TECHNICAL FIELD
[0001] This invention relates to lamellar gel detergent liquids.
BACKGROUND
[0002] For hand wash detergent liquids with high cleaning power it can be useful to use
linear alkylbenzenesulphonate (LAS) rich mixtures with alkylethoxy sulphate (AES),
in particular the sodium salts of these detergent surfactants. To give the correct
sensory properties for the liquids, they should ideally have a thick and possibly
shear thinning viscosity. This Viscosity profile also enables them to suspend any
solid particles that the formulator desires to include. One possible route to the
desired rheology is to formulate the liquid so that it forms a stable lamellar gel.
In practice this has proved difficult to do unless high electrolyte (citrate) levels
are used. Stability is also compromised as the amount of ethoxylation of the AES drops
from 3 to 1 and as the amount of total surfactant in the liquid drops below 20 wt%.
The formulator would prefer to use AES with lower ethoxylation as it is less expensive
and more widely available. Formulations with high levels of citrate or other electrolyte
to generate the lamellar phase are less desirable because this electrolyte does not
contribute significantly to the cleaning performance, so it is adding cost and chemicals
for no consumer perceivable benefit. Such addition is also undesirable from an environmental
perspective. The use of lower levels of surfactant system is also desirable from an
environmental standpoint and the formulation space freed up by this reduction (and
the possible loss of cleaning power) can be rebalanced by the inclusion of high weight
efficiency performance additives. This approach to formulation of detergent liquids
and information about suitable performance additives is described in
WO09153184.
[0003] US2011220537 (P&G) relates to a similar problem. The solution adopted is to add an external structurant
to the liquid. The external structurant is a specific pH tunable amido gellant. Because
they are externally structured the liquids do not contain electrolyte at high enough
levels to make them into internally structured lamellar gels. All the liquids exemplified
are isotropic liquids with a gelled structuring premix of the amido compound added
to thicken them as the pH is adjusted. These liquids are not stable lamellar gels
and the cost and complexity of the special external structuring system and its pH
sensitivity makes such a solution unsuited for many commercial detergent liquid applications,
especially hand wash applications where near neutral pH is an advantage and formulation
cost is a major issue.
[0004] It is desirable to solve the problem of rheology adjustment by use of an internally
structured stable lamellar gel detergent liquid composition.
[0005] US6277803 (Colgate), discloses a series of examples of electrolyte gelled high active detergent
liquids (35% AD) comprising a surfactant system of alkyl olefin sulphonate (AOS),
LAS and amine oxide (AO). AES is absent in the examples. High active compositions
form stable gels relatively easily.
[0006] US2011209291 (P&G), describes detergent liquids with an external structuring system. The comparative
examples A and B omit the external structuring system. Comparative Example A uses
a low level of amine oxide and an excess of AES over LAS. This should be an isotropic
liquid although it might be an unstable lamellar gel if electrolyte were added. We
have found that stable lamellar gels are very difficult to make when the LAS / AES
ratio is less than 1:1. There is an excess of AES as in Comparative Example A.
[0007] US2005020467 (Colgate), discloses compositions that must comprise 10 to 20% of AES (claim 1).
Only example 1 has this much AES. The mixed LAS system used in example 1 gives a total
of 12.02, the AES level is 11.5. Thus this composition does have an excess of LAS
over AES. The amount of the optional amine oxide in example 1 is 5%, which is high.
There is no electrolyte present at a high enough level to make this into a lamellar
gel. This is supported by the information that it could not suspend gelatin beads.
The level of amine oxide is too high and the level of electrolyte too low to form
a stable gel.
[0008] US6972278 (Unilever), relates to lamellar gel detergent liquids that are gelled by addition
of fatty acid. The exemplified compositions have an excess of AES over LAS and no
AO. Nonionic (NI) is typically present too. The presence of high levels of fatty acid
suppresses foam generation which makes these liquids unsuitable for hand wash and
top loading automatic applications.
[0009] US4615819 (Unilever), describes high active detergent liquids, some comprising LAS and AES,
which are forced into a lamellar gel phase by adding high levels of urea as gelling
agent. No amine oxide was used. Adding high levels of gelling agent adds to cost and
makes it more difficult to include other useful ingredients into the compositions.
There is also consumer resistance to use of urea.
