Title of Invention


Abstract The present invention provides a liquid detergent composition comprising an effective amount of an enzyme, 0.001-3% wt of a perfume ingredient, and 0.005-2% wt of an anti-oxidant. It has been found that the storage stability of the enzyme -which is preferably a protease- can be drastically improved by the addition of the anti-oxidant.
Full Text C7737/V
FORM - 2
THE PATENTS ACT, 1970 (39 of 1970)
The Patents Rules, 2003
(See Section 10 and Rule 13)
HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai-400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed.

WO 2005/059077


Liquid detergent composition
Field of the invention
The present invention relates to detergent compositions
5 containing enzymes, wherein the activity of the enzyme has been stabilised against deterioration (e.g. by degradation of the enzyme molecule) during storage. The stabilised liquid enzyme- containing detergent compositions of the invention are particularly useful in methods for removing proteinaceous soils
10 from fabric substrates, so as to clean those substrates.
Background of the invention
In liquid detergent compositions,' especially those for the washing of textile fabrics, it is common' to include one or more
15 enzymes for assisting removal of various kinds, of soil. Amongst these are proteolytic enzymes, often referred to as "proteases". Proteases are used to assist in the removal of protein-based soil. However, the very nature and activity of these enzymes means
20 that they attack any other component in .the liquid composition which has a protein-like structure. As'-a result,' they can degrade other enzymes in the liquid, as well as undergo self- degradation. To counteract this, it is usual also to incorporate an enzyme stabilising system. Such stabilising
25 systems commonly consist of a boron compound, e.g. borax, together with a polyol, e.g. glycerol or sorbitol. These components are believed to form an enzyme-inhibiting complex which dissociates by dilution of the composition into the wash liquor, disabling the inhibiting effect so that the protease
30 can act upon the proteinaceous soil.
Other protease stabilisers such as calcium chloride/calcium format are also known but are not as effective as those systems based on boron. On the other hand, it may be desirable for

WO 2005/059077


environmental reasons to reduce the amount of boron in the detergent composition.
Another type of enzyme stabilizing system for use in enzyme-
5 containing liquid detergent compositions-is disclosed by US-A- 4,238,345. This document discloses that the combination of an antioxidant haying a standardized redox potential at least equal to that of ascorbic acid but less than that of sodium hydrosulphite, with hydrophylic polyol is, an effective

10 stabilising system for proteolytic enzymes,

We have found in this connection that perfumes generally degrade proteolytic and lipolytic liquid enzymes when also present in liquid detergent compositions. In particular we have found
15 that some specific perfume components particularly degrade protease and lipase enzymes when present in the liquid detergent composition.
In view of this, it is an object of the present invention to 20 provide an effective liquid detergent composition containing
both a proteolytic and/or lipolytic enzyme and a perfume
composition, and having favorable storage stability.
We have now surprisingly found that this object can be achieved by using a perfume composition in
25 composition, and combining it with an antioxidant
In other words, we have found that a protease and/or lipase-
containing liquid detergent composition having favorable
storage stability characteristics can be obtained, when that
composition contains an antioxidant in combination with a
30 perfume composition.

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Definition of the invention
Accordingly, in one aspect the present invention provides a
liquid detergent composition comprising:
a) a cleaning, effective amount of ah enzyme selected from a
proteolytic enzyme, a lipolytic enzyme, and a mixture
(b) from 0.001% to 3% by weight of a perfume composition; and
10 (c) from 0.005 to 2% by weight of an antioxidant selected from
the group consisting of an alkylated phenol (as defined herein) a-,' {J-, y-, 5-tocopherol, ethoxyquine, 2,2,4-trimethyl-1,2-dihydroquindline, 2, 6-di-tert-butyl-hydroguinone; tert-butyl-hydroxy anysole, lignosulphonic
15 acid and salts thereof," 6-hydroxy-2, 5, 7, 8-tetra-methylchroman-2-carboxylic acid (Troloxtm) / 1,2--benzisothiazoline-3-one (Proxel GXLtm), a benzofuran or benzopyran derivative (as defined herein), tocopherol sdrbate, butylated hydroxy benzoic acid and its salts,
20 gallic acid and its alkyl esters, uric acid and its salts

and alkyl esters, sorbic acid and its salts dihydroxy
and its salts, and mixture thereof
fumaric acid ,and its salts, and mixtures thereof.
Furthermore, in a second aspect the invention provides a method
25 of cleaning a fabric substrate, comprising the steps of
treating the substrate with a liquid composition of the present invention in an aqueous environment, rinsing the substrate and drying it. In a further aspect, the invention provides the use of an antioxidant as' specified in the claims in a liquid
30 laundry detergent composition containing 0.001-3% by weight of a perfume composition and a cleaning effective amount of an enzyme selected from a proteolytic enzyme, a lipolytic enzyme, an amylolytic enzyme, a cellulolytic enzyme and a
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thereof, for improving the storage stability of the liquid laundry detergent composition.
Detailed description of the invention
The Liquid_ Detergent Composition
Liquid detergent compositions generally can be considered either to be isotropic or structured* The liquid cleaning

Composition may be formulated

as a concentrated cleaning liquid

10 for direct application to a substrate, or for application to a

substrate following dilution, use of the liquid composition apparatus.

such as dilution before or during by the consumer or in washing

15 Whilst the 'composition and method according to the present
invention may be used for cleaning any suitable substrate, the preferred substrate is a laundry fabric. Cleaning may be carried out by simply leaving the substrate in contact for a
sufficient period of time with
20 or prepared from the liquid cleaning composition .preferably
however, the cleaning medium on or containing the substrate is agitated.
Product Form
25 The liquid detergent composition according to the present invention is preferably a concentrated liquid cleaning composition. Furthermore, said liquid detergent composition is preferably isotropic. It should be understood that the liquid compositions according
30 , to any aspect of the present invention have a physical form which preferably ranges from a pourable liquid, a pourable gel to a non-pourable gel. These forms are conveniently characterized by the product viscosity. In these definitions,

