 6 to 22 carbon atoms.
P~li~ul~ly preferred are the ct~ nc~ti~ n products of alcohols having an
alkyl group cont~inin~ from 8 to 20 carbon atoms with from about 2 to
about 10 raoles of ethylene oxide per mole of alcohol.
Nonh~ c~ y' ~.~ J/pro~oxylated fotty alcohol surf~t~n
The ethoxylated C6-CIg fatty alcohols and C6-CIg mixed
ethoxylated/propoxylated fatty alcohols are preferred surfactants for use
herein, particularly where water soluble. Preferably the ethoxylated fatty
alcohols are the C1o-CIg ~ u~y' ' fatty alcohols with a degree of
ethoxylation of from 3 to 50, most preferably these are the C12-CIg
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Fl~,C~,.~ly the mixed ethoxylated/lu.ouu~' ' fatty alcohols have an alkyl
chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of
from 3 to 30 and a degree of ,u~u~u~ ion of from 1 to 10.
Nonionic EO/PO ç~ ne~tes with propylene ~Iycol
The con~ll nco~inn products of ethylene oxide with a l~yd~u,ul~olP.c base
formed by the ~ua~ lLion of propylene oxide with propylene glycol are
suitable for use herein. The l~ydlu~l.ulJ;c portion of these C~
preferably has a molecular weight of from about 1500 to about 1800 and
exhibits water insolubility. Examples of ~u~pu~..ld~ of this type include
certain of the Go.. -~,l.,;ally-available PluronicTM ~u.r~,L.. ~, marketed by
BASF.
SUBSTITUTE SHEET ~RULE 26)
- WO9~/19132 - ~I/L.~
~ sa7l~
13
Noninnic EO c~ Fne~tinn products with propylene oxi~iP/Fth,ylene ~ mineadduct~
The cnn~lF~ n~qfinn products of ethylene oxide with the product resulting from
the reaction of propylene oxide and ethylf l,f~ ".;" are suitable for use
herein. The llyJIu~l~ol) c moiety of these products consists of the reaction
product of ethyl - F,~ . and excess propylene oxide, and generally has a
molecular weight of from about 2500 to about 3000. Examples of this type
of nonionic surfactant include certain of the eull~.llèl~,;dlly available
TetronicTM ~ , marketed by BASF.
Noninnic alhyl~ol~ f SU~Ct~nt
Suitable alkyl~ol~,,a~,~l.alides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from about 10
to about 16 carbon atoms and a poly~ if lf'., e.g., a pol~,~ly,,oside,
hydrophilic group containing from about 1.3 to about 10, ~l~f~,lably from
about 1.3 to about 3, most ~lef~,l~ly from about 1.3 to about 2.7 ~a~,l.ll uid_
units. Any reducing ~ iF containing S or 6 carbon atoms can be used,
e.g., glucose, galactose and galactosyl moieties can be ~ub~LiLuL~d for the
glucosyl moieties. (Optionally the llyJI~ll~lJ;c group is attached at the 2-,
3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a
glucoside or g;~l~rtn~;~le ) The ;. ~ F- bonds can be, e.g., between
the one position of the additional saccharide units and the 2-, 3-, 4-, and/or
6- positions on the preceding Q~rhs-rjf~F units.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t~glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from 10 to 18, I~I.,f~,.dl~ly from 12 to 14, carbon atoms; n is
2 or 3, IJIer~lal)ly from about 1.3 to about 3, most preferably from about
1.3 to about 2.7. The glycosyl is ~ relal~ly derived from glucose.
SUaSTlTUTE SHEET (RU~E 26)
W0 95/1913Z ~ .,.5.~
2181~716
14
Nonionic f~tty acid ~nnide ~.,. r~
Fatty acid amide s~rf~ t~nte suitable for use herein are those having the
formula:
R6-C-N(R7)2
wherein R6 is an alkyl group c~ from 7 to 21, preferably from 9 to
17 carbon atoms and each R7 is selected from the group coneietin~ of
hydrogen, C l-C4 alkyl, C 1 -C4 hydroxyalkyl, and -(C2H40)xH,.where x is
in the range of from I to 3.
.Am,rhotPric ~ L
Suitable ~l-~ t~l;c s~rf~rt~ntg for use herein include the amine oxide
~I-rh~ L IL~ and the alkyl a ~ o~,a bvAylic acids.
A suitable example of an alkyl aphodi~,alb.Aylic acid for use herein isMiranol(TM) C2M Conc. ", ,., r~ by ~iranol, Inc., Dayton, NJ.
Amine Oxi-lP ~llrf~t~nt
Amine oxides useful in the present invention include those c~ ~,.,-lc
having the formula:
O
1`
R3(oR4)XN(R5)2
wherein R3 is selected from an alkyl, lly~LvA~alkyl, acylamidopropoyl and
alkyl phenyl group, or mixtures thereof, c-..-l ;,.;..~ from 8 to 26 carbon
atoms, preferably 8 to 18 carbon atoms; R4 is an aLlcylene or
l.yL~,A~alkylene group c-...l ~;..;..~ from 2 to 3 carbon atoms, preferably 2
ca~bon atoms, or mixtures thereof, x is from O to 5, ~l~f~,lably from O to 3;
and each R5 is an alkyl or llyd~lvA~alky~ group c....li-;..;,.~ from I to 3,
preferably from I to 2 carbon atoms, or a pol~ oxide group
C-...1~1;ll;ll~ from I to 3, ~lef~ 1, ethylene oxide groups. The R5
wo 95119132
2180716
' 15
groups can be attached to each other, e.g., through an oxygen or nitrogen
atom, to form a ring structure.
These amine oxide "" r~ n~ i in particular include C1o-C18 alkyl
dimethyl amine oxides and Cg-C1g alkoxy ethyl dilly~LvAyeLhyl amine
oxides. Examples of such materials include dimethyloctylarnine oxide,
diethylde~ylall.i--e oxide, bis-(2-lly~LvAyeL-llyl)dodecylamine oxide,
dimethyldodecylamine oxide, dl~lvlJyl~eL~ c.,ylalllille oxide,
methylethylhexadecylamine oxide, dodecylamidopropyl dill~L~Iyl~lllille
oxide, cetyl dimethylarnine oxide, stearyl dimethylarnine oxirl~ ~Rllow
dimethylamine oxide and dimetnyl-2-ll~Lu~yu~,L~d~yl~ullule oxide.
Preferred are C1~-C1g alkyl dimethylamine oxide, and C10-l8 acylamido
alkyl dimethylamine oxide.
W i L ~; v I i C ., l l ~ rA ~
Zwi~l;ullic ~-1- rA~ can also be ill~vllJvldLed into the detergent
cu" .l-v,~ nx hereo These ~, ~ rA~ lA II~ can be broadly ~rAsr~ ibed as
d~ dLi~,., of i~cvllda~.y and tertiary amines, d~,.;vALi~ i, of heterocyclic
S~co.ldaly and tertiary amines, or ~ dLi~is of 4u.~t~ lllA. y A. "" .~ .. ,; "- ",
~uat,lll~ -"~ ,-l,--"ortertiarysl r~ c~ u~ Betaineand
sultaine" rA-~ aree~ l_yzwitterionic~, ,A-IA,IXforuseherein.
BlotRin~ r~
The betaines useful herein are those c~ "l-ù~ c having the formula
R(R')2N+R2COO- wherein R is a C6-C1g IIJLùc_vyl group, preferably a
Clo-C16 allcyl group or C10 16 acylarnido alkyl group, each Rl is
typically Cl-C3 alkyl, preferably methyl,m and R2 is a Cl-Cs 11YdIU~--IJYI
group, ~ C~l~ly a Cl-C3 alkylene group, more preferably a Cl-C2
alkylene group. FYRmrl of suitable betaines include coconut
acylamidopropyldirnethyl betaine; II~A~de~,~l dimethyl betaine; C12-14
acylamidv~lv~ylbetaine; Cg 14 acylRmi~h~Yyldiethyl betaine; 4[C14-16
acy 11ll~,l--y ~o y ] I ~al I~VAY~ ~1~/, C 1 6-- I 8
acylRmi~o~lim~thylbetaine; C12 16 acylamido~ yl-betaine;
[C12 16 a~ l.,Llly~ I.ylbetaine. Preferred betaines are C12-18
dimethyl-amrnonio h~ 'r and the C10 18 acylamidu~,lv~-cule (or
W095/19132 ~ 1 8~71~ '
16
ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also
suitable for use herein.
