Note: Descriptions are shown in the official language in which they were submitted.
20 1 0442 C7151(R)
LIQUrr~ DETEl~GEl~T COMPOSITION
The present invention relates to liquid detergent compositions which
contain a pt lV;~yZ~ bleach compound.
It has been proposed in EP 293 040, published November 30,1988 and EP
294 904, published December 14,1988 to incorporate solid, water-soluble
p~ Ay~ll bleach compounds m liquid detergent compositions. The
compositions as disclosed in these patent application comprise substantial
amounts of water miscible solvents for ensuring that the amount of
available oxygen dissolved in the liquid phase is not greater than 0.5%.
These high amounts of solvents are however i~",~l;",~ disadvantageous in
that they tend to decrease the solid-suspending properties of the detergent
composition, because they are believed to prevent the internal structuring of
the liquid detergent composition.
It has now surprisingly been found that stable aqueous liquid bleach
; l lg detergent compositions can be f~rm ~ t~fl, which are structured.
These ~ osili~ s do not need to contain high -structure destabilizing-
amounts of solvents for bleach stabilisation. Lower amount of solvents are
especially preferred, because it is believed that the absence of high levels of
solvents renders it possible to make detergent-structured compositions
having good solid-suspending properties.
A~uldil~,ly the present invention relates to an aqueous structured liquid
detergent composition comprising one or more detergent active materials
and a ~ y~ll bleach compound, said detergent composition having a
pH above 6.5, being structural and showing less than 25% volume increase,
preferably less than 10%, more preferred less than 5% while stored at a
temperature of between 20 and 37C for three months after preparation.
Preferably the detergent composition comprises less than a *
structure destabilizing amount, more preferably less
20~ 0442
2 C 7151 (R)
than 10% by weight Or a water m;cr~hlf- organic solvent.
The present invention is cnnl Prn~t with LLU~ LuLed
liquid detergent compositions, such c~Lu- LULed liquids
5 can be "internally structured" whereby the ~LLu-;LuLe is
formed by primary ingredients and/or they can be
~Luu~uL~d by seonftAry additives such as certain cros6-
linked polyacrylates or clays, which can be added as
"external c,LLuuLuL,~ s'' to compositions of the
10 invention.
Such structuring is very well known in the art and may
be deliberatQly brought about to endow properties such
as cu.,~ preferred flow properties and/or turbid
15 appearance. Many ~.LLuuLuL~d liquids are also capable of
sllcp~-nrt~n~ particulate solids such as detergency
builders and abrasive particles.
Some of the di~ferent kinds o~ active-structuring which
20 are possible are described in the reference ~.A. Barnes,
"Detergents" , Ch. 2 . in R. Walters (Ed), " h~ LL~:
Industrial Applications", J. Wiley & Sons, Letchworth
1980. In general, the degree of ordering o~ such systems
increases with increasing surfactant and/or electrolyte
25 u~ t ~.Lions. At very low c~,l.cel.LL~Itions, the
surfactant can exist as a molecular solution, or as a
solution of spherical micclles, both of these being
isotropic. With the addition of further surfactant
and/or electrolyte, ~LLuu~uLed (antisotropic) systems
30 can form. They are referred to respectively, by various
terms such as rod-micelles, planar 1 ~ r D~LU~;~ULeS~
1 -llAr droplets and liquid crystalline phases. Often,
different workers have used dlfferent t~rm1nnlogy to
refer to the ~.LLuuLuLes which are really the same. For5 instance, in European patent specil'tn?.tion EP-A-151 884,
l Ar droplets are called "spherulites" . The presence
and identity of a surfactant structuring system in a
liquid may be det~-rmtn--cl by means known to those skilled
in the art for example, optical techni~ues, various
-` ~ Z0~10442
3 C 7151 tR)
_~ ~tLlcal mea-,uL. ~, x-ray or neutron diffraction,
and 8 ' ~ , electron mi~;Lusuu~y.
Electrolyte may be only dissolved in the aqueous
5 continuous phase or may also be present as g -~pPn~
solid particles. Particles of solid matQrials which are
~n~slllhle in the aqueous phase may be s~rPn~P~
alternatively or in addition to any solid electrolyte
particles .
mree common product forms in this type are liquids for
heavy duty fabrics washing and liquid abrasivQ and
general purpose cleaners. In the first class, the
~ ~L~ P~l solid can comprise suspended solids which are
15 substAnt;Ally the same as the dissolved electrolyte,
being an eYCeSs o~ same beyond the solubility limit.
miS solid is usually present as a ~ LU~I~Cy builder,
i.~. to counteract the effects of calcium ion water
hardness in the wash. In the second class, the sl~pc~n~Pd
20 solid usually comprises a particulate abrasive,
insoluble in the system. In that case the electrolyte,
present to contribute to the structuring o~ the active
material in the dispersed phase, is generally dif~erent
~rom the abrasive ~ . In certain cases, the
25 abrasive can however comprise partially soluble salts
which dissolve when the product is diluted. In the
third class, the structure is usually used for
~hirkPn~n~ the product to give uu~ preferred flow
properties, and sometimes to suspend pigment particles.
Compositions of the f irst kind are described in for
example our patent specification EP-A-38,101 whilst
_ le~ of those in the second u~.Le~uLy are described
in our spPn~ cAtion EP-104,452. Those in the third
35 category are for example, described in lJS 4,244,840.
The dispersed :~Lu~;~uLlng phase in these liquids is
generally believed to consist of an onion-like
configuration comprising Cullc6ll~Lic bilayers of
Z~)1044Z
4 C 7151 (R)
detergent active molecules, between which i5 trapped
water (aclueous phase) . ~hese conflguratio ls of active
material are somQtimes referred to as 1; -11 ;'lr droplets.
It i8 believed that the close-packing of these droplets
5 enables the solid materials to be kept in suspension.
The 1 -llAr droplets are themselves a sub-set of
11 11 Ar ~sLLu-;LuLe_3 which are capable of being formed in
detergent active/aqueous electrolyte systems. For the
purpose of the present invention, detergent compositions
10 of the 1~ -11 Ar droplet type are preferred.