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and unless indicated explicitly to the contrary, throughout this specification, all stated viscosity's are those measured at a shear rate of 21 s_1 and at ;a temperature of 25 °C.
5 Pourable liquid 'compositions according to any aspect of the present invention preferably have a viscosity of no more than
1,500 mPa.s, more preferably no more-than'1,000 mPa.s, still
more preferably, no more than 500 mPa,.s.
10 Compositions according to any aspect of the present invention which are pourable gels, preferably have a .viscosity of at least 1,500 mPa.s but no more that 6,000 mPa.s, more preferably no more than 4,000 mPa.s, still more preferably no more than 3,000 mPa.s and especially no more than 2,000 mPa.s.
Compositions according to any aspect of the present invention which are non-pourable gels, preferably have a viscosity of at • least 6,000 mPa.s but no more than 12; 000 .mPa.s, more preferably no more than 10,000: mPa s still more preferably no
20 more than 8,0Q0'mPa.s and especially no more than 7,000 mPa.s.
Physically stable
For the purpose of this invention a composition is physically stable when less than 2% phase separation occurs after 2 week storage at 37°C'. With isotropic liquids this phase separation
25 generally starts with the liquid becoming hazy.
Preferably the amount of water in the liquid-detergent composition is from 5 to 95%, more preferred from 30 to 80%, by
30 weight.

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The liquid detergent composition of the invention from 0.005 to 2% by weight of an anti-oxidant,. Preferably, the anti-oxidant is present at a concentration 'in the range of 0.01 to 0.08% by
5 weight.
Anti-oxidants are substances as described in Kirk-Othmers (Vol 3, pg.424) -and in Uhlmans Encyclopedia'-(Vol 3, pg 91).
10 One class of anti-oxidants used; in the present invention is alkylated phenols having the general formula:

wherein R is C1-C22 linear or branched 'alkyl, preferably methyl or branched C3-C6 alkyl; C3-C6 alkyl, 'preferably methoxy; R1 is
15 a C3-C6.branched alkyl, preferably tert-butyl; x is 1 or 2. Hindered phenolic compounds are a preferred type of alkylated phenols according to this formula. A preferred hindered phenolic compound of this type toluene (BHT).
Furthermore, the antioxidant used in the composition of the
invention is selected from the group consisting of a-, (3-, y-,
8-tocopherol', ethoxyquine', 2,2,i4-trimethyl-l, 2-
dihydroquinoline, 2,6-di-tert-butyl hydroquinone, tert-butyl-
25 hydroxy anisole, lignosulphonic acid and salts thereof, and
mixtures thereof. It is noted that ethoxyquine (1,2-dihydro-6-

ethoxy-2,2,4rtrimethylchinolin)is marketed under the name
RaluquinTM by the company RashigTM

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Other type of antioxidant used in the present invention are 6-hydroxy-2,5, 7, 8-tetra-methylchromari-2-carboxylic acid (TroloxTM) and l,2-benzisothiazoline-3-one (Proxel,, GXLTM) .
5 A further class of anti-oxidants which may be suitable for use in the present invention is a benzofuran Or benzopyran derivative having the formula:

wherein R1 and R2 are each independently alkyl or R1 and R2 can
10 be taken together to form a C5-C6 cyclic' hydrocarbyl moiety; B is absent or CH2; R4 is C1-C6 alkyl; R5 is hydrogen or -C(O)R3 wherein R3 is hydrogen or C1-C19 alkyl; R6 is C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is -CH2OH,. or - CH2A wherein A is a nitrogen comprising unit, phenyl,, or substituted phenyl.
15 Preferred nitrogen comprising A units include amino,
pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.
Anti-oxidants such as tocopherol sorbate,-,btitylated hydroxy
20 benzoic acids and, their salts, gallic acid and its alkyl
esters, uric acid and its salts and alkyl esters, sorbic acid
and its salts, and dihydroxy fumaric acid and its salts may
also be used. The preferred types of anti-oxidaniJs for use in the present
25 invention are 2,6-di-tert-butyl— hydroxy-toluene (BHT), α-, β , y-, δ-tocopherol, 6-hydroxy-2,5,7, 8-tetra-methylchroman-2-carboxylic acid (Trolox™), 1,2-benzisothiazolIne-3-one (Proxel GXL™) and mixtures thereof. The most preferred anti-oxidants

WO 2005/059077


are 2,6-di-tert-butyl-hydroxy-toluene (BHT, 1,2-benzisothiazoiine-3-one (Proxel GXLTM) and mixtures thereof.

Perfume component
5 The liquid composition of the present invention comprises
between 0.001 to 3,wt/wt % of a perfume composition, preferably between 0.01 to*2.wt/wt % of a perfume composition. Said perfume composition preferably comprises-at least 0.01% by weight based on the liquid composition of a perfume component
10 selected from terpenes, ketones, aldehydes and mixtures thereof. The perfume composition may fully consist of the perfume component but generally the perfume composition is a complex mixture -of perfumes of various differing perfume classifications. In this regard, the perfume composition
15 preferably comprises at least 0.1%, more preferably at least 1.0%, still more preferably at least 5% by weight of the perfume component. At higher levels of the perfume component, the positive effect of the antioxidant with regard to the storage stability of the liquid composition is greater.
Having regard to the terpene perfume component, the present invention has particular utility with the following preferred terpene perfume components:




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# # str( )# #
Having regards to the ketons perfume component the present
5 invention has particular utility to the/following preferred ketonic perfume components:



vertof ix 'coeur





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With regard to the aldehydic perfume component, the present invention has particular utility with the following preferred aldehydic perfume components: # # str(







Aldehyde C12
) # #

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Cyclosia base


5 "Detersive enzyme", as used herein, means "any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry application. Enzymes are included in the present detergent compositions for a variety of purposes, including removal of protein-based, saccharide-based or triglyceride-
10 based stains, for the prevention of refugee dye transfer, and for fabric restoration.
The composition of the invention contains an enzyme selected from a protease, a lipase, an amylase, a cellulase and mixtures thereof. Preferably, said composition contains a protease
15 enzyme.
Other suitable enzymes include oxidases, peroxidases, 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
20 activity and/or stability optima stability to active detergents, builders and the like. In this

respect bacterial or fungal enzymes

are preferred, such as

bacterial amylases and proteases,' and fungal cellulases.
25 Enzymes are normally incorporated into detergent or detergent
additive compositions at levels sufficient to provide a
"cleaning-effective amount". The term "cleaning effective
amount" refers to any amount capable of producing a cleaning,


W0 2005/059077 PCT/EP2004/013373
■ ■
stain removal, soil removal, whitening, deodorizing, or freshness improving effect on; substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight; more typically 0.001 m
5 to 3 mg, of active enzyme per gram of the detergent
composition. Stated otherwise,1 the compositions herein will typically comprise from 0.0001% to'- 10%, preferably, from 0.001% to 5%, more preferably 0.005%^1% by weight of a commercial enzyme preparation.
The Proteolytic Enzyme
Endopeptidases (proteolytic enzymes or proteases) of various qualities and origins and having activity in various pH ranges of from 4-12- are available and can be used in the instant
15 invention. Examples of suitable proteolytic enzymes are the subtilisins, which can be obtained from particular strains of B. subtilis, B. lentus, B amyloliquefaciens and B licheniforirtis, such as the commercially available subtilisins Savinase™, Alcalase1", Relase™,
20 supplied by Novo Industri A/S,copehagen, Denmarks or
Purafect1", PurafectOxP™ and Properase™ as supplied by Genencor International. Chemically or genetically modified variants of these enzymes are included such as described in WO-A-99/02632 pages 12 to 16 and in WO-A-99/20727 and also variants with
25 reduced allergenicity as described -in WO-A-99/00489 and WO-A-99/49056.
It should be understood that the protease is present in the
liquid detergent composition of the invention in a dissolved or
30 dispersed form, i.e., the protease is not encapsulated to
prevent the protease from the liquid composition. Instead the
protease in more -or less in direct contact with the liquid

WO 2005/059077


Suitable examples' of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain
5 of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE™ by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB*1', 243,784 to Novo. Other suitable proteases include ALCALASE^, and SAVINASE™ from
10 Novo and MAXATASE™ from International; Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP-A-
130,756, and Protease B as disclosed in EP-A-303,761 and EP-A-
130,756. See also a high pH protease from Bacillus sp. NCIMB
40338 described in,WO-A-93/18140 to Novo. Enzymatic detergents
15 comprising protease, one or more other enzymes/; and a
reversible protease inhibitor are described in WO-A-92/03529.
Other preferred proteases include those of WO-A-95/10591. When
desired, a protease having decreased adsorption and increased
hydrolysis is available as described in WCHA-95/07791. A
20 recombinant trypsin-like protease for detergents suitable
herein is described in WO-A-94/2558
Useful proteases are also described in PCT publications: WO-95/30010,. WO-95/30011, WO-95/2997'9.
Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those- described in".EP-A-251,446 (particularly pages 17, 24 and 98) , arid which is called herein "Protease B", and in EP-A-199,40'4, which refers to a modified
30 bacterial serine proteolytic enzyme: which is called "Protease A" herein, Protease A as disclosed in EP-A-130,756.

WO 2005/059077.


The preferred liquid laundry detergent compositions according to the present invention comprise atleasts0.001% by weight, of a protease enzyme. However, an effective amount of protease enzyme is sufficient for use in the -liquid laundry detergent
5 compositions described herein, The term an effective amount" refers to any amount capable of producing*, a cleaning, stain removal soil removal, whitening, deodorizing, or freshness

improving effect on substrates

such' as fabrics. In practical

terms for current commercial preparations, typical amounts are
10 up to about .5 mg by weight, more typically 0.001 mg to 3 mg, of active enzyme per gram of the detergent 'Composition. Stated otherwise, the compositions herein will typically comprise from

0.001% to 5%; preferably 0.01% 1% "by weight of a commercial

15 is up to 0.2%, preferably from the composition of pure enzyme
4 x 10~5% to 0.06% by weight of

Lipolytic Enzyme
As outlined above, the liquid

composition of the invention may

20 also contain a lipolytic enzyme. In particular, the composition may contain 10 - 20,000 LU per gram of .the detergent composition of a lipolytic enzyme "selected from the group consisting of Lipolase, Lipolase ultra LipoPrime, Lipomax, Liposam, and lipase from Rhizomucor miehel (e.g. as described
25 in EP-A-238,023 (Novo Nordisk)

Suitable other enzymes for use in the compositions of the invention can be found in the enzyme classes of the esterases and lipases, (EC 3.1.1.*, wherein the asterisk denotes any
30 number) .

