[0001] This invention relates to detergent compositions intended for fabric washing.
[0002] It is now conventional for detergent compositions designed for front-loading washing
machines to be formulated as low-sudsing compositions. The commonest types of low-sudsing
compositions are the so-called "ternary" products, i.e. those based on mixtures of
anionic surfactants, most commonly long chain alkyl benzene sulphonates and nonionic
surfactants in which the sudsing capacity is controlled by the use of a calcium soap,
formed in situ by the reaction of sodium salts of fatty acids and calcium ions forming
part of the water hardness. The nonionit surfactant also exerts an effect in controlling
foam in these formulations as well as contributing to the detergency properties of
the system. The detergencies obtained from the compositions outlined above, which
are embodied in consumer products such as "Persil Automatic" and "Bold Automatic"
(registered Trade Marks) are quite acceptable.
[0003] We have now discovered that by careful selection of anionic surfactants, detergent
compositions can be produced which do not require the presence of nonionic surfactants
but which exhibit equivalent detergency and suds control to those of ternary products.
At the same time the use of long chain alkyl benzene sulphonates, which can be environmentally
unsatisfactory, is avoided.
[0004] According to the present invention there is provided a detergent composition comprising
an anionic sulphate surfactant or mixture of such surfactants having
(a) a calcium salt solubility product greater than 1 x 10-12 moles3 litre-3
(b) a maximum critical micelle concentration of 6 x 10-2 gms/litre
together with a non-soap anti-foam.
[0005] The significance of the parameters (a) and (b) in selecting the anionic surfactant
for use in this invention can be summarised as follows:
The calcium salt solubility product is a measure of the tendency of the substance
to precipitate from a solution containing calcium ions and anionic surfactant ions.
In the absence of nonionic surfactants, which help to solubilise the other surfactants
; in the normal binary or ternary detergent formulations, control of precipitation
boundaries is extremely important.
[0006] The critical micelle concentration, of course, determines the point at which a substance
attains maximum surface activity.
[0007] For the purposes of this invention, both the solubility product and the critical
micelle concentration are measured at 60°C in the presence of 0.05 moles/litre of
sodium chloride.
[0008] Reference to Tables 1 and 2 will enable the skilled man to determine which sulphate
surfactants are inside and which are outside the invention.

[0009] As implied above, mixtures of different detergent active sulphates can be used, providing
that the solubility product and critical micelle concentration of the mixture lies
in the required range.
[0010] The anionic surfactant may be present in the mixture in an amount of from 5 to 35%,
preferably, for economic reasons, from 5 to 25% by weight of the composition.
[0011] The specified anionic surfactants are sulphates rather than sulphonates, since in
general the sulphates are much more biodegradable than the sulphonates. Within the
sulphate class, primary and secondary alkyl sulphates are preferred.
[0012] Most preferred are the high crystalline fraction secondary alkyl sulphates (i.e.
those in which a high percentage of the material has the sulphate group attached .
at the 2 or 3 position), particularly the C
16-18 sulphates and the C
15-16 primary alcohol sulphates.
[0013] The second essential component of the compositions of this invention is a non-soap
anti-foam compound. Typical of non-soap anti-foam compounds are phosphate esters,
both used alone and used in conjunction with waxes or hydrophobic oils such as mineral
and vegetable oils. Silicone anti-foams and derivatives of nitrogen-containing heterocyclic
compounds such as s-triazine may also be used.
[0014] In general, the non-soap anti-foam compounds of this invention may be present in
the compositions in amounts from, 0.05%, which would be the minimum amount which could
possibly be effective, to 5%, which would be the practical maximum having regard to
the extreme efficacy of the majority of non-soap anti-foam compounds, to their expense
and to the necessity for keeping as much room in the composition as possible for other
compounds.
[0015] In greater detail, the phosphate esters which may be used, optionally in salt form,
have the following general formula:

