Note: Descriptions are shown in the official language in which they were submitted.
~05~3~3~
This invention relates to liquid cleaning composi-
tions comprising a polyphosphate builder. Such compositions
include both liquid detergent solutions comprising a surface
active agent such as are currently employed as dishwashing
and textile detergents and also highly alkaline solu~ions
comprising little or no surface active agent such as are
used for cleaning hard surfaces, e.g. the insides of ovens
and for machine dishwashing bottle washing and beer keg
washing. The present compositions may have various degrees
of aqueous dilution and in the extreme case may be stable
suspensions or gels. The polyphosphate solutions may al50
be dried by suitable means to provide a solid builder com-
position. In the gel or suspension form the compositions
may be used in cosmetic detergents, e.g. shaving creams.
Polyphosphate huilders are useful in all such compositions
both for their sequestering effect on heavy metal ions,
notably calcium ions, ana for their detergent builder proper-
ties additional to this sequestering effect.
Considerable efforts have been made to provide
satisfactorily built cleaning compositions of the types
instanced above but as yet a number of problems xemain.
The primary difficulty in the case of liquid
cleaning compositions arises from the variegated nature of
the necessaxy ingredients coupled with the properties which
the liquid cleaning composition must possess. In the case
- Qf compositions comprising sur~ace active agents in solu-
~ion the primary problem may be expressed as that of pro-
viding a composition which has a sufficient concentration
of surface active agénts and builder in the same solution
to give a satisfactory cleaning performance but which at
the same time is homogeneous, has a chill point well below
room temperature and a short reliquifaction time at room
~.
~5~38~
temperature after storage at low temperature. In addition
in order to gain acceptance the solution should be sufficient-
}y concentrated that a container of moderate siz~ containing
the solution will provide an acceptable number of washings -
about as many washings as an equivalent sized container of
solid detergent. All these requirements are onerous in that
they increase the necessity of the builder and sur~ace active
agents having a high compatibility. Compatibility limita-
tions are o~ten further aggravated by the need for further
ingredients such as a silicate (as a corrosion inhibitor)
suds builders, and organic solvents. In the case of highly
al~aline liquid cleaning compositions comprising little or
no surface active agent similar problems arise in relation
to the compatibilities in aqueous solution of the phosphate
builder and the alkaline ingredient which is nQrmally a
caustic alkali or a sodium silicate or a mixture of the
two.
Attempts to mitigate these problems have been
concentrated on varying the nature of the surace active
agent and the builder so as to discover a combination
having a large degree of compatibility or in incorporating
a further ingredient into the composition which is designed
to homogenise the solution. Combinations of these approach-
es have also been used.
However, the scope for variation is limited by the
desired properties of the composition and the success in
alleviating the above problems has been limited.
The scope for varying the nature of the surface
active ingredients (where used) is limited by the required
detergency characteristics of the composition, that is not
all surface active agents possess the foaming properties
(either high or low foaming ability may be desired) mild-
-- 3
~ S03t~1
ness washing ability and low cost which are required for use
in liquid detergents. A notable difficulty arises in the
case of the non-ionic surface active agents having the low
foaming pr~perties essential in liquid detergents for use in
automatic dishwashing machines as well as other desirable
washing properties. Such non ionic surfactants may be
dissolved only with difficulty in concentrated alkaline
builder solutions-unless certain specialised ingredients
are added to bring about compatibility (see for example
B.P. 991980).
A variet~ of homogenising agents designedto in-
crease the compatibility of the vaxious ingredi~nts are also
widely used in many types of cleaning compositions. Most
widespread among these are the so-called "hydrotropes",
notably sodium or potassium, salts of benzene, toluene or
xylene sulphonic acids and triamyl phosphate. Various
organic copolymers have also been suggested (see for examplç
B.P. 943353) and the incorporation of "assistant solubilizers"
such as ethanol or ethylene glycol has also been proposed.
The disadvantage of all these additional ingredients
is that they contribute little or nothing to the actual cle~n-
ing properties of the composition so that the expense of their
incorporation must be weighed solely against their ability to
enable the c~ncentration of the builder or surface active
agent in the solution to be increased. Moreover the dilution
o the cleansing effect resulting from the use of such homo-
genizers lessens the effectiveness of the composition.
The third major possibility of increasing the com
patibility of the ingredients of the compositions lies in the
variation of the nature of the builder. The scope for such
variation is however limited. The condensed phosphates are
the most widely accepted Idetergent builders and many of these
~ _ 4
:~61 503~
have been examined. The ma]or commercially accepted poly-
phosphate builder salts are the alkali metal pyrophosphates
and the alkali metal tripolyphosphates and the alkali metal
hexametaphosphates. For liquid detergent compositions the
most widely accepted builder is potassium pyrophosphate.
Whilst this compound is acknowledged to be a less effective
builder than other compounds such as sodium tripolyphosphate
potassium pyrophosphate is relatively free from the dis-
advantag s of limited compatibiliky with other ingredients
in detergent solutions and of hydrolysis in aqueous solutions
which attach to the tripolyphosphates. Even so potassium
pyrophosphate is
I
- 4~ -
~0sa~38:~
not as compatible with surface active agents as might be
desired and the problems outlined above still hinder the
development of liquid detergents.