Slllts~in~ Surfo~AtAArt
The sultaines useful herein are those co~ uullds having the formula
(R(RI)2N+R2S03- wherein R is a C6-C1g llydlu~ yl group, preferably a
Clo-C16 alkyl group, more preferably a C12-C13 alkyl group, each Rl is
typically Cl-C3 alkyl, preferably methyl, and R2 is a Cl-C6 l~ydlu~,albyl
group, preferably a Cl-C3 alkylene or, preferably, hydroxyalkylene group.
rholytic surfoAtont
Ampholytic s--rfA~ ' can be ill~,u.~ol_ ' into the detergent compositions
herein. These surfactants can be broadly described as aliphatic derivatives
of secondary or tertiary amines, or aliphatic deriva,ives of ~l~t.,lu~y~lic
secondary and tertiary amines in which the aliphatic radical can be straight
chain or branched.
Cotinn; ~ ~ulru~ t~ ,
Cationic ~. . rU ;A~ can also be used in the detergent cAmlrn~Aitinnc herein.
Suitable cationic ~... rU .l ~ include the 4~Ab.ll~aly a - - surfactants
selected from mono C6-C16, preferably C6-CIo N-alkyl or alkenyl
U~ ., ,.. ;~.. , ~UIr ~ wherein the remaining N positions are ~ by
methyl, llydlu~yclllJI or 1IYdIUAYIJIUIJ~YI groups.
1~ ' f B~ .r System
A highly preferred . of the detergent cnrArn~Aitinn~A herein is
a detergent builder system wherein said detergent builder system is
preferably present at a level of from 0.5% to ~0% by weight, more
-l.,f~,ldbly from 1% to 60% by weight, most l,lef~,lably from 2% to
40% weight of the compositions.
SUBSTITUTE SHEET (RULE 26
~ WO 95/19132 2 1 ~ 0 7 1 6
The detergent builder system is preferably water-soluble, and can,
for example, contain builder compound selected from ~ I I. ;c
poly~;~buAylates or their acid forms, homo or copolymeric
poly~,~uboAylic acids or their salts in which the pol~,~l,oAylic acid
comprises at least two carboxylic radicals separated from each other
by not more th?t two carbon atoms, the alkali metal, AII""..";,~-" or
A I lc h . I ~ ; 1; 1 1 1 1 I salts of 1 I ~ dtc,s, borates, ~ , and
mixtures of any of the foregoing.
Suitable water-soluble IllUllolll~,liC or oligomeric CA-IJUAYI~l~
builders can be selected from a wide range of cc.",l.~u ..l~ but such
CV..~I.U.III~1C preferably have a first carboxyl log~ithmic
acidity/constant (pK1) of less than 9, preferably of between 2 ar~d
8.5, more preferably of between 4 and 7.5.
The CCUbUAYI~ or poly~ Aylate builder can be ".. ,.. - ;c or
oligomeric in type although ,..~ "-- ;c POIY~ IJu~lates are
generally preferred for rea~.ons of cost and p. . r(,. IIIA.~P ~,.,~."". . ;~,
and oligomeric builders can be selected from acyclic, alicyclic,
l-.~lucy~ lic and aromatic carboxylates.
Suitable carboxylates CIIIIIA;II;II~ one carboxy group include the
water soluble salts of lactic acid, glycolic acid and ether d~ d~
thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and
821,370. Polycarboxylates C~IIIA;II;II~ two carboxy groups include
the water-soluble salts of succinic acid, malonic acid,
(C;~ 1;UAY) diacetic acid, maleic acid, diglycolic acid, tartaric
acid, tltrorlic acid and fumaric acid, as well as the ether
CA bUAyl~t~ tiPcrrihed in German Offenl~ I..;n 2,446,686, and
2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl
carboxylates ~ccrihed in Belgian Patent No. 840,623.
r~ly~,~ubu~l ~t~ CV'IIA;II;II8 three carboxy groups include, in
particular, water-soluble citrates, AC~ t~ and "~ as well
as succinate d~ ,dti~ such as the CA bU~Y.. ~ YIU~ j~
described in British Patent No. 1,379,241, la~,lu,~y,,~ "
descrihed in British Patent No. 1,389,732, and A.";"~
~Perrihed in Neth~orlAAl~lc ~rplirAtirn 7205873, and the
WO95/19132 P~I/u., S
~18~7~
18
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
Poly.,~l,u,.y' containing four carboxy groups include
oxy~ disclosed in British Patent No. 1,261,829, 1,1,2,2-
ethane I~ u~ulJuJ~ylates~ 1,1,3,3-propane k~ uuu~ylates and
1,1,2,3-propane lt~ bu~y- roly~ u~y' containing sulfo
include the aulruau~, de~ivatives disclosed in
British Patent No~. 1,398,421 and 1,398,422 and in U.S. Patent No.
3,936,448, and the sulfonated pyrolysed citrates described in British
PatentNo. 1,439,000.
Alicyclic and l~t~,lu~y~,lic polycarboxylates include cyclopentane-
cis,cis,cis ~ ,~bu~y' , cyclu~ p~.-~.,a,bù~y'
2,3,4,5-~ uru~ - cis, cis, cis~ lJu~y' , 2,5-
I~Llally~llvrul~l~ - cis - J;~ ux.~ , 2,2,5,5-1~lldlly~llurulall -
k;lla~bu~y~ ~, 1,2,3,4,5,6-hexane - I~ u~y' and
~,~bw-y~ yl derivatives of polyhydric alcohols such as sorbitol,
mannitol and xylitol. Aromatic poly~ubu~y' include mellitic
acid, pyromellitic acid and the phthalic acid derivatives disclosed in
British Patent No. 1,425,343.
Of the above, the preferred POIYI~IJU~ are
l~yJIU~ JU~ nf:~injn~ up to three carboxy groups per
molecule, more particularly citrates.
The parent acids of the n~on~ .ri(~, or oligomeric p~ly~,c,.bu~ylate
chelating agents or mixtures thereof with their salts, e.g. citric acid or
citrate/citric acid mixtures are also ~ as . ,~ull~l~L of
builder systems of the detergent ,,~
Specific examples of carbonate builder compound include the alkali
metal ~albu...~t~,a, ~ ,, and sesqui. ~bul~tua~
Specific examples of phosphate builders are the alkali metal
L,il,olyl ~:, ' s, sodium, potassium and
,U~lU~llU~Ull~lt~, sodium and potassium and i-l 1~,,,;l-,-,
SUBSTITUTE SHEET (RULE 26)
WO 95/19132 r~-,u., i ~'/1
218~7~ 6
19
~ylul.llo~ sodium and pûtassium orthorho~rh~t~P, sodium
polymeta/rho~rh~tp in which the degree of poly~ dlion ranges
from about 6 to 21, and salts of phytic acid. Preferably, no
- rho~l.h~.e builder compound is present.
The compositions may also include less water soluble builders
although ~,~r~l~bly their levels of ill~o.~,uldlion are ",;";",;,~-~
Examples of such less water soluble builders include the crystalline
layered silicates, and the largely water insoluble sodium
~IIImin(~ tP~
Alk~lini~
An alkalinity source is a preferred c~" "~ . . ,L of the ~. " "~ ;on~
herein. A useful alkalinity source is provided by silicates which also
provide china care ~lo~. lLi~, to the deterger~t fonnlll~ti- n Suitable
silicates include the water soluble sodium silicates with an SiO2:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being
preferred, and 2.0 ratio being most preferred. The silicates may be in
the form of either the ~IIlyLuu~ salt or a hydrated salt. Sodium
silicate with an SiO2: Na20 ratio of 2.0 is the most preferred silicate.
Silicates are preferably illCOI~ul ~d in the c ~ ; l ;onc of the invention
at a level of from 1% to 50%, ~I~c~,~dbly from 5% to 40%, most preferably
from 5% to 30% by weight.
A~l~lition~l bl- ~ I",~ nt~
The detergent cu...~ herein may include ~ agents,
liti~ln~l to any diacyl or tetraacyl peroxide L~ species, selected
from chlorine bleaches, inorganic p~ Illydl~.~ salts, p~.u~yd~,;d bleach
U~ and organic ~ yu~,;ds.
T_ere may be provided a means of delaying the release of oxygen bleach,which could inc!ude any diacyl and/or tetraacyl bleaching species, into the
wash solution. Said means may be provided, for example by coating a
granular bleach co, ~ ~l ù,, . IL with a lly~Lu~llot - coating, or by choice of
_
W095/1913~ ~I8U7~ '
physical form of the bleach which has a slow rate of dissolution by virtue,
for example of its density or particle size.
