TEPZZ_664 55B_T

(19)

(11) EP 1 664 255 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C11D 1/83 (2006.01) C11D 17/00 (2006.01)
04.12.2013 Bulletin 2013/49 C11D 3/20 (2006.01)

(21) Application number: 04764443.0 (86) International application number:

PCT/EP2004/009466
(22) Date of filing: 23.08.2004
(87) International publication number:
WO 2005/026303 (24.03.2005 Gazette 2005/12)

(54) GEL LAUNDRY DETERGENT COMPOSITION

GELARTIGE WÄSCHEWASCHMITTELZUSAMMENSETZUNG
COMPOSITION DE DETERGENT EN GEL POUR LESSIVE

(84) Designated Contracting States: (72) Inventor: HINES, John David,

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR c/o Unilever R & D
HU IE IT LI LU MC NL PL PT RO SE SI SK TR Bebington, Wirral Merseyside CH63 3JW (GB)

(30) Priority: 16.09.2003 EP 03255759 (74) Representative: Bristow, Stephen Robert et al

Unilever Patent Group
(43) Date of publication of application: Colworth House
07.06.2006 Bulletin 2006/23 Sharnbrook
Bedford, MK44 1LQ (GB)
(73) Proprietors:
• Unilever N.V. (56) References cited:
3013 AL Rotterdam (NL) EP-A- 0 724 011 WO-A-94/28108
Designated Contracting States: WO-A-99/06519 US-A- 5 538 662
AT BE BG CH CZ DE DK EE ES FI FR GR HU IT LI US-B1- 6 362 156
LU MC NL PL PT RO SE SI SK TR
• Unilever PLC
London
EC4Y 0DY (GB)
Designated Contracting States:
CY GB IE
EP 1 664 255 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 664 255 B1

Description

Field of the invention

5 [0001] The present invention relates to stable gel laundry detergent compositions. In particular, the invention relates
to stable, transparent, shear thinning, heavy-duty, lamellar-phase gel laundry detergent compositions, comprising anionic
and nonionic surfactant material, and preferably a gelling agent.

Background of the invention

10
[0002] For a variety of reasons, it is often greatly desirable to suspend particles in liquid detergent compositions. For
example, because there are certain components (e.g. bleaches, enzymes, perfumes) which readily degrade in the hostile
environment of surfactant-containing detergent liquids, these components are often protected in capsule-type particles
(see, for example, US-A-5,281,355) and these capsule-type particles may be suspended in liquid detergent compositions.
15 Other components that may be protected and suspended in this way are, for instance, polyvinylpyrrolidone, aminosili-
cones, soil release agents and antiredeposition agents. Such particles may vary significantly in size but, usually, their
size is in the range of from 300 to 5000 micrometers.
[0003] Furthermore, when the liquid detergent composition is translucent or transparent, it may be desirable to suspend
coloured particles or capsules of similar size in said liquid composition so as to improve the visual appearance thereof.
20 [0004] Shear thinning gel-type detergent compositions are generally suitable for stably suspending particles therein,
since they usually have adequate viscosity when in rest or under very low shear. On the other hand, owing to their shear
thinning properties, such gel-type compositions have much lower viscosity when under pouring shear.
[0005] One way of formulating such gel-type detergents is by changing a non-gelled formulation so as to form an
internal lamellar-phase structure therein which structure gives the desired properties to the thus-formed gel-type deter-
25 gent.
[0006] WO-A-99/27065, WO-A-99/06519 and US-A-5,820,695 disclose gel-type laundry detergent compositions hav-
ing an internal structure. These documents teach systems wherein soap or fatty acid in combination with sodium sulphate
and a rather specific surfactant system are used to form a gelled structure by the formation of lamellar phases.
[0007] Alternatively, shear thinning gel-type detergent compositions may be formulated by adding specific ingredients
30 to a non-gelled detergent formulation, typically at low dosage, so as to induce gellation.
[0008] Examples of this route for preparing gelled detergents are disclosed in US-A-6,362,156. More specifically, this
document discloses shear thinning, transparent gel-type laundry compositions comprising a polymer gum, such as
Xanthan gum, which gum is capable of forming stable continuous gum networks which can suspend particles.
[0009] However, when using a polymer additive such as the polymer gum disclosed in US-A-6,362,156, so as to form
35 the gelling structure, it is generally required to carry out several specific steps in the manufacturing process in order that
the gel structure is properly formed. These steps are relatively costly and make the manufacturing process rather time-
consuming.
[0010] In addition, the ’structure’ of the gel-type detergent composition disclosed by US-A-6,362,156 resides in the
dispersed polymeric network and not in the continuous bulk phase, which remains essentially isotropic in nature. For
40 that reason, particles suspended in this system tend -over time- to migrate through the network leading to asymmetrical
dispersions which is clearly not desirable for a gel-type detergent product.
[0011] Alternatively, US-A-5,952,286 discloses skin cleansing compositions comprising lamellar phase dispersions
from rad micellar surfactant systems, and additionally a structurant for establishing the lamellar phase, whereby said
structurant may be a fatty alcohol. These compositions are structured as lamellar vesicles, and are opaque, and therefore
45 unsuitable for the visual display of suspended particles or capsules.
[0012] Furthermore, copending US patent application 10/251,738 and European patent application 02257682.1 dis-
close stable shear-thinning tranlucent gel laundry detergent formulations comprising a fatty acid respectively a fatty
alcohol as gelling agent. Without wishing to be bound by theory, it is believed that these types of gelling agent interact
with aggregates present in the respective detergent formulations so as to promote the formation of planar lamellar
50 structures similar to those found in internally structured detergent gels, such as e.g. disclosed by WO-A-99/27065.
[0013] However, a major disadvantage of this technology relating to shear-thinning, stable, structured detergent gels
is that such products structured by lamellar phases are often rather turbid in appearance. As a consequence, their
transparency often leaves to be desired.
[0014] In view of this, it is an object of the present invention to find a stable shear-thinning lamellar-phase gel laundry
55 detergent formulation which is highly transparent or translucent and provides favourable visual appearance so as to
clearly demonstrate the presence of any particles, beads or capsules suspended therein. It is another object of the
invention to provide a shear thinning lamellar-phase gel laundry detergent formulation that has both favourable trans-
parency and cleaning performance.