We have now discoverecl a ranye of polyphosphate
builder salts suitable for use in liquid cleansingcompositions
which considerably reduce the aforesaid disadvantages in com-
parison with the aforementioned known polyphosphate builders.
The invention provides a cleaning composition which comprises
from 4 to 25~ by weight expressed as the weight of P2O5 on
the total weight of the composition of a mixture of a plu-
rality of polyphosphate salts of one or more primary,
secondary or tertiary amines which mixtura has been obtained
by forming an aqueous polyphosphoric acid solution comprising
from 80 to 88% by weight of phosphorus pentoxide which has
been allowed to reach equilibrium and subsequently reacting
the said polyphosphoric acid solution with a primary r
secondary or tertiary amine without causing any substantial
hydrolysis of the polyphosphate species present in the acid;
from 0.1 to 50~ by weight of a water-soluble surfactant.
~0 The following advantageous properties ~or the
compositions of the invention may be listed:
(1) High se~uestering ability for calcium and
magnesium ions;
12) Exceptionally good detergent builder properties
in addition to sequestering ability;
(3) Compatibility in aqueous solution with highly
alkaline reagents and surface active agent
substantially better than that of the conven-
tional builder solutions;
(4) Satisfactory viscosi~ies over a broad range
of solids contents leading to convenient
- 5
,. ~, :.
1~03~3~
handling. Such properties are desirable in the
formuiation of liquid cleansing products.
It is to be understood that whilst the mixtures are
not necessarily superior to conventional builders in all the
above respects, they are nevert!heless uniquely valuable in
the combination of these properties which they possess.
The builder solutions are obtained by neutralisation
of aqueous polyphosphoric acid solutions comprising from 80 to
88% by weight of phosphorus pentoxide. The polyphosphoric
acid species present in such solutions are in equilibrium
with one another and the over-all composition is governed
solely by the P205 content o~ the acid as is illustrated in
the Canadian Journal of Chemistry, Vol34 (1956) p.790, where
the compositions of a number of acids which are useful
according to our invention are detailed. These species are
primarily the straight chain polyphosphoric acids.
Useful aqueous polyphosphoric acid solutions may
be made by conventional means such as by concentration of
orthophosphoric acid solutions or by dilution of polyphosphoric
acid solutions having greater than the desired P205 content
with water. Whilst the presence of other materials in the
polyphosphoric acid solutions is not excluded, it is desirable
that these solutions be substantially unadulterated and poly-
phosphoric acid solutions derived by any of the above
mentioned procedures from phosphorus pentoxide obtained by the
burning of electrothermally produced phosphorus are preferred.
Polyphosphoric acid solutions derived by the solution of P205
in so-called "wet process" phosphoric acid ob~ained by
acidification of phosphate rock are also useful according
to the invention. The e~uilibria detailed above between
-- 6
~OSi~3~
the various polyphosphate acid species contained in a poly-
phosphoric acid having a particular P205 content are set up
virtually immediately in that acid but preferably the acid
is allowed to equilibrate before the neutralisation stPp,
e.g. by allowing them to stand for a period of time at room
temperature before neutralisation commences. Suitable times
are from one minute upwards.
The mixtures in aqueous solution may be obtained
by the reaction of the polyphosphoric acid solutions with a
primary, secondary or tertiary ~mine. In the term 'amine'
as used herein are included all compounds having an amino
grouping which are capable of neutralising phosphoric acid,
i.e. all compounds having an amino grouping other than one
at~ached to a carboxyl group, regardless of the other con-
stituents of the molecule so that, for example, this term
includes amino acids and substituted amines such as alkanol-
amines. Preferred amines have molecular weights below 200,
most preferably below 150. Particularly valuable amines
include mono-, di- and tri-ethanolamines and propanolamines.
Other amines which may be used include morpholine, mono-, di-
and tri-ethyl, n-propyl, iso~propyl and n-, iso- and sec-
butylamines, N,N-dimethyl-ethanolamine, aminoethylethanolamine,
N-2-aminoethylethanolamine, N-methyldiethanolamine, N-methyl-
morpholine, N-ethylmorpholine, N,N-diethylethanolamine, N-
methylethanolamine.
It may be desirable to effect the reaction step
simultaneously with a dilution to bring about the desired
final concentration of the builder solution, provided that
such dilution does not bring about hydrolysis of the poly-
phosphate anion species present. It is characteristic of
the builder solutions for present use that the spectrum of
polyphosphate anions present, substantially corresponds to
~0~6338~
that present in the original polyphosphoric acid solution.
Hydrolysis of polyphosphate anions is preferably avoided by
maintaining the pH of the reaction medium in the-range 4-12,
preferably 6-12i most preferably 7-10, and the temperature
below 70C, preferably below 40C, say 15C to 70c, or 15C
to 40C.
