[0001] This invention relates to a detergent composition, in particular to a detergent composition
for washing fabrics.
[0002] Fabric washing compositions contain, as an essential ingredient, a surfactant system
whose role is to assist in the removal of soil from the fabric and its suspension
in the wash liquor. Suitable detergent active materials fall into a number of classes,
including anionic, nonionic and cationic materials and marketed products contain materials
selected from one or more of these classes.
[0003] The most widely used anionic detergent active materials are the alkyl benzene sulphonates
and these provide satisfactory results especially at high temperatures. There has
been a desire to find alternative anionic surfactants for use in circumstances when
alkyl benzene sulphonates are undesirable, but generally speaking the performance
of other anionic detergent active materials is unsatisfactory.
[0004] Among such alternative anionic surfactants are the primary alcohol sulphates (PAS)
otherwise known as alkyl sulphates. PAS may be derived from both synthetic and natural
alcohols containing from about 8 to 18 carbon atoms. Examples of suitable alcohols
which can be used in alkyl sulphate manufacture include decyl, lauryl, myristyl, palmityl
and stearyl alcohols and the mixture of fatty alcohols derived by reducing the glycerides
of tallow and coconut oil. Natural alcohols, for example tallow or coconut alcohol,
give rise to straight chain, or linear, PAS. Synthetic alcohols for example those
produced by the Oxo process can give rise to straight or branched chain PAS.
[0005] In the past PAS derived from tallow fat that is to say linear PAS has been recommended
for use in fabric washing compositions. Thus, GB 1 399 966 (The Procter and Gamble
Company) discloses a detergent composition in which the surfactant system is a mixture
of sodium tallow alkyl sulphate and a nonionic detergent active material. However,
tallow PAS suffers from the disadvantage that its performance at low temperatures
is poor. With the trend towards lower wash temperatures this becomes a serious disadvantage.
[0006] GB 1 399 966 referred to above also discloses the possibility of using the PAS derived
from coconut oil, also linear. The performance of tallow PAS at low temperatures is
poor.
[0007] The consumer expects a single product to perform satisfactorily both at high and
low temperatures, neither tallow PAS nor coconut PAS can achieve this.
[0008] In our patent application EP 342 917A it is suggested that a PAS which has a wider
spread of chain lengths than is derivable from either tallow or coconut alcohol can
perform better than tallow PAS at low temperatures and better than coconut PAS at
higher temperatures. The PAS disclosed in EP 342 917A are derived from either synthetic
or natural alcohols but are all linear PAS.
US 3 480 556 discloses C₁/C₂ branched PAS in a formulation for dishwashing. JP 721
232 discloses a detergency negative for the replacement of C₁₁ linear PAS with branched
PAS of unspecified branching.
[0009] We have now found that there are benefits in performance, particularly in the removal
of oily soil when branched PAS materials are used, especially when they are combined
with certain types of nonionic surfactant. These benefits can be seen over a range
of temperatures.
[0010] Thus according to a first aspect of the present invention there is provided a detergent
composition for washing fabrics, the composition containing a surfactant system comprising
an anionic surfactant the major ingredient of which is a branched chain primary alkyl
sulphate with primary alkyl chain length between 10 and 20 carbon atoms.
[0011] In compositions of this invention, the branched PAS preferably contains more than
10% by weight of branching based on the total weight of PAS, more preferably between
15% and 70% by weight of branching, most preferably between 30% and 65% of branching
based on the total weight of PAS.
[0012] The branches preferably contain at least four carbon atoms, and comprise at least
5% by weight of the branching based on the total weight of PAS.
[0013] It is preferred to use branched PAS having a range of primary alkyl chain lengths
for example between 12 and 18 carbon atoms, or between 12 and 16 carbon atoms, most
preferably between 13 and 15 carbon atoms.
[0014] The water soluble salts of these anionic surfactants are preferred, especially the
alkali metal salts thereof.
[0015] Preferred compositions according to the invention include from 2% to 50%, such as
from 4% to 30% by weight of the surfactant system.
[0016] In addition to the branched PAS materials according to the invention, other PAS materials
may be included in the composition, for example linear PAS.
[0017] The compositions of the invention also preferably contain a nonionic surfactant.
We have found it to be of advantage if such a nonionic surfactant has an HLB of less
than 10.5, preferably less than 10.
[0018] Suitable nonionic surfactants which may be used are the reaction products of compounds
having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols,
acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either
alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C₆-C₂₂)
phenols-ethylene oxide condensates, the condensation products of aliphatic (C₈-C₁₈)
primary or secondary linear or branched alcohols with ethylene oxide, and products
made by condensation of ethylene oxide with the reaction products of propylene oxide
and ethylenediamine.
[0019] When alkylene oxide adducts of fatty materials are used as the nonionic surfactants,
the number of alkylene oxide groups per molecule has a considerable effect upon the
HLB of the nonionic surfactant. The chain length and nature of the fatty material
is also influential, and thus the preferred number of alkylene oxide groups per molecule