[0010] US7297674 (Unilever), describes electrolyte gelled low active LAS / nonionic detergent liquids
which have mono or polyethylene glycol dialkyl ether added to improve their clarity.
The examples in this document do not comprise the AES that is desired for hand wash.
It is suggested to be possible to add AES but there is no disclosure that this may
cause problems for maintenance of stable lamellar gels and no suggestion to add any
amine oxide to the compositions. Furthermore the nonionic content would make the exemplified
liquids unsuitable for hand wash where foam generation is desired.
[0011] US7022657 (Unilever), relates to detergent liquids that are gelled by addition of a fatty alcohol.
Comparative composition D, without the fatty alcohol gelling agent, is isotropic.
It has more AES than LAS and also contains a relatively high level of nonionic. Composition
C is gelled by addition of the fatty alcohol. There is no suggestion to add amine
oxide to these compositions. Fatty alcohols suppress foam and are undesirable in hand
wash compositions.
[0012] US2004058840 (Unilever), makes a general disclosure of lamellar gels formed with LAS and AES.
There is no suggestion to use amine oxide. No AES is used in the examples.
[0013] "Gel" as used herein means a shear thinning, lamellar gel, with a pouring viscosity
in the range of from 100 to 5000 mPas (milli Pascal seconds), more preferably less
than 3000 mPas, most preferably less than 1500 mPas, and which also has a critical
shear stress higher than 10 Pa, more preferably higher than 15 Pa, most preferably
higher than 20 Pa, but not exceeding 100 Pa.
[0014] The concept of "gel" in the art is frequently not well defined. The most common,
loose definition, however, is that a gel is a thick liquid. Nevertheless, a thick
liquid may be a Newtonian fluid, which does not change its viscosity with the change
in flow condition, such as honey or syrup. This type of thick liquid is very difficult
and messy to dispense. A different type of liquid gel is shear-thinning, i.e. it is
thick at low shear condition (e.g. at rest) and thin at high flow rate condition.
[0015] Shear-thinning rheological properties can be measured with a viscometer or a sophisticated
rheometer and the correct measurement spindle. The plot of viscosity vs. shear rate
will reveal whether the sample is shear thinning or not.
[0016] As used herein, "pouring viscosity" means viscosity measured at a shear rate of 20
s
-1. It can be read off the plot of viscosity vs. shear rate.
[0017] The critical shear stress is the shear stress at which viscosity drops dramatically.
[0018] As used herein, "lamellar" means that liquid crystals within the gel have lipid layers
(sheets). Lamellar structures can be detected by polarized light microscope. The majority
of these lamellar structures remain in a mixture of sheet and vesicles. Stable lamellar
phases are in fact the results of a mixed mesophase. This is where the lamellar phase
is coexistent with another elongated micelle phase (isotropic).
[0019] As used herein, "lamellar gels" means gels that have lamellar phase structure, either
alone or intermixed with isotropic phase (known as L1).
SUMMARY OF THE INVENTION
[0020] A lamellar gel shear thinning aqueous detergent liquid comprising from 5 to 25 wt%,
preferably 8 to 18 wt%, of a detergent surfactant system, which surfactant system
comprises:
- a) Alkyl benzene sulphonate,
- b) (poly)ethoxylated alkyl sulphate, preferably SLES 1 EO,
The ratio of a) to b) being from 4:1 to 1:1,
- c) at least 1 wt% amine oxide, and,
- d) optionally nonionic surfactant,
The ratios of (a+b) to c being at least 10:1 and (a+b) to d being at least 2:1, the
liquid further comprising:
- e) from 1 to 12 wt%, preferably from to 4 to 9 wt% electrolyte,
- f) water, and
- g) at least 2 wt% performance additives selected from soluble benefit agents, insoluble
benefit agents and mixtures thereof.
[0021] Advantageously the performance additives are selected from the group comprising:
enzymes, polymers, fluorescent whitening agents, shading dyes, encapsulated perfume,
encapsulated fabric care materials.
[0022] Preferably the composition comprises less than 0.5 wt%, more preferably, zero nonionic
surfactant.
[0023] Preferably the composition comprises less than 1 wt% soap/fatty acid.
[0024] The SLES 1 EO is the more difficult to make into a stable gel. The invention is particularly
useful to allow the lower ethoxylation of SLES 1 EO and SLES 2EO to be utilised in
the compositions. The invention is particularly useful for compositions which comprise
SLES 1 EO.