where A is -OH or R
2O(EO)
m-, R
1 and R
2 are the same or different C
12-C
24, preferably C16-C22, straight or branched chain, saturated or unsaturated alkyl groups,
especially C
16-C
18 linear saturated groups and m and n are the same or different and are 0 or an integer
of from 1 to 6. Preferably, A is -OH and n is 0, so that the compounds are the monoalkyl
phosphoric acids, preferably with linear alkyl groups. If any ethylene oxide (EO)
groups are present in the alkyl phosphoric acids, they should not be too long in relation
to the alkyl chain length to make the calcium or magnesium salts soluble in water
during use.
[0016] In practice, the alkyl phosphate compounds are commonly mixtures of both mono- and
di-alkyl phosphoric acids, with a range of alkyl chain lengths. Predominantly monoalkyl
phosphates are usually made by phosphorylation of alcohols or ethoxylated alcohols,
when n or m is 1 to 6, using a polyphosphoric acid. Phosphorylation may alternatively
be accomplished using phosphorus peroxide, in which case the mixed mono- and di-alkyl
phosphates are produced. Under optimum reaction conditions only small quantities of
unreacted materials or by-products are produced, and the reaction products can advantageously
be used directly in the detergent compositions.
[0017] When a mixture of phosphate ester and wax is to be used as the non-soap anti-foam
compound the wax may be of synthetic, mineral, vegetable or animal origin.
[0018] The waxes should normally melt at a temperature between about 20°C and about 120°C,
preferably not more than about 90°C and especially in the range of about 30°C to about
70°C, i.e. lower than the maximum intended wash temperatures for the detergent compositions.
When waxes having melting points above the maximum intended wash temperatures are
used they should be adequately dispersed in the wash liquor by suitable incorporation
in the original detergent compositions.
[0019] The preferred waxes are of mineral origin, especially those derived from petroleum,
including microcrystalline and oxidised microcrystalline petroleum waxes, petroleum
jelly ("Vaseline") and paraffin waxes. Petroleum jelly is correctly a semi-solid wax,
usually having a melting point about 30-40°C, but is for convenience here grouped
with other solid waxes. Synthetic waxes such as Fischer-Tropsch and oxidised Fischer-Tropsch
waxes, or Montan waxes, or natural waxes such as beeswax, candelilla and carnauba
waxes may be used if desired. Any of the waxes described may be used alone or in admixture
with other waxes. The waxes should be readily dispersible in the detergent liquor
but not soluble therein and, preferably, they should not have very high saponification
values, e.g. not in excess of about 100. It is advantageous to include emulsifying
or stabilising agents for the waxes in the detergent compositions.
[0020] Examples of suitable oils which may be used if desired are vegetable oils such as
sesame oil, cotton seed oil, corn oil, sweet almond oil, olive oil, wheat germ oil,
rice bran oil, or peanut oil, or animal oils such as lanolin, neat's foot oil, bone
oil, sperm oil or cod liver oil. Any such oils used should of course not be highly
coloured, of strong odour or otherwise unacceptable for use in a detergent composition.
[0021] The remaining components of the composition are conventional and will be present
in conventional amounts. Sodium ortho-, pyro- and tripolyphosphates are amongst several
suitable detergency builders which are well known and commercially available, whilst
many more have been described in the literature, especially in recent patent specifications
on replacements for these phosphate based materials. Other detergency builders which
may be mentioned by way of example are alkali metal carbonates, especially sodium
carbonate, alkali metal polyphosphonates, e.g. sodium ethane-1-hydroxy-1,1-diphosphonate,
alkali metal amine carboxylates, such as sodium nitrilotriacetate and sodium ethylenediamine
tetraacetate, alkali metal ether carboxylates, such as sodium oxydiacetate, sodium
carboxy- methyloxysuccinate, sodium carboxymethyloxymalonate and homologues thereof,
alkali metal citrates, alkali metal mellitates and salts of polymeric carboxylic acids,
such as sodium polymaleate, copolyethylenemaleate, polyitaconate and polyacrylate.
When sodium carbonate is used as a detergency builder, it is advantageous to have
present some calcium carbonate having a surface area of at least about 10 m
2/g, as described in UK patent 1,437,950.
[0022] Another type of detergency builder which can be used, either alone or in admixture
with other builders, is a cation exchange material, especially a sodium aluminosilicate
such as described in UK patent 1,429,143 or in Netherlands patent application 7403381.
Preferred materials of this type have the formula:

and may be amorphous or crystalline, with some bound water usually in an amount of
about 10-30% depending on the drying conditions used. Such sodium aluminosilicate
materials should, of course, be very finely divided so as to minimise deposition on
the fabrics during washing.
[0023] The amount of the detergency builder which is used is normally from about 5% up to
about 80% by weight of the composition, preferably about 10% to about 60%, and the
ratio by weight of the detergency builders to the detergent active compounds which
are used is generally from about 10:1 to about 1:5 parts by weight.
[0024] The detergent compositions of the invention may take any of the usual physical forms,
preferably as solid compositions, for example as powders, granules, flakes, ribbons,
noodles or tablets, or they may be in liquid or paste form. The detergent compositions
may also be made by any of the conventional processes for making detergent compositions,
especially by the technique of slurry making and spray-drying in the case of the preferred
powder detergent compositions.
[0025] The detergent compositions of the invention may also include any of the conventional
optional additives in the amounts usually employed in detergent compositions. Examples
of these additives include powder flow aids such as finely divided silicas and aluminosilicates,
other lather controllers, anti-redeposition agents such as sodium carboxymethylcellulose,
oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate,
per-acid bleach precursors such as tetraacetylethylenediamine, chlorine-releasing
bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroiso-
cyanuric acid, fabric softening agents such as clays of the smectite and illite types,
anti-ashing aids, starches, slurry stabilisers such as copolyethylenemaleic anhydride
and copolyvinylmethylether-maleic anhydride, usually in salt form, inorganic salts
such as sodium silicates and sodium sulphate, and usually present in very minor amounts,
fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides:
and colourants. The detergent compositions usually have an alkaline pH, generally
in the region of pH 9-11, which is achieved by the presence of alkaline salts, especially
sodium silicates such as the meta-, neutral or alkaline silicates, preferably at levels
up to about 15% by weight.
[0026] The invention is illustrated by the following Examples in which parts and percentages
are by weight except where otherwise indicated.
Example 1
[0027] A series of fabric washing powders having the following formulation were prepared
by spray-drying and post-dosing techniques.

[0028] The powders were used to wash polyester cotton test cloths soiled with a soil consisting
of a mixture of inorganic materials and a synthetic sebum. The detergent efficiency
was followed by determing the reflectance of the washed cloth and expressing this
as a percentage of the reflectance of the unsoiled cloth. The washing procedures were
carried out in Tergotometers (registered Trade Mark) using water of 40° French hardness,
a temperature of 60°C, a product concentration of 0.15% and a 50 cpm agitation rate.
[0029] The results are shown in Table 3.

Example 2
[0030] Two detergent powders according to the following formulation were prepared by spray-drying
and post-dosing techniques.

[0031] In one of the powders, the anionic detergent was the sodium salt of C
16-C
18 high crystalline fraction secondary alkyl sulphate (SALS) and in the other it was
the sodium salt of C
12.5 alkyl benzene sulphonate (DOBS-055) prepared by sulphonation of dodecylbenzene obtained
from Shell Chemicals Limited as DOBS-055.
[0032] Naturally soiled cotton articles were halved and washed in a Hotpoint (registered
Trade Mark) washing machine. The washing time was 10 minutes, the cloth to liquor
ratio was 2.3 kg to 37 litres and the temperature 55°C.
[0033] One half of each divided article was washed with the powder containing SALS and half
with that containing DOBS-055. For each set of conditions a total of 18 articles were
halved and used in 6 tests.
[0034] After washing, the test pieces were assessed by a panel of trained assessors. The
results are shown in Table 4.