The ~eroxYqen bleach
The compositions according to the present invention
15 comprise a peroxygen bleach. ~his bleach L may
be present in the system in solubilized form, but also
possible is that only part of the peroxygen bleach is
5~ h71770d, the L~ 7n;n~ part being present as solid
p~u~y~el~ particles which are Sll~r~n~7Pd in the system.
Examples of suitable p~LU~y~7~ include
l~y-lL~ peroxide, the pel. uL~tes, persulfates, peroxy
disulfates, peLI~ho~,,hates and the crystalline
pl:Lu,~ylLy-lL~-tes rormed by reacting hydLuc7dll peroxide with
25urea or alkali metal carbonate. Also ~nrArAI71 ;-ted
7,~1DArh~A may be u8ed. Preferred hlPArh~A are only
partially soluble in the system such as for example
diperoxy~ rAn~'~ oic acid (DPDA) or other peracid
crystals and perboratetetrahydrate. The bleach . _ L
30 is preferably added in an amount CULL~ .ng to 0.1 to
15% by weight Or active oxygen, more prererred from o . 5
to 596 active oxygen, typically from 1. 0 to 3. 0 9~ active
oxygen .
35 The bleach ingredients may for example be added to the
composition as a dry particulate material or as a
predispersion o~ ble~ch particles. Ir peLbuLe.te-
tetrahydrate bleaches are used, a suitable - ~ial
available bleach dispersion is Proxsol (ex ICI),
-
5 2 0 1 0 4 4 2 C 7151 (R)
altQrnatlvely perborat~-tetrahydratu crystals may b~
~ormed in-sltu ~or example as d~nrihed ln EP 294 904.
Deteraent active r~aterials
In the wldest deflnltlon the detergent actlve materlals
in general, may comprlss one or more sur~actants, and
may be selected from anlonic, catlonlc, nonlonic,
zwitt~r10n~c and amphoteric species, and (provided
10 mutually compatible) mixtures thereo~. For example, they
may be chosen from any o~ the classes, sub-clas3es and
specif ic materials described in "Sur~ace Activ~ Agents"
Vol. ~, by Schwartz & Perry, Interscience 1949 and
"Sur~ace Active Agents" Vol. II by Schwartz, Perry
15 Berch (Interscience 1958), in the current edition o~
"2IcC~ I,eol,'s Emulsi~lers & Detergents" pl~hl~h~-d by the
McCutcheon division of MAm~f~ctllring Confectioners
Company or in Tensid-~ hPnh~lrch", H. Stache, 2nd }5dn.,
Carl Hanser VerlAg, Munchen & Wien, 1981.
Suitable n~n~on~c surfactants include, in particular,
the reaction pLvd~.~;L~ of ~ _ - having a l.~dLv~hobic
group and a reactive 1~ydL~-.~ atom, ~or example
aliphatic Al.~nhnl~, acids, amides or alkyl phenols with
25 alkylene oxides, e~peci~l ly ethylene oxide either alone
or with propylene oxidQ. Spee~c nnn~nn1c detergent
are alkyl (C6-Clg) primary or seCon~Ary linear
or hrAn- h~-cl AlcnhnlF~ with ethylene oxide, and products
made by ennAQn~ation o~ ethylene oxide with the reaction
30 products oi~ propylene oxide and ethyl~n~ m~ne. other
so-called non~nn~n detergent ~ _ '~ include long
chain tertiary amine oxides, long chain tertiary
rhn8rh~n~ oxideg and dialkyl 8ll1rhnY1~
35 Also possible is the use of saltin~-out resistant
active materials, such as for example described in EP
328 177, pllhl;~h,~-l August 16, 1989, especially the use
o~ alkyl polyglycoside surfactants, such as for example
disclosed in EP 70 074, published January 19, 1983
X
~ 20 1 0442
6 C 7151 (R)
Preferably thQ levQl of nonionic surfactants is more
than 1 % by weight of the composition, preferably from
2.0 to 20.0 %.
5 Suitable anionic surfactants are usually ~-ter-noluble
alkali metal salts of organic sulphates and 5~lrhnn~tes
having alkyl radicals containing ~rom about 8 to about
22 carbon atoms, the term alkyl being used to include
the alkyl portion of higher acyl radicals. Examples o~
10 suitable synthetic anionic detergent ~ .ds are
sodium and potassium alkyl sulphates, ~cppc~l ly those
obtained by sulphating higher (C8-cl8) Al cnhnl A
produced for example from tallow or coconut oil, sodium
and pota6sium alkyl (Cg-C20) benzene sl~lrhnnAtes~
15 particularly sodium llnear sC~r~nAAry alkyl (C10-C15)
benzene Slll rhn"Ates; sodium alkyl glyceryl ether
sulphates, ~-cpe~;Ally those ethers of the higher
alcohols derived from tallow or coconut oil and
synthetic alcohols derived from petroleum; sodium
20 coconut oil fatty monoglyceride sulphates and
sulphonates; sodium and potassium salts of sulphuric
acid esters of higher (C8-C18) ~atty alcohol-alkylene
oxide, particularly ethylene oxide, reaction pL~ldU~;~S;
the reaction PL~I1U~ S of fatty acids such as coconut
25 fatty acids esteri~ied with ~ceth~onl~ acid and
neut--Al ~ A with sodium hydroxlde; sodium and potassium
salts of fatty acid amides of methyl taurine; alkane
- 1 rhnnAtes such as those derived by reacting alpha-
olefins (C8-C20) with sodium bisulphite and those
30 derived from reacting para~ins with S02 and C12 and
then hydrolysing with a ba~e to produce a random
sulponate; and ole~in slllrhnnAtes~ which term is used to
describe the material made by reacting olefins,
particularly C10-C20 alpha-olefins, with S03 and then
35 neutralising and hydrolysing the reaction product. The
preferred anionic detergent, -c are sodium
(cll-cl5) alkyl benzene sulphonates and sodium
(C16-Clg) alkyl sulphates.
2010442
7 C 7151 (R)
Generally the level of the above mentioned l~v.. 30ap
anionic surractant meterials is rrom 1-40 % by weight of
the composition.
5 Preferably the weight ratio Or synthetic anionic
surfactants to nnn~nn1~ surractants is from 10: 1 to
1: 10.