[0025] Addition of the amine oxide provides stable LAS rich relatively low (10% and 15%)
active detergent (AD) lamellar gels using as little as 2 wt% citrate as lamellar generator
electrolyte.
[0026] The resulting liquid compositions are stable, thick and have rheology that can suspend
microcapsules, such as perfume encapsulates.
[0027] The alkyl benzene sulphonate is preferably linear alkylbenzene sulphonate.
DETAILED DESCRIPTION OF THE INVENTION
Surfactants
[0028] Surfactants assist in removing soil from the textile materials and also assist in
maintaining removed soil in solution or suspension in the wash liquor. Anionic or
blends of anionic and nonionic surfactants are a preferred feature of the compositions.
The amount of anionic surfactant is preferably at least 5 wt%. Preferably, the anionic
surfactant forms the majority of the surfactant.
Anionic
[0029] The composition comprises an alkylbenzene sulphonates, preferably a linear alkylbenzene
sulphonate having an alkyl chain length of C
8-C
15. The counter ion for anionic surfactants is generally an alkali metal, typically
sodium, although other counter-ions for example MEA, TEA or ammonium can be used.
[0030] Suitable linear alkyl benzene sulphonate surfactants include Detal LAS with an alkyl
chain length of from 8 to 15, more preferably 12 to 14.
[0031] The composition further comprises an alkyl polyethoxylate sulphate anionic surfactant
of the formula (I):
RO(C
2H
40)
xSO
3-M
+ (I)
where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated,
M is a cation which makes the compound water-soluble, especially an alkali metal,
ammonium or substituted ammonium cation, and x averages from 1 to 15.
[0032] Preferably R is an alkyl chain having from 12 to 16 carbon atoms, M is Sodium and
x averages from 1 to 3, preferably x is 1; This is the anionic surfactant sodium lauryl
ether sulphate (SLES). It is the sodium salt of lauryl ether sulphonic acid in which
the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 1
mole of ethylene oxide per mole.
Nonionic
[0033] If nonionic surfactants are used then suitable examples include primary and secondary
alcohol ethoxylates, especially C
8-C
20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide
per mole of alcohol, and more especially the C
10-C
15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to
10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants
also include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide).
Mixtures of nonionic surfactant may be used. When included therein the composition
contains from 0.2 wt% to 10 wt%, preferably less than 1 wt% nonionic.
Amine Oxide
[0034] The compositions comprise at least 1 wt% and prefereably no more than 10 wt% of an
amine oxide of the formula (II):
R
1 N(O)(CH
2R
2)
2 (II)
In which R
1 is a long chain moiety each CH
2R
2 are short chain moieties. R
2 is preferably selected from hydrogen, methyl and -CH
2OH. In general R
1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated,
preferably, R
1 is a primary alkyl moiety. R
1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
[0035] Preferred amine oxides have R
1 is C
8-C
18 alkyl, and R
2 is H. These amine oxides are illustrated by C
12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
[0036] A preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine
oxide or DDAO. Such an amine oxide material is commercially available from Huntsman
under the trade name Empigen® OB.
[0037] Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl
Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine
oxide manufacturers.
[0038] Whereas in certain of the preferred embodiments R
2 is H, it is possible to have R
2 slightly larger than H. Specifically, R
2 may be CH
2OH, for example: hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine
oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
[0039] Preferred amine oxides have the formula (IV):
O
- - N
+(Me)
2R
1 (IV)
where R
1 is C
12-16 alkyl, preferably C
12-14 alkyl; Me is a methyl group.
Additional surfactants
[0040] Other surfactants than the preferred LAS, SLES, and amine oxide may be added to the
mixture of detersive surfactants. However cationic surfactants are preferably substantially
absent.
[0041] Some zwitterionic surfactant, for example carbobetaine, may be present. A preferred
zwitterionic material is a carbobetaine available from Huntsman under the name Empigen®
BB. Betaines improve particulate soil detergency in the compositions.
[0042] Although less preferred, some alkyl sulphate surfactant (PAS) may be used, especially
the non-ethoxylated C
12-15 primary and secondary alkyl sulphates. A particularly preferred material, commercially
available from BASF, is Sulfopon 1214G.