Delayed release of the oxyegrl bleach into the wash solution can be
adv~nt~ o~lc in the prevention of ~ ,i"~ of silverware in washload,
particularly when a COIIIIJOII~ designed to plU~ .,ly coat the silver in
the wash is also included in the fo~n~ ti~n Such silver tarnish
prevention t~rhnoiogies are disclosed in the Applicant's co-pending
European Applications Nos. 9370004.4, 93870090.3, 93201918.5 and
93202095.1.
Chlorin~ bl~ hir~ ~Szerltc
Chlorine bleaches include the alkali metal hypochlorites and .I,Iv,;" ~ d
cyanuric acid salts. The use of chlorine bleaches in the c~",~ ;on of the
invention is preferably ",;,,i",;, -i and more preferably the cu..,l-o~;lionc
contairl no chlorine bleach.
In- ræ~nir ~ bl~ hi~ ~ntc
The detergent c-.."~ c herein ~ .bly include an irlo}ganic
perhydrate salt, normally in the forrn of the sodiurn salt preferably at a
level of from 1% to 40% by weight, more ~ f~ably from 2% to 30% by
weight and most preferably from 5% to 25% by weight of the
c-.",l,. ~;l;-,nc
F--- } 1 of inorganic ~ Ldtt; salts include perborate, ~ Oildt~,
~'~ L ' . ' , p~rc~llf~ and p~ rcilir~t~ salts. The inorganic p.,lllydlaLt:
salts are normally the alkali metal salts. The inorganic p~.ll.~Ldt~: salt may
be included as the crystalline solid without ~ ition~l ~IUt~iUII. For
certairl ~-,-llydla~ salts however, the preferred Py~cllti~nc of such granular
~u~ o~;lionc utilize a coated form of the material which provides better
storage stability for the ~ .llydlaL~: salt in the granular product.
Sodium perborate can be in the form of the IllvllOhy~Lal~ of nominal
formula NaB02H202 or the t~,L dlly-L~e NaB2H22-3H2
- WO 95119132 r~
~8~7~
21
Sodium ~ I.a.~vlldL~, which is a preferred perhydrate for inclusion in
detergent compositions in accordance with the invention, is an addition
compound having a formula cv~ -lillg to 2Na2C03.3H202, and is
available cvllllll~ ;ally as a crystalline solid. The ~ ,a.~ullat~. is most
preferably ill~ul~Gldt~d into such ~.."I,o~;~inni in coated form. The most
preferred coati lg material cn~ mixed salt of an alkali metal sulphate
and carbonate. Such coatings together with coating processes have
previously been described irl GB-1;466,799, granted to Interox on 9th
March 1977. The weight ratio ofthe mixed salt coating material to
p~ allvvll..t~ lies in the range from 1: 200 to 1: 4, more ~ c~,~dbly from 1
: 99 to 1: 9, and most ~JIl,fclably from 1: 49 to 1: 19. P~l~ f~dbly~ the
mixed salt is of sodium sulphate and sodium carbonate which has the
general formula Na2SO4.n.Na2CO3 wherein n is form 0.1 to 3, preferably
n is from 0.15 to 1.0 and most preferably n is frorn 0.2 to 0.5.
Another suitable coating material is sodium silicate of SiO2: Na2O ratio
from 1.6: 1 to 3.4: 1, ~ fcl~ly 2.8: 1, applied as an aqueous solution to
give a level of from 2% to 10%, (normally from 3% to 5%) of silicate
solids by weight of the ~ ll,vll~le. ~f~ , silicate can also be
included in the coating. Other suitable coating materials include the alkali
and alkaline earth metal sulphates and Call,Vildt. ...
PvLasa;ulll p~ lV2~y~ lf1tP iS another inorga~ilic p~,lllydl. t~, salt of
"~.,.f"l". ~c in the detergent C~..l.l.h- :1;""~
r~...~-- :,1 blP~h ~ vl ~
The detergent G~ "` herein also preferably include a ~.,lv.~c.c;d
bleach ~ Vl (bleach activator), usually in c-,...l.;" ,1;nn with an
inorganic p~llly~La~e salt. r~lv~a~ id bleach ~ ulavli~ are normally
;llcv.~vl..t.,d at a level of from 1% to 20% by weight, more preferably
from 1% to 10% by weight, most preferably from 1% to 7% by weight of
the 5~ ~1 v~ ..,c
The p~lv~a,;d bleach IJI-;i~Ul:~VI~ typically contain one or more N- or O-
acyl groups, which ~ ,UI:lVl~ can be selected from a wide range of
classes. Suitable classes include ar~ydrides, esters, imides and acylated
. , , _ . _ _ _ , _ .
W095119132 r."-l~ s~
2 1 8 ~ 22
;L l ivi1Li~ of imidazoles and oximes, and examples of useful materialswithin these classes are disclosed in GB-A-1586789. The most preferred
classes are esters such as are disclosed in GB-A-836988, 864798, 1147871
and 2143231 and imides such as are disclosed in GB-A-855735 &
1246338.
Particularly preferred bleach precursor compounds are the N,N,NI,Nl tetra
aCI,~ylat-_d CvllllJuulldS of formula
(CH3CO)2-(CH2)X-(CH3CO)2 wherein x can be O or an integer between
1 & 6.
Examples include tetra acetyl methylene dia,nine (TA~ID) in which x=l,
tetra acetyl ethylene diamine (TAED) in which x=2 and Llllaac~Lyl
hexylene diarnine (TAHD) in which x--6. These and analogous
cU.,.l.v.. 1~ are described in GB-A-907356. The most preferred
p~lv~ya~ ;d bleach precursor is TAED.
Another preferred class of ~I,.v~a~,;d bleach activator c~ vu,.-is are the
amide, 1.~ c~ .v~ describedinEP-A-0170386.
Other p~,lv~a.,id bleach precursor c~,...l.vu-.ll~ include sodium trimethyl
hexanoyloxy benzene sulfonate and sodium acetoxy benzene sl~lfi~n~P
Or~nic ~r . V~,..~i,ic
The detergent cc- ..~ ons may also contain organic ~..v~yal,ids at a
level of from 1% to 15% by weight, more ~ f~ lably from 1% to 10% by
weight of the cv..-~v~ilion.
Useful orgariic ~.v~a~,ids include the amide ,.~ rd p~ .v~ya ,ids
r~ ribed in EP-A-0170386.
Other orgarlic p~v~al,ids include diperoxy dodPc InP~ioc acid, diperoxytetra ~Pc~nP~ioc acid, di~J~ .v~yllf ~ ;oc acid, mono- and
di~.,.a ~,laic acid, morlo- and di~. Ib~ .ylic acid, monoperoxy phthalic
acid, ~ .~vic acid, and their salts as disclosed in, for example, EP-A-
0341 947.
~ W0 95119132 2 1 8 ~ 7 1 6 P~
23
Lime s~ aA~IL
The compositions herein may contain a lime soap .~ AIIt cQrnro~n-1
which has a lime soap ~ ;n~ power (LSDP), as defined hereinafter of
no more than 8, preferably no more than 7, most preferably no more than
6. The lime soap .lialJ~.laAII~ c~mroun~l is preferably present at a level of
from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most
preferably from 2% to 10% by weight ofthe c-.",l~v~;~,onc
A lime soap '~ AIlL is a material that prevents the ~ AI;on of alkali
metal, A~lllll~lllllll~ or amine salts of fatty acids by calcium or .,~ "
ions. A InlmrAricAl measure of the e~. Ii~,.,l..,;.a of a lime soap ~ A. Il iS
given by the lime soap ~I;c~ . power (LSDP) which is ~
using the lime soap ~ , test as described in an article by H.C.
Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages
88-90, (1950). This lime soap dispersion test method is widely used by
rrActitil.n~rc in this art field being referred to, for example, in the
following review articles; WN. Linfield, Surfactant Science Series,
Volume 7, p3; W.N. Linfield, Tenside Surf. Det., Volume 27, pageslS9-
161, (1990); and M.K. NAgA.~ W.F. Masler, CosmPtiAS and Toiletries,
Volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of
r~icp~r.cin~ agent to sodium oleate required to disperse the lime soap
deposits for~ned by 0.025g of sodium oleate in 30ml of water of 333ppm
CaC03 (Ca:Mg--3:2) equivalent hardness.