WO 2005/059077


A characteristic: feature of lipases is that they exhibit interfacial activation. This means that "the enzyme activity is much higher on a*substrate which has formed-interfaces or micelles, than on fully dissolved: substrate:. Interface
5 activation is reflected in a sudden increase in lipolytic activity when the substrate concentration*is raised above the critical micel concentration (CMC) of the substrate, and interfaces are formed. Experimentally this phenomenon can be observed as a discontinuity in the graph of enzyme activity
10 versus substrate concentration. Contrary to lipases, however, cutinases do not exhibit any substantial interfacial activation.
Suitable lipase enzymes for detergent- usage include those
15 produced by,microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P."
20 Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, ' Japan; Chromobacter viscosum lipases from U;S1 Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
25 Pseudomonas gladioli. LIPOLASE™ enzyme derived from Humicola lanyginosa and commercially available from Novo, see also EP-A-341,947, is a preferred lipase for use herein. Lipase and
amylase variants stabilized against peroxide enzymes are described in WO-A^-94/14 951 to Novo. See also WO-A-92/05249
30 Cutinase enzymes suitable for use herein are described in WO-A-88/09367 to Genencor.

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Of main interest for the present invention are fungal lipases, such as those from Humicola lanuginosa and Rhizomucor miehei. Particularly^suitable for the present invention is the lipase from Humico1 a- lanuginosa strairi DSM 4109, which is described in
5 EP-A-305 216 (Novo Nordisk), and which is commercially
available as Lipolase (TM). Also suitable are variants of this enzyme, such ;as described in WO-A-92/05249,, WO-A-94/25577, WO-
A-95/22615, WO-A-97/04079, WO-A 00/60063. -97/07202> WO-A-99/42566, WO-A-is the variant D96L which is Especially preferred
10 commercially available from Novozymes as Lipolase ultra, and the variant, which is sold by Novozymes under the trade name Lipo Prime.
The lipolytic enzyme suitable
suitable form, i.e. the form

a granular composition, a

slurry of the enzyme, or with,carrier material (e.g. as in EP-A-258,068 and the Savinase (TM) and.Lipolase (TM) products of Novozymes). A good way of adding the enzyme to a liquid
20 detergent product is in the form of a slurry containing 0.5 to 50 % by weight of the enzyme in a ethoxylated alcohol nonionic surfactant, such as described in EP-A-450,702 (Unilever).

Other enzymes
25 Other optional suitable enzymes that may be included alone or
in combination with any other enzyme may,- for example, be oxidoreductases, transferases hydrolases,' lyases, isomerases and ligases. Suitable members of these enzyme classes are 1992: recommendations of the
30 Nomenclature Committee of the International Union of
Biochemistry and Molecular Biology on the nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press.

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Examples of the oxidoreductases are oxidases such as glucose oxidase, methanol oxidase, bilirubin oxidase catechol oxidase, laccase, peroxidases such as lignihase and those described in WO-A-97/31090, monooxygenase, dioxygenase such as lipoxygenase
5 and other oxygenases as described in WO-A-99/02632, WO-A-
99/02638, WO-A-99/02639 and the cytochrome based enzymatic
bleaching systems described in WO-A-99/02641:.
Peroxidase enzymes may be used in combination with oxygen
10 sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for " solution bleaching or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution known peroxides includes horseradish peroxidase ligninase and
15 haloperoxidases such as choloro-or bromo-peroxidase
A range of enzyme materials and means for their incorporation into synthetic detergent compositions is adies can. also be
disclosed in WO-A-93/07263 and WO-A-93/07260 to Genencor International, WO-A-
20 89/08694 to Novo, and US-A-3,553,139.
A process for enhancing the efficacy of the bleaching action of oxidoreductases is by targeting, them to stains by using antibodies or antibody fragments as described in WO-A-98/56885.

25 Antibodies can also be added to control, enzyme activity as described in WO-A-98/06812.
A preferred combination is a detergent composition comprising of a mixture of the protease, lipase, amylase and/or cellulase
30 of the invention together with one or more plant cell wall degrading enzymes.

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Suitable amylases include those of bacterial or fungal origin. Chemically or genetically modified variants of these enzymes are included as described in WOj-A-9.9/02 632 pages 18,19. Commercial cellulase are sold under the trade name PurastarTM
5 Purastar OxAmTM, (formerly Purafact Ox AmTM ) by Genericor;
Termamyl™, Fun-gamy 1™, Duramyl™, ' Natalase™, all available from Novozymes.

Amylases suitable herein include, for example, alfa-amylases 10 described in GB^1,296,839 to Novo; RAPIDASE™, International
Bio-Synthetics, Inc. and TERMAMYL™,-Novo. FUNGAMYL™ from Novo
is especially useful.
See, for example, references disclosed in WO-A94/02597
Stability-enhanced amylases can be obtained from Novo or from
15 Genencor International. One class of highly preferred amylases
herein have the commonality of being derived using site-directed mutagenesis from one or more of the Baccillus amylases, especially the Bacillus cc- amylases, regardless of whether one, two or multiple amylase strains are the immediate
20 precursors.
Oxidative stability-enhanced amylases, vs.- the above-identified reference amylase are preferred for Use especially in
bleaching, more preferably oxygen bleaching, as distinct from
25 chlorine bleaching, detergent compositions herein. Such
preferred amylases include (a) an amylase according to WO-A-94/02597, known as TERMAMYL™.
Particularly preferred amylases herein include amylase variants 30 having additional modification in the immediate parent as
described in WO-A-95/10603 and are available from the assignee, Novo, as DURAMYL™. Other particularly preferred oxidative

