[0001] The present invention relates to liquid detergent compositions and, particularly,
to such compositions having a high alkalinity and comprising a high level of silicate.
[0002] Alkaline liquid detergent compositions are well known in the fabric- and dishwashing
art. They require a high pH and high buffer capacity to deliver detergency, to saponify
or neutralise acidic soils and emulsify oils.
[0003] It is also well known that silicates are attractive materials to provide buffer capacity
and alkalinity since, in addition to these properties, they contribute to soil-deflocculation,
anti-redeposition, water-softening, corrosion-inhibition and chemical stability of
active chlorine.
[0004] To formulate fully, a liquid detergent composition, it is often required to have
an aqueous liquid medium which is capable of suspending particulate or undissolved
materials which may be present due to the necessary high levels of some of the functional
components. Although by internal or external structuring, it has been possible to
formulate aqueous liquid media capable of providing the required suspending properties,
it has proved difficult to formulate such compositions having a high alkalinity and
comprising a high level of silicate which do not suffer from unacceptable rheological
behaviour, in particular under non-ideal low-temperature conditions. The large increase
in viscosity which results from crystallisation of the silicate under non-ideal low-temperature
conditions, gives rise to a serious reduction in pumpability which, particularly in
the industrial and semi-industrial applications of such liquids, is unacceptable.
[0005] To avoid the crystallisation problem, the formulator of this type of composition
is therefore forced either to reduce the level of the commonly used sodium metasilicate
to well below 10% by weight, or to use silicates of higher solubility, such as the
neutral or alkaline waterglasses, and accept the concomitant lower alkalinity and
hence lower performance.
[0006] In the United States Patent No. 4,556,504, structured alkaline built liquid detergent
compositions are disclosed, comprising high levels of the more alkaline silicates,
such as sodium metasilicate. The structured medium is based on a mixed ethylene/propylene
oxide alcohol condensate and a cross-linked polyacrylate polymer. In general, these
compositions have a good stability and rheology at a wide temperature range. However,
it has been found that, under practical cold-storage conditions, silicate crystal
formation takes place owing to the presence of unintended nucleating sites such as
corroded metal parts, debris and the like. Owing to such crystal formation, the viscosity
of the liquid composition sharply increases and the pumpability of the composition
is reduced to an unacceptable level.
[0007] We have now found that the above disadvantages can be mitigated by limiting the weight
ratio of the total amount of free sodium ions to the amount of silicate anions to
below a certain value and supplementing alkalinity by non-sodium alkali.
[0008] Accordingly, the present invention provides an aqueous liquid alkaline structured
detergent composition comprising a nonionic detergent surfactant, a detergency builder,
a dissolved sodium silicate, an alkaline agent and a structuring polymer agent, the
amount of all dissolved sodium silicate material and the amount of all alkaline agent
being such that the resultant amount of the alkali metal silicate is at least 10%
by weight of the total composition and the weight ratio of the amount of free sodium
cations to the amount of silicate anions expressed in terms of silicon dioxide is
equal to or below 0.7:1, sufficient alkaline agent being present to provide the composition
at an aqeuous solution concentration of 1% by weight with a pH value of at least 11.
[0009] The compositions according to the invention provide aqueous liquid aqueous liquid
structured detergent agents of high alkalinity and having high silicate levels. These
are readily pourable and pumpable under non-ideal practical cold storage conditions
and are easily formulated with conventional, readily available detergent ingredients.
[0010] The liquid detergent compositions of the invention comprise, as a first essential
ingredient, a nonionic detergent surfactant, primary examples of which are the condensation
products of ethylene oxide, propylene oxide and/or butylene oxide with alkylphenols,
primary or secondary aliphatic alcohols, and fatty acid amides. Primary straight-chain
alcohols are preferred. In general, the number of carbon atoms in the alcohol or amide
portion is from 7 to 24, preferably from 8 to 18 and most preferably from 12 to 15.
The average number of moles of alkylene oxide in the above nonionics varies from 1
to 30, mixtures of different nonionics including nonionics of a higher degree of alkoxylation
also being suitable. Preferably, the alcohol or amide is condensed with from 4 to
15 moles of ethylene oxide optionally in combination with propylene oxide, and most
preferably they are condensed with 6 to 12 moles of ethylene oxide.
[0011] The nonionic detergent surfactant is normally present in an amount of at least 2%
by weight of the composition, the amount of 2 to 5% by weight being preferred for
dishwashing applications, the amount of 5 to 15% by weight being preferred for fabric-washing
applications.
