Note: Descriptions are shown in the official language in which they were submitted.
5 S ~ ` .
~ Cl08+
LIQUID DETERGENT_COMPOSITIONS
The present invention relates to liquid detergent
compositions and more particularly to built liquid
detergents compositions containing an active
oxygen-aon~aining compound.
For many years, many ~olid heavy d~ty washing
compositions have contained one or more active
oxygen-containing compounds (s~me~imes called per-eompounds :
or peroxygen compoùnds) in order to oxidise and de-colouriæe
~arious stains commonly encoun~ered in household l~undry,
and to thereby complement the other components of the
washing composition. However, it h~s been reGogni~ed that .
even in such solid co~posltions where the ac~ive
oxygen-containing compounds and the alkaline component~ of
the ~ashing composition are both in solid form, there iLs a
t~ndency for the activity of the active oxyg~n-containing
aompound to di~inish during ~torage of the ~ashlng
composition, on account o~ :Lnteractio~ of the percompollnd
with the alkaline componen~s and water vapour in the air
~urrounding the composition. ~he rate of 108~ of act~vity
o~ the ~olid active oxygen-contaIni~g compound aan be ~ . ~
~igniicantly r~duced to acceptable level3 by aontaating the ~:
compoun~ with various peroxygen compound 3tabilisers, o~
which a particularly appropriate qort aompri~es ~lkali or
alkalin~ earth matal silicates, as described for example in
GBPS 1,553,505 to Interox Che~icals Ltd, and alte~na~ively
~ 17'15~ 0
- 2 - GC108~
or additionally coatin~ the solid particles of the compound
with a suitable organic or inorganic barrier to prevent the
compound coming into contact with the other ~omponents of
the washing co~position. Examples of compositions
stabilised by coating are described in VSP 3847830 assigned
to Laporte Industries Limited and USP 3992317 and USP
4105827, both assigned to Interox S.A
Examination of the prior art demonstrates a marked
reluctance on the part of producers o cletergent
compositions to employ built aqueou~ alkaline liquid
detergent compositions containing a peroxygen compound. For
example, USP 3850831 assigned to Mo Och Domsjo Aktiebolag
deliberately employs non-aqueous compositions instea~ of
aqueous compositions because they were unable to prevent
rapid decomposition of the peroxyge~ compound during ~torage
of the aqueous composition. In USP 3852210, a~signecl to
Flow Pharmaceuticals Inc., the liquid detergent aompc~sition
described was builder-free, and its pH was adjusted by
addition of acid to pH 4 in the example in which the
stability of ~hat compo ition was tested. More reaently~ in
USP 4166794, assigned to Colgate~Palmolive liquid
bleach-softener compositions containing hydrogen peroxide
were de~cribed, but ~uch compositions contained cationic
compounds instead of anionic surfactants, did not include a
builder and their pH was adju~ted to pH 4 to 5.
It is not ~urprising that the prior art ~ought ways to
side-step the problems of providlng a ~torage-stab~le heavy
duty alkaline liquid detergent composition containing an
active oxygen-containing compound cuch as hydrog~n peroxide,
because the problems are much greater than for solid
compo~itions. By virtue o~ the faat that all the
components are in the li~uid phase, they are inevitably
alway~ in intimate contact with each other and cannot be
separated ~rom the others simply by a coating technique.
3r~ Thi~ would not matter i~ the other aomponent~ in aombination
were comp~tlble with hydrogen peroxide, ~ut in praatice thia
ia not the aa~e. Two of the main contributora to hydrogen
1745SO
_ 3 _ GC108+
peroxide instability are anionic surfactants and builders
such as polyphosphate which are both time-honoured, readily
available and cost effective components of washing
compositions, but which generate mildly alkaline conditions
in an aqueous concentrate, often from pH 8~5 to 9.5 when
present in the ranges of concentrations suitable for a
detergent concentrate. The instability of hydrogen peroxide
under such conditions can be seen from the~following
results. A solution of 10 per cent tetra-potassium
pyrophosphate and 5 per cent hydrogen peroxide in
demineralized water lost 62 per cent of the available oxygen
(activity of the active oxygen-containing compound) within a
fortnight and a similar composition containing the
corresponding sodium salt lost: 44 per cent within a week.
The significance of this becomes more plain when it is
recalled that pyrophosphate in low concentrations, and
especially ~nder acidic conditions, is employed as a
stabilizer for hydrogen peroxide. It will, thus, be
recognised that the problem of providing a storage stable
aqueous alkaline detergent composition and especially a
built detergent composition presents difficulties that are
peculiar to such compositions.
It has also been suggested that detergent compositions
can include organic complexing agents as builders. When
small amounts of organic complexing agents, such as about 1
per cent by weight were tested at 32C for long-term storage
compatibility with hydrogen peroxide under mildly alkaline
conditions, the result was, in general, an unacceptable loss
of peroxidic activity. For example, an aqueous hydrogen
peroxide solution containing 1 per cent o~ ethylenediamine
tetraacetic acid,tetra sodium salt lost a remarkable 96 per
cent within two weeks and that containing 1 per cent o~
nitrilotriacetic acid, trisodium salt lost an incredible 79
per cent in one week. A solution of hydrogen peroxide
~S containing 1~3 per cent o~ ethylene diamine tetra(methylene
phosphonic acid), potassium salt lost 50 per cent within a
week. Clearly, the a~orementioned results demonstrate that
:~ 1745~0
- 4 - GC108~
in such compositions the hydrogen peroxide is not storage
stable under such alk~line conditions. ~oreover, when
alkali metal silicates which act as stabilisers fo~ solid
percompounds are introduced even at 1 % into s~abilised
alkaline detergent compositions described hereinafter a more
rapid loss of available oxygen occurs.Therefore, the need
for a storage-stabilised aqueous alkaline detergent
composition is still to be satisfied.
There is a further complicating fac~or to ~e borne in
mind when considering the feasibility of producing a useful
liquid detergent composition that is stabilised against loss
o peroxide activity. When such liquid compositions are
used for laundering, their primary use, they are merely
diluted so that there is no change in the physical state of
the composition such as occurs when a solid compo ition is
dissolved. Hence, those compounds which are includ~d in the
concentrated detergent composition to prevent interaction of
the peroxide with other components during storage inevitably
are still present in the wash solution in the same weight
2~ ratio to the peroxide and with continuing capability to
prevent interaction. It would therefore be expectçd that if
a high ratio of stabiliser to peroxide is ~employed in~order
to obtain a mix of improved storage stability, the rate and
extent of utilisation of the peroxide would be impaired,
which would manifest itself in impaired washing performance.
It is an object of the present invention to provide an
li~uid detergent composition in a concentrated form which
can be diluted to form a washing and laundering solution.
It is a further object of some embodiments of the
present lnvention to provide aqueous alkaline detergent
compositions containing a builder and hydrogen peroxide
stabiliaed suf~icently to avoid the use of ~pecial vent~d
containers.
It is a ~till urther object o~ certain embodiments o~
the present invention to provide aqueous alkaline detergent
compositions containing a builder and hydrogen peroxide
stabilised against excessive decomposition during ~torage,
~ 7~55~
- 5 - _ v~
which provide a washing performance substantially the s~me
as for the corresponding un~tabilised composition.