Previous attempts to neutralise polyphosphoric acid
solutions having a P2O5 content in the range 80-88~ by weight
have failed to appreciate the necessity of avoiding the hydro
lysis o~ the polyphosphate species during the neutralisation
step. For example B.P.919,249 describes the neutralisation
of a phosphoric acid solution containing 84% by weight of P2O~
u~ing a mixture of diethanolamine and potassium hydroxide.
The resulting polyphosphate is claimed to be a useful builder
in liquid detergents however in order to incorporate suffi-
cient builder in a liquid detergent solution the presence of
a water miscible organic cosolvent such as ethanol is essen-
tial. The amine builder salts of our invention made under
the conditions outlined above are sufficiently compatible with
detergent solutions to enable the use of such an organic co~
soIvent to be avoided if desired. However the presence of
such cosolvents in the compositions of our invention is not
excluded.
In B.P.1066234 there is described a solid detergent
builder which is produced by the neutralisation of a poly-
phosph~ric acid solution containing 83~ by weight of P2O5
with an excess of an alkali metal salt, preferably the
carbonate. Although this patent teaches the desirability
of avoiding the hydrolysis of the polyphosphate anions
present it is only concerned with the alkali-metal salts
and their use in admixture with alkali-metal carbonates as
solid detergent builders.
-- 8
~S03~
The mixtures for present use are preferably those
obtainable by reaction of the said phosphoric acids and the
said amines in a 1:1 ratio of c~cidic hydrogen atoms in the
polyphosphoric acid(s) to hydrogen atoms bonded to nitrogen
in the amine but compounds obtainable by partial neutralisa-
tion of the polyphosphoric acids by the amines also have
utility. In the general case of builders will be compounds
obtainable by the reaction of the said polyphosphoric acids
with amine in a ratio of from 1:10 to 10:1 say 1:5 to 5:1
prefPrably 1:1 to 3:1 expressed as the ratio of amine groups
to phosphorus atoms.
- In any case reaction be~ween the amine and the poly~
phosphori~ acia mixture preferably proceeds to a final pH of
from 4 to 12 preferably from 4 ko 10 most preferably from 7
to 1~.
The builder salts are conveniently obtained b~ the
straightforward addition of the polyphosphoric acid to the
amine or the aqueous solution thereof fQllowed by concentra-
tion or dilution as required for the proposed use.
In the case of the salts derived from amines which
contain an hydroxy substituent on their carbon chain it is
necessary to maintain the water content of the system at a
sufficient level so as to ensure the desired salt formation
occurs rather than esterification such as is described in
USP 3728419, a water level of above 15% by weight is normally
sufficient. In general we prefer to maintain the water con-
tent in the builder salt solution in the range 20-40% by
weight si~ce this facilitates the handling o~ the product.
In the case of amines which do not contain a hydroxyl
group and therefore cannot be esterified this restriction is
not essential although it is preferred to maintain the water
content of the system above 25% by weight. Decrease in this
g
1~5~3~
water content results in a progressive tendency to form a
solid product and such processes are less preferred.
A particularly valuable and unlooked for property
is that aqueous solutions of the mixtures may, within certain
proportion ranges, depending upon the amine involved, comprise
concentrations of the said polyphosphate salt mixture in
excess of the solubility limit for a true solution whilst
remaining as stable suspensions or gels which are useful as
builders for paste type cleaning agents such as oven ~leaners
and other highly alkaline hard surface cleaners as well as
cosmetic cleaners in paste form such as shaving creams. ~he
aqueous cleaning compositions of the invention are according-
ly defined
- 9A
3~3~
herein as including solutîons wherein the polyphosphate mix-
tures are in sol and suspension form as well as in true solu-
tions. Mixtures as hereinbefore defined which are in the
form of stable aqueous suspensions constitute a preferred
aspect of this invention. In general, such suspension-type
solutions will comprise from 35 to 60% by weight of poly-
phosphate mixture expressed as weight of P205 on the total
weight of polyphosphate mixture plus-water present. However,
the minimum concentration at which the suspensions are formed
varies somewhat with the nature of the cation and suspensions
of the invention may variously comprise from 40 to 60, 40 to
50 and 45 to 60% by weight of the polyphosphate mixture (on
the aforementioned basis) depending upon the amine concerned.
Solutions of the builders thus formed may provide a
solid builder for incorporation into solid detergent formula-
tions with other conventional ingredients. Preferably they
are sprayed as solutions onto preformed solid detergent com-
positions. Such solid detergent formulations constitute a
~urther aspect o~ the invention.
The mixtures are used in the novel cleaning composi-
tions in a wide ra~ge of concentrations depending upon the
envisaged application and upon the solubility of the mixture.
They will be present in concentrations of from 4 to 25% by
weight, more usually ~rom 6 to 18%, e.g. from 10 to 15% by
weight (all these percentages being expressed as percentages
of P2O5 from the respective polyphosphates~ on the total
weights of the compositions. Aqueous solutions of the poly-
phosphate mixtures as hereinbefore defined comprising at least
4%, preferably at least 10~ thereof, on the aforesaid basis
constitute a further aspect of this invention. Preferred
such solutions comprise from 6 to 18%, more specially from
10 to 16% by weight of the mixture on the aforesaid basis.