2
 EP 1 664 255 B1

[0015] It has been surprisingly found that these objects could be achieved by applying the shear thinning transparent
gel laundry detergent composition of the present invention, containing a clarity-improving agent, as specified in claim 1.

Definition of the invention

5
[0016] Accordingly, the present invention provides a shear thinning, transparent lamellar-phase gel laundry detergent
composition, comprising a surfactant system containing surfactant material selected from an anionic surfactant, a nonionic
surfactant or a mixture thereof, and from 0.1 to 10% by weight of a clarity improving agent being a glycol dialkyl ether
selected from a mono- or polyethylene glycol dialkyl ether having the formula
10
(CpH2p+1) O - (CH2CH2O)n - (CqH2q+1) (I),

a mono- or polypropylene glycol dialkyl ether having the formula

15 (CpH2p+1)O - (CH2CH(CH3)O)n - (C qH2q+1) (II),

and mixtures thereof,

wherein p and q independently are integers in the range of from 1 to 5, and n is an integer in the range of from 1 to 50,
preferably 1 to 10, more preferably 1 to 5, wherein said composition is structured internally by a lamellar phase such
20 that the phase volume of material present within the lamellar structure is at least 0.75.
[0017] The present invention is also concerned with the use of a glycol dialkyl ether as a clarity improving agent in a
shear thinning, transparent, lamellar-phase gel laundry detergent composition of the invention.
[0018] The present invention further provides a method of improving the clarity and transparency of a shear thinning,
transparent, lamellar-phase gel laundry detergent composition, said method comprising the steps of
25
(a) preparing said composition by mixing the ingredients thereof, said composition comprising a surfactant system
containing surfactant material selected from an anionic surfactant, a nonionic surfactant or a mixture thereof, and
(b) adding from 0.1 to 10% by weight of a glycol dialkyl ether according to the invention, to said composition, whereby
the resulting composition is structured internally by a lamellar phase such that the phase volume of material present
30 within the lamellar structure is at least 0.75.

Detailed description of the invention

[0019] The gel laundry detergent composition of the invention is structured internally by a lamellar phase such that
35 the phase volume of material present within the lamellar structure is at least 0.75 and preferably greater than 0.9. In
other words, the neat liquid crystal lamellar phase occupies at least 75%, preferably at least 90% of the volume occupied
by the detergent composition of the invention. Most preferably, the detergent composition of the invention is characterised
by the substantial absence of any other phases. As a practical test for determining this property of a composition of the
invention, this composition is centrifuged at 25° C and at 2000 x g (where g = 9.81 ms-2) for 6 hours; after this treatment
40 said composition does not yield any separate layer of more than 25 of the total height of the centrifuged composition
when held in a cylindrical container of uniform thickness.
[0020] The lamellar phase composition of the invention is characterised by a neat liquid crystal lamellar phase, com-
prising the surfactants and, optionally, the gelling agents present in the composition, and arranged at the molecular level
in planar lamellar bi-layers with the other ingredients of the composition dispersed in the spaces between the hydrophilic
45 faces of the lamellar sheets. Such a lamellar phase is conventionally referred to in several ways: as "neat phase", Lam
phase (Laughlin), L phase (Luzatti), G phase (Winsor) or D phase (Ekwall) (see RG Laughlin, "The Aqueous Phase
Behaviour of Surfactants", for example). The presence of the lamellar phase can be observed optically using birefringence.
[0021] The microstructure of such a lamellar phase system at the mesoscopic (as opposed to molecular) level may
be vescicular or continuous planar or a combination thereof including any other combinations of variable curvatures.
50 Such a lamellar phase gel laundry detergent composition is desirably highly transparent, such that particles (if present)
can be suspended therein and can easily be seen, for improving visual appearance.
[0022] By "transparent", it is meant that light is easily transmitted through the composition of the invention and that
objects on one side of the gel composition are at least partially visible from the other side of the composition. Alternatively,
the transparency of the gel detergent composition is defined in that said composition has suitably at least 50%, preferably
55 at least 70% transmittance of light using a 1 centimeter cuvette at a wavelength of 410-800 nm, preferably 570-690nm,
whereby the composition is measured in the absence of dyes.
[0023] The lamellar-phase gel composition of the invention is also preferably an aqueous composition having a free
water concentration of more than 25%, more preferably more than 50% by weight.

3
 EP 1 664 255 B1

[0024] Furthermore, the lamellar-phase gel laundry detergent composition of the invention is generally relatively vis-
cous, and has preferably a viscosity of at least 100 Pa.s, more preferably at least 500 Pa.s, when in rest or up to a
shear stress of 10 Pa.
[0025] As a consequence, the composition of the invention is very suitable for stably suspending relatively large
5 particles, such as those having a size of from 300 to 5000 microns.
[0026] Furthermore, syneresis leading to a net migration of suspended matter has never been observed in the gel
composition of the invention. Preferably, the composition of the invention contains 0.1 to 10% by weight of suspended
particles having a size within the range mentioned above.
[0027] On the other hand, the shear thinning properties of the gel laundry detergent composition of the invention are
10 such that its viscosity under a shear stress of 100 Pa or greater is at most 5 Pa.s, preferably at most 1 Pa.s, more
preferably at most 0.5 Pa.s. The shear thinning behaviour of the gel composition of the invention ensures that it can be
easily poured. Furthermore, a micro-emulsion is desirably not present in said gel composition.
[0028] The lamellar-phase gel detergent composition of the invention is also stable, which means that it does not
phase separate when stored for at least 2 weeks at room temperature. Furthermore, the surfactant system contained
15 in the gel laundry composition of the present invention is preferably substantially free of any amphoteric or zwitterionic
surfactant.