WO 2005/059077


stability-enhanced amylase include those described in WO-A-94/18314,; to Genencor International and. WO-A-94/02597 to Novo Or WO-A-95/09909 A to Novo.
5 Suitable cellulases include those of bacterial or fungal origin. Chemically or genetically modified variants of these enzymes are included as described in WO-A-99/02632, page 17. Particularly useful cellulases are the endoglucanases such as the EGIII from Trichoderma longibrachiatum as described in WO-
10 A-94/21801 and: the E5 from Thermomonosporafusca as described in WO-A-97/20025. Endoglucanases may consist of a catalytic domain and a cellulose binding domain or a catalytic domain only. Preferred cellulolytic' enzymes are sold under the tradename Carezyme™, Celluzyme*" and Endolase™ by Novo Nordisk
15 A/S; Puradax™ is sold by Genencor and KAC™ is sold by Kao corporation; Japan.
Detergent enzymes are usually incorporated in an amount of 0.00001% to 2%/ and more preferably'"6.001%'to 0.5%, and even
20 more preferably 0.005% to 0.2% in terms of pure enzyme protein by weight of the composition. Detergent enzymes are commonly employed in the form of granules made of crude enzyme alone or in combination with other components in the detergent composition. Granules of crude enzyme are used in such an
25 amount that the pure enzyme is 0.001 to 50 weight percent in the granules. The granules are used in an amount of 0.002 to 20 and preferably 0.1 to 3 weight percent. Granular forms of detergent enzymes are known as Enzoguard granules, prills, marumes or T-granules. Other suitable, forms of enzymes are
30 liquid forms such as the "L" type liquids from Novo Nordisk, slurries of enzymes in noniohic surfactants such as the "SL" type sold by Novo Nordisk and microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP" and "CC".

WO 2005/059077 PCT/EP2004/013373
The enzymes can be added as separate single ingredients (prills, granulates, stabilised liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (e.g. cogranulates). Enzymes in liquid detergents can be stabilised
5 by various techniques as for example disclosed in US-A-4,261, 868 and US-A-4,318,818.
The detergent compositions of the present invention may additionally comprise one or more biologically active peptides
10 such as swollenin proteins, expansins, bacteriocins and peptides capable of binding to stains.
The liquid composition of the invention, may comprise from 1 to
15 90%, preferably from 10 to 70% by weight of a surfactant, preferably selected from anionic, nonionic, cationic, zwitterionic active detergent materials or mixtures thereof. Preferably, the compositions herein comprise 12 to 60% by weight of surfactant, more preferably 15 to.40% by-weight.
Non-limiting examples of surfactants useful herein typically at levels from about 10 % to about 70%, by weight, include the conventional Cn-Cie alkylbehzene sulphonates ("LAS") , the Ci0-Ci8 secondary (2,3) alkyl sulphates of the formula CH3(CH2)x(CHOS03-
25 M+)CH3 and CH3 (CH2)y (CHOS03-M+) CH2CH3 where x and (y +• 1) are
integers of at least about 7, preferably, at least about 9, and M is a water-solubilising cation, especially sodium, unsaturated sulphates such as oleyl sulphate, C10-Ci8 alkyl alkoxy carboxylases (especially the EO 1-7 ethoxycarboxylates),
30 the C10-C13 glycerol ethers, the Cio-Cis alkyl polyglycosides and their corresponding sulphated polyglycosides, and G12-C18 alpha-sulphonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such "as the C12-C18 alkyl

WO 2005/059077


ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-Ci2 alkyl phenol alkoxylates (especially
ethoxylates and' mixed ethoxy/propoxy), C12'-C18 betaines and
i '■.-.■.
sulphobetaines ("sultaines"), Ci0;-C18 amine oxides, and the 5 like, can also be included in the overall compositions. The Ci0-Cia N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO-92/06,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-18N-(3 -
conventional soaps may also be the branched-chain C10-C16
10 methoxypropyl) glucamide. C10.-C20 used. If high sudsing is desired, soaps may be used.

for detersive purposes can
Other anionic surfactants useful
15 also be included in the liquid compositions hereof* These can include salts (including, for example, Sodium potassium, ammonium, and substituted ammonium salts such a mono-, di- and triethanolamirie salts) of soap, d9-C2o linear alkylbenzenesulphonates, C8-C22 primary of secondary
20 alkanesulphonates, Cs-C24 olefinsulphonates, sulphonated
polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, paraffin sulphonates, alkyl phosphates, isothionates such astheacyl isothionates,
25 N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulphosuccinatesj monoesters of sulphosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulphosuccinate-(especially saturated and unsaturated C6-C14 diesters),,N-acyl-sarcosinates, sulphates
30 of alkylpolysaccharides such as the sulphates of
alkylpolyglucoside, branched primary alkyl sulphates, alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2.0')jcCH2COO-M+ wherein R is a C8-C22 alkyl, k is an

WO 2005/059077


integer from 0 to 10, and M is a soluble salt- forming cation, and fatty acids esterified with isethionic acid and neutralised with sodium:hydroxide. Further examples are given in Surface Active Agents and Detergents (Vol. I and II by Schwartz, Perry
5 and Berch).. . .
The liquid detergent compositions of the'present invention preferably comprise at least about 5%, preferably at least 10%,

more preferably at least 12% and

less than 70%, more preferably

10 less than 60% by weight, of an anionic surfactant.
Alkyl alkoxylated sulphate surfactants are "a preferred type of anionic surfactant. These surfactants are water soluble salts or acids typically of the formula RO(A)mS03M wherein R is an
15 unsubstituted "C10-C24 alkyl or hydroxyalkyl, group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about
0.5 and about 6r more preferably between about 0.5 and about 3,
20 and M is hydrogen or a water soluble cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulphates as well as alkyl propoxylated sulphates are contemplated herein. Specific
25 examples of substituted ammonium cations include methyl-,
dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium,. dimethyl piperdinium and cations derived from alkanolamines, e.g., monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
30 Exemplary surfactants are Ci2~Ci8 alkyl. polyethoxylate (1.0) sulphate, C12- Cis alkyl polyethoxylate (2.25) sulphate, Ci2-C18 alkyl polyethoxylate (3.0) sulphate, and C12-C18 alkyl

