CA2586054A1 - Detergent compositions comprising encapsulated perfumes and lipases - Google Patents

Abstract

Detergent compositions comprising high efficiency lipase enzymes and particles comprising encapsulated perfumes. Preferred perfumes have a boiling point at 760 mm Hg, of 260~C or lower and a calculated CLogP of at least 3Ø The encapsulated perfume particles are useful in laundry compositions in order to provide efficacious perfume delivery at all stages of the wash, particularly during the laundering stage.

Description

DETERGENT COMPOSITIONS

Technical field The present invention relates to detergent compositions, particularly laundry detergent compositions and in particular to detergents comprising lipolytic or lipase enzymes.

Background of the Invention and Prior Art Lipase enzymes have beeii used in detergents since the late 1980s for removal of fatty soils. It is known that lipase enzymes impact perfumes of detergent compositions containing them. The selection of perfumes for use in detergent compositions coinprising lipase enzymes is documented in EP-A-430315, where it is described that in order to coinbat malodours resulting from the use of lipase enzynles, perfumes should be used that comprise at least 25% by weight of defined perfmne materials and less than 50%
by weight of esters derived from fatty acids with 1-7 carbon atoms.
Until relatively recently, the main commercially available lipase enzymes worked particularly effectively at the lower moisture levels of the drying phase of the wash process. However, more recently, higher efficiency lipases have been developed that also work effectively during the wash phase of the cleaning process. Examples of such enzymes are as described in W000/60063 and Research Diselsoure IP6553D. This malces it even more difficult for the detergent formulator to produce consumer acceptable perfumes in a climate where consumers' expectation is increasingly for pleasant perfumes at all stages of the washing process. One particular area where the impact of lipase on the perfume in the detergent composition can be most noticeable to consuiners is after storage and as a result, during the washing process. This can be a particular problem for detergents for use in hand-washing processes. The present inventors have found that the problems described above can be alleviated even for detergent formulations comprising the new high efficiency lipase enzymes. Furthermore, the present inventors have found specific preferred perfames for use in such detergent formulations.

Definition of the Invention In accordance with the present invention there is provided a detergent coinposition comprising:
1. a lipase which is a polypeptide having an amino acid sequence which: (a) has at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) compared to said wild-type lipase, coinprises a substitution of an electrically neutral or negatively charged amino acid at the surface of the three-dimensional structure within 15Angstroms of El or Q249 with a positively charged amino acid; and (c) coinprises a peptide addition at the C-terminal; and/or (d) comprises a peptide addition at the N-terminal and/or (e) meets the following limitations:
i) comprises a negative amino acid in position E2 10 of said wild-type lipase; ii) comprises a negatively charged amino acid in the region corresponding to positions 90-101 of said wild-type lipase; and iii) comprises a neutral or negative amino acid at a position corresponding to N94 of said wild-type lipase and/or has a negative or neutral net electric charge in the region corresponding to positions 90-101 of said wild-type lipase; and 2. an encapsulated perfume particle comprising (a) an at least partially water-soluble solid matrix comprising one or more water-soluble hydroxylic compounds, preferably starch; and (b) a perfume oil encapsulated by the solid matrix.
The lipase enzyme may be a polypeptide as defined above, meeting criteria (a) and (b) and (c) and/or (e).
In a further embodiment of the invention, the encapsulated perfume oil comprises at least 1% by weight or at least 5wt% or even at least 10% by weight, or even at least 20%, 30, 40, 50, 60, 70, 80 or 90 % by weight of at least one perfume ingredient having a boiling point at 36KNm 2(760mmHg) of 260 C or lower and a calculated loglo of its octanol/water coefficient P (ClogP), of at least 3Ø In a further embodiment, the encapsulated perfume oil comprises at least one ester derived from fatty acids with 1-7 carbon atoms, generally at least 1% by weight or at least 5wt% or even at least 10% by weight, or even at least 20%, 30, 40, 50, 60, 70, 80 or 90 wt% ester by weight based on the weight of the total perfume oil in the encapsulated perfume particle. The inventors have found that two particular perfume esters are especially sensitive to the presence of lipase enzymes so that the invention is particularly beneficial where the encapsulated perfume oil comprises benzyl acetate and/or phenylethyl acetate.
In a further embodiment of the invention, there is provided a detergent composition comprising a perfume composition, said perfume composition coinprising the perfume oil in the encapsulated perfume particle and any optional additional pefuine oil, said perfume coinposition comprising at least 10% by weight, or at least 20, 30, 40, 50, 60, 70, 80 or even 90 wt% of one or more perfume components having a molecular weight of greater than 0 but less than or equal to 350 daltons, at least 80% of said one or more perfume components having a cLogP of at least 2.4, said perfume composition comprising at least 5% of said one or more perfume components having a cLogP of at least 2.4.