The clarity improving agent

20 [0029] The shear thinning, transparent lamellar-phase gel laundry detergent composition of the present invention
contains from 0.1 to 10%, preferably from 0.5 to 5%, more preferably from 1 to 4%, by weight, of a clarity improving
agent being a glycol dialkyl ether as specified in claim 1. Such relatively low amounts were observed to be quite sufficient
for obtaining a highly transparent gel laundry composition showing favourable cleaning performance.
[0030] Preferably, the clarity improving agent is a glycol dialkyl ether according to formula (I) or (II), wherein p and q
25 are integers having equal values. More preferably, the clarity improving agent of the invention is a glycol dialkyl ether
according to formula (I) or (II) wherein said ether has straight chain alkyl groups.
[0031] The clarity improving agent is most preferably selected from the group consisting of polyethylene glycol dibutyl
ether and polypropylene glycol dibutyl ether.
[0032] Without wishing to be bound by theory, it is believed that in the present case the amphiphilic nature of the glycol
30 dialkyl ethers of the present invention causes them to partition preferentially into the lamellar structures , thus enhancing
the liquid-like nature and flexibility thereof. This in turn leads to a decrease in fracturing of the lamellar phase and,
consequently, the clarity of the composition is increased.

Gelling agent
35
[0033] Preferably, the lamellar-phase gel laundry composition of the invention comprises from 1 to 8%, more preferably
from 3 to 6%, by weight of a gelling agent.
[0034] Such a gelling agent may suitably be a fatty alcohol having the formula R1-(CHOH)-R2 , wherein R1, R2 are
independently selected from hydrogen and saturated or unsaturated, linear or branched, C1-C16 alkyl groups, whereby
40 the total number of carbon atoms in the fatty alcohol is between 8 and 17.
[0035] Preferably a fatty alcohol gelling agent is used that has the above formula, wherein R1 is hydrogen and R2 is
selected from saturated or unsaturated, linear or branched C 9-C13 alkyl groups. Favourable results could generally be
obtained when applying as gelling agent a fatty alcohol in which the total chain length is similar to the average chain
length of the surfactants present in the formulation. Such a gelling agent is preferably selected from the group consisting
45 of 1-decanol, 1-dodecanol, 2-decanol, 2-dodecanol, 2-methyl-1-decanol, 2-methyl-1-dodecanol, 2-ethyl-1-decanol, and
mixtures thereof. Commercially available materials that are particularly suitable for use as gelling agent include Neodol
23 or Neodol 25 produced by Shell Chemical Co., Exxal 12 or Exxal 13 produced by Exxonmobil Chemical Co. and
Isalchem 123 or Lialchem 123 produced by Sasol Chemical Co.
[0036] The gelling agent may also suitably be a non-neutralised fatty acid having the formula R3-(COOH)-R4, wherein
50 R3 and R4 are independently selected from hydrogen and saturated or unsaturated, linear or branched C1-C22 alkyl
groups, whereby the total number of carbon atoms in the fatty acid is between 10 and 23. Such a fatty acid gelling agent
is preferably selected from oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid and
mixtures thereof.
[0037] Furthermore, the gelling agent may suitably be a naturally obtainable fatty acid selected from tallow, coconut,
55 and pal kernel fatty acids.

4
 EP 1 664 255 B1

Anionic surfactant

[0038] The anionic surfactant that may be present in the gel composition of the invention is preferably selected from
the group consisting of linear alkyl benzene sulphonates, alkyl sulphonates, alkylpolyether sulphates, alkyl sulphates
5 and mixtures thereof.
[0039] The linear alkyl benzene sulphonate (LAS) materials and their preparation are described for example in US
patents 2,220,099 and 2,477,383, incorporated herein by reference.
[0040] Particularly preferred are the sodium, potassium and mono-,di-,or tri-ethanolamminium linear straight chain
alkylbenzene sulphonates in which the average number of carbon atoms in the alkyl group is from 11 to 14. Sodium salt
10 of C11-C14, e.g. C12, LAS is especially preferred.
[0041] Preferred anionic surfactants also include the alkyl sulphate surfactants being water soluble salts or acids of
the formula ROS03M, wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-
C18 alkyl group, more preferably a C12-C15 alkyl or hydroxyalkyl, and wherein M is H or a cation, e.g. an alkali metal
cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium, especially mono-, di-, or tri- ethanolam-
15 monium. Most preferably, M is sodium.
[0042] Further preferred anionic surfactants are alkyl sulphonates, and desirably those in which the alkyl groups contain
8 to 26 carbon atoms, preferably 12 to 22 carbon atoms, and more preferably 14 to 18 carbon atoms.
[0043] The alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulphonates can be
employed, although they are not as good with respect to biodegradability. The alkyl substituent may also be terminally
20 sulphonated or may be joined to any carbon atom on the alkyl chain, i.e. may be a secondary sulphonate. The alkyl
sulphonates can be used as the alkali metal salts, such as sodium and potassium. The preferred salts are the sodium
salts. The preferred alkyl sulphonates are the C10 to C18 primary normal alkyl sodium sulphonates.
[0044] Also, alkyl polyether sulphates are preferred anionic surfactants for use in the composition of the invention.
[0045] These polyether sulphatesmay be normal or branched chain alkyl and contain lower alkoxy groups which can
25 contain two or three carbon atoms. The normal alkyl polyether sulphates are preferred in that they have a higher degree
of biodegradability than the branched chain alkyl, and the alkoxy groups are preferably alkoxy groups.
[0046] The preferred alkyl polyethoxy sulphates used in accordance with the present invention are represented by the
formula:

30 R1-O(CH2CH2O)p-SO3M,

wherein:

R1 is C8 to C20 alkyl, preferably C12 to C15 alkyl;

35 p is 2 to 8, preferably 2 to 6, and more preferably 2 to 4; and
M is an alkali metal, such as sodium and potassium, or an ammonium cation. The sodium salt is preferred.