-- 10
. . _ . . _
~S(~31~1L
The proportion of surface active agent in the novel
compositions may vary within wide limits just as with known
such compositions, depending upon the use in question. Novel
compositions will comprise from 0.1 to 50~ by weight of sur-
face active agent and in particular cases may comprise say
from 0.1 to 5%, e.g. 0.5 to 3% by weight in the case of a
hard surface cleaner and from 10 to 50%, e.g~ 20 to 30% in
the case of a heavy duty liquid detergent.
The surface active agents which may be employed in
the novel compositions include non-ionic, anionic, cationic
and amphoteric surface active agents, generally such as
these mentioned in Volume 19, pages 507-566 of the Encyclo-
paedia of Chemical Technology, Second Edition by Kirk- Othmer
published by Interscience 1969.
Particular surface active agents which may find
use in the novel compositions include: alkyl aryl sulphonates
such as lithium, sodium, potassium, ammonium or other water-
soluble salts of sulphonic acids of alkyl-substituted benzenes
such as decyl toluene, dodecyl-x~ylene, octylbenzene, nonyl-
benzene~ decylbenzene, tridecylbenzene, tetradecylbenzene,
pentadecylbenzene, dodecylbenzene and hexadecylbenzene;
Olefin sulphonates such as water-soluble alkali
metal and alkaline earth metal mono- or di-olefin sulphonic
acids comprising from 8 to 24 carbon atoms;
Alkali metal or ammonium alkyl sulphates in which
the alkyl groups have from 10 to 18 carbon atoms and polyoxy-
ethylenated and polyoxypropylenated derivatives thereof;
Alkali metals or ammonium salts of alkane sulphonates;
Alkali metal or ammonium salts of sulphosuccinated
materials of the average general formula:
01
l2 C (OCH2 C~n OR2 ` `
- O3S - CH2 CO2
-- 11
1 ~05~38~
wherein n is from 0 to 25, R is hydrogen or a methyl group
and R2 an alkyl group having f:rom 8 to 25 carbon atoms.
- Amine oxides such as those described ~n B.P.943,353
having the formula RlR2R3NO, w:herein Rl is an alkyl radical
having from 9 to 25, preferably 10 to 16 carbon atoms and R
and R2 are methyl or ethyl groups:
Betaines of the general formula
+ R~
Rl - N - R3
. R4 - CO2
wherein R2 and R3 are alkyl or alkenyl groups cvntaining from
1 to 6 carbon atoms and are preferably methyl groups, R4 is
an~alkyl group containing from 1 to 6 carbon atoms and Rl is
an alkyl or alkenyl group containing from 8 to 18 carbon atoms:
. Amido-amine derivatives having the formula
~ Rl . I
N(CH2~n N
. where R represents an alkyl or alkenyl group having from 8 to
20 carbon atoms, Rl and R2 are the same or different groups
selected from hydrogen atoms, methyl or ethyl groups and n is
an integer in the range 1 to 4 and corresponding amines and
betaine derivatives.
Polyoxethylene compounds of the general formula
RO(CHCHRlO)xH where R is an alkyl, aryl, alkaryl, alicyclic,
acyl, amino or alkylamino group; Rl is hydrogen or an alkyl
group having from 1 to 4 carbon atoms and x is from 3 to 100,
usually from 6 to 50. Such compounds include fatty alcohol
polyethoxylate~, fatty acid polyethoxylat~s, polyethylene
glycol ethers, mixed polyethylene and polypropylene glycol
ethers, amine and diamine polyethoxylates~ and ~atty alkyl-
olamide ethoxylates:
- 12
i(~Sa3~
¦ Fatty alcohol phosphates and polyethoxylated and
¦ polypropyloxylated deriva'es thereof:
Fa~ty acid soaps.
- The novel compositio:ns comprising surface active
agents will normally be compou:nded by addition of an aqueous
solution of the surface active agent (or agents) used to a
solution of the polyphosphate mixture, optionally followed
by dilution although other means may also be used.
In the case o highly alkaline cleaners of the in-
vention comprising little or no surfactant, the proportion of
polyphosphate salt mixture will generally represent from 2 to
20% by weight (expressed as P2O5) in the composition, prefer-
ably 5 to 15%, whilst the alkaline component or components,
which will normally be sodium hydroxide and/or an alkali
- metal silicate salt such as soaium metasilicate will generally
be present in a proportion of from half to twice by weight of
the weight of the polyphosphate salt mixture (expressed as
weight of solid material). In the case of caustic alkalis
such as sodium and potassium hydroxide these might typically
represent from 10-15% by weight of the total solids content
of the composition. Where alkali metal silicate salts are
used, these mi~ht typically represent from 25 to 40~ by weight
of the total solids content of the composition. Alkali metal
~ilicates ~or present use are preferably those having an
M20:SiO2 ratio of from 0.5:1 to 2:1 where M is soaium or
potassium, sodium metasilicate being particularly preferred.
