[0001] The present invention relates to liquid detergent compositions suitable for use especially,
but not exclusively, in fabric washing, shampoos, and above all, in manual dishwashing
operations in both hard and soft water.
[0002] The term "dishes" as used herein means any utensils involved in food preparation
or consumption which may be required to be washed to free them from food particles
and other food residues, greases, proteins, starches, gums, dyes, oils and burnt organic
residues.
[0003] Light-duty liquid detergent compositions such as are suitable for use in washing
dishes are well-known. Many of the formulations in commercial use at the present time
are based on a sulphonate-type anionic detergent, especially an alkyl benzene sulphonate,
in conjunction with an alkyl polyethoxy sulphate (alkyl ether sulphate). The sulphonate-type
detergent generally predominates.
[0004] The use of conventional dishwashing liquids based on alkyl benzene sulphonate/alkyl
ether sulphate or on alkyl sulphate/alkyl ether sulphate is seen to have deleterious
influence on the hand condition of users. Hence mildness in washing-up liquid is considered
a desirable quality, and many specially formulated products on the market make claims
for it.
[0005] Protein denaturation by surfactants is considered to be one of the major causes of
skin irritation and skin roughness induced by surfactants (G Imokawa et al. JOACS
52, 484-489, Dec 1975). The degree of surfactant denaturation of protein depends on
the type of surfactants and their concentration.
[0006] At present, the dishwashing formulations that are on the market which are less interactive
with protein and hence considered to be milder are those based on a combination of
ether sulphates and amine oxides. See for example US-A-3 928 249 (Procter & Gamble).
In place of amine oxides, betaines can also be used. See for example US 4 554 098.
However, such formulations - particularly with amine oxides - are expensive, not only
because the active ingredients are expensive, but also because they require a large
amount of expensive hydrotropes such as xylenesulphonate and/or ethanol to produce
liquids which are stable and of acceptable viscosity.
[0007] EP 0232153 (Unilever) discloses detergent compositions based upon a mixture of anionic
and nonionic surfactants together with lather boosters, at least some of the anionic
surfactants being alkyl ether sulphate.
[0008] It is preferred to include high amounts of nonionic surfactants in order to produce
a mild system because such surfactants are inert towards proteins in the skin and
because nonionic-containing formulations require lesser amounts of expensive hydrotropes.
[0009] Nonionics have also been shown to have a good soil removing potential, particularly
of greasy soils often found on dishes. However, nonionics as a class are low foamers
and produce unstable lather.
[0010] GB 2 165 855 (Colgate) discloses mild nonionic-based light duty liquid detergents
wherein the nonionic component exceeds 50% by weight of the total detergent content.
However, for reasons stated above, such high nonionic-based formulations would have
foam performance deficiencies.
[0011] US 4 554 098 (Colgate) mentioned above discloses a mild dishwashing formulation based
on an alkyl ether sulphate containing an average of 5 to 12 moles of ethylene oxide
in the molecule. However, such ether sulphates are not commercially easily available.
Also, it is believed that the dioxane level in ether sulphate raw material increases
with the increase in EO content of ether sulphate. Therefore, for ease of commercial
exploitation the use of widely used and generally available ether sulphates containing
less than 5 EO is preferred.
[0012] Therefore there is need for the development of more cost-effective mild dishwashing
formulations, which are based on relatively less expensive detergent raw materials
and which also require lesser amounts of expensive hydroptropes.
[0013] The present invention is based on the realisation that cost-effective mild liquid
dishwashing formulations with adequate performance can be obtained by careful choice
of the active ingredients and their preparation, in particular by restricting the
main anionic detergent active present and including also selected amounts of alkyl
ether sulphate, lather boosters and non-ionic detergent active material.