[0047] The surfactant system of the invention may additionally contain fatty acid soaps. These can be derived from
saturated and non-saturated fatty acids obtained from natural sources and synthetically prepared. Examples of such
40 fatty acids include capric, lauric, myristic, palmitic, stearic, oleic, linoleic and linolenic acid. The non-neutralised fatty
acids may also suitably function as gelling agent, as above described.
[0048] The concentration of the anionic surfactant in the gel composition of the invention is preferably in the range of
from 5 to 50%, more preferably from 5 to 25% by weight. The anionic surfactant material may be incorporated in free
and/or neutralised form.
45
Nonionic surfactant

[0049] The surfactant system in the gel composition of the invention may also contain a nonionic surfactant.
[0050] Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilizing poly-
50 alkoxylene or a mono- or d-alkanolamide group in chemical combination with an organic hydrophobic group derived, for
example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in
which primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof), preferably having from 8 to
20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylene.
Also common are fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acidradical contains from
55 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms. In any of the mono- and di-
alkanolamide derivatives, optionally, there may be a polyoxyalkylene moiety joining the latter groups and the hydrophobic
part of the molecule.
[0051] In all polyalkoxylene containing surfactants, the polyalkoxylene moiety preferably consists of from 2 to 20 groups

5
 EP 1 664 255 B1

of ethylene oxide or of ethylene oxide and propylene oxide groups. Amongst the latter class, particularly preferred are
those described in European specification EP-A-225,654. Also preferred are those ethoxylated nonionics which are the
condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with from 3 to 11 moles of ethylene
oxide. Examples of these are the condensation products of C11-13 alcohols with (say) 3 or 7 moles of ethylene oxide.
5 [0052] The nonionic surfactant is preferably present in the gel composition of the invention at a concentration of from
5 to 50% by weight, more preferably from 5 to 30% by weight.

Builders

10 [0053] Builders that may be used according to the present invention include conventional alkaline detergent builders,
inorganic or organic, which can be used at levels of from 0% to 50% by weight of the gel composition, preferably from
1% to 35% by weight.
[0054] Examples of suitable inorganic detergency builders that may be used are water soluble alkali metal phosphates,
polyphosphates, borates, silicates, and also carbonates and bicarbonates. Specific examples of such builders are sodium
15 and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates, and car-
bonates.
[0055] Examples of suitable organic detergency builders are: (1) water-soluble amino polycarboxylates, e.g. sodium
and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2 hydroxyethyl)-nitrilodiacetates; (2) water-soluble
salts of phytic acid, e.g. sodium and potassium phytates; (3) water-soluble polyphosphonates, including specifically
20 sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium and potassium salts of methylene
diphosphonic acid; sodium and potassium salts of ethylene diphosphonic acid; and sodium and potassium salts of
ethane-1,1,2-triphosphonic acid.
[0056] In addition, polycarboxylate builders can be used satisfactorily, including water-soluble salts of mellitic acid,
citric acid, and carboxymethyloxysuccinic acid, salts of polymers of itaconic acid and maleic acid, tartrate monosuccinate,
25 and tartrate disuccinate.
[0057] Desirably, the detergency builder is selected from the group consisting of carboxylates, polycarboxylates,
aminocarboxylates, carbonates, bicarbonates, phosphates, phosphonates , silicates, borates and mixtures thereof.
[0058] Alkalimetal (i.e. sodium or potassium) citrate is most preferred builder material for use in the invention.
[0059] Amorphous and crystalline zeolites or aluminosilicates can also be suitably used as detergency builder in the
30 gel composition of the invention.

Enzymes

[0060] Suitable enzymes for use in the present invention include proteases, amylases, lipases, cellulases, peroxidases,
35 and mixtures thereof, of any suitable origin, such as vegetable, animal bacterial, fungal and yeast origin. Preferred
selections are influenced by factors such as pH-activity, thermostability, and stability to active bleach detergents, builders
and the like. In this respect bacterial and fungal enzymes are preferred such as bacterial proteases and fungal cellulases.
[0061] Enzymes are normally incorporated into detergent composition at levels sufficient to provide a "cleaning-effective
amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal,
40 soil removal, whitening, or freshness improving effect on the treated substrate. In practical terms for normal commercial
operations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram
of detergent composition. Stated otherwise, the composition of the invention may typically comprise from 0.001 to 5%,
preferably from 0.01 to 1% by weight of a commercial enzyme preparation.
[0062] Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from
45 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly
concentrated detergent formulations.
[0063] Suitable examples of proteases are the subtilisins that are obtained from particular strains of B. subtilis and
B.licheniformis. One suitable protease is obtained from a strain of Bacillis, having maximum activity throughout the pH-
range of 8-12, developed and sold as ESPERASE ® by Novo Industries A/S of Denmark.
50 [0064] Other suitable proteases include ALCALASE ® and SAVINASE ® from Novo and MAXATASE ® from Inter-
national Bio-Synthetics, Inc., The Netherlands.
[0065] Suitable lipase enzymes for use in the composition of the invention include those produced by microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB-1,372,034. A very suitable
lipase enzyme is the lipase derived from humicola lanuginosa and available from Novo Nordisk under the tradename
55 LIPOLASE™.