[0012] The nonionic detergent surfactant can be used as sole detergent surfactant as in
general will be the case in dishwashing compositions where only minor amounts of e.g.
anionic detergent surfactants are acceptable.
[0013] However, in particular, in fabric-washing compositions, the nonionic detergent surfactant
can also be used in combination with other detergent surfactants which may be of any
conventional type. Suitable are the synthetic anionic detergent surfactants of the
sulphate and sulphonate types, such as the sodium, potassium and ammonium salts of
the C
9-C
20 alkyl benzene sulphonic acids, of the C
8-C
22 primary or secondary alkane sulphonic acids, of the Ca-C24 olefin sulphonic acids,
of the sulphonated carboxylic acids, of the C
8-C
22 alkyl sulphuric acids, and of the Ca-C24 alkyl polyglycolethersulphuric acids containing
up to 10 moles of ethylene oxide. Also suitable are alkali metal or alkanolamine soaps
of C
10-C
24 fatty acids; cationic detergent surfactants, such as the quaternary ammonium compounds,
in particular the dialkyl dimethyl ammonium halogenides; and amphoteric or zwitterionic
detergent surfactants, such as N-alkylamino acids, and sulphobetaines. In view of
cost, preference is given to mixtures of nonionic and anionic detergent surfactants.
[0014] The total amount of detergent surfactant in the fabric-washing oriented applications
varies from 5 to 40% by weight of the composition, from 5 to 25% by weight being the
preferred range.
[0015] The detergent compositions of the invention are built compositions and preferably
contain from 5% to 35%, in particular 10% to 30% and most preferably from 10% to 25%
by weight of a detergency builder. Typical examples of suitable detergency builders
are the phosphate builders, such as sodium or potassium salts of triphosphoric acid,
pyrophosphoric acid, orthophosphoric acid, polymetaphosphoric acid and mixtures thereof.
Further suitable builders include the alkyl phosphonate esters, the carbonate salts,
the zeolites, and the organic builders, such as the alkali metal citrates and polycarboxylates,
in particular the nitrilotriacetates, and mixtures thereof.
[0016] An essential feature of the present invention is the inclusion of a high level of
silicate in fully dissolved form. The selection of the silicate(s) should be such
that in the final composition, the weight ratio of the amount of free sodium cations
to the amount of silicate anions expressed in terms of silicon dioxide is equal to
or below 0.7:1. Preferably, this is achieved by using a single sodium silicate which
can be represented by the formula Na
2O.(SiO
2)
n, with n = >1.1. Suitable examples thereof are sodium disilicate, sodium trisilicate,
and the alkaline and neutral waterglasses, and the mixtures thereof. In particular,
the neutral waterglasses, i.e. Na
2O·(SiO
2)
3.3-3.5, are preferred. The liquid detergent compositions comprise at least 10% by weight
of the sodium silicate to benefit fully from the advantages derived from the silicate
component.
[0017] Preferably, the sodium silicate is included in the range of from 10 to 25% by weight
of the total composition, the range of from 15 to 22% being especially preferred.
[0018] In view of the relatively low alkalinity of the sodium silicates suitable for inclusion
in the present compositions, it is necessary to supplement alkalinity to provide the
composition at an aqueous solution concentration of 1% by weight with a pH value of
at least 11. A feature of the present invention is that such should occur while keeping
the weight ratio of the amount of free sodium cations to the amount of silicate anions
(as expressed in terms of silicon dioxide) equal to or below 0.7:1. Accordingly, any
alkaline agent capable of providing a 1% solution of the composition with a pH value
of at least 11 and not introducing free sodium anions in an amount which would exceed
the above-specified ratio is suitable. Preferably, potassium hydroxide is used. The
amount of alkaline agent is dictated by the required pH value and varies from 5 to
30% by weight of the total composition.
[0019] Preferably, a combination of neutral waterglass and potassium hydroxide in an about
equal weight ratio is used, or else with the potassium hydroxide in some excess.
[0020] In the final composition, the weight ratio of the amount of free sodium cations (introduced
by whatever source) and the amount of silicate anions (as expressed in terms of silicon
dioxide) should be equal to or below 0.7:1, a weight ratio equal to or below 0.6:1,
in particular 0.5:1, being preferred. A preferred lower end to all of these ratio
ranges is 0.1:1.