depends upon the nature and chain length of the fatty material.
[0020] We have found it of advantage that the weight ratio between the anionic surfactant
and the nonionic surfactant lies between 10:1 and 1:4, most preferably between 4:1
and 1:3.
[0021] The surfactant system may include other surfactant materials in addition to the specified
alkyl sulphate and the above mentioned nonionic materials. These other surfactant
materials may be selected from other anionic detergent active materials, zwitterionic
or amphoteric detergent active materials or mixture thereof.
[0022] Any such further surfactant materials should preferably be present at a level which
is no more than 25% preferably not more than 10% of the total amount of surfactant
in the composition.
[0023] The other anionic detergent active materials may be the usual water-soluble alkali
metal salts of organic sulphonates having alkyl radicals containing from about 8 to
about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher
acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium
and potassium alkyl (C₉-C₂₀) benzene sulphonates, particularly sodium linear secondary
alkyl (C₁₀-C₁₅) benzene sulphonate; sodium alkyl glyceryl ether sulphates, especially
those ethers of the higher alcohols derived from tallow or coconut oil and synthetic
alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates
and sulphonates; the reaction products of fatty acids such as coconut fatty acids
esterified with isethionic acid and neutralised with sodium hydroxide; sodium and
potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such
as those derived by reacting alpha-olefins (C₈-C₂₀) with sodium bisulphite and those
derived from reacting paraffins with SO₂ and Cl₂ and then hydrolysing with a base
to produce a random sulphate.
[0024] The compositions of the invention may contain a detergency builder material, this
may be any material capable of reducing the level of free calcium ions in the wash
liquor and will preferably provide the compositions with other beneficial properties
such as the generation of an alkaline pH and the suspension of soil removed from the
fabric. The amount of builder material in a composition of this invention may in particular
be from 15% to 60% by weight of the composition.
[0025] Examples of phosphorous-containing inorganic detergency builders, when present, include
the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates,
metaphosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate
builders include sodium and potassium tripolyphosphates, orthophosphates and hexamataphosphates.
[0026] Examples of non-phosphorous-containing inorganic detergency builders, when present,
include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline
and amorphous aluminisilicates. Specific examples include sodium carbonate (with or
without calcite seeds), potassium carbonate (with or without calcite seeds), sodium
and potassium bicarbonates and silicates.
[0027] Examples of organic detergency builders, when present, include the alkali metal,
ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl
carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium,
lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids
and citric acid.
[0028] It is preferred that the compositions according to the invention be alkaline, that
is at the concentration of 1 g/l in distilled water at 25°C the pH should be at least
8, preferably at least 10. To this end the compositions may include a water-soluble
alkaline salt. This salt may be a detergency builder or a non-building alkaline material.
[0029] Apart from the ingredients already mentioned, a number of optional ingredients may
also be present.
[0030] Examples of other ingredients which may be present in the composition include fabric
softening agents such as fatty amines, fabric softening clay materials, lather boosters
such as alkanolamides, particularly the monoethanolamides derived from palm kernel
fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching
agents such as sodium perborate and sodium percarbonate, peracid bleach precursors,
chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts
such as sodium sulphate, and; usually present in very minor amounts, fluorescent agents,
perfumes including deodorant perfumes, enzymes such as proteases, cellulases and amylases,
lipases germicides and colourants.
[0031] Although detergent compositions generally include sodium sulphate it may sometimes
be desirable to have compositions which are sulphate free or contain low levels of
sulphate.
[0032] The detergent compositions according to the invention may be prepared by a number
of different methods according to their physical form. In the case of granular products
they may be prepared by dry-mixing or coagglomeration. A preferred physical form is
a granule incorporating a detergency builder salt and this is most conveniently manufactured
by spray-drying at least part of the composition. In this process a slurry is prepared
containing the heat-insensitive components of the composition such as the surfactant
system, builder material and filler. The slurry is spray-dried to form base powder
granules with which any solid heat-sensitive ingredients may be mixed, such ingredients
including bleaches and enzymes. The specified nonionic surfactants can be liquidified
by melting or solvent dissolution and sprayed onto the base powder granules, rather
than including them in the slurry for spray-drying. The invention will now be described
in more detail in the following non-limiting examples.
Examples 1 to 4
[0033] Wash liquors were prepared in water having a hardness of 24°FH (equivalent to a free
calcium ion concentration of 2.4 x 10⁻³ molar). The wash liquor contained the equivalent
of 6g/l of a composition containing (by weight)