[0014] According to a first aspect of the present invention, there is provided a stable
detergent composition in liquid or gel form containing from 10 to 80% by weight of
an active detergent mixture and also containing water, the active detergent mixture
comprising:-
(a) anionic detergent active other than alkyl ether sulphate;
(b) alkyl ether sulphate having an average ethoxylation value of between 1 and 5,
the weight ratio of components (a) to (b) being in the range 2:1 to 1:10, preferably
in the range 2:1 or 1.5:1 to 1:3, more preferably 2:1 to 1:2; and
(c) betaine and/or amine oxide, the molar ratio of components (a) to (c) being in
the range 3:1 to 1:3, more preferably 2:1 to 1:2; and
(d) a water-soluble nonionic detergent active material in an amount of more than 35%,
but less than 50% by weight of the active detergent mixture.
[0015] For reasons of cost-effectiveness, and availability of materials, at least a major
proportion of the component (a) is selected from secondary alkane sulphonate, alkylbenzene
sulphonate, primary alkyl sulphate, fatty acid ester sulphonate, dialkylsulphosuccinate
and 2-alpha olefin sulphonate.
[0016] Compositions of the invention can give performance in detergency tests as good as
those of conventional compositions containing alkyl benzene sulphonate, but are considerably
milder.
[0017] It is particularly surprising that mildness of predominantly nonionic-based formulations
can wholly be maintained by substituting a substantial portion of the nonionic with
ether sulphates containing less than 5 EO, but enhancing the foam performance significantly
and thus improving cost effectiveness.
[0018] Although in principle the concentration of the active detergent mixture may be as
high as desired in the range 10 to 80%, provided that a stable liquid or gel product
can be obtained, the range of 5 to 60% by weight is preferred, and aqueous liquid
compositions with an active detergent mixture in the range of 5 to 40% by weight are
of especial interest.
[0019] Six detergent actives have been mentioned above as possibilities for component (a).
Secondary alkane sulphonate may generally be produced by a free radical reaction,
either a sulphochlorination reaction (Reed reaction) of a paraffin
RH + SO₂ + Cl₂ → RSO₂Cl + HCl
followed by hydrolysis and neutralisation, or by a sulphoxidation reaction
RH + SO₂ + ½ O₂ → RSO₃H
followed by neutralisation.
[0020] The secondary alkane sulphonate component (a) will normally be a mixture of materials
of different alkyl chain lengths, of the formula
R₁R₂CHSO₃X
where R₁ and R₂ which may be the same or different are each a straight or branched
chain alkyl group having at least one carbon atom, the alkyl chain length (ie. total
number of carbon atoms of R₁ and R₂ plus 1) preferably being in the range 13 to 18,
and X is a solubilising cation. An example of such material is SAS 60 of Hoechst (SAS
is a Trade Mark) which is produced by a sulphoxidation process.
[0021] A suitable secondary alkane sulphonate produced by a sulphochlorination process is
Mersolat (trade mark) of Bayer.
[0022] Alkylbenzene sulphonate for use in component (a) is preferably derived from an alkylbenzene
with a C₈ to C₁₆ primary or secondary alkyl group. This may in particular be C₈ to
C₁₃ alkyl. Suitable alkylbenzene sulphonates are Dobs 102 of Shell and Marlon A of
Huls.
[0023] Primary alkyl sulphate is preferred (primary alcohol sulphate) for use in component
(a) and is preferably of the formula
ROSO₃X
where R is a C₈ to C₁₈ primary alkyl group and X is a solubilising cation. Suitable
is Dobanol 23A of Shell in which R is predominantly C₁₂ and C₁₃. As well be explained
in more detail below alkyl sulphate is a constituent of alkyl ether sulphates which
provide component (b).
[0024] Suitable detergent-active dialkyl sulphosuccinates are compounds of the formula

wherein each of R₁ and R₂, which may be the same or different, represents a straight-chain
or branched-chain alkyl group having 3 to 12 carbon atoms, preferably from 4 to 10
carbon atoms and more preferably from 6 to 8 carbon atoms, and X represents a solubilising
cation.
[0025] The alkyl groups R₁ and R₂ are preferably straight-chain or (in mixtures) predominantly
straight-chain.