It is also possible, and E t.~ preferred, to include
10 an alkali metal soap of a mono- or di-carboxylic acid,
PCpQC~Al ly a soap of an acid having from 12 to 18 carbon
atoms, for example oleic acid, ric~n~lP1~- acid, and
fatty acids derived from castor oil, rapeseed oil,
yLuu~ L oil, coconut oil, pAlmkP~nPl oil, alk(en)yl
15 s~rinAtec e.g. dodecyl succinates or mixtures thereof.
The sodium or potassium soaps of these acids can be
used. Preferably the level of soap in compositions Or
the invention is form 1 - 40 % by weight Or the
composition, more ~LefelLed ~rom 5 - 25 %.
In many (but not all) cases, the total detergent active
material may be present at from 2% to 60% by weight of
the total composition, ror example from 5% to 40% and
typically rrom 10% to 30% by weight. However, one
25 preferred class Or compositions comprises at least 20%,
most prererably at least 25% and Pcpc~c~lly at least 30%
of detergent active material based on the weight of the
total composition.
30 Compositions according to the invention are pre~erably
physically stable in that they yield no more than 2% by
volume phase separation when stored at 25-C for 21 days
from the time of preparation. ~cppci~lly prererred are
compositions which do not yield any phase separation
35 upon storage ror 21 days at 25 C.
Compositions according to the invention, preferably have
solid-s~ rPn~ln~ properties in that they yield less th2n
5 % by volume of s~Ai- t after storage for 21 at 25-C,
~ 20'q 04a~2
8 C 7151 (R~
more preferably less than 2 % by volume se~ - L is
formed, most preferably 6ub6tantially no visible
seA~- ~ is formed.
5 Preferably composition6 according to the invention
comprise less than a 6tructure de6tabilising amount o~
water m1~cihl~ solvent, preferably less than 10% by
weight, for example less than 7.5%, more preferred less
than 5%, P~p~clAlly preferred less than 2.0%, typically
10 less than 0 . 5% by weight of a water miscible solvent.
DPp~n~ln~J on the other ingredients of the composition,
it is however sometimes possible to incvL~vLate low
levels of water miscible solvents, say from 0.1 to 8 %
15 by weight, more pre~erred from 2 to 6 %, without the
o. ~;uL~Ice of structure destabilisation. In particular it
has been found that these low levels of water ml~c~hle
solvent6 may adv~ vusly be u6ed in combination with
relatively high levels of dissolved electrolyte, say
2 0 more than 2 2~ by weight, more pre eerred more than 5 % by
weight, ~:pQr~i~l ly preferred between 10 and 50 % by
wcight. Bleach containing compositlons comprlslng water
m~:r~hle 60lventg at level6 whlch do not prevent the
~ormation of ~Lu~;~uLlng~ ln partlcular internal
25 structuring, are also embraced within the 6cope of the
present invention.
Example6 of water-misclble solvents are lower allphatic
monoalcohols, ethers of dlethylene glycol and lower
30 -- 1 lrhAtlc monoalcohols, and mixtures thereo~.
Vol - ,f :~hi 1 i tY
I lquid detergent composition6 according to the invention
35 are volume stable in that they show less than 25%
preferably less than 10%, more preferably less than 5%
volume increase during storage at a t~ CI~ULt between
20 and 37-C for a period of three months after
preparation .
Z0~04~
9 C 7151 (R)
Although the type Or container for storage is believed
not to be critical, g~n~rAlly liquid detergent
compositions according to the invention will be stored
5 in closed bottles, say of 1.5 litre, which optionally
may include venting means, for rPl~ n~ generated
oxygen.
When a solid pe~;~,..y~ bleach ~ _ L is present in an
10 aqueous system, generally part Or the bleach material
will be solubilized in the form Or pQracid and/or
ll~dL~ell peroxide in the aqueous phase. One of the
problems o~ten obsel~,.d in such systems is the occurence
Or oxygen evolution, due to the de ~nition Or this
15 peracid or llydLo5~ell peroxide into acid and/or water and
oxygen. The oxygen bubbles rormed may either emerge rrom
the liquid or be trapped in the liquid, thereby causing
a volume increase. A similar oxygen evolution i8
obsorved when the bleach ~_ _ such as ror instance
20 llydLo~él~ peroxide i8 totally solubilized in the system.
The present invention provides liguid detergent
compositions wherein the volume increase is kept at an
acceptable level of less than 25%, pre~erably less than
25 10%, more ~L~areLLed less than 5 %. during storage Or
the composition at a temperature between 20 and 37-C ror
three months after preparation.
The par2meter3 to be varied in the composition to bring
30 about the desired volume stability efrect may for
example be the pH, the physical state o~ the lln~i cc~lved
bleach particles when present, the amount o~ dissolved
bleach, the presence o~ stabilising agents, the amount
of dissolved bleach activators, the viscosity Or the
35 product directly after preparation, the presence of
viscosity reducing polymers, the presence of gas bubbles
in the composition directly arter preparation and the
presence of antiroam agents. The choice of an optimum
value of these parameters is ~r~n~nt on the nature and
20:L0442
10 C 7151 (R~
the cholce of the actiVQ materials which are present in
the composition.
The half life time of the solubilized peracid or
5 llydLU-J~ll peroxide should preferably be increased for
increasing the volume stability of the composition. Not
only the amount of oxygen formed per time unit is less
by increasing the stability of the peracid or llydLO~el~
peroxide, also -and this has been found more important-
10 an increase in the life time of these . - ,u~ c will
~llow the oxygen bubbles to be formed upon A~ ition
of the peracid or l~ydLUlJ~n peroxide to grow in size. An
increase in the size of the bubbles to be formed i5
c~n~iAPred advantageous in that these larger bubbles
15 have been found to be less prone to contribute to the
volume increase of the liguid detergent composition, in
other words they tend to escape from the liguid rather
than being sl-cp ~nA~cl into the system.
20 Preferably the halr-life time of the lly~LU~n peroxide
or peracid is be more than 3 weeks preferably more than
6 weeks at 37-C at the conditions in the detergent
composition, pre~erably more than 8 weeks e~c~pec1:~l ly
preferred more than 10 weeks. Most pL~ f~LL~ d between 10
25 and 20 weeks.