Detailed Description of the Invention All percentages and ratios herein are calculated by weight unless otherwise indicated. Percentages and ratios are calculated based on the total composition unless otherwise indicated. The nomenclature used herein describing the enzymes, for example relating to amino acid modifications, amino acid groupings and amino acid identity is as in W000/60063.
The lipase enzymes suitable for use in the present invention may be selected from the group consisting of enzymes capable of hydrolyzing ester bonds, classified by EC
number 3.1, preferably enzymes that hydrolyze carboxylic ester bonds, classified by EC
number 3.1.1 Within this class, particularly preferred are lipases classified by EC number 3.1.1.3 and most preferred are those with first wash performance such as are described in W000/60063, W099/42566, W002/062973, W097/04078, W097/04079 and US5869438.
The preferred lipase enzymes are described in W000/60063. The preferred lipases suitable for use in the present invention as described in W000/60063 are described with reference to a lipase that is the wild-type lipase derived from Humicola Lanuginosa strain DSM 4109 (reference lipase). The reference lipase is also referred to as Lipolase (registered trade name of Novozymes). It is described in EP258068 and EP305216 and has the amino acid sequence shown in positionsl-269 of SEQ ID No 2 of US5869438.

The most preferred first wash lipase for use in the present invention is available under the tradename LIPEX (registered tradename of Novozymes), a variant of the Hunaicola lanuginosa (Tlzernaomyces lanuginosus) lipase (Lipolase registered tradename of Novozymes) with the mutations T231R and N233R.
The lipase enzyme incorporated into the detergent compositions of the present invention is generally present in an amount of 10 to 20000 LU/g of the detergent composition, or even 100 to 10000 LU/g. The LU unit for lipase activity is defined in W099/42566. The lipase dosage in the wash solution is typically from 0.02 to 2 mg/1 enzyme, more typically from 0.1 to 2mg/1 as enzyme protein.
The lipase enzyme may be incorporated into the detergent composition in any convenient form, generally in the form of a non-dusting granulate, a stabilised liquid or a coated enzyme particle. Alternatively a slurry, may be suitable.
The at least partially water soluble hydroxylic compounds useful herein are preferably selected from carbohydrates, which can be any or mixture of: i) simple sugars (or mono-saccharides); ii) oligosaccharides (defined as carbohydrate chains consisting of 2-10 monosaccharide molecules); iii) polysaccharides (defined as carbohydrate chains consisting of at least 11, or more usually at least 35 monosaccharide molecules); and iv) starches.
Both linear and branched carbohydrate chains may be used. In addition chemically modified starches and poly-/oligo-saccharides may be used. Typical modifications include the addition of hydrophobic moieties of the form of allcyl, aryl, etc. identical to those found in surfactants to impart some surface activity to these compounds.
Other examples of suitable encapsulating materials include all natural or synthetic gums such as alginate esters, carrageenin, agar-agar, pectic acid, and natural gums such as gum arabic, gum tragacanth and gum karaya, chitin and chitosan, cellulose and cellulose derivatives including i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropyl methyl cellulose (HPMC);
iii)carboxymethylcellulose (CMC); iv) all enteric/aquateric coatings and mixtures thereof.

Particularly preferred encapsulating matrix materials comprise starches.
Suitable examples can be made from, raw starch, pregelatinized starch, modified starch derived from tubers, legumes, cereal and grains, for example corn starch, wheat starch, rice starch, waxy corn starch, oat starch, cassava starch, waxy barley, waxy rice starch, 5 sweet rice starch, amioca, potato starch, tapioca starch, oat starch, cassava starch, and mixtures thereof.
Modified starches suitable for use as the encapsulating matrix in the present invention include, hydrolyzed starch, acid thinned starch, starch esters of long chain hydrocarbons, starch acetates, starch octenyl succinate, and mixtures thereof.
The term "hydrolyzed starch" refers to oligosaccharide-type materials that are typically obtained by acid and/or enzymatic hydrolysis of starches, preferably corn starch.
Suitable hydrolyzed starches for inclusion in the present invention include maltodextrins and corn syrup solids. The hydrolyzed starches for inclusion with the mixture of starch esters have a Dextrose Equivalent (DE) values of from about 10 to about 36 DE.
The DE
value is a measure of the reducing equivalence of the liydrolyzed starch referenced to dextrose and expressed as a percent (on a dry basis). The higher the DE value, the more reducing sugars present. A method for determining DE values can be found in Standard Analytical Methods of the Member Companies of Corn Industries Research Foundation, 6th ed. Corn Refineries Association, Inc. Washington, DC 1980, D-52.
Starch esters having a degree of substitution in the range of from about 0.01%
to about 10.0% may be used to encapsulate the perfume oils of the present invention. The hydrocarbon part of the modifying ester should be from a C5 to C16 carbon chain.
Preferably, octenylsuccinate (OSAN) substituted waxy corn starches of various types such as 1) waxy starch: acid thinned and OSAN substituted, 2) blend of corn syrup solids:
waxy starch, OSAN substituted, and dextrinized, 3) waxy starch: OSAN
substituted and dextrinized, 4) blend of corn syrup solids or maltodextrins with waxy starch:
acid thinned OSAN substituted, and then cooked and spray dried, 5) waxy starch: acid thinned and OSAN substituted then cooked and spray dried, and 6) the high and low viscosities of the above modifications (based on the level of acid treatment) can also be used in the present invention.