[0026] Among dialkyl sulphosuccinates that may advantageously be used in the composition
of the invention are the C₆/C₈ unsymmetrical materials described and claimed in GB
2 105 325 (Unilever); the dioctyl sulphosuccinate/dihexyl sulphosuccinate mixtures
described and claimed in GB 2 104 913 (Unilever); and the mixtures of symmetrical
and unsymmetrical dialkyl sulphosuccinates described and claimed in GB 2 108 520 (Unilever).
[0027] Appropriate alpha-olefin sulphonates will generally be in the range having from twelve
to sixteen carbon atoms.
[0028] An example of such a material is Liporan 440, a C₁₄ alpha-olefin sulphonate from
Lion Corporation, Japan.
[0029] Appropriate fatty acid ester sulphonates are of formula

where
R₁ is straight or branched C₈ to C₁₆ alkyl
R₂ is straight or branched C₁ to C₄ alkyl
and
X is a solubising cation
R₁ is preferably C₁₀ to C₁₂ and
R₂ is preferably butyl.
[0030] Component (a) of the active detergent mixture may also include one or more other
detergent actives used in liquid compositions, for example alkyl glyceryl ether sulphonates,
or alkyl sarcosinates. The amount is preferably less than half of component (a), more
preferably not more than a quarter of it.
[0031] The second essential component (b) of the active detergent mixture is alkyl ether
sulphate (sometimes called alcohol ether sulphate or alkyl polyethoxy sulphate) having
at least one ethylene oxide residue per molecule. This will normally be provided by
incorporating into the composition an alkyl ether sulphate which is a mixture of materials
of the general formula:
R - (OCH₂CH₂)
n OSO₃X
wherein R is a C₁₀ to C₁₈ primary or secondary alkyl group, X is a solubilising cation,
and
n, the average degree of ethoxylation, is from 1 to 5, preferably from 3 to 4. Particularly
preferred values of
n are 3 and 4. R₃ is preferably a C₁₀ to C₁₆ alkyl group. In any given alkyl ether
sulphate, a range of differently ethoxylated materials, and some unethoxylated material,
will be present and the value of
n represents an average. The unethoxylated material is, of course, alkyl sulphate and
this contributes to component (a).
[0032] The amount of alkyl sulphate in any alkyl ether sulphate will depend on average degree
of ethoxylation
n. When
n is 3, alkyl sulphate typically constitutes 15 to 20% of the mixture, and less than
this when
n is 4 or more. When the proportion of alkyl sulphate is low, it may prove convenient
to ignore it. Nevertheless, it contributes to component (a).
[0033] When the average degree of ethoxylation is 2, alkyl sulphate typically constitutes
30% of the mixture provided as "alkyl ether sulphate". Such a mixture can provide
both component (b) and component (a), with the latter then consisting entirely of
alkyl sulphate.
[0034] We have found that it is not feasible to use alkyl ether sulphate with an average
degree of ethoxylation below 1.5. Unless the alkyl sulphate content of the ether sulphate
is providing much or the whole of component (a), it is preferred that the alkyl ether
sulphate is provided by material with an average of at least 2 or 2.5 ethylene oxide
residues per molecule.
[0035] Alkyl ether sulphate contains molecules with differing numbers of ethylene oxide
residues in a statistical distribution. In an alkyl ether sulphate where the average
degree of ethoxylation is 1.5 or greater, the proportion of molecules with a single
ethylene oxide residue will not be substantially greater than the proportion with
two ethylene oxide residues, nor the proportion with the most frequently encountered
number of ethylene oxide residues (if this is more than two). Therefore this feature
is an observable characteristic of component (b). If the average degree of ethoxylation
is 2 or more, as preferred, the proportion of molecules with a single ethylene oxide
residue will be less than the proportion with two ethylene oxide residues and the
proportion with the most frequently encountered number.
[0036] Preferred alkyl ether sulphates of the component (b), excluding alkyl sulphate, are
mixtures of compounds of the above formula
R-(OCH₂CH₂)
n-OSO₃X
in which
n is any positive integer, with the proviso that the average EO value is less than
5.