According to the present inv~ntion there is provided a
stabilised aqueous built liquid detergent composition
comprising at least 4 % of an ani~nic sulphate or sulphonate
surfactant and/or of a non-ionic ethoxylate surfactantr at
least 5 % of a builder selected from alkali metal
polyphosphates, and carboxylic acid complexing builders, at
least 2 % hydrogen peroxide, sufficient alkali metal aryl
sulphonate hydrotrope to maintain the cornposition in a
single phase, either by itself or in conjunction with other
component~, and a stabilising amount of a combination
comprising a low molecular weight mono-hydroxy aliphatic
alcohol, and/or a polyhydroxy alipha~ic carboxylate and an
aminomethylene phosphonate ~r hydroxy alkyl diphosphonate.
Percentages for any componer.t herein are by weight, based on
the composition, unless specifically stated to the contrary.
The anionic surfactant, especlally suita~ly, is an
alkyl aryl sulphonate and in order to a~sist its
1 20 biodegradability is preferably a linear alkyl aryl
! sulphonate. The alkyl group preferably contains from 9 to
1 18 carbon atoms, particularly the decyl, dodecyl or
¦ tetradecyl g~oups. Although o~her aryl groups can be used,
I the aryl group is normally benzene. Examples of suitable
! 25 commercially available alkaIi metal alkyl aryl sulphonates
~ are available under ~he trade names WARCODE~ K54 from
j Warwick Chemicals, England, NANSA SS60 from Albright and
I Wilson, England and especially HETSULF 60S from Heterene
j Chemical~ Co, New ~ersey. Other anionlc ~urfactanta that
:3~1 demonstrate compatability wlth hydrogen peroxide include
alkyl ~ulpho~uccinamate, the alkyl group prePerably
cont.aining ~rom 12 to 18 carbon atoms. A commercially
available example o~ suah a compound is ALCOPOL FA from
Allied Colloid~, England. 9uitable anionic ~ulphate
surfac~ants include primary alcohol ~ulph~te~ and primary
alcohol ether sulphate~, the alkyl group in the alcohol
moiety of ~uch compound~ normally containlng frcm 9 to 18
~ 17~550
- 6 - ~C108
and frequently from 12 to 15 carbon atoms. Commercially
available examples of such compounds include PERLANKROL
D.S.A., E~S.D. and E.A.D. being respec~ively a sodium
primary alcohol sulphate, sodium pri~lary alcohol ether
sulphater and ammonium primary alcohol ether sulphate, all
available from Diamond Shamrock. Other us~able sulphonate
surfactants include n alkane and olefin sulphonates, the
aliphatic moiety normally containing at least 12 and often
from 13 to 18 carbon atoms. Examples of such compounds are
available under the trade name HOSTAPUR S.A.S. and O~S. from
Hoechst (UK). Mixtures of any two or more of the foregoing
anionic surfactants can be employed.Generally the
concentrate contains at least 3 ~ of the anionic sulphate
and/or sulphonate surfactant and usually not more than 15 %.
In many embodiments of the present invention, the
non-ionic surfactant component of the composition is
selected from primary alcohol ethoxylates and linear
secondary alcohol ethoxylates. The alcohol component in each
of these compounds preferably has a carbon chain length of R
in the yeneral formula RO(C2H~O)nH of at least 9 and
frequently not more than 18 carbon atoms extending away from
the ethoxylate moiety. In many commercially available
compounds, the linear carbon chain of R is in the range of
from 11 to 16 carbon atoms and in many cases the surfactant
is derived from a mixture of alcohols.
In the ethoxylate moiety of such compounds, the degree
of ethoxylation n is generally in the range of from 5 to 20
and in many very desirable ethoxylates, n is from 7 to 12.
~owever,it is desirable also to take into account the
relative proportions o the two moieties in the non-ionic
surfactant involved, and this is oten expressed in terms o~
the weight proportion of the ethoxylate moiety in the
molecule. The proportion is desirably at least 50 %,
normally not more than 85 % and preerably at least 60 % up
to 80 ~. ~ most desirable range o suractants contains
from 60 to 80 %, preferably 65 to 75 ~ by wèight of the
ethoxylate moiety and ~he alcohol moiety is a linear Cl~,
i i 7~ 55 (:~
- ? GC10
C13, C1~, Cls or Cl~ or a mixture of linear alcohols havin~
an average carbon chain length within the range of 1~ to 16.
It will be recognised that in many p~eferred alcohol
et~oxylates, the ratio oc.the num.ber of carbon atoms in R to
the degree of ethoxylation n in the ethoxylate ~oiPty is
generall~l in the range o Erom 3:2 to 2:1~ Examples OL
suitable commerc1ally available alcohol ethoxylates are
available under the trademark ~Y~PERONIC grades A.7, A.9,
and A.ll, all from I.C.I., EnglandJ in which R is a mi~ture
~0 'f ~13 and Cls and the degree of etho,~ylation are
respectively 7, 9 and 11, TER~ITOL (Trademark) q~ades 15-.S-9
and 15-S-12, from Union Carbide, U.~.A., being Cll_l~ linear
secondary alcohol ethoxylates, having degrees of
ethoxylation of respec~ively 9 and 12, LUBROL (Trademar~)
grades 12 A.9 and 17 A.10 from I.C.I., England~ the aqerage
chain lengths of ~ being respectively 1~. and 17 and the
degrees of ethoxylaticn 9.5 and 10 ET~YLAN (Trademark)
arades CD9112 and D259, both from Dia~ond Shamrock, and ~IJ
(Trademark) grades 3~ 7~ and 98, being respectively the
lauryl, stearyl and oleyl ethers of polyoxyethylenes and
RENEX ~Trademark) grade 20 being a polyoxyethylene mixed
fa~ty acid ester available from Honeywell Atlas. ~ ~urther
polyethylene oxide condensate that can be employed is
available under the trade mark MY~ON grade 100 from Warwick
Chemicals. Mixtures of two or more ethoxyl~ted surfac~an~s
can be used. The amount of nor. ionic surfac~ant used is
normally at least 3 % and frequently not mo~e than 15 ~.
A third essential component o~ the built liquid
detergent comp~sition o~ the presen~ invention is a hu1lder
selected ~rom polyphosphate and car~o~ylic acld complexin~
builder~. Among~t ~he polyphosphates, it is e~peciall~
suitab}e to empl~y pyrophosphates, an~ ore partlc~lar~y ~.h~
tetra potassium or tetra sodium ~alts or mix~ure~ thereof.
In many embodiments, the tetra-potas~ium pyropho~phate sa~.t
i~ ~elec~ed, by vir~ue of its solubiliLy being 3uperior to
that o the corresponding sodium ~a~t in concentrated li~uid
detergent composition~. ~lthough it is possibl~ to employ a
di-alkali metal dl-hydrogen pyrophosphate as a propor~ion of
the polyphosphate builder, its incorporation, eg ~0-~0 ~ of
~ ~ 7~5!~g3
- 8 - GC108+
the polyphosphate builder mix tends to produce a lower pH in
the washing solution obtained simply by dissolution of the
liquid detergent composition, providing a wash ahd stain
removal detectably inferior to that obtained when the tetra
c alkali metal salt is employed instead, in otherwise
identical compositions. The polyphosphate can be introduced
into the detergent composition either as a solid which is
dissolved, or in the form of an aqueous solution, but the
percentages given herein are of a dry weight basis.
n The organic complexing builders conte~plated herein
tend to fall into three classes, hydroxycarboxylic acid,
aminocarboxylic acid and oxacarboxylic acid. Amongst
hydroxycarboxylic acid builders, a particularly suitable
one is citric acid, usually introduced as the tri~alkali
lS metal salt, and on cost grounds, as the trisodium salt.