6
 EP 1 664 255 B1

Other optional components

[0066] In addition to the anionic and nonionic surfactants described above, the surfactant system of the invention may
optionally contain a cationic surfactant.
5 [0067] Furthermore, alkaline buffers may be added to the compositions of the invention, including monethanolamine,
triethanolamine, borax, and the like.
[0068] As another optional ingredient, an organic solvent may suitably be present in the gel composition of the invention,
preferably at a concentration of up to 10% by weight.
[0069] There may also be included in the formulation, minor amounts of soil suspending or anti-redeposition agents,
10 e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose or hydroxy-propyl methyl cellulose.
[0070] Optical brighteners for cotton, polyamide and polyester fabrics, and anti-foam agents such as silicone oils and
silicone oil emulsions may also be used.
[0071] Other optional ingredients which may be added in minor amounts, are soil release polymers, dye transfer
inhibitors, polymeric dispersing agents, suds suppressors, dyes, perfumes, colourants, filler salts, antifading agents and
15 mixtures thereof.
[0072] The invention will now be illustrated with reference to the following examples, in which parts and percentages
are by weight.

Examples A1-A7, B1-B7

20
[0073] The following basic gel laundry detergent compositions were prepared:

Wt %
Component: A B
25 Propylene glycol 4.75 4.75
Borax 2.3 0.0
Sodium Silicate 0.0 2.0
NaOH (50%) 0.5 0.5
30
LAS-acid 8.5 8.5
Nonionic surfactant 6.5 6.5
C12-14 alcohol 4.0 4.0
Protease enzyme 0.45 0.0
Perfume 0.2 0.2
35 Water balance to 100 balance to 100

[0074] To these basic formulations A and B were added varying amounts of the clarity improving agent diethylene
glycol dibutyl ether, such that the following sets of final formulations were obtained:
40
Wt% clarity improving agent
Formulations A1 and B1 0.0
Formulations A2 and B2 0.3
Formulations A3 and B3 0.5
45 Formulations A4 and B4 1.0
Formulations A5 and B5 2.0
Formulations A6 and B6 3.0
Formulations A7 and B7 5.0

50
[0075] In other words, formulations A1-A7 respectively B1-B7 have been derived from the basic formulations A and
B, by adding to these basic formulations varying amounts of the clarity improving agent diethylene glycol dibutyl ether,
such that for each final formulation the indicated concentration of said clarity improving agent is obtained.
[0076] The thus-obtained final formulations were all detergent gels. The clarity of the obtained formulations was meas-
55 ured using the following procedure:
[0077] The formulation to be measured is poured slowly into a suitable flat bottomed, transparent vessel, such as a
cylindrical vial. This vessel containing the formulation is then placed over a black cross, printed in black ink using standard
3.0 point lines on white paper. A visual assessment is made of the visibility of the cross when viewed through the

7
 EP 1 664 255 B1

formulation and more of said formulation is added to the container until the cross can only just be visualised through the
gel. At this point, a measurement is taken of the height of the formulation in the container; in other words, the path length
through which the cross is only just seen. This measurement is taken in a well-lit room and by a consistent operator.
Alternatively, a light box may be placed under the paper on which the cross is printed to provide consistent illumination
5 from below. This latter adjustment may modify the scale of the result, but in our experience does not change the relative
results obtained when all measurements are carried out consistently.
[0078] The results of these clarity measurements carried out using the method described above are given for the
formulations listed in the tables below. For formulations having higher clarity, greater heights or visual path lengths were
observed:
10
Formulation A1 A2 A3 A4 A5 A6 A7
Height/mm 27 32 35 37 46 52 58

15
Formulation B1 B2 B3 B4 B5 B6 B7
Height/mm 6 6 6 7 35 50 57

[0079] In the first case of basic formulation A and derivative final formulations A1-A7, the starting formulation A is a
20 reasonably clear gel of good transmittance which is improved significantly by addition of the clarity improving agent. In
the second case of starting formulation B and derivative final formulations B1-B7, the starting formulation B is a rather
opaque gel of which the transmittance is improved dramatically by addition of the claimed clarity improving agent.

25 Claims

1. A shear thinning, transparent lamellar-phase gel laundry detergent composition, comprising a surfactant system
containing surfactant material selected from an anionic surfactant, a nonionic surfactant or a mixture thereof, and
from 0.1 to 10% by weight of a clarity improving agent being a glycol dialkyl ether selected from
30 a mono- or polyethylene glycol dialkyl ether having the formula

(CpH2p+1)O - (CH2CH 2O)n - (CqH2q+1) (I),

a mono- or polypropylene glycol dialkyl ether having the formula

35

(CpH2p+1)O -(CH2CH(CH3)O)n - (CqH2q+2) (II),

and mixtures thereof,

wherein p and q independently are integers in the range of from 1 to 5, and n is an integer in the range of from 1 to
40 50, preferably 1 to 10, wherein said composition is structured internally by a lamellar phase such that the phase
volume of material present within the lamellar structure is at least 0.75.

2. A composition according to claim 1, wherein the clarity improving agent is selected from the group consisting of
polyethylene glycol dibutyl ether and polypropylene glycol dibutyl ether.
45

3. A composition according to claim 1 or claim 2, wherein the concentration of the clarity improving agent is from 0.5
to 5% by weight.

4. A composition according to any preceding claim, wherein the composition further comprises from 1 to 8% by weight
50 of a gelling agent.