The novel compositions may also comprise known
adjuvants for liquid cleaning compositions such as antisoil
redeposition agen~s, e.g. carboxymethyl cellulose, polyvinyl
pyrrolidone, or the sodium salts of a copolymer of di-
isobutylene and maleic anhydride, optical brightening agents;
perfumes; dyes; bacteriostats and bacteriocides; opacifying
- 13
~OS~3~3 IL
agents; colorants; sudsing agents, e.g. ethanolamides such as
coconut ethanolamide and fatty allcohols such as lauryl
alcohols; phase stabilisers such as lower aliphatic alcohols
and homogenizing agents. Although the polyphosphate builders
generally permit less homogeniz:;ng agent to be present than
would be necessary with convent:ional phosphate builders, the
preferred c~mpositions of the invention are those which in-
clude a so-called hydrotope such as an alkali metal, alkaline
earth metal or ammonium salt of benzene-, naphthaline-, an
alkylbenzene - or an alkyl naphthalene - sulphonic acid having
not more than 5 aliphatic carbon atoms. Preferred
such hydrotopes are sodium xylene sulphonates ~sold by
Albright and Wilson Limited under the registered trade name
Eltesol'), sodium toluene sulphonate, sodium benzene sul-
phonate and sodium naphthalene sulphonate. Preferably hydro-
topes are present in the novel compositions in proportions of
from 2 to 20% by weight, more preferably 2 to 10%, most
preferably 3 to 5%. In the case of hard surface cleaners of
the inventiont it may also be desired to incorporate a
chlorine-releasing agent which is preferably sodium hypo-
chloride although chlorinated isocyana~es can also be used.
Normally, chlorine-releasing agents, where used, will be
- present in a concentration such as to give from 0.5 to 3~,
e.g. 1 to 2~ available chlorine ~w/v) which is roughly
equivalent in the case of sodium hypochlorite. For 8-12
v~v sodium hypochlorite.
Compositions of the invention may be employed to
¦ advantage in a range of cleaning applicatisns such as the
cleaning of textiles, including wool, wood, leather, metal
earthenware, china and stone as well as for human use.
The polyphosphate builders of the invention are
~ - 14
~1~350315~1
particularly applicable in liquid detergent compositions
designed for the cleaning of fine fabrics. These compositions
will normally contain from 4 to 10~ of the polyphosphate ex-
pressed as the weight of P205 and from O to 5% of a suitable
surfactant which is preferably a non-ionic surfactant.
.
- 14A ~
~05~3~3~
The invention is illustrated by the following
Examples i~l which all parts are expressed on a weight basis
and all proportions of proprietary surfactant ingrsdients
are expressed in terms of active ingredient (a.i.) any water
present in the surfactant as aclded being included in the
given proportions of total water.
Example
A composition was made up as follows:
Monoethanolamine polyphosphate comprising
36.75% by weight P2O5 and 63.25% by weight 8% expressed P2O5
Monoethanolamine
~ "NANSA" (Trademark) SS 60 15%
2 "EMPINMIN" (Trademark~ KSN 27 8%
Lauric/myristic monoethanolamide 2%
3 "ELTESOL" ~Trademark~ SX 93 3.7% a~i.
Water to 100%
(I) Trade name for a 60% w/w aqueous paste of sodium
dodecylbenzene sulphonate supplied by Albright & Wilson
Ltd.
(2) Trade name for a 27% aqueous solution of ethoxylated
sodium lauryl sulphate comprising three ethylene oxide
groups per molecule supplied by Albright & Wilson Ltd.
- (3) Trade name for a 93% sodium xylene sulphonate supplied
by Albright & Wilson Ltd., the balance of the material
being sodium sulphate and water.
The product was suitable for use as a dishwashing
detergent for manual use, being a clear homogeneous liquid
at ambient temperature. By contrast the same formulation
wherein the monoethanolamine polyphosphate was replaced by
tetrapotassium pyrophosphate at a level of 8% as P2O5
separated into two phases.
15 -
Exam~e 2 1~381
\
A composition was made up having the same composition as that of
Eample I save that it contained I2~ (expressed P205 )
monoethanolamine pol~phosphate and 4.7% Eltesol SX 9~. Again,
the composition was a clear homogeneous liquid at room temperature
suitable for use as a dishwashing detergent.
By contrast, the same composition with sodium tripolyphosphate
substituted at equivalent P205 content ~or the monoethonolamine
polyphosphate separated into two distinct phases at room temp-
I0 erature. The same result was obtained when pota~siumpyrophosphate was likewise substituted ~or the monoethanolamine
polyphosphate.
Example 3
I5 A composition was made up as ~ollows:
Monoethanolamine polyphosphateI6.8% (expressed as P205)
Nansa SS 60 I5~ a.i.
Lauric/myristic monoethanolamide 2%
Eltesol SX 9~ 3.7% a.i.
Water to I00%
This composition was again a clear homogeneous liquid at room
temperature suitable ~or use as a dishwashing detergent.
By contrast, replacement o~ the monoethanolamine polyphosphate
~y I6.8% (expressed as P205) of potassium pyrophosphate gave a
composition which subsisted as two phases at ambient temperature.