[0037] Examples of preferred alkyl ether sulphates for use in the present invention are
Dobanol (Trade Mark) 23-3 from Shell in which the degree of ethoxylation (n) is 3
and the equivalent material in which the degree of ethoxylation is 4. These materials
which are based on C₁₂-C₁₃ (50% of each) primary alcohol (about 75% straight chain,
25% 2-methyl branched). Another preferred material is an alkyl ether sulphate based
on Lial (Trade Mark) 123 from Chimica Augusta, which is a branched chain primary alcohol
with a degree of ethoxylation of 3 to 4 and with a similar alkyl chain length distribution
to Dobanol 23. Also preferred is Empicol MD (Trade Mark) from Albright and Wilson,
with degree of ethoxylation of 4 and based on middle-cut coconut alkyl group.
[0038] A suitable example of a secondary alcohol ether sulphate is a material derived from
an alcohol such as Tergitol 15/S/3 (trade mark) of Union Carbide (this material itself
is not at present available). The conventional process of manufacture of secondary
alkyl ether sulphates is such that there is only a very small quantity of alkyl sulphate
in the product.
[0039] Component (b) provides at least 12% of the active detergent mixture, preferably it
provides at least 20 or 30%. It preferably provides not more than 40% of the active
detergent mixture. However, component (b) could form up to 50% of the mixture if component
(b) contributes substantially or wholly to component (a).
[0040] The solubilising cations of the anionic detergent actives of components (a) and (b),
denoted as X in the formulae above, may be any which provide the desired solubility
of the anionic material. Monovalent cations such as alkali metal ions, ammonium and
substituted ammonium are typical. Divalent ions giving adequate solubility may be
used, and especially magnesium ions may be present to improve soft water performance
and can be incorporated as magnesium salt of the anionic actives or as inorganic magnesium
salts, or in the hydrotrope system.
[0041] Component (c) is a betaine or amine oxide or a mixture thereof. It is preferred to
avoid using substantial amounts of these, especially amine oxides, for the sake of
economy and consequent cost effectiveness. Preferably then the amount of amine oxide
is not more than 10% by weight of the active detergent mixture. Preferably the amount
of betaine is not more than 30% by weight of this mixture. The total amount of amine
oxide and betaine is preferably not more than 30% and more preferably not more than
15% or 10% by weight of the active detergent mixture. It is preferred to use betaines
alone.
[0042] Suitable betaines include simple betaines of formula

and amido betaines of formula:

[0043] In both formulae R is a C₈ to C₁₈ straight or branched alkyl group. It may be a lauryl
group or a middle cut coconut alkyl group. R₆ and R₇ are each C₁ to C₃ alkyl or C₁
to C₃ hydroxyalkyl. Examples of sulphobetaines have the above formulae with -CH₂CO⁻₂
replaced by
-(CH₂)₃SO⁻₃ or

[0044] A suitable simple betaine is Empigen BB from Albright & Wilson. It has the formula
quoted above in which R is C₁₂ to C₁₄ alkyl, derived from coconut, and R₆ and R₇ are
both methyl. Also preferred is Tego L7 from Goldsmidt, which has a whole coconut alkyl
group.
[0045] Suitable amine oxides have the formula
R R₆ R₇ N-O
wherein R is a straight or branched chain C₈ to C₁₈ alkyl group and R₆ and R₇ are
each C₁ to C₃ alkyl, or C₁ to C₃ hydroxyalkyl. A suitable amine oxide is Empigen OB
from Albright & Wilson. In it R is middle-cut coconut alkyl and R₆ and R₇ are both
methyl.
[0046] Component (d) is one or more water-soluble non-ionic detergent active materials,
eg. materials conventionally used in detergent formulations. The betaines and amine
oxides of component (c) do not form part of component (d).
[0047] Component (d) is preferably a polyalkoxylated material, notably it is one or more
ethoxylated non-ionic detergent active materials. It is then desirable that such material
should have an HLB value in the range from 12.0 to 16.0.