WO 2005/059077


polyethoxylate (4.0) sulphate wherein M is: conveniently selected from sodium and potassium.
The liquid detergent compositions of the present invention
5 preferably comprise at least about 5%, preferably at least 10%, more preferably at least 12% and less than 70%, more preferably less than 60% by weight, of a nonionic surfactant.
Preferred nonionic surfactants such as C12-C18 alkyl ethoxylates
10 ("AE") including the so-called, narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy) , block alkylene oxide condensate of C6 to C12 alkyl .phenols,* alkylene oxide condensates of C8-C22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic™-
15 BASF Corp.), as well as semi polar nonionics (e.g., amine
oxides and phosphine oxides) can be used in the present liquid compositions. An extensive disclosure of these types of surfactants- is found in US-A-3,929,678.
20 Alkylpolysaccharides such as disclosed in US-A-4, 565, 647 are

s in. the liquid compositions d nonionic; surfactants are
also preferred nonionic surfactant: of the invention. Further preferred the polyhydroxy fatty acid amidesv _ ■
A particularly desirable surfactant of this type for use in the 25 liquid compositions herein is alkyl-N-methyl glucamide.
Other sugar-derived surfactants, include the-N-alkoxy. polyhydroxy fatty acid amides, such as >c'io-C18 N-(3-
I 'r
methoxypropyl) glucamide. The N-prdpyl through N- hexyl C12-Ci8 30 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cio-Gi6 soaps may be used.

WO 2005/059077


Another preferred anionic surfactant is a salt of fatty acids Examples of fatty acids suitable for-use of the present invention include pure or hardened fatty acids derived from
5 palmitoleic,. safflower, sunflower/" soybean, oleic,.linoleic, linolenic, ricinoleic, rapeseed oil or "mixtures thereof. Mixtures of saturated and unsaturated fatty acids can also be used herein.

10 It will be recognised that the

fatty acid will be present in

the liquid detergent composition primarily in the form of a

sodium, potassium, ammonium, ammonium, triethanol ammonium,
soap. Suitable cations include, monoethanol .ammonium diethanol tetraalkyl ammonium, e.g., tetra methyl ammonium up to
15 tetradecyl ammonium etc. cations.
The amount of fatty acid will vary depending on the particular

final* liquid "detergent
%, more preferably 1-20 most
present .in the inventive liquid
characteristics desired in the composition. Preferably 0 to 30
20 preferably 5-15% fatty acid is composition.
Mixtures of anionic and nonionic surfactants are especially useful in a liquid detergent composition of the invention.
25 Liquid detergent compositions of the invention may contain
secondary alcohols exemplified and isopropanol are suitable.
various solvents as carriers.
Low molecular weight primary or
by methanol, ethanol, propanol,
Other suitable carrier materials are glycols, such as mono-, 30 di-, tri-propylene glycol, glycerol and polyethylene glycols

(PEG) having a molecular weight

of from 200 to 5000.

WO 2005/059077


The compositions may contain from 1% to'50%, typically 5% to 30%, preferably .from 2% to 10%, by weight of such carriers.
Detergency builder
5 One or more detergency builders may be suitably present in the liquid detergent composition of the invention.
Examples of suitable organic detergency builders, when present, include the alkaline metal, ammonium and-substituted ammonium
10 polyacetates,. carboxylates, polycarboxylates, polyacetyl carboxylates, carboxymethyloxysuccinatesY"
carboxymethyloxymalonates, ethylene diamine-N,N-disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tet'ramine hexa-acetic acid salts,.:N-alkyl !imino diacetates or
15 dipropionates, alpha sulpho- fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonates and mixtures thereof.
Specific examples include sodium, potassium, lithium, ammonium 20 and substituted ammonium salts of ethylenediamino-tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate.
25 Other optional ingredients
The compositions herein can further comprise a variety of optional ingredients. A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, 30 carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar compositions, etc.

WO 2005/059077,


If high sudsing is desired, suds boosters such as the C10-Ci6 alkanolamides. can be incorporated into the compositions, typically at 1%- 10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds
5 boosters. -If desired, soluble magnesium salts such as MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
10 Chelating Agents
The liquid detergent compositions herein may also optionally contain one or more iron, copper and/or manganese chelating agents. "Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates,
15 polyfunctiohally- substituted.aromatic chelating agents and mixtures therein, all as hereinafter defined.
If utilised, these chelating agents" will generally comprise
from about 0.1% to about 10% by weight of the detergent

20 compositions herein. More preferably> if utilised the chelating
agents will comprise from about ;0.1% to about 3.0% by weight of
such compositions.
Clay Soil Rempyal/Anti-redepositibn Agents
25 The compositions of the present'invention can also optionally
contain water- soluble ethoxylated/amines having clay soil
removal and antiredeposition properties.
Liquid detergent compositions typically contain;.about 0.01% to
about 5% of these agents.
One preferred soil release and anti-redeposition agent is
ethoxylated tetfaethylenepentamine. Exemplary ethoxylated
amines are further described in US-A-4,597,898.