[0021] A pH value of at least 11 at a 1% product concentration has been found adequate,
but pH values of at least 12 are preferred for dishwashing and heavy duty fabric-washing
applications.
[0022] The present compositions are externally structured and for this purpose they contain
a structuring or thickening polymeric agent compatible with and stable to the high
alkalinity of the compositions. Particularly suitable are the water-soluble polymers
of acrylic acid, cross-linked with about 1% of a polyallyether of sucrose having an
average of about 5.8 allyl groups for each sucrose molecule, the polymer having a
molecular weight in excess of 1,000,000. Examples of such polymers are found in the
Carbopol series, such as Carbopol 934, 940 and 941. Carbopol is the Registered trademark
of B F Goodrich Co Ltd, the manufactures of these polymers. The preferred polymer
is Carbopol 941. Depending on the viscosity which is desired, they are included in
the range of from 0.1% to 1% by weight. Preferably they are included in the range
of from 0.2% to 0.8% by weight of the total composition.
[0023] Suitable viscosities of the compositions of the present invention range from 0.3
to 30 Pa.s, in particular from 0.4 to 1.5 Pa.s (measured at 20°C and 20 sec 1).
[0024] The liquid detergent compositions may further contain any of the adjuvants conventionally
used in this type of composition, e.g. sequestering agents such as ethylenediaminetetraacetate
and diethylenetetraamine methylene phosphoric acid; soil-suspending and anti-redeposition
agents such as carboxylethylcellulose, polyvinylpyrrolidone and the maleic anhydride/vinylmethylether
copolymer; fluorescent agents; anti-oxidants; hydrotropes; conditioning agents; perfumes;
germicides and colourants. Further, the addition of lather-depressors such as liquid
polysiloxane or wax anti-foam compounds; alkaline stable enzymes; bleaches, such as
e.g. sodium sulphite and potassium dichlorocyanurate, may be necessary to formulate
a complete detergent composition suitable for use in machine washing operations.
[0025] The invention will now be further illustrated in the following examples, all amounts
being in percentages by weight unless otherwise specified.

The formulation according to Examples 1 to 9 are physically stable at 37°C, 20°C and
-5°C.
Examples 10-13
[0026]

The formulations according to Examples 10 to 13 are physically stable at 37°C, 20°C
and -5°C.
1. An aqueous liquid alkaline structured detergent composition comprising a nonionic
detergent surfactant, a detergency builder, a dissolved sodium silicate, an alkaline
agent and a structuring polymer agent, the amount of all dissolved sodium silicate
material and the amount of all alkaline agent being such that the resultant amount
of the alkali metal silicate is at least 10% by weight of the total composition and
the weight ratio of the amount of free sodium cations to the amount of silicate anions
expressed in terms of silicon dioxide being equal to or below 0.7:1, sufficient alkaline
agent being present to provide the composition at an aqueous solution concentration
of 1% by weight with pH value of at least 11.
2. A composition according to claim 1, wherein the nonionic detergent surfactant is
selected from the condensation products of ethylene oxide, propylene oxide and/or
butylene oxide with alkylphenols, primary or secondary aliphatic alcohols, and fatty
acid amides.
3. A composition according to either preceding claim, wherein the nonionic detergent
surfactant is present in an amount of at least 2% by weight.
4. A composition according to any preceding claim, wherein the detergency builder
is present in an amount of from 5 to 35% by weight.
5. A composition according to any preceeding claim, wherein the composition contains
a single sodium silicate which can be represented by the formula Na20.(Si02)n where n > 1.1.
6. A composition according to claim 5, wherein the dissolved sodium silicate is selected
from sodium disilicate, sodium trisilicate, and the alkaline and neutral waterglasses,
and the mixtures thereof.
7. A composition according to any preceding claim, wherein the sodium silicate is
present in the range of from 10 to 25% by weight of the total composition.
8. A composition according to any preceding claim and comprising from 5 to 30% by
weight of potassium hydroxide.
9 A composition according to any preceding claim and comprising a composition of neutral
waterglass and potassium hydroxide in about equal weight ratio.
10. A composition according to any preceding claim, wherein the weight ratio of the
amount of free sodium cations to the amount of silicon anions is equal to or below
0.6:1.
11. A composition according to any preceding claim, wherein the pH of the composition
is at least 12.
12. A composition according to any preceding claim, having a viscosity in the range
of from 0.3 to 30 Pa.s.