Mixtures of the hydroxycarboxylic acid builders and
polyphosphates, for example citric acid and
tetrapyrophosphate both in salt form, can also be usedt
often in a weight ratio of 2:1 to 1:2. Where a rather
higher pH of the mix is desired, an alkaIine adjuster,
sodium metaborate is very suitable.It is desirable to use
not more than about 20 % of pyrophosphates amd where
tripolyphosphate is used not more than about 10 to 15 %.
Within the class of aminocarboxylic acid builders,
nitrilo triacetic acid, normally alkali metal sal~ thereof,
I (NTA) is most prominent. Generally use of the salt tends to
j produce a somewhat higher pH than of a corresponding weight
! of hydroxycarboxylic acid complexing builder and probably as
¦ a result thereof the resultant built detergent composition
1 30 tend8 to show ~lightly in~erior hydrogen peroxide ~tability.
¦ At higher conaentrations within ~he a~orementioned range or
j b~lilder* it is pre~erable to downwardly adjust the pH of the
mix hy introducing it in part acid ~orm. In practice, o~ten
not more than 10% N~A is employed. It can be employed to
complement hydroxycarboxylic acid builders, the resulting
mixture therewith generating an intermediate pH, ~or example
a mixture o~ 12 to 6~ sodium citrate and 3 to 9% N~A.
~ 5t~
- g - GCl08+
Similar mixtures of NTA with polyphosphates such as
~etrapyrophosphates can also be utilised.
Within the class of oxacarboxylic acids,
carboxymethyloxysuccinate deserves mentioned. For practical
reasons it is preferable to employ from 5 to 8% of this
builder. Where higher than 8% builder is desiredr the
balance above 8% is more advantageously provided by one of
the other aforementioned builders.
The sulphonate hydrotropes are suitably the alkali
metal salts of benzene or methyl-sub~tituted benzene
sulphonates, most commonly xylene sulphonate and toluene
sulphonate. Preferably the sodium or potassium salt is
employed. A proportion of the hydrotrope can be provided by
incorporation of one or more ethoxylated phosphate esters.
Such esters chemically can be regarded as phosphate ester
derivatives of the aforementioned non-ionic ethoxylate
surfactants described hereinbefore. In many embodiments,
the product used is a mixture of the two. The degree of
ethoxylation in the ethoxylated moiety is generally the
range from 2 to 12 and often in the range of 2 to 6, and the
carbon chain length of the hydrophobic alkyl group R is
normally from 9 to 18. Whilst it is possible to employ the
closely related ethoxylated alkyl phenol phosphate esters,
in which the alkyl group is often from C8 to C12, their use
~S for such purposes is being in~reasingly viewed with
hostility by water authorities because suitable methods have
not yet been found to degrade them biologically. The
phosphate esters often are available in the acid form and
they can be employed as such in the liquid detergent
compositions oE the pre~ent invention, but their use in that
way does tend to lower the pH of the composltion and o~ the
subseque~nt washlng solution and i~ desired, the phosphate
e~ter can be partially or completely neutralised with alkali
metal hyclroxide, espe~lally sodium or potassium hydroxide,
3~, ox ammonium hydroxide~
~ n general, the total proportion of sulphonate
hydrotrope plus ethoxylated phosphate ester is normally
. '
- 10 - GC108+
selected within the range of from 3 % to 12 %, of which the
sulphonate hydrotrope is ~requently from 3 to 9 % and the
ethoxylated phosphate ester the balance. A small proportion
of ethoxylated phosphate ester, for example from 1 to 3 %
r,can be advantageous in improving the washing abillty of the
composition for certain commonly encountered stains like
cocoa, for example where the ratio of the anionic to
non-ionic sur f actant is relatively high, such as at
approximately 1:1 or higher.
10The stabiliser system for hydrogen peroxide in the
composition comprises an amino methylene phosphonate or
hydroxy alkyl diphosphonate and either or both of a low
molecular weight aliphatic alcohol, and a polyhydroxy
aliphatic carboxylate. The low molecular weight aliphatic
alcohol is most preferably ethanol, particularly in the view
of its combination of properties in that, not only does it
effectively and surprisingly improve the storage stability
of hydrogen peroxide in the composition, in combination with
the other components despite the fact that its presence
tends to increase the alkalinity of the solution, as
measured by a standard pH electrode, but it also cooperates
with the aforementioned hydrotropes in retaining a one phase
system and consequently provides higher flexibility in
formulating compositions. The low molecular weight
aliphatic alcohol is employed, preferably, in an amount of
at least 5 % of the composition and are generally not more
than 15 %. In many embodiments it is employed within the
range of from 7 to 12 %. The higher weight aliphatic
alcohols such as propanol and butanol are considerably less
3n desirable by virtue, it is believed, of their poorer water
solubility 90 that the compounds can be employed to only a
much smaller proportion of the composition than can ethanol.
By way o~ example, many o~ the compositions described herein
containin~ comparatively high amounts of sur~actant and
~S builder can remain in a single-storage stable phase when
they contain ln ~ of ethanol, but when the same amount of
butanol or propanol is employed instead, phase separation
S ~ ~
~ GC108+
oc~urs.
The polyhydroxy aliphatic carboxylate generally
contains at least 5 carbon atoms and normally up to 10
carbon atoms. Although the carbon chain in the molecule can
be branched, in many effective examples the compound is
linear, terminating at one end in a carboxylate group, and
preferably having a chain length of 5, 6 or 7 carbon atoms.
Desirably all, or at least the majority of the remaining
carbon atoms are substituted by an hydroxyl group. The
compound can be in acid form, but preferably is neutralised
with an alkali metal, preferably sodium or potasium.
Preferred compounds of this class include the acid or
neutralised forms of gluconic acid and glycero-ido
heptonate. Preferably, the polyhydroxy compound is employed
1~ in an amount of at least 0.08 % of the composition and in
many cases not more than 1 ~.
The phosphonate component of the stabilised system can
be introduced in the acid form, but it will be recognised
that, if the acid form is employed initially, to a certain
2~ extent the resultant solution will have a lower pH and
impairment of overall washing performance can thereby ensue.
The phosphonate component is therefore introduced preferably
in an at least partial alkali metal salt ~orm. By the term
"amino methylene phosphonates" is meant any compound
containing an amino group substituted by a methylene
phosphonic acid group or salt thereo~. Many suitable
phosphonates can be represented by the general formula, in
acid form:-
[H2o3PcH2~ ~N(cH2po3H2)(c~2)p ~ q ~N(MePO3H2)~
in which p is normally ~rom ~ to 6 and q is normally ~rom 0
I to ~. ~lighly desirable examples are ethylene diamino tetra
I (methylene pho5phonic acid) hexa potassium salt, and
diethylene triamino penta (methylene phosphonic acid) or h~x
potassium salt. Further suitable examples include
hexamethylene diamino tetra (methylene phosphonic acid),
penta sodium salt and amino tri(methylene phosphonic acid)
penta sodium salt. Where desired, one or more of the
5 ~j ~
- 12 - GC108+
methylene groups linking the amino group~ can be substituted
at the carbon atom by a lower alkyl group or at one carbon
only by an hydroxyl group or the substituents of two such
suitably spaced, preferably adjacent carbon atoms can
combine to form cyeloaliph~tic ring preferably containing 5
or 6 carbon atoms.