WO 2005/059077


Other types of preferred antiredeposition agent include the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Any optical brighteners or other brightening or whitening agents known in.the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the liquid
10 detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, ..but are not necessarily limited to, derivatives of stilbene, pyrazolone, cournarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5-
15 and 6-membered- ring heterocycles, and other miscellaneous agents -. Examples; of such brighteners are disclosed in "The Production and Application Of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley &.Sons, New York (1982).
20 Suds Suppressors
Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in
25 US-A-4,489,455 and US-A-4,489,574 and-in front-loading European-style washing machines. .
A wide variety of materials may.be. used as suds suppressors, and suds suppressors are well known to those skilled in the
30 art. See, for example, Kirk Othmer Encyclopedia of Chemical
Technology, Third Edition, Volume, 7, pages 430- 447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and

\k) 2005/059077


soluble salts therein. See US-A-2,954,347. The monocarboxylic fatty acids and salts thereof used' as suds suppressor typically have hydrocarbyl chains of 10 to about'24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the
5 alkali metal salts such as sodium,.potassium, and lithium
salts, and..ammonium and alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high
10 molecular weight hydrocarbons such as paraffin, fatty acid
esters (e.g., fatty acid triglycerides)-, fatty acid esters of
monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone),

15 The preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or -emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles
20 wherein the polyorganosiloxane,is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in US-A-4,265,779.
For any detergent compositions to be used in automatic laundry
25 washing machines, suds should not form to the extent that they overflow the washing machine.
Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant
30 that the formulator of the composition can select an amount of this suds controlling agent that"will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines. The compositions herein

WO 2005/059077


will generally comprise from 0.1% to about 5% of suds suppressor.
Fabric Softeners
Various through-the-wash fabric softeners, especially the
5 impalpable smectite clays of US-A-4,062,647 as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide-fabric softener benefits concurrently with fabric cleaning; 'Clay softeners can be used
10 in combination with amine and cationic so'fteners as disclosed, for example, in US-A-4,375,416 and US-A-4,291,071.
Dye Transfer Inhibiting Agents
The compositions -Of the present invention may also include one or more materials effective for inhibiting the transfer of dyes
15 from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting "agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone* and N-1- vinylimidazole, manganese phtahalocyanine, peroxidases-, and mixtures thereof. If
20 used, these agents typically comprise; from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
25 Optionally, the composition according to the present invention may contain a bleach or bleach system.
This bleach or bleach system may be, for' example: (a) a peroxygen bleach species alone and/or in combination with a bleach activator and/or a transition metal catalyst; and (b) a
30 transition metal catalysts in "a composition substantially devoid of peroxygen species.

WO 2005/059077 PCT/EP2004/013373
Bleaching catalysts for stain removal have been developed over recent years and may be used in the present invention. Examples of transition metal bleaching catalysts that may be used are
5 found, for example, in: WO-01/48298, WO-00/60045, WO-02/48301, WO-00/29537 and WO-00/12667. The catalyst may alternatively be provided as the free ligand that forms; a complex in situ. Bleach activators are also well known, in the art. The exact mode of action of bleach activators for peroxybleach compounds
10 is hot known, but it is believed that peracids are formed by reaction of the activators with, the inorganic peroxy compound, which peracids then liberate actiye-dxygen by decomposition. They are generally compounds which contain N-acyl or O-acyl residues in the molecule and which exert their activating
15 action on the peroxy compounds on contact with these in the washing liquor.
Typical examples of activators within these groups are polyacylated alkylene diamines, such.N,N,N3,1"
20 tetraacetylethylene diamine (TAED) and N,N,N1N,1
tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylgylcoluril (TAGU); triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid ester. ~
25 Peroxygen bleaching agents are also welliknown in the art, for example, ■ peracids (e.g., PAP), perborates, percarbonates, peroxyhydrates, and mixtures thereof. Specific preferred examples include: sodium perborate, commercially available in the form of mono- and tetra-hydratesy and sodium carbonate
30 peroxyhydrate. Other examples of peroxyl species and activators
as well as other transition metal catalyst are found in WO-
WO 2005/059077


It is also preferred to include in the compositions, a stabiliser for the bleach or bleach system, for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate
5 organic phosphonate or salt thereof. These stabilisers can be used in acid or salt form which is the calcium, magnesium, zinc or aluminium salt form. The stabiliser may be present at a level of up to about 1% by weight, preferably between about 0.1% and about 0*5% by weight.
Since many bleaches and bleach systems are. unstable in aqueous liquid detergents and/or interact unfavourably with other components in the composition, e.g* enzymes, they may for example be protected, e.g. by encapsulation or by formulating a
15 structured liquid composition, whereby they are suspended in
solid form.
The invention will now be illustrated, by way of the following non-limiting examples, in which all parts and percentages are
20 by weight unless otherwise indicated.

WO 2005/059077


The following ^base' liquid detergent formulation was prepared:

Ingredient 5 LAS acid
Proxel GXL
Sorbitol . 10 Borax.10H2O:
Prifac 7 908
Protease enzyme 15 Water

% by weight
0.4 balance to 100

Wherein: ,
LAS acid = C10-C14 alkyl benzene sulphonic acid;
sLES'= sodium lauryl ether sulphate.(with on average 3 ethylene 20 oxide groups);
NI 7EO'= C12-C13 fatty alcohol ethoxylated with an average of 7
ethylene oxide groups;
MPG = monopropylene glycol;
Prifac 7908 = palmkernel fatty acid 25 Proxel GXL - biocide (20% active)
To various samples of this '•base' liquid formulation 0.06% by weight based on said formulation of several types of perfume component -as indicated in the. tables below- were added such
30 that, as a result, each sample contains a different type of perfume component. To other samples of this 'base' formulation not only 0.06% by weight of said perfume components but also