5. A composition according to claim 4, wherein the gelling agent is a fatty alcohol having the formula

R1-(CHOH)-R2 (III),
55

wherein:

8
 EP 1 664 255 B1

R1, R2 are independently selected from hydrogen and saturated or unsaturated, linear or branched, C1 - C16
alkyl groups,
whereby the total number of carbon atoms in the fatty alcohol is between 8 and 17.

5 6. A composition according to claim 5, wherein the fatty alcohol gelling agent is selected from 1-decanol, 1-dodecanol,
2-decanol, 2-dodecanol, 2-methyl-1-decanol, 2-methyl-1-dodecanol, 2-ethyl-1-decanol, and mixtures thereof.

7. A composition according to claim 4, wherein the gelling agent is a non-neutralised fatty acid having the formula

10 R3- (COOH) -R4 (IV),

wherein:

R3 and R4 are independently selected from hydrogen and saturated or unsaturated, linear or branched C1-C22
15 alkyl groups, whereby the total number of carbon atoms in the fatty acid is between 10 and 23.

8. A composition according to claim 7, wherein the fatty acid gelling agent is selected from oleic acid, lauric acid,
myristic acid, palmitic acid, stearic acid, linoleic acid, linolenic acid and mixtures thereof.

20 9. A composition according to claim 4, wherein the gelling agent is a naturally obtainable fatty acid selected from tallow,
coconut, and palm kernel fatty acids.

10. A composition according to any preceding claim, wherein the surfactant system contains an anionic surfactant
selected from the group consisting of linear alkyl benzene sulphonate, alkyl polyether sulphate, alkyl sulphate, alkyl
25 sulphonate and mixtures thereof.

11. A composition according to any preceding claim, wherein the anionic surfactant is present at a concentration of from
5 to 50% by weight, preferably from 5 to 25% by weight.

30 12. A composition according to any preceding claim, wherein the nonionic surfactant is an ethoxylated alcohol having
3 to 11 ethylene oxide groups.

13. A composition according to any preceding claim, wherein the nonionic surfactant is present at a concentration of
from 5 to 50% by weight, preferably from 5 to 30% by weight.
35
14. A composition according to any preceding claim, wherein the composition additionally comprises a detergency
builder selected from the group consisting of carboxylates, polycarboxylates, aminocarboxylates, carbonates, bi-
carbonates, phosphates, phosphonates, silicates, borates, and mixtures thereof.

40 15. A composition according to any preceding claim, wherein the composition has at least 50%, preferably at least 70%,
transmittance of light using a 1 centimeter cuvette at a wavelength of 410-800 nm, preferably 570-690 nm, whereby
the composition is measured in the absence of dyes.

16. Use of a glycol dialkyl ether as a clarity improving agent in a shear thinning, transparent, gel laundry detergent
45 composition according to any of claims 1-15.

17. Method of improving the clarity and transparency of a shear thinning, transparent, lamellar-phase gel laundry de-
tergent composition, said method comprising the steps of

50 (a) preparing said composition by mixing the ingredients thereof , said composition comprising a surfactant
system containing surfactant material selected from an anionic surfactant, a nonionic surfactant or a mixture
thereof, and
(b) adding from 0.1 to 10% by weight of a glycol dialkyl ether, as specified in claim 1, to said composition,
whereby the resulting composition is structured internally by a lamellar phase such that the phase volume of
55 material present within the lamellar structure is at least 0.75.

9
 EP 1 664 255 B1

Patentansprüche

1. Scherentzähende, transparente Waschmittelzusammensetzung für Wäschereien in Form eines Gels mit lamellen-
förmiger Phase, die ein Tensidsystem aufweist, das ein Tensidmaterial, das aus einem anionischem Tensid, einem
5 nichtionischen Tensid oder einem Gemisch davon ausgewählt ist, und 0,1 bis 10 Gew.-% eines die Klarheit ver-
bessernden Mittels enthält, das ein Glycoldialkylether ist, der ausgewählt ist aus
einem Mono- oder Polyethylenglycoldialkylether mit der Formel

(CpH2p+1)O-(CH2CH2O)n-(CqH2q+1) (I),
10
einem Mono- oder Polypropylenglycoldialkylether mit der Formel

(CpH2p+1)O-(CH2CH(CH3)O)n-(CqH2q+1) (II),

15 und Gemischen davon,

wobei p und q unabhängig voneinander ganze Zahlen im Bereich von 1 bis 5 sind und n eine ganze Zahl im Bereich
von 1 bis 50, vorzugsweise 1 bis 10 ist, wobei die Zusammensetzung im Inneren von einer lamellenförmigen Phase
strukturiert wird, so dass das Phasenvolumen des innerhalb der lamellenförmigen Struktur vorhandenen Materials
mindestens 0,75 beträgt.
20
2. Zusammensetzung nach Anspruch 1,
wobei das die Klarheit verbessernde Mittel aus der Gruppe ausgewählt ist, die aus Polyethylenglycoldibutylether
und Polypropylenglycoldibutylether besteht.

25 3. Zusammensetzung nach Anspruch 1 oder 2,

wobei die Konzentration des die Klarheit verbessernden Mittels 0,5 bis 5 Gew.-% beträgt.

4. Zusammensetzung nach einem der vorstehenden Ansprüche,

wobei die Zusammensetzung ferner 1 bis 8 Gew.-% eines Geliermittels aufweist.
30
5. Zusammensetzung nach Anspruch 4,
wobei das Geliermittel ein Fettalkohol mit der Formel

R1-(CHOH)-R2 (III)
35
ist, worin:
R1 und R2 unabhängig voneinander aus Wasserstoff und gesättigten oder ungesättigten, linearen oder verzweigten
C1-C16-Alkylgruppen ausgewählt sind, wobei die Gesamtzahl der Kohlenstoffatome im Fettalkohol 8 bis 17 beträgt.