[0048] Component (d) may be a polyethoxylated aliphatic alcohol having an alkyl chain length
of from C₈ to C₁₈ preferably C₈ to C₁₆, and an average degree of ethoxylation of from
4 to 14. Suitable nonionic detergents include short-chain high-foaming ethoxylated
alcohols of the general formula
R - (OCH₂CH₂)
m - OH
wherein R is an alkyl group, preferably straight-chain, having from 8 to 18 better
8 to 16 and yet more preferably 9 to 12, carbon atoms, and the average degree of ethoxylation
m is from 5 to 14, more preferably 6 to 12. An especially preferred nonionic detergent
is Dobanol 91-8 from Shell, in which R is C₉-C₁₁ (predominantly straight-chain) and
m is 8, or alternatively Lialet C₁₁-10 EO.
[0049] Alternative suitable materials are those in which R is a secondary alkyl having from
8 to 18, preferably 11-15, carbon atoms and
m is from 5 to 14 preferably 6-12. An example is Tergitol 15/S/12 of Union Carbide
(not available at present) or the material of the Softanol A series (from Japan Catalytic).
[0050] Preferably the polyethoxylated alcohol mixture is stripped, to reduce odour imparted
to the composition.
[0051] Another possibility for the component (d) is an ethoxylated alkanolamide of the general
formula
R-CO-

(R₈)(OCH₂CH₂O)
pH
wherein R is a straight or branched alkyl having from 7 to carbon atoms,
R₈ is an ethyleneoxy or propyleneoxy group
Y is hydrogen or -R₈(CH₂CH₂O)
qH
p is 1 or more and q is 0, 1 or more
R may be lauryl or coconut alkyl. Examples of ethoxylated alkanolamide are Amidox
L5 and Amidox C5 from Stepan Chemical Company.
[0052] Further possibilities for component (d) are ethoxylated alkylphenols and ethoxylated
fatty acids, ie. polyethyleneglycol esters of fatty acids.
[0053] Component (d) constitutes at least 35% by weight of the active detergent mixture,
but less than 50%.
[0054] Optionally present within the active detergent mixture of the composition of the
invention may be one or more mono- or dialkanolamides, preferably C₈ to C₁₈, more
preferably C₁₀-C₁₈ carboxylic acid mono- or di(C₂-C₃) alkanolamides. These have the
general formulae
R₄ - CO - NHR₅ and R₄ - CO - N(R₅)₂ respectively
wherein R₄ is a C₇-C₁₇ aliphatic group, preferably straight-chain and preferably saturated,
and R₅ is a hydroxyethyl or hydroxypropyl group. R₅ is preferably a 2-hydroxyethyl
group.
[0055] Materials of this type are generally made from fatty acids of natural origin and
contain a range of molecules having R₄ groups of different chain lengths; for example,
coconut ethanolamides consist predominantly of C₁₂ and C₁₄ material, with varying
amounts of C₈,C₁₀, C₁₆ and C₁₈ material. Preferred are ethanolamides derived from
so-called middle cut coconut fatty acid, most preferably from lauric acid.
[0056] The mono- and di-ethanolamides may range from 5% to 20% of the detergent mixture.
[0057] As well as the active detergent mixture and water, the liquid detergent compositions
of the invention will generally need to contain one or more hydrotropes. Hydrotropes
are materials present in a formulation to control solubility, viscosity, clarity and
stability but which themselves make no active contribution to the performance of the
product. Examples of hydrotropes include lower aliphatic alcohols, especially ethanol;
urea; lower alkylbenzene sulphonates such as sodium, toluene and xylene sulphonates
and combinations of these. Preferred are alcohol, urea and xylene sulphonate. Hydrotropes
are expensive and take up room in a formulation without contributing to its performance,
and it is therefore desirable to use as small quantities of them as possible.
[0058] For example, the use of amine oxides as mentioned above requires a large amount of
alcohol as hydrotrope. For this reason and because of expense, it is preferred to
avoid the use of a substantial amount of any tertiary amine oxide in the present invention.
[0059] In preferred forms of this invention the weight of hydrotrope in the composition
is not more than 12% of the weight of the active detergent mixture.
[0060] The compositions of the invention may also contain the usual minor ingredients such
as perfume, colour, preservatives and germicides.