Polymeric lime soap 'II`lJ` ~ suitable for use herein are described in the
article by M.K ~T~æ ; and W.F. Masler, to be found in Cosmetics and
Toiletries, Volume 104, pages 71-73, (1989). F , ' of such polymeric
lime soap .I;~p. .~ ; include certain water-soluble salts of copolymers of
acrylic acid, ~ &~l~ylic acid or mixtures thereof, and an acrylamide or
a~ d acrylamide, where such polyrners typically have a molecular
weight of from 5,000 to 20,000.
Su. rA-,ku,~ having good lime soap 1;~ l capability will inc I u~e
certain arnine oxides, betaines, 5~1 r~ , alkyl ethoxysulfates and
ethoxylated alcohols.
_ _ _ . . .
WO9S/19132 r~,l",~,5. /1
~807~6
24
Exemplary surfactants having a LSDP of no mo}e than 8 for use in accordwith the invention include C16-Clg dimethyl amine oxide, C12-C1 8 alkyl
ethoxysulfates with an average degree of ethoxylation of from 1-5,
particularly C 1 2-C 1 5 alkyl ethoxysulfate, , r~ with a degree of
ethoxylation of about 3 (LSDP=4), and the C13-Cls ethoxylated alcohols
with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold
under the trade names Lutensol AOi2 and Lutensol A030 .~ . ly, by
BASF GmbH.
Or~nic polym~oric C~
Organic polymeric culll~vullds may be added to the detergent
culll~vsi~ions herein. By organic poly~ .;c colll~uulllls it is meant
essentially any polymeric organic colll~ùullds commonly used as
,r..~ l anti-l~,d~ ilion and soil a lalJ~. la;Vll agents in detergent
COIlll~a;liOnS.
Organic polymeric c--~ I-u~ ~I may be il~COI~ul- ~d into the detergentculllpvailions of the invention at a level of from 0.05% to 30%,
preferably from 0.5% to 15%, most ~Icf~lably from 1% to 10% by
weight of ~e co~ v~
Organic polymers cont~inin~ acrylic acid or its salts having an
average -' ' weight of less than 15,000, I~lc;llan~. referred to
as low m~ r weight acrylic acid c~,..l~;..;..~ polymer, are
particularly preferred organic polymeric c~.~..l.u~ herein.
The low ",~ weight acrylic acid C~ ;";,~ polymers
preferably have an average l~lf lP~ weight of less than 15,000,
preferably from 500 to 12,000, more ~l~,f~.lably from 1,500 to
10,000, most EJIcf~,labl~ from 2,500 to 9,000.
The low mf ~ r weight acrylic acid ~ polymers may be
either homopolymers or copolyrners including the essential acrylic
acid or acrylic acid salt monomer urlits. Copolymers may include
essentially any suitable other .llùnc,~ ,l units including modified
W09~ 9132 r~ .'c~~~l
~18~71~
25
acrylic, fumaric, maleic, itaconic, aconitic, mPs~rnni~ citraconic and
methyl~n~m~lnnic acid or their salts, maleic anhydride, acrylamide,
alkylene, villylll~ yl ether, styrene and any mixtures thereof.
Preferred cullllll~ ially available low molecular weight acrylic acid
cnnt~inin~ homopolymers include those sold under the tr~ n~nnP
Sokalan PA30, PA20, PA15 and PA10 by BASF GmbH, and those
sold under the L~ Acusol 4SN by Rohm and Haas.
Preferred low mrl ' weight acrylic acid cu .~ copolymers
include those which contain as monomer units: a) from 90% to 10%,
preferably from 80% to 20% by weight acrylic acid or its salts and b) from
10% to 90%, preferably from 20% to 80% by weight of a ~..I"I;L..~ ~
acrylic .llo~ ,. or its salts having the general formula -[CR2-CRl(CO-
O-R3)]- wherein at least one of the, ~ Rl, R2 or R3, ~ f~,.ably
R1 or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R1 or R2 can be a
hydrogen and R3 can be a hydrogen or aLkali metal salt. Most preferred is
a ~.I.,I.L. ~ d acrylic IlWllUIII~,I wherein Rl is methyl, R2 is hydrogen (i.e. a
methyl acrylic acid l.l~l~olll~,.). The most preferred copolymer of this type
has a molecular weight of 3500 and contains 60% to 80% by weight of
acrylic acid and 40% to 20% by weight of methyl acrylic acid.
Preferred cullllll.,l-,;àlly available low m- !~c~ r weight acrylic acid
~..1~;..;..~ copolymers include those sold under the lI~ F Sokalan
CP10 by BASF GmbH.
Other suitable poly~.~,lylaL~/modified pOlya~,lyl..~ cop~lyllle.~ include
those copolymers of ....~ ... t t. d aliphatic carboxylic acids disclosed in
U.S. Patents No.s 4,530,766, and 5,084,535 which have a molecular
weight of less tharl 15,000.
Further examples of organic polylll~,.;c c-....l,u-~ include the water
soluble organic homo- or co-polylll.,.;c pol~,~l,u~ylic acids or their
salts in which the poly~albu~ylic acid c~ - at least two
carboxyl radicals separated from each other by not more than two
carbon atoms. Polymers of the latter type are disclosed in GB-A-
1,596,756. F--- _~1 of such salts are the copolymers of
WO 95/19132 r~ 'c ~
~8~7~
26
polyacrylate with maleic ~IIIy~Lidc having a molecular weight of
from 20,000 to 70,000, especially about 40,000.
Other suitable organic polymeric c~...,l,v~ include the polymers of
acrylamide and acrylate having a mo' ~ l~r weight of from 16,000 to
100,000, and the acrylate/fumarate copolymers having a ~ r weight
of from 16,000 to 80,000.
The polyamino c~-mrolm~le are useful herein including those derived from
aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and
EP-A-35 1 629.
Other organic polymeric c~ .v~ suitable for ill~vl~vld~ion in the
detergent cvlll~v~iliOnS herein include cellulose d~,.;vd~ , such as
lll~;llylc~ los~ ~,albv~.glll~lllylcellulose and IlyL~ ;llyl~P~ 5l-
Further useful organic polymeric c~ v~ are the polyethylene glycols,particularly those of m~ r weight 1000-10000, more particularly 2000
to 8000 and most preferably about 4000.
Polymeric dye tr~ncfer inhihiti~sF ~entc
The detergent ~ herein may also cornprise from 0.01% to 10
%~ fi,~ably from 0.05% to 0.5% by weight o~pol~ ; dye transfer
i~hihitin~ agents.
The polymeric dye tra.~fer inhibiting agents are ~f~,.dbly selected from
polyamine N-oxide polymers, copolymers of N-
vill~l~yllvlidone and N-v~lglhl, ' '-, pol~villyl~.vlidone
polymersc~"~ thereof
WO 95/19132 r~
218~7~
27
a) Polyi1min~ N-nxi~ polym~rs
Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:
p
I
~I) Ax
R
wherein P is a polyl..c. ' '^ unit, whereto the R-N-O group can be
attached to, or wherein the R-N-O group forms part of the polyl~ ble
unit or a culll~illaLion of both.
o
A is NC, CO, C, -O-,-S-, -N-; x is O or l;
R are aliphatic, ethu~yla~cd ~lirh~tir~^ aromatic,
h~ t~,.c~ ,lic or alicyclic groups or any culllbil~ ion
thereof whereto the nitrogen of the N-O group can be
attached or wherein the nitrogen of the N-O group is part
of these groups.
The N-O group can be l~ c~ cd by the following general
~ll U.,lUACS:
O O
1`
(Rl)x -N- (R2)y --N- (Rl)x
,. I ", ,~, , .
(R3)z
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or C~llll,illd~iùlls thereof, x or/and y or/and z is O or 1 andwherein the nitrogen of the N-O group carl be attached or wherein the
WO 95119132 1 ~
2~71~
28
nitrogen of the N-O group forms part of these groups. The N-O group can
be part of the pùly~ ;sdble unit (P) or can be attached to the polymeric
backbone or a combination of both.
Suitable poly~ -c N-oxides wherein the N-O group forms part of the
polyll.~ ~lc unit comprise polyamine N-oxides wherein R is selected
from aliphatic, aromatic, alicyclic or l.~,t~lv~lic groups. One class of said
polyamine N-oxides comprises the group of polyamine N-oxides wherein the
nitrogen of the N-O group forms part of the R-group. Preferred polyamine
N-oxides are those wherein R is a ll~t~,lu~,y~,lic group such as pyrridine,
pyrrole, imi~l~7nl~, pyrrolidine, rirl-rj~lin~, quinoline, acridine and
derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine
N-oxides wherein the nitrogen of the N-O group is attached to the R-group.