Electrolyte
[0043] The preferred electrolyte is sodium citrate, especially trisodium citrate. Other
suitable electrolytes include: Sodium Formate, Sodium acetate, Potassium acetate,
Sodium thiosulphate and Sodium sulphite.
Performance additives
EPEI
[0044] A particularly preferred class of polymer for use in the composition is polyethylene
imine, preferably modified polyethylene imine. Polyethylene imines are materials composed
of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen
is replaced by another chain of ethylene imine units. These polyethyleneimines can
be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst
for example carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide,
hydrochloric acid, acetic acid, and the like. Specific methods for preparing these
polyamine backbones are disclosed in
U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939;
U.S. Pat. No. 3,033,746, Mayle et al., issued May 8, 1962;
U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16, 1940;
U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and
U.S. Pat. No. 2,553,696, Wilson, issued May 21, 1951.
[0045] Preferably, the EPEI comprises a polyethyleneimine backbone of about 300 to about
10000 weight average molecular weight; wherein the modification of the polyethyleneimine
backbone is intended to leave the polymer without quaternisation. Such nonionic EPEI
may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified
PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine
backbone. The ethoxylation may range from 9 to 40 ethoxy moieties per modification,
preferably it is in the range of 16 to 26, most preferably 18 to 22.
[0046] The polyethyleneimine polymer is present in the composition preferably at a level
of between 0.01 and 25 wt%, but more preferably at a level of at least 2 wt% and/or
less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non-soap surfactant
to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, or even to 5:1.
Polyester soil release polymer
[0047] The compositions may include 0.5 wt% or more of a soil release polymer which is substantive
to polyester fabric. Such polymers typically have a fabric substantive midblock formed
from propylene terephthalate repeat units and one or two end blocks of capped polyalkylene
oxide, typically PEG 750 to 2000 with methyl end capping.
Other polymers
[0048] In addition to a soil release polymer there may be used dye transfer inhibition polymers,
anti redeposition polymers and cotton soil release polymers, especially those based
on modified cellulosic materials.
Enzymes
[0049] It is preferable that at least one or more enzymes may be present in the compositions.
Preferably at least two, more preferably at least three different classes of enzymes
are used in combination. Lipase is a particularly preferred enzyme. The composition
preferably contains from about 5 to about 20000 LU/g of a lipase.
[0050] Protease is also preferably present. Suitable proteases include those of animal,
vegetable or microbial origin. Microbial origin is preferred.
[0051] Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin.
Chemically modified or protein engineered mutants are included.
Suitable cellulases include those of bacterial or fungal origin. Chemically modified
or protein engineered mutants are included.
[0052] Pectate lyases (also called polygalacturonate lyases) may be included. Examples of
pectate lyases include pectate lyases that have been cloned from different bacterial
genera for example Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from
Bacillus subtilis and
Bacillus sp.
[0053] Examples of suitable mannanases (EC 3.2.1.78) include mannanases of bacterial and
fungal origin. In a specific embodiment the mannanase is derived from a strain of
the filamentous fungus genus Aspergillus, preferably
Aspergillus niger or Aspergillus aculeatus.
[0054] The enzyme and any perfume/fragrance or pro-fragrance present may show some interaction
and should be chosen such that this interaction is not negative. Some negative interactions
may be avoided by encapsulation of one or other of enzyme and pro-fragrance and/or
other segregation within the product.
Enzyme Stabilizers
[0055] Any enzyme present in the composition may be stabilized using conventional stabilizing
agents, e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar
alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate
ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid,
and the composition may be formulated as described in e.g.
WO 92/19709 and
WO 92/19708.
Lignin compounds
[0056] When a lipase enzyme is included a lignin compound may be used in the composition
in an amount that can be optimised by trial and error. Lignin is a component of all
vascular plants, found mostly between cellular structures but also within the cells
and in the cell walls.
[0057] Preferably the lignin compound comprises a lignin polymer and more preferably it
is a modified lignin polymer. A modified lignin polymer as used herein is lignin that
has been subjected to a chemical reaction to attach chemical moieties to the lignin
covalently. The attached chemical moieties are preferably randomly substituted.