The stability of the peracid or llydLUl'J61~ peroxide may be
increased in several ways such as for instance a
decrease in pH of the composition. It has been found
30 that the volume stability of the liguid detergent
composition increases by decreasing the pE~ of the
composition. Therefore, for the purpose of formulation
volume stable compositions it is preferred to avoid the
use of excessive high pH values. Preferably the pH of
35 the detergent compositions is less than 12, more
preferred less than 11.5, ecpe~lly preferred between
between 6.5 and 11, typically from 7 to 10.
It has al60 been found that the volume stability of the
201 0442
11 C 7151 (R)
detQrgent compositions according to thQ present
invention can be ~ :~v~d by using bleach particles
which are Pn~ArslllAted. These Pn~Ar~ ated bleach
particles constitute part or all Or thQ bl~ach present
5 in the composition, the particles are mainly present in
the composition in undissolved rOrm.
The presencQ Or bleach particles in l~n~solved form is
also prererred when the bleach particles arQ not
10 ~n-Arsl~lAted. HighQr levcls of llnA~nlved bleach ar~
prQferred, becausQ it is believed that bleach
instability is mainly instability of dissolved bleach.
Prererably at least 10% by weight, more preferably at
least 30%, ~rer~Ally prererred more than 50~, most
15 pre~erably more than 75 % or even more than 90 % by
weight Or the bleach i8 present in l~nr~ olved I~orm. Ir
pQrboratQ hl ~A~ hP~ are used it has been round that the
amount Or dissolved bleach is reduced if the pH o~ the
composition is relativ~ly high say from 7-11, more
20 prererably from 7 . 5 to 10.
Pre~erably the weight average 1 ~; t - t Or the
lln~ olved bleach particles is rrom 0.5 to 100
mi~ tar~ n~pec~lly S to 60 micrometer. A method rOr
25 obtaining thQse small particles is described in
EP 294 904.
One way Or ensuring that the bleach is present in
lln~ 501ved rorm ig to increase the amount Or
30 electrolyte in the composition, therewith reducing the
solubility Or the bleach ~ _ in the system.
Suitable electrolytes ror this purpose are ror $nstance
thQ at least partially water soluble carbonate, sulphate
and hAlogen~ salts and ~ horAte. othQr prererred
35 electro]vtes arQ salting out electrolytQs.
For the purposes of the present invention the expression salting out
electrolyte has the same meaning as in EP 79 646, published May 25,
1983, namely those electrolytes which have a Iyotropic
Z010442
12 C 7151 (R~
number of less than 9 . 5 .
Typical eYamples of salting out electrolytes are water-
soluble builder salts, such as alkali metal ortho- and
5 y,L~,~o~yllates, the alkali metal tripolyphosphats~s, such
as sodium tripolyposphate, the alkali metal silicates, -
borates, -carbonates, -sulphates, alkal i metal citrates;
alkali metal salts of nitri 1 oncet~te; alkali metal salts
of ca b~ ryy succinate. Instead of the alkali metal
10 salts the illm salts can be used. Particularly
preferred is the use of sodium tripolyphosphate and or
sodium (di) silicate as the salting out electrolyte.
For ensuring an adequate reduction in solubility o~ the
15 bleach ~ L~ the dissolved part Or the electrolyte
constitutes preferably more than 2 % by weight o~ the
composition, more preferred more than 5% by weight,
D~pec~ y ~L~5~eLled between 10 and 50 9~ by weight.
20 For obtaining good volume stability, preferably the
compositions according to the present invention also
comprise a st~hil i ~in~ agent for the bleach ' _ -nt.
Suitable stAhil ~Dr8 are well-known in art and include
EDTA, MA7nDsi~ silicates and rho~l h- ~tes such as ror
25 instance the Dequest range ex M- naAnto and Naphthol ex
Merck. Preferably the amount of s~hi 1 i P~in~ agent is
rrom 0. 05 to 5 % by weight o~ the composition, more
preferred from 0 . 05 to 1~ o~ the composition.
30 Compositions of the present invention may comprise one
or more bleach activator agents. These materials when
,_ ~ lnecl with a peroxy bleach in the wash, will activate
ll~lL~,g~ll peroxide at a low t~ LULe: of from 15 to
55C therewith allowing the effective use of peroxide
35 hlD Irhe~ at low washing temperatures.
The bleach activators used in the present invention,
often also referred to as peroxyacid bleach precursors
are conventionally organic ~ ds having one or more
20 1 0442
13 C 7151 (~)
reactive acyl groups, whlch at rQlatively low
tt, ~~ atu~Q react with hydrogenpQroxid~ causing thQ
formation Or organi¢ peroxyacids, the latter providing
for a more errectiv~ bleaching action at lower
5 temperatures than l~.I-oy~l peroxlde itself.
The best known organic bleach activator Or practical
importance is N,N,N,N'-tetraacyl ethylene diamlnQ,
normally re~erred to as TAED. Another well-known bleach
10 activator is sodium-4-benzoyl oxybenzene 8l-l rh~n~te
normally referred to as BOBS, as d~ osed in
GB 863 988, published June 9,1960.
Examples of other organic bleach activators are other
15 n-acyl substituted amides, for example tetraacetyl
methylene diamine; carboxylic acid anhydrides for
example 8~ c~n~-~, benzoic and phthalic anhydridess
carboxylic acid esters, for example sodium acetoxy
benzene sulphonates acetates such as glycerol-
2 0 triacetats, glucos~ pentaactetate and xylose-
te~rn~cetate and acetyl salicylic acid.
Preferably TAED is used as the bleach activator. The
p- -:r~L-~ level Or bleach activator in the liquid
25 ~etergent is from 0.1 to 10 % by weight ~L~feLably ~ro~
0.5 to 5 % by weight o~ the composition.
Pre~erably the bleach activator is present in the
system in at least partly l-nd1~solved form. Pre~erably
30 at least 10% by weight, more preferably at least 30~,
P~pe~iAlly preferred mor~ than 50% by weight o~ the
activator is present in l~n~ olved form.