Other suitdble polyamine N-oxides are the IJUI yalllillC; oxides
whereto the N-O group is attached to the poly ' '- unit.
Preferred class of these poly~ , N-oxides are the pol~,.l- il~C N-oxides
having the general formula (I) wherein R is an arolrqti~k ~ ù-,y~lic or
alicyclic groups wherein the nitrogen of the N-0 functional group is part of
said R group. Examples of these classes are poly~..lil.~ oxides wherein R is
a h~,t~,lu~,y~lic compound such as pyrridine, pyrrole, imidazole and
derivatives thereof.
Another preferred class of pOI~a.llil~ N-oxides are the pùl~ , oxides
having the general formula (I) wherein R are aromatic, heterocyclic or
alicyclic groups wherein the nitrogen of the N-0 functional group is attached
to said R groups. Examples of these classes are pul~ .. ilæ oxides wherein R
groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer inhibiting properties.
Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,
SUBSTITUTE SHEET (RULE 26)
WO 95119132 . ~
21~7~5
29
polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures
thereof.
The amine N-oxide polymers of the present invention typically have a ratio
of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount
of amine oxide groups present in the polyamine oxide polymer can be
varied by appropriate copolyl~ ion or by ~I Iuulid~e degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to
I: 1000000. More preferably from 1:4 to 1:1000000, most preferably from
1:7 to 1:1000000. The polymers ofthe present invention actually
c llcullll.c~c.s random or block copolymers where one monomer type is an
amine N-oxide and the other IllOliUIII~,I type is either an amine N-oxide or
not. The amine oxide unit of the polyamine N-oxides has a PKa < 10,
,f~ lably PKa < 7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of
polylll.,. ;..d~ion. The degree of poly . ". .; ~1 ;nn is not critical provided the
material has the desired water-solubility and dye-, ~ power.
Typically, the average molecular weight is within the range of 500 to
1000,000; U~cr~.al~ly from 1,000 to 50,000, more preferably from 2,000 to
30,000, most ~Icfcldbly from 3,000 to 20,000.
b) Copolym~r~ of N-vi-~yl~l~ulidone ~n-l N-vi-lylimi-~7r1e
Preferred polymers for use herein may comprise a polymer selected from
N-vinylimida_ole N-villyll,~..ulidone copolymers wherein said polymer
has an average mn~ r weight rarlge from 5,000 to 50,000 more
preferably from 8,000 to 30,000, most ~.c~.dbly from 10,000 to 20,000.
The preferredN-vinylim~ 7~ N-vi-lyl~yllulidone copolymers have a
molar ratio of N-vinylimidazole to N-villyl~1.lolidone from I to 0.2, more
preferably from 0.8 to 0.3, most ~l~f~ lably from 0.6 to 0.4 .
.
c) Polyv;,~ylvyl,oli~ n~
The detergent culll,uo~ilions herein may also utilize polyvillyl~yllulidone
("PVP" having an average
WO 95119132 P~
~8~71~
weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more
preferably from 5,000 to 50,000, and most preferably from 5,000 to
15,000. Suitable polyvillylE,yllulidones are cu~ . ially vailable from
ISP Corpo~ation, New York, NY and Montreal, Canada under the product
names PVP K-l5 (viscosity molecular weight of 10,000), PVP K-30
(average molecular weight of 40,000), PVP K-60 (average molecular
weight of l 60,000), and PVP K-90 (average molecular weight of 360,000).
PVP K-15 is also available from ISP Corporation. Other suitable
polyvi--yl~y-lulidones which are cull.-...,l~ially available from BASF
Cooperation include Sokdlan HP 165 and Sokalan ~ 12.
Polyvil.yll.~..ùlidone may be i~lc~ll.ul..t~,1 irl the detergent cc,...p~si~ionsherein at a level of from 0.01% to 5% by weight of the detergent,
~f,.~ly from 0.05% to 3% by weight, and more
f..ably from0.1%to2%byweight.Theamountof
polyvi..yl~y..ulidone delivered in the wash solution is ~ C~.dbly from 0.5
ppm to 250 ppm, preferably from 2.5 ppm to l50 ppm, more ~ ,C~.ably
from 5 ppm to 100 ppm.
d~ PolyvinyloY~7nlidnn~o
The detergent c~ herein may also utilize polyvinyloY~7l)li~inn~c
as polymeric dye transfer
inhibiting âgents. Said polyvinylnY~7~ nn-o~ have an average molecular
weight of from 2,500 to 400,000, ~ fi ~ably
from 5,000 to 200,000, more ~-I f~ .~ly from 5,000 to 50,000, and most
~-~r,,.dbly from 5,000 to 15,000.
The amount of polyvinyloxazolidone illCC l~ d in the detergent
c~ .ù~ may be from 0.01% to 5% by weight, preferably from 0.05%
to 3% by weight, and more preferably from 0.1% to 2% by weight. The
amount of polyvinyl~Y~7nl i-lnn~ delivered in the wash solution is typically
from 0.5 ppm to 250 ppm, ~I~.C~ lably from 2.5 ppm to l50 ppm, more
.f~ lably from S ppm to 100 ppm.
WO 95119132 r_l/ll~. 5 ~ /1
21~0~1~
e) Polyvirlylimiri~7r 1e
The detergent crlmroeiti- ns herein may also utilize polyvillyl;..,i~i~7r le as
polymeric dye transfer inhibiting
agent. Said polyvil.ylilllida7oles preferably have an average
molecular weight of firom 2,500 to 400,000, more ~ ably firom 5,000 to
50,000, and most ~ ably firom 5,000 to 15,000.
The amount of polyvillyliulli-l~ule iUI~,vl~val ~d in the detergent
cbl''l'o~ ne may be firom 0.01% tû 5% by weight, ~l~f Idbly firom 0.05%
to 3% by weight, and more preferably from 0.1% to 2% by weight. The
amount of polyvil,ylill.ida7ole delivered in the wash solution is firom 0.5
ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more ~ ,fi .ably
from 5 ppm to 100 ppm.
~e~vy rnPt~l ir n s~u~
Heavy metal ion s~ t~n~llY are usefi~ lY hereirl. By
heavy metal ion s~.lu~i~ha l~Y it is meant c~ which act to
sequester (chelate) heavy metal ions. These c~ may also
have calcium and ",~ .. chelation capacity, but IJI, f~ idlly
they bind heavy metal ions such as iron, ~ and copper.
Heavy metal ion se~lu~ ~hallL are ~l~ .C._ldlJly present at a level of
firom 0.005% to 20%, more ~ ,f~,lably from 0.05% to 10%, most
fi,.dl~ly firom 0.1% to 5% by weight ofthe ~- --l.v~ .c
Heavy metal ion ~ IY which are acidic in nature, having for
example rl~o~ ..,;c acid or carboxylic acid fimrtir~n~liti~e, may be
present either in their acid form or as a cv , ' l~alt with a suitable
counter cation such as an alkali or aL~caline metal ion, ~-.. --.. ;,--.. , or
~"I.,I;I.it. ~-i nllllll~.ll;ll... ion, or any mixhJres thereo Preferably any
salts/c--mr'^~Pe are water soluble. The molar ratio of said counter
cation to the heavy metal ion s,~lu- ~11n~1 is preferably at least 1:1.
Wo95/19132 ~~
716
32
Suitable heavy metal ion se~lu~aLIduL. for use herein include the
organo Rrnin~phf~srh~7nRt~e such as the amino alkylene poly
(alkylene pl~ .".~ t ,) and nitrilo trimethylene rl7-7,~,hl-1-At~ ~
Preferred organo arninorh~7s~h~ s are diethylene triamine penta
(methylene rh~ AIr) and 1~ ylene diamine tetra
(methylene pllh~ .",A~
Other suitable heavy metal ion se~.l.,..L~GU.L. for use herein include
nitrilotriacetic acid and polyGU~ lOcGul,-,~ylic acids such as
ethyl~ acid, ethy1 ~ ;A-ll;llr pentacetic acid, or
ethy!~ Ir ~ F f~iellrrinif acid. Especially preferred is
ethyl~ ,F-I;- ";"-o N,N' ~ lcrinif~ acid (EDDS), most preferably
present irl the form of its S,S isomer, which is preferred for its
hiof~f~ Rhility profile.