[0034] The sodium metaborate was included as being equivalent in ionic strength to 8% sodium
perborate monohydrate which would be present in practice. The bleach is left out of
these experiments to avoid confusion between detergency and bleaching effects in the
interpretation of the results. The anionic surfactants used were as set out in the
following table:

ELFAN 280 is ex Akzo, SYNPROL SULPHATE is ex ICI, DOBANOL 45 SULPHATE is the sulphate
of DOBANOL 45 alcohol ex Shell, LIAL 145 SULPHATE is the sulphate of LIAL 145 alcohol
ex Enichem.
[0035] In examples 1 to 4 the nonionic surfactant was SYNPERONIC A7 (ex ICI) which is principally
C₁₃/C₁₅ alcohol ethoxylated with an average of 7 moles of ethylene oxide mixed with
SYNPERONIC A3 (ex ICI) which is principally C₁₃/₁₅ alcohol ethoxylated with an average
of 3 moles of ethylene oxide. This mixture has an HLB of approximately 9.
[0036] The wash liquors were used to wash a fabric load at liquor to cloth ratio of 50:1.
The load included a number of polyester monitors to which had previously been applied
an amount of H³ tagged triolein. Measurement of the level of tagged triolein after
washing, using standard radio-tracer techniques, gives an indication of the degree
of detergency, i.e. soil removal, obtained.
[0037] The wash time was 20 minutes with an agitation of 70 rpm. Washes were isothermal
at 40°C.
[0038] The results obtained were as follows:

[0039] From these results it is apparent that the branched chain PAS outperforms the linear
chain PAS.
Examples 5 to 7
[0040] Experiments were conducted in a similar manner to Examples 1 to 4 excepting that
the wash temperature was 30°C and the water used was 25°FH (equivalent to 2.5 x 10⁻³
mol/l of calcium).

[0041] In this case sodium chloride was included as being equivalent in ionic strength to
8% sodium perborate monohydrate.
[0042] In Examples 5 to 7 the nonionic surfactant mixture had an HLB of approximately 9.
[0043] The results were as follows:

[0044] These results show that branched PAS outperforms the linear PAS.
Examples 8 to 11
[0045] Experiments using the method and compositions as used in Examples 6 and 7 were carried
out at 30°C and 60°C on a different soiled polyester.

[0046] These results show that a higher level of C₄ or greater branching in the PAS gives
rise to a higher percentage of oily soil removal at both low and high temperatures.
Examples 12 to 13
[0047] Wash liquors were prepared in water having a hardness of 24°FH to give a product
concentration of 6g/l from a composition containing (by weight)

1 is C₁₃/C₁₅ sulphate with 46% branching of which 78% is methyl and 5% is butyl or
higher.
2 is a sulphate with 35% branching of which 50% is methyl and 21% is butyl or higher.
[0048] The wash liquors were used to wash a fabric load as in Example 1.
[0049] The results obtained were as follows.

From these results it is apparent that branched PAS with a high percentage of butyl
branching outperforms PAS with a low percentage of butyl branching.
Examples 14 to 15
[0050] Examples 12 and 13 were repeated with nonionic detergent active in the formulation.

The results obtained were as follows.

Examples 16-18
[0051] Example 12 was repeated using three different PASs in place of SYNPROL SULPHATE.
The results obtained were as follows:

These results show that branched PAS performs better than straight chain PAS.