One way of ensuring that the activator is pre6ent in
35 llnd ~ olved rOrm is the use Or ~n~rs~ ted activator
materials. Another method is to increasQ the amount of
~31ectrolytQ in the composition, therewith reducing the
solubility of the activator in the system. Suitable
electrolytes ror this purpose are ~or instance the at
X
~, 201044~
14 C 7151 (R)
least partially water solublc carbonate, sulphate and
halogenide salts and metaborate. Other preferred
electrolytes are salting out electrolytes as defined
hereabove .
For ensuring an adequate reduction in solubility, the
dissolved part of the electrolyte constitutes preferably
more than 2 ~ by weight of the composition, more
preferred more than 5% by weight, ~periAlly preferred
10 between 10 and 50 ~ by weight.
AB to the viscosity of the product directly a~ter
preparation, it has been found that a lower value for
the viscosity generally increases the volume stability
15 of the bleach cr~nt~;nin~ product. Also for lower
viscosities are genrally preferred by the cu.._ - r .
EIowever, for providing solid-s~lcp~n~lin~ properties, low
viscosities should pre~erably be avoided. "~ o~ in
selecting the most a~L~""Llate viscosity of the
20 product, a balance should be sought between better
stability and ~ - -acceptance at lower viscosities
and increased solid sllcp~n~l; n~ properties at higher
viscosities .
25 Generally it is preferred that for good volume stability
and good ~ --acceptance, the viscosity is
preferably less than 2,000 mPas at 21 5-1, more
preferred less than 1,500, most preferred between 20 and
1,000, F~cpec;Ally preferred ~rom 30 to 500. For good
30 solid sl~cpF~n~;n~ properties, it is preferred that the
viscosity is more than 1,000 mPas at 10-4 8-l, more
preferred more than 10,000, r~Cp~clAlly pre~erred more
than 100, 000.
35 The terhn~ eC for obtaining the initial viscosity as
desired are well-known in the art, and include for
example the ay~ late choice of active ingredients,
the adaptation of the level of dissolved electrolyte and
the inclusion o~ viscosity modifying agents. A pre~erred
20 1 0442
15 C 7151 ~R)
way for regul~tlng the viscosity o~ the product is th~
inclusion o~ polymers in th~ composition.
Viscosity and/or stability regulating polymers which are
5 preîerred for incorpora~ion in compositions according ~o
t:he invention include def locculating polymers e . g those
having a hydrophilic b~-kb--n~ and at least one hydro
phobic side chain. Such polymers are described in our
copending British patent appl ;m~t;~nR 8813978.7, published
December 2 0 , 1 9 8 9 , ( corresponding to EP 3 4 6 9 9 5 ),
8924479.2, published May 16, 1991, 891478.4, published
May 16, 1991, and 8924477.6, published Nay 15, 1991.
Othcr polymers which could advnntAgeo~l y b~ used for
15 viscosity regulation are described in EP 301,882
~Unilever P~C) and EP 301,883 (Unilever PLC). Preferably
thQ amount Or viscosity regulating polymer, especially
dQ~locc~ A~ting polymers, is from 0.1 to 59~ by weight Or
thQ total composition, more prererred rrom 0. 2 to 29~ .
As to the presencs of gas bubbles in the det-:~,J6,.~
composition according to the invention, it has been
round that botb thn size and the level o~ gas bubbles
are ~ ~"1 pA t.~rs for det~rm~n~n~ th~ volume
25 Btability o~ the compo8ition. ~;~n~rAlly gas bubbles in
th~ rorm o~ air or oxygen bubbles are i---L~l~,c~d into
lisluid detergent compositions during proces~in~ o~ the
composit$on, which usually involves a mixing stage.
It has been ~ound that it is generally preferred to
reduce the amount of gas which is prcsent in the
composition ~ust aftQr preparation. Preferably tho
volume fr~ction o~ gali bubbles ls less than 5.0t,
pre~erably less than 3.5~, most y~erelLad less than
2.0%, ~p~ciAlly 1Q88 than 1 ~ or evcn less than 0.5 %.
It has also been found that when gas bubbles are
present, the volume stability of the liquid detergent
compositlon ir.~;, a8e8 when at cv.~ al~t ga~ content the
40 average tl~ '~r o~ the gas bubbles in inv,~
16 Z01044;~
Pref erably the average diameter o~ thQ gas bubbles i5
above 0 . 25 mm, more pre~erred above 0 . 4 mm, most
preferred above 0 . 5 mm.
5 Several techniques can be used for reducing the amount
of gas bubbles and for increasing the size of the gas
bubbles .
For example the presence o~ an anti~oam agent both
10 reduces the volume fraction of gas bubbles and increases
the size of the bubbles present. Preferably the anti~oam
agents are added at a level above the level commonly
used for ~oam reduction of detergent compositions.
Preferably the level of antifoam agent is more than 0 . 2%
15 o~ the detergent composition, more pre~erred more than
0.3i of the composition, ~cpeciAlly pre~erred ~rom 0.4
to 2 . 0% o~ the composition. Suitable anti~oam agents
include cl 1 ~ con~ antifoam agents, such as dimethyl
polysiloxanes and/or silica particles.
Furth~ e it has been ~ound that the use of lower
shear-rates in the mixing of the detergent compositions
of the invention, decreases the amount of gas bubblas in
the composition. A similar decrease can be observed when
25 mixing the detergent composition under deaerated
conditions, by centrifuging the detergent composition
after mixing, by leading a stream of large gas bubbles
through the composition during or a~ter mixing and by
vacuum deaeration of the product a~ter mixing.
30 ~e:por-l Illy pre~erred for obtaining the desired result is
the centrifuging of the composition in the absence of
8llcpc-n~ d 801id8 and/or the vacuum deaeration Or the
composition .