Still other suitable heavy metal ion s~ J7t~ for use herein are
;I";"-~.l;R~ ;r acid d, .;vG.li~s such as 2-1-yd-~ lyl diacetic acid
or glyceryl imino diacetic acid, described in EPA 31 ~ 542 and EPA
399 133.
rn one preferred aspect of the invention any heavy metal ion
s~lue.,~ , pGuLi~ulG, ly where said 5~ ,1 C.J~ 5 organo
amino~ f.~J...I~o,~ , is sprayed onto puw~ ,d sodium
sulphate prior to i~ ...alion into granular c~,."l~,sl;~ in accord
with the invention. rnis s~ep leads to enhanced s~lu~ ~11r .1 stability
in the gra~ular detergent matrix.
(~ryst~l p~owth inhihitf,r
A preferred c~ - .L of tne detergent c- ~ ~;l ;f ne hereirl is a
crystal growth inhibitor selected frorn organo 1;~ acid or
oneofitssalL~/c ~' - Theorgano .I;I.Ilh~ O.~ir, acidc.,~ J~I-'IL
is ~ l~ f~.dbly present at a level of from 0.005% to 20%, more
~ f~,.G,~ly from 0.1% to 10%, most ~I.,f~,.dbly from 0.2% to 5% by
weight of the c~ ne
' . ` '
WO gS/19132 r~l,u~
218~
33
The organo di~JI.ùsluholl;c acid ul~ l,ù.~.... may be present in its acid
form or in the form of one of its salts or cnmrlrYrs with a suitable
counter cation and reference ~ U;lldl~ to the acid implicitly includes
reference to said salts or . . ' r-s Preferably any salts/cnnlrir YPc
are water soluble, with the alkali metal and alkaline earth metal
salts/comrl~Y~ being especially preferred.
The organo riirhnsphnni~ acid is Ul~ Lly a Cl-C4 ~ hvo~Jllvllic
acid, more preferably a C2 di~l.us~uh~,...c acid, such as ethylene
hncrh( - acid, or most preferably ethane l-hydroxy-l,l-
l,r~.. r acid (HEDP).
Enzvme
Another optional ingredient useful in the detergent cnmrnCitions herein is
one or more enzymes.
Preferred enzymatic materials include the ~ ~,;ally available lipases,
amylases, neutral and alkaline prûteases, esterases, cellulases and
,~lu~i.l~s conventionally ill~,UlU'l I into detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred ~ lly available protease enzymes include tbose sold under
the LlaJc~ s Alcalase, Savinase, Durazym, and Esperase by Novo
Industries A/S (Denmark), those sold under the b ' - Maxatase,
Maxacal and Maxapem by Gist-Brocades, those sold under the tradename
FN, FNA and FN-2 by Genencor International, and those sold under the
tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme
may be i..cu.,uu. ~ into the . . onC in a.,~,ul i~.lce with. the invention
at a level of from 0.0001% to 2% active enzyme by weight of the
COII.~ .n
Preferred amylases include, for example, -amylases obtained from a
special strain of B li~ uru~-..o~ described in more detail in GB-1,269,839
(Novo). Preferred ~ullll..~ll,ially available amylases include for example,
those sold under the 1. ' - Rapidase by Gist-Brocades, and those sold
under the tradename Termamyl and BAN by Novo Industries A/S.
SUBSTITUTE SHEET (RULE 26)
WO 95/19132 21 8 ~ 71 ~
34
Amylase enzyme may be incorporated into the composition in acculd, .lcewith the invention at a level of from 0.0001% to 2% active enzyme by
weight of the c~ 0~1 irln.
Lipolytic enzyme (lipase) may be present at levels of active lipolytic
enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by
weight, most preferably from 0.001% to 0.5% by weight of the
c~-,..l.rl~ilirne,
The lipase may be fungal or bacterial in origin being obtained, fpr
example, from a lipase l.lU.lUl;illg strain of E~llrnicola sp.or Th~ . 1 l l. .ll ~y.
sp. or pSP~ mrlnac psP.~ a1ral~PnPc or r~ do"~c n"~ Lipase
from cl~Pnnir~ally or g~n.otically modified mutants of these strains are also
useful herein.
A preferred lipase is derived from E~ "~ pqPI~ alralu~en~c which
is described in Granted European Patent, EP-B-02 18272.
Another preferred lipase herein is obtair~ed by cloning the gene from
~llrnicola lanl~5~in~ca and ~A~ lg the gene in ~cpP~illllc nryza, as
host, as described in European Patent Arplicati~n~ EP-A-0258 068, which
is cul.~ ,.ally available from Novo Industri A/S, Bagsvaerd, Derlmark,
under t~he trade name Lipolase. This lipase is also described in U.S. Patent
4,810,414, Huge-Jensen et al, issued March 7, 1989.
F,n7,ymP Stahili7i--~p SyctPm
Enzyme-c~ .;..g c~ herein may comprise from 0.001% to
10%, ~ f .dbly fro~n 0.005% to 8%,most ~.efi,.al)ly from 0.01% to 6%,
by weight of an enzyme st~hili7in~ system. The enzy~ne stabilizing
system can be any stabilizing system which is comp~ihle with the
detersive enzyme. Such stabilizing systems car~ comprise calcium ion,
boric acid, propylene glycol, short chairl ca bu~lic acid, bororlic acid, and
mixtures thereo Such stabilizing systems can also comprise reversible
protease inhibitors.
~ WO 95/19132 2 1 8 ~ 7 1~ .'CTI[1595/0û571
The c~ ~ l inne herein may further comprise from 0% to 10%,
preferably from 0.01% to 6% by weight, of chlorine bleach a-,dvG~ .a,
added to prevent chlorine bleach species present in many water supplies
from attacking and ina~ aLi lg the enzymes, especially under alkaline
cnnriition~ While chlorine levels in water may be small, typically in the
range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume
of water that comes in contact with the enzyme during washing is usually
large; ac~,ullillgly, enzyme stabilit~ in-use can be problematic.
Suitable chlorine SCa~ l arlions are widely available, and are illllctr~tr~d
by salts C~ nllllll.lll;lllll cations or sulfite, bisulfite, Ll,io~"lril~
thiosulfate, iodide, etc. ~ntin~drl~ntc such as calbàllL~t~ â3CUl~ ~ etc.,
organic amines such as ethyl~ . .r.l._. ";~ ~.,t~ r~l ~c acid (EDTA) or alkali
metal salt thereof""..~ ol-~..;.,- (MEA), and mixtures thereof can
likewise be used. Other conventional SCaVGIIg~,la such as bisulfate, nitrate,
chloride, sources of hydrogen peroxide such as sodium perborate
LGLlnlly~t~ ~ sodium perborate ~IlVI~oll~LdL~ and sodium p...~,~ul,ù~ , as
well as rlln~ , cnn-l~nced ~ 0~ acetate, benzoate, citrate,
formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can
be used if desired.
CorrnQ;--n inhibitnr
The c ~ 1 v~ onC may alsû contain corrosion inhibitor which is preferably
incul~vl. t~d at a level of from 0.05% to 10%, preferably from 0.1% to 5%
by weight of the c~ rJ~ ."
Suitable corrosion inhibitors include paraffin oil typically a ~ d~ ,,;nA,,
branched aliphatic llyJlu~,albOIl having â number of carbon atoms in the
range of from 20 to 50; preferred paraffin oil selected from ~,le~.,,.;,,^~,Lly
branched C2s 45 species with a ratio of cyclic to noncyclic lly~hu~,a~ulls
of about 32:68; a paraffin oil meeting these 1~ 1; c is sold by
Wint~rch~ll, Salzbergen, Germany, under the trade name WINOG 70.
Other suitable corrosion inhibitor cul~c.~ld~ include l~.,,.~uhiaLule and
any d~,-;vd~ s thereof, IlI~ and diols, especially Il~ ,~L~ with
4 to 20 carbon atoms including lauryl nl~,-,a~l, thiophenol, thinn Irthol,
WO 95119132
~18û71~ P~l/u ~
36
thionalide and thio~nthr~nr.l. Also suitable are the C12-C20 fatty acids, or
their salts, especially aluminium Ll;aLcdlalt~. The C12-C20 hydroxy fatty
acids, or their salts, are also suitable. Pl,~ o~ d octa-decane and other
anti-oxidants such as 1~ L~ly~LvAyluluene (BHT) are also suitable.