Fluorescent Agents
[0058] It may be advantageous to include fluorescer in the compositions. Usually, these
fluorescent agents are supplied and used in the form of their alkali metal salts,
for example, the sodium salts. The total amount of the fluorescent agent or agents
used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to
0.5 wt %.
[0059] Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade
Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure
Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g.
Blankophor SN.
[0060] Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole,
disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2'
disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}
stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
Bleach Catalysts
[0061] Compositions may comprise a weight efficient bleach system. Such systems typically
do not utilise the conventional percarbonate and bleach activator approach. An air
bleach catalyst system is preferred. Suitable complexes and organic molecule (ligand)
precursors for forming complexes are available to the skilled worker, for example,
from:
WO 98/39098;
WO 98/39406,
WO 97/48787,
WO 00/29537;
WO 00/52124, and
WO00/60045, incorporated by reference. An example of a preferred catalyst is a transition metal
complex of MeN4Py ligand (N,N-bis(pyridin-2-yl-methyl)-1-,1-bis(pyridin-2-yl)-1-aminoethane).
Suitable bispidon catalyst materials and their action are described in
WO02/48301. The bleach catalyst may be encapsulated to reduce interaction with other components
of the liquid during storage.
[0062] Photobleaches may also be employed. A "photobleach" is any chemical species that
forms a reactive bleaching species on exposure to sunlight, and preferably is not
permanently consumed in the reaction. Preferred photo-bleaches include singlet oxygen
photo-bleaches and radical photo-bleaches. Suitable singlet oxygen photo-bleaches
may be selected from, water soluble phthalocyanine compounds, particularly metallated
phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate,
nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has
1-4 SO
3X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such
compounds are described in
WO2005/014769 (Ciba).
[0063] When present, the bleach catalyst is typically incorporated at a level of about 0.0001
to about 10 wt%, preferably about 0.001 to about 5 wt%.
Perfume
[0064] A free oil perfume is preferably used. In addition, a particularly preferred option
is to use an encapsulated perfume.
[0065] It is even more preferable that the perfume is not only encapsulated but also that
the encapsulated perfume is provided with a deposition aid to increase the efficiency
of perfume deposition and retention on fabrics. The deposition aid is preferably attached
to the encapsulate by means of a covalent bond, entanglement or strong adsorption,
preferably by a covalent bond or entanglement.
Further Optional performance additives
[0066] The compositions may contain one or more other ingredients. Such ingredients include
viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering
agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants,
sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and
ironing aids. The compositions may further comprise colorants, pearlisers and/or opacifiers,
and shading dye.
Shading dyes
[0067] Shading dye can be used to improve the performance of the compositions. Preferred
dyes are violet or blue. It is believed that the deposition on fabrics of a low level
of a dye of these shades, masks yellowing of fabrics. A further advantage of shading
dyes is that they can be used to mask any yellow tint in the composition itself. Examples
of shading dyes are alkoxylated thiophene dyes, acid violet 50, direct violet 35,
direct violet 99, direct violet 9, solvent violet 13, disperse violet 28, disperse
blue 165.
[0068] Shading dye can be used in the absence of fluorescer, but it is especially preferred
to use a shading dye in combination with a fluorescer, for example in order to reduce
yellowing due to chemical changes in adsorbed fluorescer.
Builders and sequestrants
[0069] The detergent compositions may also optionally contain further organic detergent
builder or sequestrant material. Examples include the alkali metal, succinates, malonates,
carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid,
mellitic acid, benzene and polycarboxylic acids. Other examples are DEQUEST
™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy
phosphonates.
[0070] Other suitable organic builders include the higher molecular weight polymers and
copolymers known to have builder properties. For example, such materials include appropriate
polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and
their salts, for example those sold by BASF under the name SOKALAN
™.
[0071] If utilized, the further organic builder materials may comprise from about 0.5% to
20 wt%, preferably from 1 wt% to 10 wt%, of the composition. The preferred further
builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
A preferred sequestrant is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid), for
example sold as Dequest 2010. Also suitable but less preferred as it gives inferior
cleaning results is Dequest® 2066 (Diethylenetriamine penta(methylene phosphonic acid
or Heptasodium DTPMP).
Buffers
[0072] The presence of some buffer is preferred for pH control; preferred buffers are MEA,
and TEA. If present they are preferably used in the composition at levels of from
1 to 15 wt%.