40 6. Zusammensetzung nach Anspruch 5,

wobei das Geliermittel in Form von Fettalkohol aus 1-Decanol, 1-Dodecanol, 2-Decanol, 2-Dodecanol, 2-Methyl-1-
decanol, 2-Methyl-1-dodecanol, 2-Ethyl-1-decanol und Gemischen davon ausgewählt ist.

7. Zusammensetzung nach Anspruch 4,

45 wobei das Geliermittel eine nicht-neutralisierte Fettsäure mit der Formel

R3-(COOH)-R4 (IV)

ist, worin:
50 R3 und R4 unabhängig voneinander aus Wasserstoff und gesättigten oder ungesättigten, linearen oder verzweigten
C1-C22-Alkylgruppen ausgewählt sind, wobei die Gesamtzahl der Kohlenstoffatome in der Fettsäure 10 bis 23
beträgt.

8. Zusammensetzung nach Anspruch 7,

55 wobei das Geliermittel in Form von Fettsäure aus Oleinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearin-
säure, Linolsäure, Linolensäure und Gemischen davon ausgewählt ist.

9. Zusammensetzung nach Anspruch 4,

10
 EP 1 664 255 B1

wobei das Geliermittel eine Fettsäure ist, die natürlich erhalten werden kann und aus Talg-, Kokos- und Palmkern-
fettsäuren ausgewählt ist.

10. Zusammensetzung nach einem der vorstehenden Ansprüche,

5 wobei das Tensidsystem ein anionisches Tensid enthält, das aus der Gruppe ausgewählt ist, die aus linearem
Alkylbenzolsulfonat, Alkylpolyethersulfat, Alkylsulfat, Alkylsulfonat und Gemischen davon besteht.

11. Zusammensetzung nach einem der vorstehenden Ansprüche,

wobei das anionische Tensid in einer Konzentration von 5 bis 50 Gew.-%, vorzugsweise von 5 bis 25 Gew.-% vorliegt.
10
12. Zusammensetzung nach einem der vorstehenden Ansprüche,
wobei das nichtionische Tensid ein ethoxylierter Alkohol mit 3 bis 11 Ethylenoxidgruppen ist.

13. Zusammensetzung nach einem der vorstehenden Ansprüche,

15 wobei das nichtionische Tensid in einer Konzentration von 5 bis 50 Gew.-%, vorzugsweise von 5 bis 30 Gew.-%
vorliegt.

14. Zusammensetzung nach einem der vorstehenden Ansprüche,

wobei die Zusammensetzung ferner einen Builder mit Waschvermögen aufweist, der aus der Gruppe ausgewählt
20 ist, die aus Carboxylaten, Polycarboxylaten, Aminocarboxylaten, Carbonaten, Bicarbonaten, Phosphaten, Phos-
phonaten, Silicaten, Boraten und Gemischen davon besteht.

15. Zusammensetzung nach einem der vorstehenden Ansprüche,

wobei die Zusammensetzung einen Lichtdurchlassgrad von mindestens 50 %, vorzugsweise mindestens 70 %
25 aufweist, wenn eine 1 cm Kuvette bei einer Wellenlänge von 410 bis 800 nm, vorzugsweise von 570 bis 690 nm
verwendet wird, wobei die Zusammensetzung ohne Farbstoffe gemessen wird.

16. Verwendung eines Glycoldialkylethers als die Klarheit verbesserndes Mittel in einer scherentzähenden, transpa-
renten Waschmittelzusammensetzung in Form eines Gels für Wäschereien nach einem der Ansprüche 1 bis 15.
30
17. Verfahren zum Verbessern der Klarheit und Transparenz einer scherentzähenden, transparenten Waschmittelzu-
sammensetzung für Wäschereien in Form eines Gels mit lamellenförmiger Phase, wobei das Verfahren die folgenden
Schritte aufweist:

35 (a) Herstellen der Zusammensetzung durch Mischen ihrer Bestandteile, wobei die Zusammensetzung ein Ten-
sidsystem aufweist, das ein Tensidmaterial enthält, das aus einem anionischem Tensid, einem nichtionischen
Tensid oder einem Gemisch davon ausgewählt ist, und
(b) Zugeben von 0,1 bis 10 Gew.-% eines Glycoldialkylethers nach Anspruch 1, zu dieser Zusammensetzung,
wobei die entstehende Zusammensetzung im Inneren von einer lamellenförmigen Phase strukturiert wird, so
40 dass das Phasenvolumen des innerhalb der lamellenförmigen Struktur vorhandenen Materials mindestens 0,75
beträgt.

Revendications
45
1. Composition de détergent de lessive sous forme de gel à phase lamellaire transparente pseudo-plastique, compre-
nant un système tensioactif contenant un produit tensioactif choisi parmi un tensioactif anionique, un tensioactif non
ionique ou un mélange de ceux-ci, et de 0,1 à 10 % en poids d’un agent clarifiant étant un éther dialkylique de glycol
choisi parmi
50 un éther dialkylique de mono- ou de polyéthylène glycol répondant à la formule

(CpH2p+1)O- (CH2CH2O)n- (C qH2q+1) (I),

un éther dialkylique de mono- ou de polypropylène glycol répondant à la formule

55
(CpH2p+1)O-(CH2CH(CH3)O)n-(CqH2q+1) (II),

et les mélanges de ceux-ci

11
 EP 1 664 255 B1

dans laquelle p et q représentent indépendamment des nombres entiers dans la plage de 1 à 5, et n représente un
nombre entier dans la plage de 1 à 50, de préférence de 1 à 10, dans laquelle ladite composition est structurée sur
le plan interne par une phase lamellaire de manière à ce que le volume de phase de la matière présente dans la
structure lamellaire soit au moins de 0,75.
5
2. Composition selon la revendication 1, dans laquelle l’agent clarifiant est choisi dans le groupe constitué de l’éther
dibutylique de polyéthylène glycol et de l’éther dibutylique de polypropylène glycol.