S--~lC `'~1'1"~``;'~ Sy~tPm
The cvlll~G~iLions herein may comprise a suds ~u~lJIL,aillg system
preferably present at a level of from 0.01% to 15%, more preferably from
0.05% to 10%, most preferably frorn 0.1% to 5% by weight oft~e
c..llll.oa;lion. A suds ~U~IC~;~iLlg systern is a highly preferred c~",~ ,F ,L
of the cvllllJvailiOns when the, ~ r~ systern c~ high foaning
sllrf~t~nt
Suitable suds ~U~ ,.,aillg systems for use herein may comprise essentially
any known antifoam c~ v~ 1 in~ Ain~, for example silicone antifoam
cU",I)v"..~l~ 2-alkyl alcanol antifoam cc,l"l-u-~ , and paraffin antifoam
c..",l,v~
By antifoam cullll,vulld it is meant herein any c-.."l.v. "-1 or mixtures of
cu~ vullds which act such as to depress the foaming or sudsing produced
by a solution of a detergent c~ mr-~cition~ in the presence of
agitation of that solution.
Particularly preferred antifoam ~u".l~u~ for use herein are silicone
antifoam CvllllJuu~l~S defined herein as arly antifoam c- ,,,.I~u-- ,A includinga silicone c~ Such silicone antifoam c~....l.u-~ c also typically
contain a silica c- ~ The term "silicone" ac used herein, and in
general ;1llUU~511OU~ the industry, c ~Icvlllr a variety of relatively high
m~ ' weight polymers C~-- . 1 7; - .; . ~ siloxane ur~its arld ll~ Lv~,~l yl
group of various types.
Other suitable antifoam cvll.~uullds include the Illvllo-,a.iJu~ylic fatty acidsand soluble salts thereof. These materials are described in US Patent
2,954,347, issued Sept~mhpr 27, 1960 to Wayne St. John. The
mvl~occubu~lic fatty acids, and salts thereof, for use as suds aulJIJI~ ;,
typically have llyLù~ l chains of 10 to about 24 carbon atoms,
~ WO95tl9132 ~1~071~ . .,. ~o -/I
Gbly 12 to 18 carbon atoms. Suitable salts include the alkali metal
salts such as sodium, puL~,siulll, and lithium salts, and ~."""~ " and
alkanol "",.,m.il"" salts.
Other suitable antifoam CUlll~uullllS include, for example, high molecular
weight llyLù~,~bulls such as paraffin, fatty esters (e.g. fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic Clg-C40
ketones (e.g. stearone) N-alkylated-amino triazines such as tri- to hexa-
alkyl",~ ";"~s or di- to tetra at,kyldiamine cht,ulLl;G~ul.,~, formed as
products of cyanuric chloride with two or three moles of a primary or
SC~,OIlv~y amine c~ ;";,-~ I to 24 carbon atoms, propylene oxide, bis
stearic acid amide and ,..~ yl di-alkali metal (e.g. sodium,
pvLh~,.,iulll,lithium)~ o~ t~-andrl~f~c~ esters. Thelly~Lu~,all,ùlls,
such as paraffin and h~l~F~ffin, can be utilized in liquid form. The
liquid hyLucG bv~s will be liquid at room ~ " ~ and ;~ v.~ ;c
pressure, and will have a pour point in the range of about -40C and about
5C, and a minim-lm boiling point not less than 110C (,.1."~ . ;c
pressure). It is also known to utilize waxy hy~hu~. bvl~ " ~ S lGbly
having a melting point below about 100C. EIydLv-,a.bvll suds ~U~ Vl~
are dPsr~ihe~l for example, in U.S. Patent 4,26S,779, issued May 5, 1981
to Gandolfo et al. The lly-hvc&bùlls, thus, include aliphatic, alicyclic,
aromatic, and heterocyclic saturated or ~ t ~ ly~Luc~- I,vll~, having
from about 12 to about 70 carbon atoms.
Copolymers of ethylene oxide and ~,Iu~ lc oxide, particularly the mixedc ;llVAy' I/propoxylated fatty alcohols with an alkyl chain len~,th of from
10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a
degree of ~IùL~v~yla~ion of from I to 10, are also suitahle antifoarn
c~u".l.v~ for use herein.
Suitable 2-alky-alcanols antifoam cr...,l.v~ for use herein have been
d~erribed in DE 40 21 265. The 2-alkyl-alcanols suitable for use herein
consist of a C6 to C16 alkyl chain carrying a terminal hydroxy group, and
said alkyl chain is ~ I ;I 't- d in the alpha position by a C l to C l o alkyl
chain. Mixtures of 2-alkyl-alcanols can be used in the cc,...po~iLions
accu..lh~g to the present invention.
. ,
WO95/1913~ r~ 5
~ d7~
38
The c~mrsciti~nc herein may contain organic solvents, particularly whenform~ t~d as liquids or gels. The cnmrociti~-nc in accord with the
invention y.~,r~l~ly contain a solvent system present at levels of from 1%
to 30% by weight, ~ lably from 3% to 25% by weight, more preferably
form 5% to 20% by weight of the composition. The solvent system may
be a mono, or mixed solvent systern. Preferably, at least the major
c..,. ~ of the solvent system is of low volatility.
Suitable organic solvent for use herein has the general formula
RO(CH2C(Me)HO)nH, whereirl R is an alkyl, alkenyl, or alkyl aryl group
having frorn I to 8 carbon atoms, and n is an integer from 1 to 4.
Preferably, R is an alkyl group c~--,l~;,.;,,~ 1 to 4 carbon atoms, and n is 1
or 2. Especially preferred R groups are n-butyl or isobutyl. Preferred
solvents of this type are l-n-bulu~l,lu~,uc-2-ol (n=l); and I (2-n-butoxy-
I-methylethoxy)propane-2-ol (n=2), and mixtures thereof.
Other solvents useful herein include ~e water soluble CARBITOL
solvents or water-soluble CELLOSOLVE solvents. Water-soluble
~ CARBITOL solvents are c~ u~",-1~ of the 2-(2-alk ,~ ,Ay)ethanol
class wherein the alkoxy group is derived from ethyl, propyl or butyl; a
preferred water-soluble carbitol is 2-(2-bU~JA~ _llu~)ethanol also known
as butyl carbitol. Water-soluble CELLOSOLVE solvents are compounds
of the 2-alkoxyetho,Yy ethanol class, with 2-lJu~ ;hu~ll~lol being
preferred.
Other suitable solvents are ber~7yl alcohol, and diols such as 2-ethyl- 1,3-
h,~Y~ ,l and 2,2,4-trimethl-1,3-p~ I ol.
The low 1(. 1 ~ weight, water-soluble, liquid polyethylene glycols are
also suitable solvents for use herein.
The alkane mono and diols, especially the Cl-C6 aLI~ane mono and diols
are suitable for use herein. Cl-C4 ~ llollyL;c alcohols (eg: eth~nol.
propanol, isu~lu~allol, butanol and rnL~tureS thereof) are preferred. with
WO 95119132 P.,IIlJ.. ,.,. /1
~07le
39
ethanol particularly preferred. The C l-C4 dihydric alcohols, including
propylene glycol, are also preferred.
Ely-l- ùll v~
Hy~huLIupc may be added to the compositions herein, and is typically
present at levels of from 0.5% to 20%, pl~f~ldbly from 1% to 10%, by
weight.
Useful lly.LuLrulJ~,s include sodium, put~aaiuul, and ~mmr~nillm xyleneslllfon~t~e sodium, ~uL~;,a;ulll, and ~,,,,.v.,;l~.. toluene slllfon~t~ sodium
pUL~iUIII and ~ cumene sulfonate, and mixtures thereof.
01h~r option~ rP-liPnte
Other optional ill~ di. l~l~ suitable for inclusion in the c..",l"~;tionc hereininclude perfumes, colours and fillers.
pH of ~he Cvl~ h~;lionc
The cvlll~oaiLions preferably have a pH as a 1% solution in distilled
water at 20C of from 8.5 to 13.0, preferably from 9.5 to 11.5, most
preferably from 9.8 to 11Ø
The pH of the c~ n~ may be adjusted by the use of various
pH adjusting agents. Preferred a~ ~ifi~ti~n agents include inorganic
and o}ganic acids inrlllf~in~, for example, L~bv~yldLe acids, such as
citric and succinic acids. Bic~ ~ bv~lut~, " pa~ticularly sodium
~ic~lvùllclt~, are useful pH adjusting agents herein. A highly
preferred ~ ifir~tion acid is citric acid which has the ad~, ~ of
providing builder capacity to the wash solution.
Forrn of the cv.~ ionc
The detergent cv...l.o~;linnc herein can be formlll~t-od in any desirable form
such as powders, tablets, ~ulUIdt~ ~ pastes, liquids and gels.