Visual Cues
[0073] The compositions may comprise visual cues of solid material that is not dissolved
in the composition. Preferred visual cues are lamellar cues formed from polymer film
and possibly comprising functional ingredients that may not be as stable if exposed
to the alkaline liquid. Enzymes and bleach catalysts are examples of such ingredients.
Also perfume, particularly microencapsulated perfume.
Packaging and dosing
[0074] The liquids may be packaged as unit doses in polymeric film adapted to be insoluble
until added to the wash water. More preferred the liquids are supplied in multiuse
plastics packs with a top or bottom closure. A dosing measure may be supplied with
the pack either as a part of the cap or as an integrated system.
[0075] The invention will now be further described with reference to the following nonlimiting
examples.
EXAMPLES
[0076] 3 LAS/SLES ratios were tested. Each ratio was repeated with 3 types of SLES as the
AES (SLES 1 EO, 2EO, 3EO). After mixing the surfactants the sample was left for one
day to equilibrate. To complete the matrix an amount of electrolyte was then added
to the sample in an amount from zero to 15 wt% as indicated. The resulting compositions
were left to equilibrate for a second day. The Electrolyte used was in all cases Trisodium
Citrate (TSC). The levels of electrolyte added were, 0, 2, 4, 6, 8, 10, 12.5, and
15 wt%. We always used the same order of addition.
[0077] Each composition was then stability tested for one week (Freeze Thaw: 21°C down to
-15°C).
[0078] In Tables 1 to 12:
- AD = active detergent, surfactant weight percent of composition.
- ISO = isotropic liquid
- ULG = Unstable lamellar gel
- SLG = Stable lamellar gel
[0079] Compositions without any AO lamellar gel stabiliser are comparative (Tables 1, 3,
5, 7, 9 and 11).
[0080] Compositions with AO are detailed in Tables 2, 4, 6, 8, 10 and 12.
The amount of EO in the SLES seems to be important for the formation of lamellar liquids
(3EO>2EO>1 EO). Without AO no composition was stable at 10 wt% AD with 1 EO. In the
absence of AO, high levels of citrate were needed to stabilise the lamellar gels using
2EO and 3EO. This level of citrate is undesirable for commercial products.
[0081] Even at 15 wt% AD, it remained impossible to form stable lamellar gels without AO
at lower electrolyte concentrations. The stable lamellar gel compositions are all
found in the LAS rich ratios.
[0082] At 15 wt% AD there are 3 compositions that are stable for SLES 2EO and six for SLES
3EO. As with the 10 wt% AD without AO compositions, these stable compositions require
high (10+ wt%) electrolyte concentrations. This level of electrolyte is undesirable
for a commercial product because it interferes with other salt based components that
the formulator wishes to include.
[0083] Again it is impossible to form a stable lamellar gel with SLES 1 EO in these comparative
compositions. However, the increase in active level to 15 wt% can help to drive lamellar
formation, especially for SLES 3EO.
[0084] Incorporation of amine oxide (1.5 wt% Empigen® OB) into the compositions improves
the lamellar gel formation. This is especially useful at lower electrolyte concentration
and for compositions using the SLES 1 EO. The greatest benefit occurs for the lower
surfactant level of 10 wt% (anionic).
[0085] With amine oxide present there are opportunities to generate stable lamellar gels
that survive freeze thaw with every type of SLES (1 EO to 3EO).
[0086] At 15 wt% AD with 1.5 wt% Empigen® OB, lamellar gel formation is highly boosted compared
to the formulation without amine oxide. The stable gels are easier to form with increasing
degree of ethoxylation of the SLES.
[0087] The formation of stable lamellar gels becomes even easier as the AD is further increased
to 20 wt%. When it gets as high as 25 wt% the benefit of inclusion of AO is minimal
because the higher active levels already provide for stable lamellar gel formation
at these surfactant ratios.