[0061] The stable liquid detergent compositions of the invention may be used for all normal
detergent purposes especially where foaming is advantageous, for example, fabric washing
products, general purpose domestic and industrial cleaning compositions, carpet shampoos,
car wash products, personal washing products, shampoos, foam bath products, and above
all, manual dishwashing.
[0062] The invention is further illustrated by the following non-limiting Examples.
EXAMPLES
Examples 1-4
[0063] The foaming performance and mildness of various aqueous formulations were compared.
These formulations I and II falling within the scope of the present application were
compared with a comparable composition (A) containing over 50% by weight of nonionic
active.
[0064] Foaming performance was assessed by means of a modified Schlachter-Dierkes test based
on the principle described in
Fette und Seifen 1951,
53, 207. A 100 ml aqueous solution of each material tested, having a concentration of
0.04% active detergent in 24°H water (French hardness) at 45°C was rapidly oscillated
using a vertically oscillating perforated disc within a graduated cylinder. After
the initial generation of foam, increments (0.2 g) of soil (9.5 parts commercial cooking
fat, 0.25 partsoleic acid 0.25 parts stearic acid and 10 parts wheat starch in 120
parts water) were added at 15 second intervals (10 seconds' mild agitation and 5 seconds'
rest) until the foam collapsed. The result was recorded as the number of soil increments
(NSI score): a score difference of 6 or less is generally regarded as insignificant.
Each result was typically the average of 3 or 4 runs.
[0065] Several in-vitro and in-vivo methods for evaluating protein denaturation potency
of surfactants and their mixtures have been reported (see Miyazowa et al, Int J Cos
Sci
6 33-46 1984, and the references cited therein). One such method is the study of interaction
of detergents with acid phosphatase enzyme either from skin (Prottey et al, Int J
Cos Sci
6 263-273 1984) or from Wheatgerm (Tanaka et al, Anal Biochem
66 489-498 1975).
[0066] In vivo mildness of formulations can be assessed using a flex wash test. In this
test neat products were rubbed on the forearm of panellists and rinsed. The process
was repeated four times a day for five days and the level of erythema developed was
assessed by trained assessors.
[0067] A comparison of wheatgerm acid phosphatase (WGAP) test and flex wash test results
indicated that formulations giving less than 50% enzyme inhibition under the test
conditions are substantially mild; any mildness differences between products giving
<40% inhibition do not show any detectable mildness differences in flex wash test,
indicating that the enzyme test is very sensitive an that in a real life situation
there is a threshold level of protein denaturation below which all actives and products
are indistinguishably mild. The results of the WGAP test are expressed as percentage
inhibition (ie 100% minus percentage activity remaining). Water gave no inhibition
at all, ie 100% of activity remained.
|
I |
II |
A |
Lialet 123-3S¹ |
10 |
- |
- |
Lialet 123-4S¹ |
- |
10 |
- |
Dobanol 23-A² |
- |
- |
8 |
Lialet 123-S² |
5 |
5 |
- |
Lialet C₁₁ 10EO³ |
15 |
15 |
22 |
Empigen BB⁴ |
6 |
6 |
6 |
Empigen LME⁵ |
4 |
4 |
4 |
Plunger Test (0.04% AD) |
|
|
|
24°FH |
46 |
46 |
41 |
5°FH |
45 |
46 |
43 |
% WGAP Inhibition |
23 |
21 |
12 |
1 - Alkyl Ether Sulphate |
2 - Primary Alkyl Sulphate |
3 - Nonionic |
4 - Betaine |
5 - Ethanolamide |
[0068] The Examples show that formulations I and II give a greater foaming performance than
A. Although % WGAP inhibition of A is less than I and II, the effective mildness is
no different, as explained above. Thus compositions of the present invention give
a combination of mildness and performance.
[0069] The Examples show that formulations I and II give a greater foaming performance than
A. Although % WGAP inhibition of A is less than I and II, the effective mildness is
no different, as explained above. Thus compositions of the present invention give
a combination of mildness and performance.