The aliphatic dipho~phonates can conveniently be
represented in acid form by the formula YZC(PO3H2)2 in which
Y represents an hydroxyl or amino group, the amino group
itself optionally being substituted by a lower alkyl, a
lower alkylamino or a lower hydroxyalkyl ~roup, lower
indicating from 1 to 4 carbon atoms, and Z represents a
lower alkyl, preferably methyl group. Examples of such
diphosphonates include 1 - amino ethane ~ diphosphonic
acid and 1 - hydroxyethane ~ diphosph~nic acid, and
preferably the alkali metal salts thereof. Mixtures of any
two or more of the aforementioned amino-methylene
phosphonates and/or diphosphonates can be employed, as
desired. Such a compound or compounds are preferably
employed in an amount of at least 0.075 ~ by weight of the
composition and generally an amount of not more than 1 % and
often the amount is selected from the range of 0.1 ~ to
0.4 %. Use of larger amounts than 1 % do not in yeneral
repay the additional cost of their incorporation, and for
each phosphonate an amount is reached beyond which
increasing the amount leads to impaired stabilisation.
When it is desired to include both the polyhydroxy
carboxylate and the phosphonate in the compostion, an
extremely convenient and desirable way of so doing is to
firs~ obtain or produce a premix o~ these two components in
the desired weight ratio e.g. 4:3 of the former to the
latter and then u~e the premix.
In many of the detergent compositions of the present
'invention~ the weight ratio o~ the polyhydroxy compound to
the phosphonate i~ within the range of 3 to 1 to 1 to 3 and
often within the range of 2 to 1 to 1 to 1, and their
combined % is preferably f~om 0.2 to 1.0 %. In other highly
.
5 ~ ~
~ 13 - GC108+
desirable embodiments of the present inventiorl, the lower
molecular weight aliphatic alcohol is selected within a
weight ratio to the phosphonate of from 50:1 to 2.5:1, and
pre~erably from 50 to 1 to 20 to 1, when the stabiliser
system consists of the phosphonate and the al¢ohol,
preferably employing a comparatively high amount of the
phosphonate, namely at least 0~15 % generally up to 0O4 %.
Most desirably the weight ratio is varied inversely to
variation in the phosphonate concentrate. The product of
the weight ratio of alcohol to phosphonate and the
concentration of the phosphonate expressed as a percentage
in the two component stabiliser system is preferably at
least 8 and often from 9 to 12. It is specially desirable
to employ all three stabiliser components together in the
detergent composition especially in a combined amount of at
least 0.2 ~ for the polyhydroxy compound and the
phosphonate, and at least 5 % of the aliphatic alcohol. In
many embodiments, it is convenient and advantageous to
select the components within the ranges of 0.1 to 0.4 ~ for
each of the polyhydroxy and phosphonate components and from
5 to 12 and particularly from 8 to 12 % for the aliphatic
alcohol, especially ethanol.
The hydrogen peroxide can conveniently be incorporated
in the form of the appropriate amount of concentrated
hydrogen peroxide, eg 35 to 85 % W/W hydrogen peroxide
commercially available, which often contains from 10 ppm
pyrophosphate. It is often incorporated in the solution in
the range of from 3 to 10 %, frequently from 5 to 8 % and
for industrial uses often from 10 to 20 % (expressed as
100%~) Lower concentration of hydrogen peroxide could be
employed, but in general these would not enable a desirable
amount of active oxygen to be provided in the washing
~olution unless the concentration of the other components in
the detergent composition were correspondingly reduced also.
It will be recognised that the concentration of hydrogen
peroxide in the range 5 to 8 % in the detergent composition
when diluted to form a washing solution by a ~actor selected
~7~5~
- 14 - GC108+
within the range of 100:1 to 1000:1 and often preferably
from 200:1 to 500:1 can readily provide active oxygen
concentrations commensurate with those provided by normal
concentrations of many heavy duty solid detergent
compcsitions or by the addition of an active oxygen bleach
at recommended levels to commercially obtainable active
oxygen-free liquid detergents.
In practice, the total proportion of components other
than water and hydrogen peroxide normally is selected to be
not greater than 52 %. Use of a higher proportion,
particularly where the composition contains relatively high
proportions of builder and anionic surfactants tends to
become more sensitive to phase separation. Although a total
proportion, eg below 20 % of such components could be
lS employed in compositions, whether built or not, it is more
desirable to provide such components to a total proportion
of at least 20 ~ and more preferably at least 30 % of the
liquid composition, not only from the point of view of
reducing the volume of unnecessary water to be transported
but also because the user often associates dilute products
with inferior products. In many embodiments, the totaled
proportions of components other than water and hydrogen
peroxide in the built compositions is at least 35 % and
frequently not more that 45 %.
The prefered concentration of polyphosphate or citrate
in the detergent compositions is from 9 to 16 %. The
proportion of anionic sulphate or sulphonate surfactant plus
ethoxylated non-ionic surfactant in the concentrate is
preEerably within the range of from 6 to 15 %, the weight
ratio o~ anionic to non-ionic surEactants normally being
selected within the range o~ 5:2 to 2:S, in order to produce
a balanced surfactant mix Eor the treatment of the general
mix of household stains. Where the composition is intended
for a more speci~ic stain, one that is known to be sensitive
3~ to a particular type of surfactant, then anionic to
non-ionic surfactant weight ratios outside the
aforementioned range can be readily contemplated. Hence~
1 17'15'~
- 15 - GC108+
e.g. where the product is intended primarily for greasy
stains, a lower anionic to non-ionic ratio can be mor~
desirable, for example in the range of 1 t~ 2.5 ~to 1 to 5.
Additionally, in determining the actual amounts of various
components to be incorporated in the mixture, it is
desirable to maintain the builder e.g. polyphosphate or
citrate to anionic surfactant ratio within the range of 1:1
to 5:1 and particulary from 2:1 t~ ~1 so as ~o take
advantage of the synergistic interaction between those two
components. The anionic surf~ctants are present preferably
in an amount from 3 to 8 %, and often at least 4 %, and the
builder is preferably polyphosphate or citrate, frequently
at from 9 to 16 %, and the non-ionio surfactant content is
,normally at least 3 % and again often at least 4 %, with the
lS result that the anionic sulphonate or sulphate surfactant
and nonionic ethoxylated surfactant are pr~sent in such
compositions in to~al amount advantageously o at lea~t 8 ~
Addi~ionally; it is desirable for the clstomary reasons
to incorporate in the detergent composition a qmall
proportion of detergent adjuvant~, the ~total amount of
adjuvants, generally up to 8% and in many ca~es, being fro~
1 to 5 ~. Examples of adjuvan~ include soil
anti-redeposition agents, for example polyvinylpyrrolidon~,
and sodium carboxymethylcellulose, often in an ~mount o~
from 0.1 to 0.3 % and an optical brightener or a range of
brighteners to allow for the various sorts of fibre~ rom
which household laundry articles are made, to a total amount
often in the range of 0. 5 to 2 % of the` composition. It is
generally desirable to select as brightener those o~ the
stilbene type which have demonstratable ~torage
comp~tibility with hydrogen peroxide in ~olution. In
general, the aomposition will also contaln a very sm~11
proportion of alkali metal sulphate formed during the
neutrali~ation of the anionic surfactant during i~
3S preparation. The compositlon~ can al90 include a ~mall
amount of mono-or di or tri ethanolamine, or alkali metal
borates as pH ad~uster~, but alkali metal silicates and
~ 1 7~ 5 5~
- 16 - GC108
carbonates axe excluded, or of amphoteric surfactants such
as imidazoline based fatty acid carboxysulphates. e9. from
0.5 to 2 %. The adjuvants can also include a small amount
of fo~m regu~ators, for example ethylene o~ide/propylene
oxide copolymers such as are available from Ugine Kuhlmann,
France under the Trademark PLURONIC, grades L42 and F.108,
and soaps i e. al~ali metal salts of aliphatic carboxylic
acids, having a chain length of at least 8 carbon atoms and
normally from 10 to 20 carbon atoms, examples of which
include stearate, and soaps derived from natural sources,
particularly tallow and coconut oils, again often up to 2~
by weiqht. Other adjuvants can comprise compatible tarnish -~
inhibitors, cationic softeners, dyes, perfumes and
thickeners, such as xanthan gum for citrate-built
for~ulation~.The amounts of the adjuvants can be varied by
the skilled worker within or outside the exemplified ran~es.