Table 1 - LAS /SLES 1 EO 10 wt% AD (Comparative)
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
ULG |
| 6 / 4 |
ISO |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
| 5 / 5 |
ISO |
ISO |
ISO |
ISO |
ISO |
ISO |
ISO |
ISO |
Table 2 - LAS /SLES 1 EO 10 wt% AD + 1.5 wt% AO
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
ULG |
| 6 / 4 |
ULG |
SLG |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
| 5 / 5 |
ISO |
ULG |
ULG |
ULG |
ULG |
ULG |
ULG |
SLG |
Table 3 - LAS /SLES 2 EO 10 wt% AD (Comparative)
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
| 6 / 4 |
ISO |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
SLG |
| 5 / 5 |
ISO |
ISO |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
Table 4 - LAS /SLES 2 EO 10 wt% AD + 1.5 wt% AO
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ULG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 6 / 4 |
ULG |
SLG |
ULG |
ULG |
SLG |
SLG |
SLG |
ULG |
| 5 / 5 |
ISO |
ULG |
ULG |
ULG |
ULG |
ULG |
SLG |
SLG |
Table 5 - LAS /SLES 3 EO 10 wt% AD (Comparative)
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
SLG |
| 6 / 4 |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
SLG |
| 5 / 5 |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
Table 6 - LAS /SLES 3 EO 10 wt% AD + 1.5 wt% AO
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ULG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 6 / 4 |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 5 / 5 |
ULG |
SLG |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
Table 7 - LAS /SLES 1 EO 15 wt% AD (Comparative)
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
ULG |
ULG |
| 6 / 4 |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
ULG |
| 5 / 5 |
ISO |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
Table 8 - LAS /SLES 1 EO 15 wt% AD + 1.5 wt% AO
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
SLG |
ULG |
ULG |
SLG |
SLG |
ULG |
ULG |
ULG |
| 6 / 4 |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 5 / 5 |
ULG |
ULG |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
Table 9 - LAS /SLES 2 EO 15 wt% AD (Comparative)
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
SLG |
| 6 / 4 |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
| 5 / 5 |
ISO |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
Table 10 - LAS /SLES 2 EO 15 wt% AD + 1.5 wt% AO
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 6 / 4 |
SLG |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
| 5 / 5 |
ISO |
ULG |
ULG |
ULG |
ULG |
ULG |
SLG |
SLG |
Table 11 - LAS /SLES 3 EO 15 wt% AD (Comparative)
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
| 6 / 4 |
ISO |
ISO |
ULG |
ULG |
ULG |
ULG |
SLG |
SLG |
| 5 / 5 |
ISO |
ISO |
ISO |
ISO |
ULG |
ULG |
ULG |
SLG |
Table 12 - LAS /SLES 3 EO 15 wt% AD + 1.5 wt% AO
| LAS/SLES ratio |
Wt% Trisodium citrate added |
| 0 |
2 |
4 |
6 |
8 |
10 |
12.5 |
15 |
| 7 / 3 |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 6 / 4 |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
SLG |
SLG |
| 5 / 5 |
ISO |
ULG |
ULG |
ULG |
ULG |
SLG |
SLG |
SLG |
Table 13 - Lamellar gel detergent compositions
| Ingredient |
Comp A |
Comp B |
Comp C |
| LAS |
9 |
7 |
8.75 |
| NI |
0 |
0 |
0 |
| SLES 1 EO |
6 |
0 |
3.75 |
| SLES 2 EO |
0 |
3 |
0 |
| Amine Oxide |
1.5 |
1.5 |
1.5 |
| Tri-sodium citrate |
9 |
7.41 |
5.66 |
| Encap perfume |
0.3 |
0.3 |
0.3 |
| Free oil perfume |
1 |
1 |
1 |
| Enzymes |
0.1 |
0.1 |
0.1 |
| Shading dye |
0.01 |
0.01 |
0.01 |
| TEA |
2 |
2 |
2 |
| NaOH |
0.8 |
0.55 |
0.77 |
| Dequest 2066 |
0.34 |
0.34 |
0.34 |
| Proxel GXL |
0.01 |
0.01 |
0.01 |
| Balance water |
Up to 100% |
Up to 100% |
Up to 100% |
[0088] To show that the compositions were stable lamellar gels their viscosity was measured
after storage. The results are given in Table 14.
Table 14
| Composition |
Yield stress (Pa) |
Viscosity @ 1s-1 Pa s |
Viscosity @ 21 s-1 Pa s |
Viscosity @ 106s-1 Pa s |
| Comp A |
6.78 |
15.786 |
1.211 |
0.367 |
| Comp B |
0.172 |
0.443 |
0.099 |
0.054 |
| Comp C |
3.99 |
5.545 |
0.523 |
0.192 |