35 It should be noted that the choice of the values of the
optimum set of values o~ the above r- ' ~nn~d parameters
should be detc~rmin~d for each detergent composition
individually while using the above given g~ l 1 nec. For
certain compositions it may not be n~cDss~ry to optimise
zu~04a~2
17 C 7151 (R)
all of the above given parameters. For instance for some
detergent compositions it may appear that if the amount
and size o~ the gas bubbles present in the composition
is ade~uately controlled, then a greater flexibility in
5 ~-h^,^~8~n; the viscosity and or pH of the system may be
obtained, while still resulting in compositions
satisfying the re~uired stability re~uirement. It is
however believed to be well within the ability of a
skilled man on the basis of the above ~e~-h~ng to
10 determine for each detergent composition an acceptable
set of values for the above-mentioned parameters.
OPti~^~nAl in~ redients
15 When the compositions are of 1A--11 Ar ~LLU~.;l UL~ then in
many cases it is preferred for the a~ueous continuous
phase to contain dissolved electrolyte. As used herein,
the term electrolyte means any ionic water soluble
material. However, in l; -11 Ar dispersions, not all the
20 electrolyte is n_ c~A- lly dissolved but may be
~ ^L~ APA~ as particles of solid because the total
electrolyte ~ tion Or the li~uid i5 higher than
the s^~l~lhil ~ty limit of the electrolyte. Mixtures of
electrolytes also may be used, with one or more of the
25 electrolytes being in the dissolved a~ueous phase and
one or more being substantially only in the sll-pDn~Pd
solid phase. Two or more electrolytes may also be
distributed approximately proportionally, between these
two phases. In part, this may depend on processing, e.g.
30 the order of addition of ^nts. On the other hand,
the term "salts" includes all organic and inorganic
materials which may be included, other than surfactants
and water, whether or not they are ionic, and this term
Pnl _-~.~P.~ the sub-set of the electrolytes ~water
35 soluble materials).
The only restriction on the total amount of detergent
active material and electrolyte ~if any) is that in the
1 A~-1 l Ar compositions embraced in the present invention,
ZQ~0442
18 C 7151 (R)
together they must rQsult in formation o~ an aqueous
r di5per8ion. Thug, within the ambit of the
present invention, a very wide variation in surractant
types and levels iB possible. The selection of
5 surfactant types and their proportions, in order to
obtain a physically stable liquid with the required
structure will be fully within the capability of those
skilled in the art. However, it can be mentioned that an
JL L~lIL sub-class of useful compositions is those
10 where the detergent active material comprises blends of
different surfactant types. Typical blends useful for
fabric washing compositions include those where the
primary surfactant(s) comprise n~ n1t-nle. and/or a non-
alkoxylated anionic and/or an alkoxylated anionic
15 surfactant.
In the case of blends of surfaotants, the precise
proportions of each ~ L which will result in such
physical stability and viscosity will depend on the
20 type(s) and amount(s) of the eleotrolytes, as is the
case with conventional structured liquids.
The compositions optionally also contain electrolyte in
an amount sufficient to bring about ~LL~I~;LUr lng o~ the
25 detergent active material. Preferably though, the
compositions contain ~rom 196 to 60~, Dl~pD~i~l ly from 10
to 45~6 of a salting-out electrolyte. Salting-out
electrolyte has the meaning ascribed to in spDr-if~tion
EP-A-79 646. Optionally, some salting-in electrolyte (as
30 defined in the latter spDcification) may also be
included, provided it is of a kind and in an amount
oompatible with the other, L~ and the composition
is still in ac~.,Ld~ e with the definition of the
invention claimed herein. Some or all of the electrolyte
35 (whether salting-in or salting-out), or any
substantially water insoluble salt which may be present,
may have detergency builder properties.
In any event, it is preferred that compositions
~ Z~ 0442
19 C 7151 (R)
accordlng to thQ present invention include detergency
bullder material, some or all Or which may be
electrolyte. The builder material is any material
capable Or reducing the level of rree calcium ions in
5 the wash liquor and will prererably provide the
composltion with other benericial properties such as the
generation o~ an Alk~l ~nP p~l, the 5~ pPn~inn of soil
removed rrom the rabric.
10 Examples Or rhnsrhnrous-containing inorganic detergency
builders, when present, include the water-soluble salts,
P~pP~ lly alkali metal pyrorhnsrhAtes, orthopho6phates,
polyphosphates and rhn~rh~nAte5. Speciric examples Or
inorganic phosphate builders include sodium and
15 potassium tripolyphosphates, phosphates and
h~ hogrhAte5. phnsphnnAte sequestrant builders may
also be used. Sometimes, however, it is pre~erred to
m~n~mice the amount of rhn5rhn,~,u~ Laining builders.
20 r _ 1P~3 of n~,.. rhn~,h--, us-~ ~,..Ldining inorganic
detergency builders, when present, include water-
soluble alkali metal carbonates, bi~ArhnnAtes~ silicatcs
and crystalline and amorphous al~minnqil ~cates. Specific
include sodium carbonate (with or without
25 calcite seeds), potassium carbonate, sodium and
potassium hi~-ArhnnAtes~ silicates and zeolites.
Examples of organic detergency builders, when present,
include the AlkAl ~nP metal, ammonium and substituted
30 : ~llm polyacetates, carboxylates, polycarboxylates,
polyacetyl carboxylates and polyl.yd~ y~-ulphonates .
Speci~ic examples include sodium, potassium, lithium,
i llm and substituted ~ llm salts Or
ethylPnP~i l Am; nPtetraacetic acid, nitrilitriacetic acid,
35 oxyd~ cinic acid, melitic acid, benzene polycarboxylic
acids, CMOS, tartrate mono succinate, tartrate di
succinate and citric acid.
In the context of organic builders, it is also desirable
~ 20~0442
20 C 7151 (R)
to incc,L~,Lc~te polymers which are only p2rtly dissolved,
in the aqueous continuous phase as described in
EP 301.882. q~his allows a viscosity reduction (due to
the polymer which is dissolved) whilst i~ L~n~Lclting a
5 sufriciently high amount to achieve a s~con~l~ry benefit,
espc-a~Ally building, because the part which is not
dissolved does not bring about the instability that
would occur if substantially all were dissolved.