Some especially preferred built compositions according
to the prese~t invention compri~e from B to 12 ~ in total of
anionic sulphate or sulphonate surfactant and nonionic
ethoxylated surfactants of which preferably from 3 to 8
anionic sulphate or sulphon~te surfactan~ and preferabiy
from 3 to 8 3 is non-ionic ethoxylated surfactant, from 9 to
lS ~ alkali metal preferably, potassium tetra pyrophosphate;
from 3 to 6 % alkali metal aryl sulphonate hydrotrope; from
5 to 1~ %, pr~ferably 8 to 12 ~ ethanol; from 5 to 10 %,
preferably 5 to a % hydrogen peroxide; from 0.2 to 1 ~ in
total of a polyhydroxy linear C~ or C7 aliphatic
carboxylate, preferably an alkali metal gluconate an~ an
alkali metal methylene phosphonate complexing agent,
pre~erably ~thylene diaminetetra methylene phosphonate or
hexamethylene diamine tetra methylene phosphonate or
diethylene triamine penta methylene phosphonate, pre~erably
in a weight ratio o~ ~rom 2:1 to 1:1; up to 3 ~ of detergent
adjuvants such a~ described herein, including a 40il
antiredeposition agent and an optical brightener; and the
balance, water, pre~erably from 55 to ~5 %. Other
composltions include corresponding compositions containing
at lea~t 5% builder and in which all or part of ~he 9-16~
~ ~ 7
- 17 - GCl~8
po~yphosphates or citrate builder is replaced by 4 to 7%
carhoxymethyloxy succinate or 3 to 9% NTA.
In a modification of the invention, no builder is
employed, and instead the compositions contain additional
CJ surfactant, mainly nonionic surfactant~ Consequently,
unbuilt detergent compositions according to the present
invention contain at least 5% nonionic surfactant and in
total at least 10% surfactants. The presence of the extra;
surfactants means th~t the balance of anionic to nonionic
generally favour~ the nonionic to a much greater extent than
in built composi~ions according to the present invention.
Thus, in unbuilt compositions, the anionic surfactant is
normally selected in the range of 3 to 15%, but the nonionic
is normally selected in the range of 5 to 35%. The weight
ratio of anionic surf~ctant to nonionic surfactant is
preferably selected in the range of 1:1 to 1:6, and in
practice is often likely to be in the range of 1:3 to 1:6.
The anionic surfactant often represents ~rom 3 to 10% of the
unbuilt composition and the nonionic sur~actant at least 15%
and frequently from 20 to 35%. In a specially preferred
unbuilt compositions/ the surfactants concentration i3 not
more than 40% and particularly i~ from 25 to 40~, of which
the anionic comprise~ from 3 to 8~ and the nonionia ~rom 22
to 3S~. The unbuilt aompo~itions can, in practice, be
slightly more concentrated than the built compositions.
Thus, the total proportion of components other than water
and hydrogen peroxide is generally up to 65% and frequently
from 40 to 60~.
In the other respect~, for example ~election o~ and
aoncentrations o~ hydrotrope, ~tablll8er, hydro~en peroxide
and ad~uvants~the aorementloned description or th~ built
compo~ition~ applies likewise to the unbuilt aompo5ition~
according to the present invention.
It i~ especially desir~ble that the aompo~ition3,
either built or unbuilt, be ~ree from alkali metal
carbonate~ or silicates.
The compo~itions desaribed herein can be made
~ 1 7~
- 18 - GC108+
conveniently by mixing the components in the desi~ed
proportions in a mixing tank, and to avoid and minimi~e lo~s
of hydrogen peroxide by decomposition it is preferable to
add it as the last step, or at least after the two
stabiliser components have been introdu~ed. The surfartants
are preferably mixed at a moderately elevated temperature,
often from 35 to 60 C, and then combined with the other
components which brings the mixture to near ambient for the
introduction of the hydrogen peroxide. Preferably the
1~ polypho~phate is introduced in aqueous solution, either
supplied as such by the manufacturer or prepared on site by
dissolution. The minor components, detergent adjuvants and
sulphonate hydrotrope can be mixed in with the surfactant
mix. The variou~ solutions ~nd water can be introduced
consecutively or concurrently in~o the mixing tank except as
mentioned hereinbefore that the hydrogen peroxide solution
is preferably introduced last or star~ing last. Although
the proces~ has been described in a batch manner it wi:Ll be
readily apparent to a skilled engineer how to carry out the
process on a continuo~s basis. The ~omposition~ when
throroughly mixedj can then be poured in~o containers or
dispensers. By virtue of the superior ~torage stabllity of
at least some of the embodiments, of the inventionj such as
those losing leas then 1 % Avox a week the cont~iner~ or
~5 dispensers for such embodlment~ need not be o~ the speciaily
vented and thus expensive types, but instead container~
having a slightly loose fitting closure means, such as cap
or stopper can be used.
According to a further aspect o~ the pre~ent invention,
3n wa~hing proces~es, or laundering, aacording to th~ pre~ent
invention aan be carrled out by diluting the liqu1d
concentrate o~ the pre~ent lnvention with water to a des~red
extent, and contactlng the a~ueou~ washing solution with the
articles to be washed at any temperature ~rom ambient to the
boiling point o~ the ~olution. In many proce~ses, the
process i~ carried out at hand hot temperature or hotter,
often a temperature of at least 45 C and, dependi~g on
455~
- l9 - GC108+
local washing customs, fr~quently at a temperature of at
least 60 C.
It is a feature o the present invention that there is
provided a one shot liquid detergent composition containing
not only hydrogen peroxide, but also a high concentration of
anionic and non-ionic surfactants of the order needed to
form a washing solution without the addition of any further
components. However, if it is desired, the detergent
composition described herein before can be employed in
conjunction with one or more bleach activators, i.e.
compounds which react in aqueous solution with hydrogen
peroxide to generate peroxy acids, preferably added
separately to the washing solution to prevent premature
interaction. Such compounds are normally N-acyl or 0-acyl
compounds. Typical examples of the classes of each
~ctivator which each represents, includes
N,N,N',N',-tetraacetylethylene-diamine of N-acylated
alkyleneamines, benzoic or phthalic anhydride, tetra acetyl
glycoluril,N-alkyl-N-sulphonyl-carbonamides, N-acyl
hydantoins, carbonic acid esters, triacetyl cyanurate,
0,N,N'-tri substituted hydroxylamines and diacyl peroxides
such as benzoyl glutaryl peroxide and diphthaloyl peroxide.