.... . _, . . _ _ _ _ _ _ _ _
WO 95/19132 F~ 5~
2~8~716 40
r,iq~ cu~ ;Lionc
The detergent ~Qmrogitirng herein may be fnrm~ t~d as liquid
cu~ iliûns which typically comprise from 94% tû 35% by weight,
preferably from 90% to 40% by weight, most preferably frûm 80% to 50%
by weight of a liquid carrier, e.g., water, preferably a mixture of water and
organic solvent.
Gel CO"~ ;lionc
Gel ~ - -" ~ nc are typically f .., ., . ~ with polyakenyl polyether
having a m~ cul~r weight of from about 750,000 to about 4,000,000.
Solid c~""~ ;Linng
The detergent culll~ ;li. ",c herein may also be in the form of solids, such
as powders, grarlules and tablets.
The particle size of the c-.",i~o~ of granular c~ nc should
preferably be such that no more that 5% of patticles are greater tharl
I .4rnm in diameter and not more than 5% of particles are less than O. l Smm
in diameter.
The bulk density of granular detergent c--."~ ;licnc is typically at least
450 g/litre, more usually at least 600 g/litre and more ~l~f~,lably from 650
g/litre to 1000 g/litre.
~ pror~c.cPe - ~mll~r cu" ~ nc
In general, granular detergent c~ o~;l;u.,~ can be made via a variety of
methods including dry mixing, spray drying, at;~51ulll~ld~ion and
~amll~til?n
~ WO 95/19132 2 1 8 ~ 7 1 6
41
T~ XA~PT F..~
The following examples illustrate the present invention.
In the following ~;f,,.,l.o~;l;f~nc the ab~ ;dt, ~ identifications havethe following ... ~
Citrate: Trisodium citrate dihydrate
Nonionic: C13-C1s mixed ~LIIu~yl_t~ IO~UAYI-~ f~tty
alcohol with an average degree of ethv~yl~lio.l of 3.8
and an average degree of l l~u~yl~ion of 4.5 sold
under the ~ Plurafac LF404 by BASF Gmbh.
HEDP: Ethane l-hydroxy-l,l-~ .l"-.. ic acid
DETPMP: Diethylene triamine penta (methylene
rl~ acid), marketed by
Monsanto under the ~ F Dequest 2060
MA/AA: Copolymers of 1:4 maleic/acrylic acid, average
- ' ' weight about 80,000
Poly~-~,lyl~te; A poly~.~,l yl_t~ Illv~,ol~ with an average
I~ weight of 8,000 sold under the
. ..f~ PA30 by BASF GmbH
Protease: Proteolytic enzyme sold under the trade name
Savinase by Novo Tnfllleh iPs A/S
Amylase: Amylolytic enzyme sold under the trade name
Termamyl by Novo Tnflllc1rif c A/S
Silicate: Sodium silicate (2.0 ratio)
Carbonate: Sodium carbonate
, .
WO 95/19132 r~
~8~ 116
42
PB4: Sodium perborate tetrahydrate
PB 1: Sodium p.,~ monohydrate
PC: Sodium ~ 0l~ present in coated form,
wherein the coati lg G~,lll~l ;r,e~, a mixed salt of
formula Na2S04.n.Na2C03 where n is 0.3.
PVNO: Polyvinyl pyridine N-oxide polymer of
rweight 10,000.
DAP: Di~-;L~I.,~I acyl peroxide of formula
(CH3(CH2)6C00)2, present as a urea clathrate.
TAED: Tetraacetylethyl.. ~.l;-"",~
Paraffin: Paraffin oil, sold under the Ll ~1~ .,.. ~ Winog 70
by Wintershall
W0 95119132 r ~
218~
43
FY~TrY Ie 1
The following granular machine ~ illg detergent cu~ o~iLion
were prepared.
A B C D E
Citrate 37.0 37.0 37.0 37.0 29.0
Silicate 25.7 25.7 25.7 25.7 25.7
PBI - - - - 1.9
PB48.0 8.0 - 8.0 8.7
TAED 4.1 4.1 - 4.1 4.4
DAP - 0.5 0.5 - 05
PC - - I 0.4
PVNO - - - 0.5
Protease 2.2 2.2 2.2 2.2 2.2
Arnylase 1.5 1.5 1.5 1.5 1.5
~l~vh;~ule - - - - 0.3
Paraffin 0.5 0.5 0.5 0.5 0-5
Nonionic 1.5 1.5 1.5 1.5 1.5
HEDP - - - - 0.5
Polyacrylate - 3.7 3.7 - 3.7
MA/AA 3.7 3.7 3.7 3-7
MiS~/III-);i.Lul~ to
balarlce
pH(1% 10.7 10.7 10.7 10.7 10.7
solution)
W095/19132 r~ c--~
~a7~6
44
Compositions B, C and E contain DAP in accord with the invention.
Compositions A and D arG prior art compositions.
Test method I
The ability of Compositions A, B and D to prevent the transfer of
bl~a~ dJlc food soils to a plastic substrate was assessed using the
following IG~lG~G~ .live test method.
1. A ~ ve bleachable food soil containing cartenoid type
soils was prepared by ~ iein~ equal quantities by weight of
baked beans in tomato sauce, pasta sauce ("Ragu" lldd~ c),
Tandoori marinade and ~IP ~ jam.
2. Plastic test samples were washed in a Sotax machine (which
simulates di~ ~h~,l conditions) set at 200 rpm speed using an
aqueous wash solution containing 4g per litre of water of one
of the test detergent cnmrn~itinns and 9g per litre of water of
the l~ ,.,..Llive blca~,h~lc food soil. The water was of 8%
German hardness (Ca:Mg = 3:1, equivalent to 1.44 mmol
Ca2+/litre). The wash t ~ G was 50CC at the start of
the cycle, falling to 40C at the end of the cycle, with each
wash cycle lasting 30 minutes.
3. Each of the plastic test samples was submitted to 3 C~ lliVG
wash cycles. The plastic test samples were then removed,
dried and visually graded for staining using a 4 point Scheffé
scale.
SUBSTITUTE SHEET (RULE 2~)
~ WO 95119132 2 1 8 ~ 7 1 6 , ~I~U~,S~
' 45
Test nn~thn~ rt~c~lltc
The presence of bleachable soil stainung apparent on the plastic
samples obtained using Compositions B and D æ the detergent was
compared to that obtained for the reference (Composition A).
B/A D/A
Degree of staining +3.5 + 1.0
(positive number indicates less staining for X versus Y).
The degree of staining obtained for cnlnrnsition B in accord with the
invention was less that obtained for the reference composition A or
for the comparative co.. I,u~;liol~ D which contained the polymeric dye
transfer inhibiting agent PVNO.
Test rn.o.fhn~l 2
The bleachable food soil stain removal from soiled pl~Liuw~u~
capability of , on B was compared to that of reference
Composition A using a modified version of test method 1. The plastic
test samples were prestained by being soaked in the l~ e
bl~d~ll~l~ food soil for two days. These samples were then washed
using an indentical protocol to that of test method 1, other than that no
additional soil was added to the wash solution. The samples were
graded visually for stain removal after the 3rd successive wash cycle.
Test m~hod ~ - rl-c~lt~
B/A
Stain removal +3.0
The bleachable food stain removal of c, . nn B is enhanced
versus that of reference Co~;-c ~ititm A in accord with the invention.
SUBSTITUTE SHET (RULE 26)
WO 95/19132
~g~
46
~xamp]e 2
The following tablet formulations in accord with the inventioD were
prepared by a hblet compaction process.
F G H
Citrate 23.7 23.7 23.7
Silicate 23.8 23.8 23.8
Carbonate - 14.0
PB1 1.4 1.4 5.6
PB4 6.2 6.2 6.2
TAED 3.4 3.4 3.4
DAP 0.5 0.5 0.5
Protease 1.5 1.5 1.5
Amylase 1.1 1.1 1.1
Paraffin 0.4 0.4 0.4
Nonionic 0.2 0.2 0.2
Bu~ 0.3 0.3 0.3
HEDP 0.6 0.6 0.6
Polyacrylate 2.9 2.9 2.9
DETPMP 0.4 0.4 0.4
Na2SO4 33.1 19.1 28.9
Moisture/rnisc to
balance
SU~STITUTE SHEET (RULE $)
W0 95~19132 ~ l g Q~ L,~ ~IL ,
4'7
F~m~rle 3
The DAP Cullllvull.,.ll of each of Compositions B, C and E of
Example 1 and C- mrositinn~ F, G and H of Example 2 was replaced
by dibenzoyl peroxide at identical levels of incorporation in the
cullll.u~i~ions.