10 It is further possible to include in the compositions of
the present invention, alternatively, or in addition to
the partly dissolved polymer, yet another polymer which
is substantially totally soluble in the aqueous phase
and has an electrolyte resistance of more than 5 grams
15 sodium nitrilotriacetate in lOOml o~ a 5~ by weight
aqueous solution of the polymer, said second polymer
also having a vapour ~L~UL~ in 20% aqueous solution,
equal to or less than the vapour pressure of a reference
2% by weight or greater aqueous solution Or polyethylene
20 glycol having an average r~lem~ r weight of 6000; said
second polymer having a molecular weight of at least
1000. Use of such polymers is generally described in our
EP 301, 883 .
25 Preferably the level Or n~"~ noap builder material is
rrom 5-50 ~ by weight of the composition, more ~Lb reLLed
from 5 to 35 9~.
Although it is possible to ina-.~oLe.~e minor amounts, of
30 l~ydL~LLu~es other than water-miscible solvents, we
pre~er that the compositions o~ the present invention
contain low levels or are substantially free from
llydL~LL~,~es. By lly.lL~,LL~"e is meant any water soluble
agent which tends to enhance the solubility of
35 surfactants in aqueous solution.
Apart from the ingredients already mentioned, a number
of optional ingredients may also be present, for example
lather boosters such as alkanolamides, particularly the
2~)~0442
21 C 7151 ~R)
nnl~711~7~7.~ derived from palm kernel ~atty acids
and coconut ~atty acids, ~abric Sor~ e~. such as clays,
amines and amine oxides, lather d~z~L~>a~lts~ inorganic
salts such as sodium sulphate, and, usually present in
5 very minor amounts, fluuLesc~l.L agents, per~umes,
enzymes such as proteases, amylases and lipases
~including r~7roJ;l~e (Trade Mark~ ex Novo), gp7~7i~j~PG
and colourants.
10 Compositions of the invention may be prepared by any
conventional method for the preparation o~ liquid
detergent compositions. A pret'erred method involves the
dispersing of the electrolyte (non-builder) -if any-
together with the minor ingredients except for the
15 temperature sensitive ingredients -i~ any- in water of
elevated t~ GtULe:~ followed by the addition o~ the
builder material -i~ any-, the detergent active
materials (optionally as a pre-mix) under stirring and
thereafter cooling the mixture and adding any
20 t~ LG-UL~ sensitivc minor ingredients such as enzymes
or peLrl -- and the bleach. The r7P7~l~ o~77l~ting polymer -
i~ any- may for example be added a~ter the elctrolyte
ingredient or as the f inal ingredient .
25 When peLbuLGte ~~dLc.te is used ag the hLr lch~n~
agent, it may be preferred to cool the i~inal product to
a t~LGLuL~ just above the freezing point, in order to
accelerate the recrystallisation of the perborate in
tetrahydrate form.
In use the liquid detergent compositions of the
invention will generally be diluted with wash water to
form a wash liquor, which may be used ~or detergency
~uLyoses, for example for the washing prûcess in a
35 washing machine. The cu,.c~ LGtion o~ liquid detergent
composition in the wash liquor is preferably from 0.1 to
lo % by weight, more pre~erred from 0.1 to 3 %.
The invention will now be illustrated by way o~ the
40 following Examples. In all Examples, unless stated to
~ Z0~0442
22 C 7151 (R)
the contrary, all percentages are by weight.
/
2010442
23 C 7151 (R)
R~ mnle 1
A baE~ic liquid detergent composition of the following
5 composition was prepared by addition under stirring of
the _-- ' - in the order listed. Na-Dobs was formed
in-situ by combining NaOH and Dobs-acid! Some of the
proQP~in~ water was left behind because the I~YdLUg
peroxide solution used was 27 weight % active.
_
~ABLE 1
96 by weight
Water balance
Na-Dob6 13 . 8
Synperonic 7 4 . 0
Dec,uest 2 0 6 0 0 .1
X-Naphtol 0 . 2
STP ~h~ NW 8. 6
~22 (10096) 5 . o
pHl ) 7 . 9--8 . 1
25 TABLl~ 2a. Raw material E~pecification
Csm~oncnt Su~lier
Dobs-acid (98%), Marlon AS-3 EIUl~
Synperonic 7 I . C. I .
De~uc~t 2 0 6 0 Mr-n ~qA n1- o
X-Naphtol, (p. a . ) Merck
STP, ~hP _`-,,~ NW Hoech~t
H22, 27% Brocacee
1) pH ad~u~ted with NaOH if ~cPs~:~ry.
20~0a~4:2
24 C 7151 (R)
mnle 2
By varrying the Na-Dobs/Synperonic weight ratio and
5 keeping the total amount of actives ~ ;,L~..L, the basic
detergent composition according to example 1 was
p. :pa~c d in several versions of different viscosity
direct after pr~ ation.
10 Composition A has a ratio Nâ-Dobs to Sy-l~eLOI~iC of
0.74:0.26 and a viscosity of 170 mPas at 21 s~l~
composition B had a ratio Na-Dobs to Synperonic Or
0.75:0.25 and a viscosity of 390 mPas and composition C
had a ratio Na-Dobs to Synperonic o~ 0.78:0.22 and a
15 viscosity of 1000 mPas. The compositions were stored at
37 'C.
Composition A showed in the ~irst two days of storage a
slight volume increase of about 2% by volume, after 2
20 two days the volume in decreased to a volume which was
about 1% less than the volume of the composition
directly after pL~ tion.
Composition B showed a sharp volume increase of about
25 50% by volume in the first three days of storage,
rollowed by a reduction o~ the volume until at the 5th
day the composition had approximately its original
volume .
30 Composition C showed during the first 7 days a sharp
volume increase o~ more than 125~6 by volume (~velr
a reduction of volume to the original volume of the
composition was observed after 15 days.
35 This example illustra~es that by lowering the viscosity
of the composition, the volume stability of detergent
compositions containing solubilized hydrogen peroxide
can be increased.
2~0442
25 C 7151 (R)
Exam~le 3
The composition of example 1 was prepared by the method
5 as indicated in eYample 1, with some small
modifications .
Compo6ition D was ~re~aled according to example 1, the
ratio Na-Dobs to Synperonic was 0.77:0.23. Composition E
10 was pLe~c..ed as composition D, but 0.1% Or ~il ;c~n~
antifoam was added (COLL.~ d;n~ to 0.33 % DB31 ex Dow
Corning) before mixing thQ ingredients. Composition F
was pL.~JaLed as composition D, but the composition was
deaerated by centrifuging for 5 min at 4000 G.