In comparison with the use of such activators in conjunction
with solid detergent compositions, inter-reaction between
-~5 the active oxygen containing compound and the activator can
occur more quickly by virtue of the fact that the hydrogen
peroxide is already in solution whereas for solid peroxygen
compounds, and especially the commonly used sodium perborate
tetrahy~rate at hand-hot temperatures or cooler, its rate of
dissolution can be a restraining factor. I~ an activator i5
employed in conjunction with the detergent aomposition, then
the preferred washing temperatures tend to be ~omewhat
lower, pre~erably ~alling in the the range from ambient to
fiO C. Naturally, a convenient mole ratio of activator to
3S hydrogen peroxide is from 2 to l to l to 2l and esp~cially l
to 1 in the washing solution.
Generally, the concentrates of the present invention
1 ~7~5~
- 20 - GC108+
are diluted to produce washing solutions containing from 0.1
to 1.5 gpl surfactant. In many cases, the concentration of
surfactants is within the range of 0.2 to 0.6 gpl and such
concentrations can be obtained from many of the preferred
detergent compositions of the present invention such as
those containing at least 8 ~ surfactants at a dilution of
greater than 100 to 1, and often at a dilution of from 200
to 1 to 300 to 1.
The washing period can range from as low as a minute or
1~ a few minutes e.g. 5 minutes at washing temperature at or
near the boiling point of the washing solution, e~g. from 90
to 100 C up to a period of several hours at cooler wash
temperatures, such as overnight steeping at ambient
temperature. The washing period can be varied at the
iS discretion of the user. Typical washing times at a
temperature of 40 to 70 C are of the order from 5 to 40
minutes.
In addition to laundry use, the compositions can be
used neat or after dilution to cleanse hard surfaces, such
2~ as those of enamel, paint, metal, plastic, wood, glass or
ceramics.
Having described the invention in general terms,
specific embodiments will be described hereinafter more
fully by way of example only. It will be recognised that by
, employing his general knowledge and the information
contained herein before, the expert in the field of liquid
detergents will be able to vary the proportions of
components in the composition.
7~5~
- 21 - GC108+ Can
Examples 1-4~ and 43-6~
Liquid detergent compositions according to the present
invention were prepared by the following ~eneral ro~te,
employing the weight proportions summarised in Tables 1, 2 and 3
below.
First, a mixture of the anionic and ncnionic sur~actants in
the correct proportions was heated to approximately 4~ to 45 C
with constant s~irring until a clear sol~tion occured. The
sulphonate hydrotrope and ethoxylated phosphate ester when
employed were then introduced in the desired proportions with
stirring followed by the builder, often together with a
proportion of the total deionised water content of the mixture
which cooled the mixture~ Next the ethanol the residual amount
of water the polyhydroxy carboxylate and the phosphonate
component~ were added as well as the detergent adjuvants, where
employed. Finally, the hydrogen peroxide solution was
introduced. The mixture was vigorously stirred.
In the Examples (tm) indicates the preceding word to be a
trademark which is often followed by a product/grade
description. The components used in the compositions were as
follows:
anionic surfactan~s
Al so~iu~ dodecyl benzene sulphonate - HETSULF 60S (tm)
A2 sodium linear alkyl benzene sulphonate - ~ANSA
SS60 ~tm)
A3 sodium primary alcohol sulphate - PERLANKROL DSA ttm)
amphoteric suractant
A~ imidazollne based - coconut carboxys~lphate
hydrophile M~R~NOL 3MCT (tm)
nonionia ~ur~actants
Nl Cls sec alcohol ethoxylate (n-~) T~RGITOh 15S9 (tm)
N2 middle cut primary C12 ~ ClS alcohol ethoxylate ~na9)
ETHYLAN D259 (tm)
N3 syn~hetic primary alcohol ethoxylate (n~7) SYNPERONIC
A7 ~tm)
N~ lower cut primary alcohol ethoxylate (n=9
~THY~N CD919 (tm)
' ~
5 ~
~ 22 - GC108+ Cn~
Hydrotropes
HXl sodium xylene sulphonate (SX96)
HX2 sodium xylene sulphonate - ELTESOL SX30 ttm~
Phosphate esters
HEl ethoxylate~ phosphate ester - TRITON QS3~ ~tm)
HE2 ethoxylated phosphate ester (n=2) - BRIPHOS ~2D
ttm)
polyhydroxycarboxylate
SG sodium gluconate
phosphonate stabiliser
SPl hexapotassium ethylene diamine tetra (methylene
phosphonate)
SP2 aminotris(methylene phosphonic acidl
SP3 diethylene~riaminepenta~me~hylene phosphonic
acid
SP4 hexamethylenediaminetetra(methylene
phosphonate) hexapotassium salt
SE Ethanol-industrial grade methylated spirits
HP Hydrogen peroxide - 35 % W~W aqueous solution
containing 50 pp~ pyrophosphate
~uilder
Bl Potassium tetra pyrophosphate (solid)
B2 Potassium tetra pyrophosphate (aqueous
solution) - KALIPOL 4KP (tm)
B3 Potassium polyphospate (chain length 4~ KALIPOL
18 (tm)
B4 Sodium Citrate
B5 Nitrilotriacetic acid, sodium salt
B6 Trisodium carboxymethyloxysuccinate.
Water Deionised except where marked * in which
Widnes, Cheshire municipal water was used
untreated~
~imilar compositions to one or more of the exempl1fied
compositions were obtained by substi~.utinq alternative
nonionic suractants such as poly oxyethylen~ alkyl ethers
or poly oxyethylene alkyl ethers for the speci f ied
ethoxylates, and/or substituting ammonium primary alcohol
;i ,1
;
,
~17~55~3
- 23 - GC108+
ether ~ulphate for the specified sulphate surfactant, and/or
by substituting ethoxylated phosphate mono ester of higher
degree of ethoxylation for the specified di-ester, and or by
substituting other polyphosphate builders for those
specified.
The storage stability trial for Tables 1 and 2 was
effected by transferring a small sample of the given
composition into a clean plastic bottle housed in a constant
temperature enclosure at 32 C. The available oxygen
concentration (Avox) in the composition was determined by
the standard acidified potassium permanganate titration
method on a small portion extracted from the sample and the
result obtained after storage for a given period compared
with the original content. The result given in Tables 1 and
2, is the percentage of Avox lost from the hydrogen peroxide
after 3 weeks storage, except in Examples 43 to 52 in which
it is after 4 weeks storage. The storage stability trials
for Table 3 were carried out in the same manner as that for
Tables 1 and 2 except that the temperature of the enclosure
was 50C in order to accelerate proceedings. The result is
given after 24 hours, approximately. The gluconate and
phosphonate were introduced separately, except in Examples 1
to 30 and 43 to 58 were they were provided in th e form of a
premix of SG and SPl available under the tradename POLYRON
1020.
~0
1 ~745~3
- 24 - GC108+
~able 1
Ex Weight % of component in composition
Surfactant ~ydrotrope Builder
No Nonionic Anionic
Nl N4 i~l A2 HXl HX2 HEl Bl B2 B4
1 6 4 5 15
2 6 4 5 15
3 5 5 5 15
4 5 5 5 15
4 6 5 15
6 4 6 5 15
7 3 7 5 15
8 3 7 5 15
9 3 7 5 10 15
3 7 5 10 15
11 7 5 3 15
12 7 5 3 15
13 5 5 5 15
14 5 5 5 15
16 5 5 5 15
17 5 5 5 15
43 4 6 6 15
44 4 6 6 15
4 6 6 10
46 4 6 6 10
47 4 6 6 15
48 4 6 6 15
49 4 6 6 15
4 6 6 lS
.~ ~7~ 5.~
25 - GC108
Tab1e 1 cont inued .