A composition was made up as ~ollows:
Isopropanolamine polyphosphateI2.6%
comprising 3I-82~ by weight P205(expressed as P205)
and 68.I8~ by we~ght
Isopropanolamine
~5 Nansa SS 60 I2% a.i.
(I) Empimin KSN 60 6% a.i.
Lauric/myristic monoethz~olam~de 2
I6
~L05~3~
Eltesol SX 93 2.8%
Water to 100%
(I) Trade name for a sodium lauryl ethoxy sulphate
comprising 3 ethylene oxide groups per molecule in
60% aqueous solution comprising 10% ethanol as solu-
bilizer supplied by Albright & Wilson Ltd.
The composition was a clear, homogeneous liquid
at amblent temperature, suitable fbr use as a dishwashing
detergent. As in previous examples, replacement of the
isopropanolamine polyphosphate by an equivalent amount o~
potassium pyrophosphate expressed as P2O5 gave a two~phase
composition at ambient temperature.
Example 5
A composition was made up as follows:
(I) Nansa SSA 3% a.i~
Triethanolamine 2%
Monoethanolamine 1.5%
Coconut fatty acid 8%
- Monoethanolamine polyphosphate 9.6%
as used in example I (expressed as P2O5)
(2) Eltesol PCS 93 5% a.i.
(3) "EMæILAN" (Trademark) XA 5 5% a.i.
Water to 100~
(I) Trade name for a ca. 96% dodecylbenzene sulphonic acid
supplied by Albright & Wilson Ltd.
(2) Trade name for a 93% potassium cumene sulphonate the
balance being potassium sulphate and water, supplied by
Albright & Wilson Ltd.
(3) Trade name for lauryl alcohol ethoxylate comprising
approximately 60% by weight ethylene oxide supplied by
Albright ~ Wilson Ltd.
This composition was a clear, homogeneous liquid at
- 17 ~
- lB ,
~ os~3l~l
ambient temperature and was suitable for use as a heavy
duty liquid detergent for mechanical washing appliances.
By contrast, replacement of the monoethanolamine
polyphosphate by an equivalent quantity of potassium pyro-
phosphate gave a two-phase composition at ambient temperature,
Example 6
A composition was made up as follows:
Monoethanolamine polyphosphate 12% (expressed as P2O5)
as used in example I
(I) Empilan PPE 2910 1% a.i.
Coconut fatty acid 2%
Triethanolamine 0.4%
Eltesol PCS 93 5% a.i.
Water to 100%
(I) Trade name for a high molecular weight polycondensate
of propylene and ethylene oxides supplied by Albright
& Wilson Ltd.
- The composition was a clear, homogeneous solution
for use as a dishwashing detergent for mechanical washing~
Replacement of the monoethanolamine polyphosphate by an
- ~ equivalent amount of potassium pyrophosphate gave a composition
which was a thick paste at ambient temperature.
Example 7
Two compositions were made up as follows:
Composition I
Monoethanolamine polyphosphate as 12% (expressed as
used in example I P2O5)
30% aqueous solution of ethoxylated
potassium lauryl phosphate comprisin~
5 ethylene oxide groups per molecule
and consisting essentially of a 1:1
per molar mixture of mono(laurylpen-
tethoxy) phosphate and di(laurylpen-
tethoxy) Phosphate 3.6% a.i.
Water to 100%
- 18 -
B
~L05038~
Composition 2
As (I) but with isopropanolamine polyphosphate
tas used in Example 4) replacing monoethanolamine polyphos-
phate.
Both compositions (I) and (2) were clear, homo~
geneous liquids at ambient temperature, suitable for use as
liquid detergents for hard surface cleaning.
By contrast, a composition wherein 12% (expressed
as P2O5) of potassium pyrophosphate replaced the monoethanol-
amine (or isopropanolamine) polyphosphate separated into two
distinct phases at ambient temperature.
Example_8
A composition was made up as follows:
Monoethanolamine polyphsophate 4%
as used in example I(expressed as P2O5)
(I) "EMPICOL" (Trademark) L Q 3 310% a.i.
(2) "EMPIG~N" (Trademark) BB 2~ a.i.
Eltesol SX 93 2
Water to 100%
(I) Trade name for a 33~ aqueous solution of monoethanol-
amine lauryl/myristyl sulphate supplied by Albright & Wilson
Ltd.
(2) Trade name for a 30% aqueous solution of alkyl dimethyl
betaine represented by the ~ormula R - N - Me2CH2CO2 where
R is predominately lauryl/myristyl supplied by Albright &
~ilson Ltd.
The composition was a clear homogeneous li~uid
at ambient temperature suitable for use as a liquid hand
cleanser.
By contrast a composition where potassium pyro-
phosphate replaced monoethanolamine polyphosphate at 4~ P2O5
- 19 -
iB
1, .
1()5~3~1
level was heterogeneous paste at ambient temperature.
Example 9
A composition (I) found highly suitable for both
machine and hand washing of woollen garme~ts was made up as
follows:
Nansa SSA 10% a.i.