WO 2005/059077


0.05% by weight BHT, (2,6-di-tert-butyl hydroxy toluene) were
The residual activity of the protease enzyme in all thus-formed
formulations after 2 weeks and 4 weeks storage at 37°C, was
5 determined at 40°C in a TRIS pH 9 buffer and using tetrapeptide
as substrate. For this determination, the following protocol
was used:
Samples of 70 mg of the tested liquid formulation were diluted
in 10.00 ml MiiliQ water. 10 [µl of this* solution was added to
10 an assay of 205 [µl containing 74.4 mM TRIS pH9 and 0.494 mM
tetrapeptide (succinyl-Ala-Ala-Prp-Phe-p-Nitroanilide) .
The absorbance of the tested samples at a wavelength of 450 nm was measured for 15 minutes at 40 °C, using, a spectrophotometer. The absolute changes in absorbance as, compared to the
15 absorbance measured on a freshly prepared calibration sample were correlated to the measured activity of such freshly prepared sample.' The measured protease enzyme activity is expressed as GU/ml.
The residual enzyme activity (expressed as ■•%)' is the enzyme
20 activity after storage of the liquid formulation concerned divided by the enzyme- activity measured "at t=0. Tables 1 and 2 show the effect of the addition of 0.05% by weight of BHT on the residual enzyme activity in ‘base' liquid detergent formulations additionally containing 0.06% by weight
25 of the indicated perfume components, after 2 weeks storage at 37°C respectively 4 weeks storage at 37°C.

WO 2005/059077


Table 1

Perfume component

Residual activity after 2 weeks

No BHT 0.05% BHT
5 -none- 56 '■ -■'
Zestover 16. 82
Lilial 39 "80
Octenal 13 68 '
Tridecyclenc ildehyde 14 ;■". ':;;';'70
10 Pulegone 45 .:-82
Alpha methyl iionone 39 84
Terpinolene 51 85
Terpinegene G- 48 -72
Table 2

Perfume component

Residual activity after 4 weeks

No BHT . 0-05% BHT
20 -none- 29
Zestover 5 • '7-2
Lilial 9 -68
Octenal 3 46
Tridecyclens ildehyde 4 54
25 Pulegone 16 76
Alpha methyl .ionone ' 14 78
Terpinolene 17 79
Terpinegene G 23 , 62

1. A liquid detergent composition comprising :
(a) a cleaning effective amount of an enzyme selected from a proteolytic enzyme, a lipolytic enzyme, an amylolytic enzyme, a cellulolytic enzyme and a mixture thereof;
(b) from 0.001 % to 3% by weight of a perfume composition; and
(c) from 0.005% to 2% by weight of an antioxidant selected from the group consisting of 2, 6- di-tert-butyl- hydroxy-toluene (BHT), a-, R-, y-, 6-tocopherol, 6-hydroxy-2, 5, 7, 8-tetra- methylchroman-2-carboxylic acid (Trolox™), and mixtures thereof.
2. A liquid composition according to claim 1, wherein the enzyme is a
proteolytic enzyme.
3. A composition according to claim 1 or 2, wherein the perfume composition comprises at least 0. 01% by weight based on the liquid composition of a perfume component selected from terpenes, ketones, aldehydes and mixtures thereof.
4. A liquid composition according to any of claims 1-3, wherein the antioxidant has a concentration in the range of from 0.0 1% to 0. 08% by weight.
5. A liquid composition according to any of claims 1-4, wherein the antioxidant is 2, 6-di-tert-butyl-hydroxy-toluene.

A liquid composition according to any preceding claim, wherein the enzyme is present at a concentration of from 0.001 mg to 3 mg of the enzyme per gram of liquid composition.
A liquid composition according to any preceding claim, wherein the perfume composition is present at a concentration of from 0.01 to 2% by weight: ;,
A liquid composition according to any preceding Claim, wherein said perfume composition comprises at least 5% of the perfume component.
A liquid composition according to any preceding claim, wherein the perfume component is terpene selected from the group consisting of terpinolene, gamma-terpinene, and pinane.
A liquid composition according to any preceding claim, wherein the perfume component is aldehydic perfume selected from the group consisting of trlfernal, lilial, citronella!, cyclosal, heliopropanal, zestover, aldehyde C12, tridecylenicaldehyde, cyciosia base, and octenal.
A liquid composition according to any preceding claim, wherein the
perfume component is ketone selected from the group consisting of
pulegone/vertofix coeur, veloutone, alpha- methylionone, and
damascehone. •
A method of cleaning a fabric substrate, comprising the steps of treating the substrate with a liquid composition as defined in any preceding claim in an aqueous environment, rinsing the substrate and drying it.

13. Use of an antioxidant as specified in claim 1 in a liquid laundry detergent composition containing 0.001 - 3% by weight of a perfume composition and a cleaning effective amount of an enzyme selected from a proteolytic enzyme, a lipolytic enzyme, an amylolytic enzyme, a cellulolytic enzyme and a mixture thereof, for improving the storage stability of the liquid laundry detergent composition.

Dated this 7in day of June 2006.


(S. Venkatramani) Sr. Patents Manager


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Patent Number 240376
Indian Patent Application Number 661/MUMNP/2006
PG Journal Number 20/2010
Publication Date 14-May-2010
Grant Date 06-May-2010
Date of Filing 07-Jun-2006
Applicant Address Hindustan Lever House,165-166 Backbay Reclamation,Mumbai 400 020,
# Inventor's Name Inventor's Address
1 OUWENDIJK-VRIJENHOEK Maartje Unilever R&D Vlaardingen,Olivier van Noortlaan 120,3133 AT,Vlaardingen,
2 SONMEZER Derdiyok Unilever R&D Vlaardingen,Olivier van Noortlaan 120,3133 AT,Vlaardingen,
3 VEERMAN Simon Marinus Unilever R&D Vlaardingen,Olivier van Noortlaan 120,3133 AT,Vlaardingen,
PCT International Classification Number C11D3/386
PCT International Application Number PCT/EP2004/013373
PCT International Filing date 2004-11-25
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 03078937.4 2003-12-11 EUROPEAN UNION