Ex Weight 96 of component pH ~vox
No Stabiliser HP Water loss
SE SG SPl SP2
0.20 0.15 7 B 9.3 4
2 10 " " 7 a 9. 5
3 " " 7 1 9.3 7
4 10 " " 7 a gO4
" " 7 n 9. 2 2
6 10 " " 7 c 9.2 2
7 " " 7 e 9. 2
8 10 ~ I- 7 9. 3 3
9 " " 7 8.2 4
10 10 " " 7 8. 3 2
11 n ~ 7 7~8 2
12 10 " " 7 8 . 0
13 10 0. 05 0. 04 7 9. 412
14 lû 0 . 10 0 . 0~ 7 9. 2 10
15 10 0~20 0.15 7 9.0 3
16 10 0 ~ 30 0 ~ 23 7 9. 0 3
17 10 0 . 40 0 . 31) 7 9 ~ ~ 5
43 10 0.20 0.15 7 9.4 2
44 10 0. 20 0. 15 7 9 . 1 3
0 . 20 0 15 7 7 ~ 4 3
46 10 0.20 0.15 7 7.4 2
47 0 . 20 0 . 15 7 7 . 6 3
48 10 0 . 20 0 . 15 7 7 . 7 2
49 0. 20 0 . 15 7 * 9~ 4 4
50 10 0 . 20 0. 15 7 * 9. 2 3
1 5 ~ ~
- 26 -GC108
Table 2
Ex Weight % oE component in composition
Surfactants Hydrotrope Builder
No Nonionic Anionic Amph
N2 N3 A2 A3 A4 HX2 HE2 Bl B2 B3
18 3 7 5 15
lg 3 7 5 1 15
3 7 5 2 15
21 3 7 5 3 15
'22 3 7 5 15
23 7 3 5 15
24 4 6 5 15
6 4 5 15
26 5 5 5 15
27 3 5 7 15
28 4 5 6 15
29 7 7 5 10
6 4 5 10
31 10 3.3 2 ~.5
32 10 3.3 2 6.5
33 10 3.3 3 6.5
34 10 3.3 3 13.5
3.3 3 13.5
36 5 7 5 15
37 7 7 3 15
3~ 5 5 5 10
39 5 5 S 10
51 5 4 5 15
52 6 6 5 15
5 5 Q
- 27 - . GC108+
Table 2 con~
Ex Weight ~ of component pH Avox
No Stabiliser HP Water loss
SE SG SP 1 SP 2
18 0.20 0.15 7 b 8.9 18
19 " " 7 a 8.2 14
ll .. 7 1 8.1 8
21 " " 7 a 8. 7 10
22 10 " " 7 n 9.1 4
23 10 " " 7 c 9. 2 3
24 10 " " 7 e 9 . 2 2
ll Il 7 9 . 2 4
26 10 ll I- 7 ~ 1 2
27 Il - 7 7.8 4
28 " ~ 7 8.0 6
29 ". . " 7 8.1 4
" " 7 8 . 5
31 6~5 to pH 3.3 7 2
32 6.5 to pH 3.3 7
33 6.5 to pH 3~ 3 7 6
34 6.5 to pH: 3.3 7 3
to pH 3.3 7 3
36 0.27 7 7.g
37 ll 7 8.5 2
38 ll 7 7.7 2
3~ ll 5 8.7 7
0.54 5 8.6 8
51 0~2 0.15 7 9.4 2
52 10 0.2 0.15 7 9.5 3
5 ~ ~
- 28 - GC108+
Table 3
Ex Weight ~ of component in composition
Surfactant Hydrotrope Builder HP
No ~onionic Anionic
N4 A2 HX2 Bl B4 B5 B6
53. 4 6 6 15 7
54 4 6 6 15 7
4 6 6 15 7
56 4 6 6 5 7
57 4 6 6 15 7
58 4 ~ 6 15 7
59 4 6 6 15 7
4 6 6 15 7
61 4 6 6 15 7
62 4 6 6 15 7
63 4 6 6 15 7
~4 4 6 6 15 7
Table 3 Continued
Ex Weight of components in composition pH Avox
No Stabiliser Water loss
SE SG SPl SP3 SP4 %
53 10 0.2 0.15 B 9.3 7
54 10 0.2 0.15 a 9 7
0.2 0.15 1 8 13
56 10 0.2 0.15 a 8.3 10
57 10 0.2 0.15 n 4
58 10 0.2 0.15 c 3
59 0.2 0~15 e 6
0.2 0.15 5
6~ 0.2 0.15 S
6~ 10 0.2 0.15 4
63 0.2 0.15 6
6~ 10 0.2 0.15 5
Under the storage conditions, lt was observed that
almost all the compositions exemplified remained thro~ghout
storage in a single phase despite the presence of both
i 1745~
~ 29 - GC108
hydrogen ~eroxide and polyphosphate builder in high
concentrations, and that phase stable compositions similar
to those (18,37) which separated after several months~ were
obtainable by a modest redution in the polyphosphate
concentration or addition of ethanol in amounts suE~icent to
enhance the stability of the hydrogen peroxide in the
composition or slightly more hydrotrope.
From Tables 1, 2 and 3 it can be seen that
incorporation of ethanol within the limits specified herein
in conjunction with phosphonate or phosphonatefgluconate
improves the storage stability of the alkaline composition,
and that as the level of glyconate/phosphonate stabiliser
mix is increased, the storage stability of the co~position
increases up to certain level and thereafter declines.
The washing capability of various of the above
mentioned compositions have been tested and the results are
summarised in Tables 4, 5 and 6.
The washing trials were carried out in the following
manner:-
Prestained swatches of cotton were washed in alaboratory scale washing machine, sold under the trademark
TERGO~OMET~R (US Testing Corporation) which simulates the
action of a vertical agitator type of domestic washing
machine. The machine trials were carried out under standard
conditions of two stained swatches, each of 59, being washed
at a temperature maintained at 60 C with one litre of an
aqueous washing solution containing 4 grams of the selected
detergent composition. Por the compositions according to
the present invention this resulted generally in an initi~l
~urfactant concentration in the range of ahout 0.3 to 0.5
gpl, and an initial builder concentration in the range of
rom 0.2 gpl to 0.8 gpl. The ~irst washed swatches were
removed from the wash water after 10 minutes washin~, rinsed
with cold water and dried, and the second removed after 20
or 30 minute~ washing and si~ilarly rinsed and dried. The
extent of stain removal from each swatch was determined by
mea~uring the reflectance of the swatches before and after
~ 1 7
- 30 - GC108+
washing, using a Zeiss E~EPHO (tm) Reflectance Photometer
having a Xenon lamp light source equipped with a
y-tristimulus filter. Each swatch was measured four times
with a backing of three thicknesses of material. The
S reflectance readings were averaged and the % stain removal
(abbreviate~ to %SR~ was obtained using the following
formula:
% stain removal = 100 x (R~ - Ri)/(RU - Ri~ where Ru
represents reflectance of the unstained cloth, Ri
reflectance of the cloth after staining, and Rf reflectance
of the the stained cloth after bleachingO Swatches of
cotton stained with red wine were obtained from E.M.PDA.,
St. ~allen, Swi~zerland. Swatches of other stained fabrics
were obtained by padding the appropriate fabric through an
appropriate stain solution, partially drying the fabric with
an infra red drier, and repeating the padding and drying
cycle twice more.