Triethanolamine 6%
Monoethanolamine 3%
Empimin KSN 27 2.7%
Coconut fatty acid 4%
Monoethanolamine polyphosphate 6% ~expressed as
as used in example I P2O5)
Empilan PPE 2910 2% a.i.
Optical brightening agent 0.2%
Bacteriocide 0.1~
Perfume 0.2%
: Water to 100%
A further composition (2) of similar utility was
~ also made to the same formulation save that 2% of "TRITON"
20 (Trademark~ CF32 r~placed the Empilan PPE 2910 (Triton CF32 is
a trade name for a non-ionic surface active amine poly~glycol
condensate supplied by the Rohm & Haas Company)
A composition (3) was also made up as follows:
Nansa SSA 10% a.i.
Triethanolamine 4.4
Monoethanolamine 2.2%
Empicol SDD (~) 4%
Isopropanolamine polyphosphate 6% (expressed as
as used in example 4 P2O5
Optical brightening agent 0.3%
Bacteriocide 0.1%
Perfume 0.1
Water to 100%
E~j ~v
1138~
t+) Trade name for a 40% aqueous solution of a disodium
alkylethoxy sulphosuccinate halfester where the alkyl group
are predominately lauryl/myristyl and the ethoxy group is
primarily derived from diethylene glycol (supplied by
Albright & Wilson Ltd.)
Compositions I and 2 were of the 'low-foam' type
incorporating coconut fatty acid soap with either Empilan
PPE 2910 or Triton CF32 as foam depressants. All three
composi~ions (1) (2) and (3) were clear homogeneous liquids
at room temperature.
~ ach of these compositions was compared in
standard washing tests to a typical conventional detergent
powder of the following compositions:
Sodium do~ecylbenzene sulphon~te 3
~atty alcohol polyethoxylate 4
( T I mols. Et2O)
Sodium silicate 1:2 5%
Sodium tripolyphosphate 42
Optical brightening agent 0.49
'I-ALCALASE'' (Trademark) P (+) 0.5%
Perfume 0.2%
Moisture 10
- pH (1% solution) ca. 10
(+) a protealytic enzyme supplied by Novo Industria S~
me effectiveness of compositions 1, 2 and 3 and
of the re~erence powder was then determined in duplicate
standard washing tests. These involved subjecting 40 3" by 3"
swatches of a standard test cloth to the rotating washing
action of a "LAUNDER-O-METER" (Trademark) supplied by the
Atlas Electrical Device Co. (Chicago).- Swatches were washed
in pairs (two swatches per cylinder of the loading table) with
- 21 -
38~L
the addition of 2 g of the composition under test to each
cylinder. Washing was at 80C using water of given hardness
proceeded for 20 minutes following which the swatches were
rinsed, ironed dry between cotton cloths and then compared
for light reflectance using Haxrison colour measurements with
a white tiIe reference and a light source filtered through
a green filter. Results are quoted as percentages calculated
from the equation:
~= 100 x ~Reflectance A (washed) - Reflectance A (unwashed))
_
(Refle~tance R (washed) - Reflectance R ~unwashed))
Where reflectance A is the colour scale reading
of the swatch washed in the composition under test and
reflectance R is the colour scale reading of the swatch
washed in the reference composition.
One series of tests was carried out using standard
soiled wool swatches reference "EMPA" ~Trademark) 102
(supplied by Empa Laboratories, Switzerland) using both water
of hardness 50 ppm (Ca Co3) and water of 300 ppm (Ca Co3)
hardness --the atomic ratio of Ca~Mg present in the water
being 4:1 in both cases. Results were as follows:
Soft WaterHard Water
~%) ~ (%)
Reference Powder 100 100
Composition 1 92.686.8
Composition 2 87.686.8
Composition 3 95.090.0
These results are within the range for a liquid
detergent compared with a powder and compare favourably with
results obtainable from conventional liquid detergents as
is demonstrated below.
Similar tests were also carried out using sOiled
~ - 22 ~
~1
38~
polyester/cotton swatches (60/40 Dacron/Cotton) supplied by
Test Fabrics Inc. with the following results:
Soft Water Hard Water
(% ) (~)
Reference Powder 100 100
Composition 1 89.3 118
Composition 2 75.0 122.7
Composition 3 93.8 124
Here it may be seen that the performances of
compositions of the invention actually surpass that of the
reference powder under the most testing washing conditions,
that is in hard water.
Washing colour stability tests were also carried
out on compositions 1, 2 and 3 according to I.W.S. method
number 105 using standard dyed woollen fabrics. Assessment
of colour change and staining were carried out on the British
Standards Institute Grey Scale, the preferred total being
27 points minimum.
r~
22a -
038~
Results were:
Reference Powder 23~5 Points
Composition I ~0.5 Points
Composition 2 ~0.5 Points
Composition 3 32.0 Points
To further demonstrate the improved effectiveness of the com-
position of the invention their per~ormance was compared with
IO those of similar compositions made up using conventional poly-
phosphate molecules at approximately the highest consentration
possible without causing cloudiness or precipitation or phase
separation at lower temperatures (i.e.the highest consentration
possible ror a commercially acceptable composition). These
conventlonal ~ormulations ( a B C and D) were as follows:
I5 A. Nansa SS 60 IO.0%
Empimin KNS 27 IO.0%
Tetrapotassium pyrophosphate 6.5% (expressed as P205)
+ Empilan CDE 2.5%
Eltesol SX 93 ~.0%
Optical brightening agent 0.2%
Bacteriocide O.I%
Water to I00%
+ Registered trade name for a surfactant active diethanolamide
derivati~e of "total" coconut fatty acid supplied by Albright
& Wilson Ltd.