15 Composition G was prepared as composition D, but 0 . 33%
o~ DB31 was added and the composition was de-aerated by
centrifuging for 5 min at 4000 G. The viscosity of
compositions D-G was 860 mPas after p~ tion. The
compositions were stored at room t~ _ e.ur e and the
20 volume increase and the bubble size were monitored.
Composition D showed a linear increase in volume up to a
maximum of about 75~ volume increase after 30 days of
storage. The d~ r of the gas bubbles present during
25 this period showed a similar increase from very small
(about o.l mm) to about 1.5 mm after 30 days. After 30
days the volume o~ the compositions decreased gradually
until the composition was back at its original volume
after 60 days. The bubble diameter stayed constant at a
30 value of 1.5 mm during this period.
Composition E showed a linear increase in volume up to a
maximum value of about 55~ volume increase after 30 days
of storage. The diameter o~ the gas bubbles present
35 during this period showed a similar increase from very
small (around 0 . 25 mm) to 2bout 1. 8 mm after 30 days.
After 3 0 days the volume oi~ the composition decreased
gradually until the composition was back at its original
volume aîter about 60 days.
20:iL0442
26 C 7151 (R)
Composition F showed an increase in volume during the
~irst 7 days to a maximum value of about 1096 by volume.
After 7 days the volume increase decreased to a value Or
about 096 ana remained constant during 60 days of
5 storage. The diameter of the gas bubbles present during
this period L. ~nc~d substantially ~unr~L~l-L at about 1.5
mm .
Composition G did not show a substantial increase in
10 volume during storage ~or 60 days. The diameter of the
gas bubbles present during this period showed an
increase from 1 mm to 1. 8 mm in the rirst 10 days Or
storage, and then ~;. ln~-~ constant during the ro---~nl
o~ the period.
This example illustrates that both the presence Or an
antifoam agent and/or the de-aeration Or the ~ f,i~lon
contribute positively to the stability of the liquid
detergent composition.
203L04~2
27 C 7151 (R)
Exam~le 4
Compositions were prepared according to example 1, with
5 some small modifications. Composition H was Or the
composition o~ example 1, and had a viscosity of between
400 and 600 mPas, Composition I contained in addition to
the _ 1~, of composition H 0. 596 by weight of
nc~ a~,LL~-y~ ding to 1.5 ~by weight or DB 31 which
10 was added at the beginning o~ the mixing process. For
both compositions the amount and the size of the gas
bubbles in the liquid detergent just after pL~aL-t.ion
was measured.
15 Composition H cnnl-~n~-d 5.2% by volume of gas bubbles,
the size of the bubbles was between 0 .1 and 0 . 2 mm.
Composition I contained 1.996 by volume of gas bubbles,
the size of the bubbles was between 0 . 25 and 0 . 5 mm.
This examples shows that the amount and size of gas
bubbles in the detergent composition can positively be
influenced by in~.c,L~oLc-tion of an antifoam agent during
proc~,:Si n~.
28 C 7151 ~R)
Exa~les 5-8 2 0 1 C 4 4 2
The ~ollowing compositions were prepared by addlng thQ
electrolyte to~e~hPr with the mlnor ingredients except
5 for the perfume and the enzymes to water of elevated
tti ~ al_uL~, followed by the addltion of the detergent
actlve material as a premix under stirring and
thereafter cool$ng the mixture and adding the enzymes,
p~L r, - - and the bleach .
T ~ WT ) 5 6 7 8
Na-Dobs 21 21 23.3 21
Synperonic 7 9 9 10 9
Glycerol 3 5 ~~ 3 9
15Metaborate 2 . 6 2 . 6 2 . 9 2 . 6
Nacitrate/ Citric acidl) 9 . 8 9 . 8 11.1 9 . 8
Deq tiest 2060S tas loO~) 0.4 0.4 0.4 0.4
Na-perborate tetrahydrate3) 20 20 __ 20
Na peLLvl~e - -~y.lL~te -- -- 7 . 2 --
20Enzyme, ~ A1~ e 0.8 0.8 0.8 0.8
caC12 . 2H2 o . 2 o . 2 o . 2 0 .1
F1UVLeSCer, Tinopal C8SX 0.1 0. 1 0. 1 0.1
Silicon, Dow Corning DBloO 0 . 3 0 . 3 0. 3 0 . 3
Perfume 0.3 0.3 0.3 0-3
25~P~occ~ ting polymer4) 1 1 1.1
ethanol -- -- -- 2 . 5
water -----balanc~
pH 9 9 9 9
30 1) ~rhis mixtur~ i~; used to adjust the final pH
2~ E.~y.essed as a of analysed enzyme level in the frsh
sample
3) as 100 ~ perborate, added as a dispersion (Proxsol ex
ICI, approximate 65~ perborate dispersion in water with
35 an average perborate particle size of 40 mi~ Pr.
4) dPflocc~lating polymer o~ ~ormula I o~ EP 346 995,
wherein x~50, y-0, R5~H, R6-CH3, Rl- -C0-0, R2 and R3
are absent, R4~ -C12H25, mW~ 7,500.
29 C 7151 (R)
20 1 0442
5) wt% -approximate- of total pelLoL lte, obt~Lned by
remov~l o~ the undissolved bleach particles by mild
centri f ugation .
6 ) not -~ 3~ d
5 The obtained products had the followlng rhAri~o~eristics:
5 6 7 8
Volume stability (% volume 4 3 0 n.m6)
increase, 3 months 25 C)
clear layer separ~tion no no no no
10(3 weeks 37 C)
solid 8~ Ation no no no no
(3 weeks 37 C)
Vlscosity 21 s~l 1, 350 710 800 n.m
Viscosity 10-4 s~l 5P200,000 n.m n.m n.m
15dissolved perborates5) 3 1.5 8 n.m
bleach activity % 99 99 96 n.
(2 months ambient T)
enzyme activity % 65 62 76 n.m
(2 ~nonths ambient T) 2)
X