3. Composition selon la revendication 1 ou la revendication 2, dans laquelle la concentration de l’agent clarifiant est
10 de 0,5 à 5 % en poids.

4. Composition selon l’une quelconque des revendications précédentes, dans laquelle la composition comprend en
outre de 1 à 8 % en poids d’un agent gélifiant.

15 5. Composition selon la revendication 4, dans laquelle l’agent gélifiant est un alcool gras répondant à la formule

R1-(CHOH)-R2 (III),

dans laquelle :
20
R1 et R2 sont indépendamment choisis parmi l’atome d’hydrogène et les groupes alkyles en C1-C16 linéaires
ou ramifiés, saturés ou insaturés, le nombre total d’atomes de carbone dans l’alcool gras se situant entre 8 et 17.

6. Composition selon la revendication 5, dans laquelle l’agent gélifiant constitué d’un alcool gras est choisi parmi le
25 1-décanol, le 1-dodécanol, le 2-décanol, le 2-dodécanol, le 2-méthyl-1-décanol, le 2-méthyl-1-dodécanol, le 2-éthyl-
1-décanol et leurs mélanges.

7. Composition selon la revendication 4, dans laquelle l’agent gélifiant est un acide gras non neutralisé répondant à
la formule
30
R3-(COOH)-R4 (IV),

dans laquelle :

35 R3 et R4 sont indépendamment choisis parmi l’atome d’hydrogène et les groupes alkyles en C1-C22 linéaires
ou ramifiés, saturés ou insaturés, le nombre total d’atomes de carbone dans l’acide gras se situant entre 10 et 23.

8. Composition selon la revendication 7, dans laquelle l’agent gélifiant constitué d’un acide gras est choisi parmi l’acide
oléique, l’acide laurique, l’acide myristique, l’acide palmitique, l’acide stéarique, l’acide linoléique, l’acide linolénique
40 et leurs mélanges.

9. Composition selon la revendication 4, dans laquelle l’agent gélifiant est un acide gras pouvant être obtenu naturel-
lement choisi parmi les acides gras de suif, de noix de coco et de palmiste.

45 10. Composition selon l’une quelconque des revendications précédentes, dans laquelle le système tensioactif contient
un tensioactif anionique choisi dans le groupe constitué d’un sulfonate d’alkylbenzène linéaire, d’un sulfate d’alkyl-
polyéther, d’un sulfate d’alkyle, d’un sulfonate d’alkyle et de leurs mélanges.

11. Composition selon l’une quelconque des revendications précédentes, dans laquelle le tensioactif anionique est
50 présent à une concentration de 5 à 50 % en poids, de préférence de 5 à 25 % en poids.

12. Composition selon l’une quelconque des revendications précédentes, dans laquelle le tensioactif non ionique est
un alcool éthoxylé comportant de 3 à 11 groupes oxyde d’éthylène.

55 13. Composition selon l’une quelconque des revendications précédentes, dans laquelle le tensioactif non ionique est
présent à une concentration de 5 à 50 % en poids, de préférence de 5 à 30 % en poids.

14. Composition selon l’une quelconque des revendications précédentes, dans laquelle la composition comprend en

12
 EP 1 664 255 B1

outre un adjuvant de détergence choisi dans le groupe constitué des carboxylates, des polycarboxylates, des
aminocarboxylates, des carbonates, des bicarbonates, des phosphates, des phosphonates, des silicates, des bo-
rates et de leurs mélanges.

5 15. Composition selon l’une quelconque des revendications précédentes, dans laquelle la composition présente une
transmittance de la lumière d’au moins 50 %, de préférence d’au moins 70 %, en utilisant une cuvette de 1 centimètre
à une longueur d’onde de 410 à 800 nm, de préférence de 570 à 690 nm, la composition étant mesurée en l’absence
de colorants.

10 16. Utilisation d’un éther dialkylique de glycol en tant qu’agent clarifiant dans une composition de détergent de lessive
sous forme de gel transparente pseudo-plastique selon l’une quelconque des revendications 1 à 15.

17. Procédé d’amélioration de la clarté et de la transparence d’une composition de détergent de lessive sous forme de
gel à phase lamellaire transparente pseudo-plastique, ledit procédé comprenant les étapes consistant à
15
(a) préparer ladite composition en mélangeant les ingrédients de celle-ci, ladite composition comprenant un
système tensioactif contenant un produit tensioactif choisi parmi un tensioactif anionique, un tensioactif non
ionique ou un mélange de ceux-ci, et
(b) ajouter de 0,1 à 10 % en poids d’un éther dialkylique de glycol, tel que spécifié dans la revendication 1, à
20 ladite composition, dans lequel la composition résultante est structurée sur le plan interne par une phase
lamellaire de manière à ce que le volume de phase de la matière présente dans la structure lamellaire soit au
moins de 0,75.

25

30

35

40

45

50

55

13
 EP 1 664 255 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 5281355 A [0002] • US 10251738 B [0012]

• WO 9927065 A [0006] [0012] • EP 02257682 A [0012]
• WO 9906519 A [0006] • US 2220099 A [0039]
• US 5820695 A [0006] • US 2477383 A [0039]
• US 6362156 A [0008] [0009] [0010] • EP 225654 A [0051]
• US 5952286 A [0011] • GB 1372034 A [0065]

14