Example 3
[0035] An experiment similar to that described in Example 2 was performed, except that the
pair of powders contained the sodium salt of C
15-16 primary alkyl sulphate (D56) and DOBS-055. The results are shown in Table 5.

[0036] No non-soap anti-foam is included .in any of the powders tested in Examples 2 and
3, but this omission would not significantly affect the comparison of detergency exhibited
by the two products.
Example 4
[0037] Two fabric-washing powders were prepared by spray-drying and dry-dosing techniques
according to the following formulation:

[0038] Lather studies under practical conditions were made in a Miele W429 washing machine
with a 5 lb (= 2.3 kg) naturally soiled cotton load. The main wash (95°C) programme
was selected, 100 grams of powder were dosed, and the machine was supplied with cold
24
0H (London type) water. In addition to the above powders, Persil Automatic (registered
Trade Mark), a well-known conventional low sudsing fabric-washing powder was included
in the test.
Results
[0039] Lather heights were measured every 3 minutes using an arbitrary scale on the window
of the machine.
[0040] The results are shown in Figure 1 of the accompanying drawing, and demonstrate that
Powder B exhibits similar foaming characteristics to Persil Automatic until the washing
process has lasted about 35 minutes, whereas Powder A, not containing a non-soap anti-foam
exceeded the Persil Automatic foam level after about 12 minutes.
1. A detergent composition comprising an anionic sulphate surfactant or mixture of
such surfactants having
(a) a calcium salt solubility product greater than 10-12 moles3 litre-3; and
(b) a maximum critical micelle concentration of 6 x 10-2 gms/litre;
and a non-soap anti-foam.
2. A detergent composition according to claim 1 comprising from 5 to 35% by weight
of the anionic sulphate surfactant.
3. A detergent composition according to claim 2 comprising from 5 to 25% by weight
of the anionic sulphate surfactant.
4. A detergent composition according to any one of the preceding claims wherein the
anionic sulphate surfactant comprises a primary or secondary alkyl sulphate.
5. A detergent composition according to claim 4 wherein the anionic sulphate surfactant
comprises a high crystalline fraction secondary alkyl sulphate.
6. A detergent composition according to claim 5 wherein the secondary alkyl sulphate
comprises a mixture of compounds having 16 to 18 carbon atoms in the alkyl group.
7. A detergent composition according to claim 4 wherein the anionic sulphate surfactant
comprises a C15-16 primary alcohol sulphate.
8. A detergent composition according to any one of the preceding claims comprising
from 0.05 to 5% by weight of a non-soap anti-foam.
9. A detergent composition according to any one of the preceding claims wherein the
non-soap anti-foam comprises a phosphate ester.
10. A detergent composition according to any one of the preceding claims wherein the
non-soap anti-foam comprises a mixture of a phosphate ester and a hydrophobic wax
or oil.
11. A detergent composition according to claim 9 wherein the phosphate ester has the
general formula

where A is -OH, or R
2O(EO)
m-,
R1 and R2 are the same or different C12-24 straight or branched chain, saturated or unsaturated alkyl groups,
m and n are the same or different and are 0 or an integer from 1 to 6.
12. A detergent composition according to claim 11 wherein A is -OH and n is 0.
13. A detergent composition according to claim 10 wherein the wax has a melting or
softening point in the range 30 to 70°C.
14. A detergent composition according to claim 13 wherein the wax is petroleum jelly
having a melting point of from 30-400C.
15. A detergent composition comprising an anionic sulphate surfactant having a calcium
solubility product and a critical micelle concentration as defined in claim 1, and
a non-soap anti-foam, substantially as hereinbefore described with reference to any
one of the formulations illustrated in Examples 1 to 4.