B. Nansa SS 60 8.5%
+ Empicol ESB ~ I~.0%
~0 Empilan CDE I.0%
Tetrapotassiu~ pyrophosphate 5~0~ (expressed as P205)
Eltesol SX 9~ 5.0%
Optical brightening agent 0.2
Bacteriocide O.I%
~5 Perfume o ~%
Water to IOO~
Re~istered trade name for a 27.5~ aqueous solution of sodium
lauryl ethoxy sulphate comprising two ethylene oxide groups
per molecule.
C. Triethanolamine dodecylbenzene sulphonate I4% a.i.
~mpimin K~N 27 4.0~
Tetrapotassium pyrophosphate 6.5%
(expressed as P205)
Coconut fatty acid .soap 5.0%
Triton CF ~2 4.0%
= Eltesol SCS 9~ 2.0
Optical brightening agent a ~2~
Bacteriocide O.I%
IO Perfume 0.2%
Water to I00%
= Registered trade name for a 93~ sodium cumene sulpho~ate
the balance being sodium sulphate and water - supplied by
Albri~ht & Wilson Ltd.
I5 D. Empilan KA 5 IO~
Empimin KSN 27 I.35%
Tetrapotassium pyrophosphate 3.5%
(expressed as P205)
Eltesol SX 93 5~
Optical brightening agent O.2%
Bacteriocide O.I%
Per~ume 0.2%
Water to I00%
And the washing per~ormance o~ these compositions A - D was
compared with those o~ the abo~e compositions I and 2 by the
method as before against the same re~erence powder, Standard
wool swatches (Empa I02) were used.
Results were as ~ollows (~uoted in the same basls as be~ore):
Composition So~t Water Hard Water
~ (%)~
Re~erence Powder IOO IOO
I 87 89.5
2 ~7 89.0
~ 85 82
B 85 48.o
C - 62.0
D 85.5 56
~4
~1)5a 38~
The improved detergent performance o~ the composltlons I and 2
of the invent~on is clear ~rom these results. Thls is especially
evident in the tests using hard water where the sequestering
ability of the polyphosphate builder is most ¢ritical.
A particularly striking comparison is that between the effect
of composition C and those of I and 2. Although the latter
contains less Empimin KSN 27 active ingredient~ less coconut
fatty acid lass non~ionic surfactant and less "hydrotrope"
~Eltesol SCS 93) they nevertheless exhibit improved detergent
I0 in hard water ascribable to the superior building propertles
of the polyphosphate builders of the invention over the
conventional tetrapotassium pyrophosphate.
Example~I0
I5 572 kilograms of an aqueous solution of a phosphoric acid
containing 84% by weight o~ phosphorus pentoxide representing
~2.2 parts by weight of the reaction mixture were added to a
solution of 37.9 parts o~ monoethanolamine in 29.9 parts by
weight of water in a ~acketed stainless steel vessel equiped
with a turbln mixer over a period o~ 2~ hours with efficient
cooling and stirring. The temperature was held below 40 C
throughout. The produck monoethanolamine polyphosphate was
a straw coloured vlscous liquid comprising 27.0% by weight
of P20s having a ~iscosity o~ I500 centistokes at 20C and a
density of I.~75. The product was useful according to example
No. 4
Example II
To 443g isopropanol in 297g water was added slowly, Wit~l
stirring, at between I5 and 40C 260~ of a polyphosphoric
acid solution comprising 85% by weight P205 . The pH was
between 4 and I0 throu~hout. The product was suitable ~or
use according to example No. 4
~LOSD38~;
Example 12
Isopropanolamine polyphosphate was prepared by an
analogous procedure to that used in example 10 using 24~65
parts of a polyphosphoric acid containing 84% by weight of
phosphorus pentoxide, 44.3 parts of monoisopropanolamine
and 31.05 parts of water. The product was a clear viscous
- liquid useful according to example 4.
Example 13
A composition was made up as follows:
Monoethanolamine poIyphosphate 9.6% as P2O5
(as used in example 1)
Empilan 2910 3%
Ethylene diamine tetra-acetic acid 0.2%
Phosphoric acid 2.6~
Potassium hydroxide (50%) 9.1%
Sodiu~ metasilicate penthydrate 5.0%
Formalin (40% solution) 0.2%
"ACRYSOL" (Trademark) ASE 108 ( ) 6.25
Water to 100%
(1) Acrysol ASE 108 is a registered trademark for a high
molecular weight acid copolymer emulsion supplied by the
Rohm & Haas Company.
The product was a homogeneous liquid highly
suitable for use in mechanical dishwashers.
n 26 -
~',