In the washing ~rials summarised in Table 4 and 5, the
washing solution water had a hardness of 150 ppm as calcium
carbonate in a Ca:Mg ratio of 2:1 and in those summarised in
Table 6, a hardness of 250 ppm as calcium carbonate in a
Ca:Mg ratio of 3:1
In Tables 5, and 6 the detergent composition of the
present invention additionally contained 0.5 % by wei~ht of
a bleach stable stilbene optical brightener obtainable under
the name UVITEX BHT Itm). Washing trials using compositions
C41, and C42 are present by way of comparison only. The
composition C41 was a commercially available built liquid
detergent composition WISK (tm), and C42 was an
approximately SO/SO W~W mixture of WISK (tm) with an
active~o~ygen containing bleach additive CLOROX ~ ttm).
Analysis o~ the products C41 and C42 showed that at the
levels o~ detergent compositicn employed, the wa~hing
solution contained total sur~actants in the range of 0.3 to
0.4 gpl and an initia1 builder plus p~ adjuster
concentration of about 0.4 gpl. These concentrations are
very comparable with the concentrations of surfactants and
builders present under standard conditions of use of the
invention compositions (4 gpl) and
~ 17~5t~
- 31. - GC108+
in broad terms double those when ~he invention compositions
are used at only 2 gpl.
Table 4
Example/ Washing Stain% Stain removal
comparison conditions a~ter
composition 10 min 20 min
used
48 Standard Red Wine 61 67
48 " Cocoa 28 30
48 " Tea 52 58
48 ll EMPA 101 42 47
C42 4 g/l Red Wine 56 63
C42 " Cocoa 14 19
C42 " Tea 51 60
C42 " EMPA 101 27 32
48 2 g/l Red Wine 56 63
48 " Cocoa 25 27
48 " Tea 47 54
48 " EMPA 101 33 39
C41 2 g/l Red Wine 52 60
C41 " Cocoa 16 20
C41 " Tea 40 43
C41 " EMPA 101 34 41
`1 17~5$~?
- 32 - GC108
Table 5
Example/ Washing Stain % Stain rem~val
compar~son conditions after
- composition . 10 min 20 min
used
4 Standard Red Wine63.4 65.4
4 " Cocoa 28.7 33.3
4 " Tea 53.5 55.8
4 " EMPA Standard 51.7 57.4
2 . " Red Wine59.6 64.5
2 " Cocoa 38.5 43.8
2 " Tea 42.9 56.5
2 " EMPA Standard 52.4 59.6
6 " Red Wine .59.7 66.2
6 " Cocoa 33.0 37.3
: 6 " Tea 49.7 59.8
6 I- EMPA Standard 52~5 59.1
12 " Red Wine57~6 61.8
12 " Cocoa 25.6 36.6
12 " Tea 49.1 55.5
12 " EMPA Standard 50.0 54.8
22 9/l Red Wine ; 50.8 54.6
2 n Cocoa 6.6 8.6
2 1I Tea 28.5 33.8
4 " Red Wine 53.1 56.5
4 " Cocoa 6.0 9.5
4 " ~ Tea 26.5 29.9
6 " Red Wine 50~1 52.6
6 " Cocoa 6.5 9.1
6 " Tea 26.3 29.4
C41 " Red Wine 38.5 40.6
C41 " Cocoa 2.2 3.6
C41 " Tea 4.4 10.9
C42 4 g/l mix Red Wine 44.9 53.4
C42 " Cocoa -l.S 7.8
C42 " Tea 6.2 31.6
- ~ ~ 7'1~
_ 33 _ GC108+
Table 6
Example/ Washing Stain% Stain removal
comparison conditions after
composition 10 min 20 min
used
18 Standard Red Wine 71.8 79.7
18 " Cocoa 23.7 39.1
18 " Tea 46.9 62.0
19 " Red Wine 72.7 79.8
19 " Cocoa 16.4 33.0
19 " Tea 46.6 61.2
21 " Red ~ine 71.9 80.4
21 : " Cocoa 29.0 37c8:
~ 21 " Tea 47.3 :63.2
: 26 " Red Wine 74.9 81.9
26 " Cocoa ~ 22.2 37.4
26 " Tea 50.4 66.4
2g " Cocoa 14.0 24.0
" Cocoa 15.0 14.0
: C41 2g~1 Red Wine 60.4 66.2
C41 n Cocoa 17.6 ~9.1
C41 " Tea 23.9 27.6
C41 4g/1 Red Wine 65. 67.0
C41 " Cocoa 18.2 33.9
C41 " Tea 18.2 33.9
; C42 4g/1 mix Red Wine 66.3 76.6
C42 " Cocoa 12.2 26.9
C42 " ~ea 25.2 62.3
From Tables 4, 5 and ~ it can be readily seen that the
invention compositions were very effective and, in several,
better stain removers on the range o~ stains tested than
were comparison compositions C41, C42 and C43. It will be
recogni~ed therefore, that the composi~ions oP the instant
invention combine the advantages o~ good storage stability
with good washing performance. Moreover, when washing
trials were repeated employing washing compositions that
5 5 ~
_ 34 - GC108+
omitted the phosphonate and gluconate stabilisers, but were
otherwise identical, the washing results were also
identical, being within 1 ~ stain removal, i.e. within the
limits of reproducibility of the washing tests, indicating
that the presence of the phosphonate and gluconate
stabiliser had not impaired the washing performance even
though they had considerably improved the storage stability
of the composition
Examples 65 to 69
Compositions were prepared by the method for Examples 1
to 64 except that the step relating to incorporating builder
was omitted. Tne Avox of the compositions was required
after 4 weeks storage at 32C and the washing trials were
carried out in exactly the same manner as those whose
results are summarised in Tables 4 to 6, in hard water
having a hardness of 150ppm as calcium carbonate in a Ca:Mg
ratio of 2:1.
The compositions and results are summarised in Table 7
below.
1 ~t~55~
- 35 - GC108+ Can
Table 7
Example No 65 66 67 68 69
Composition weight %
Surfactant Nl 30 30 35 2~ 20
A2 5 5 5 10
~ydrotrope HX2 5 5 5 5 5
Ethanol SE 10 10 10 10 10
Hydrogen Peroxide 7 7 7 7 7
Gluconate SG 0.20 0.20 0.20 0.20 0.20
Phosphonate SPl 0.15 0.15 0.15 0.15 0.15
Water balance
Stability
Avox Lost 3.9 1.8 1.8 3.4 2.2
~ Soil Removal
Red Wine 10 Mins 63 63 66 66 68
Red Wine 30 Mins 68 67 72 71 73
Cocoa 10 Mins 10 9 8 9 8
Cocoa 30 Mins 13 11 10 11 11
The effectiveness of the soil removal can be judged by
comparison with commercially available detergent compositions
in the USA, viz WISR (tmj and DYNAMO (tm) each at 2 gpl, on
urther examples of the stains under the same conditions of
wash temperature, water hardness and wash duration, either
alone or in 50:50 weight mix with a bleach additive
CLOROX 2 .(tm)
The comparative results are summarised below in Table 8.
Table 8
Red Wine Cocoa
10 Mins 30 10 ~ins 30
WISR ~tm) 37 40 1 6
WISR (tm) ~ CLOROX (tm) 44 61 3
DYN~MO ~tm) 50 5~ 5 10
~YNAMO (tm) ~ CLOROX (tm) 45 62 8
From the above it can be seen that the invention
compositions obtained significantly better results in the
i
~17~ )3~
- 36 - GC108+
respected red wine stain than did the commercial compositions
and in respect of the cocoa stain obtained much better result
than did the sample of WISK, alone or with added ble.ch and
comparahle with or better than the results obtained using
DYNAMO, alone or with added bleach.