Modified starches having emulsifying and emulsion stabilizing capacity such as starch octenyl succinates have the ability to entrap the perfume oil droplets in the emulsion due to the hydrophobic character of the starch modifying agent. The perfume oils remain trapped in the modified starch until dissolved in the wash solution, due to thermodynamic factors i.e., hydrophobic interactions and stabilization of the emulsion because of steric hindrance. The perfume may be adsorbed or adsorbed onto a carrier prior to encapsulation. Suitable examples of carriers are as described in WO
97/11151 or may be polymeric materials. Zeolite is a particularly preferred carrier, for example as described in more detail in W097/1 1 1 5 1.
Other known methods of manufacturing the starch encapsulates of the present invention, include but are not limited to, fluid bed agglomeration, extrusion, cooling/crystallization methods and the use of phase transfer catalysts to promote interfacial polymerization.
Other suitable matrix materials and process details are disclosed in, e.g., U.S. Pat.
No. 3,971,852, Brenner et al., issued July 27, 1976.

Perfume Oils As used herein, the expression "perfume oil" is intended to refer to perfume raw materials or ingredients, or combinations thereof. Whilst these are generally iminiscible with water under standard conditions of temperature and pressure, a small number may be miscible with water. The perfume oil may comprise one perfume ingredient or mixtures of more than one perfume ingredient. In addition to the perfume oil present in the detergent compositions of the invention via the encapsulated perfume particle, additional perfume oils may be present in the detergent via other delivery systems as discussed below. The overall sum of perfume ingredients present in the encapsulated perfume oil and any optional additional perfume oils provides the perfume composition of the detergent composition.
The inventors have found that often lipase enzymes and particularly the high efficiency lipase enzymes essential for the present invention, are problematic for perfume stability on storage and this means that the perfume fragrance detected by the consumer is not only reduced compared with the amount of perfume added into the detergent formulation but may also be adversely affected so that it is not the perfume selected by the perfumer. This problem is particularly noticeable by the consumer during the washing process and the inventors have found that not only do the encapsulated perfumes have a degree of protection on storage, but also surprisingly, the encapsulated perfumes appear to be chaperoned to the surface of the wash water by the encapsulate, providing maximum efficacy for the perfume raw materials used. The use of the encapsulated perfumes in combination with the specified lipases also provides a degree of protection from these particularly lipase-sensitive perfume raw materials.

Preferably the perfume oil present in the encapsulated perfume particle comprises one or more perfume ingredient characterized by its boiling point (B.P.) and its octanol/water partition coefficient (P). The octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water. The preferred perfume ingredients of this invention have a B.P., determined at the normal, standard pressure of about 760 mm Hg, of about 260 C or lower, preferably less than about 255 C; and more preferably less than about 250 C, and an octanol/water partition coefficent P of about 1,000 or higher. Since the partition coefficients of the preferred perfume ingredients of this invention have high values, they are more conveniently given in the form of their logarithm to the base 10, logP. Thus the preferred perfume ingredients of this invention have logP of at least 3, preferably more than 3.1, and even more preferably more than 3.2.
The boiling points of many perfume ingredients are given in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author, 1969, incorporated herein by reference.
The logP of many perfume ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP"
program, also available from Daylight CIS. This program also lists experimental logP
values when they are available in the Pomona92 database. The "calculated logP"
(ClogP) is determined by the fragment approach of Hansch and Leo ( cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B.
Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom comiectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.

Thus, when a perfume composition which is composed of ingredients having a B.P. of about 260 C or lower and a ClogP, or an experimental logP, of about 3 or higher, is used in an detergent composition, the perfume is very effusive and very noticeable when the product is used. Table 1 gives some non-limiting examples of the preferred perfume ingredients, useful in the detergent compositions of the present invention.
Particularly preferred perfume oils for encapsulation, include one or a mixture of more than one ingredient selected from octyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde (dodecanal or lauric aldehye), diphenyl oxide, alpha-Ionine, Lilial and alpha-iso "gamma" methyl lonone. These have been found to be particularly useful for masking malodours produced from fatty acid odours. These particularly preferred perfume oils may be encapsulated singly or as part of a mixture with other preferred (i.e.
listed in Table 1 below) or particularly preferred perfume oils or as part of a mixture with other perfume oils.
Table 1 Examtales of Preferred Perfume Ingredients Approx. Approx.
Perfume Ingredients BP C CIo9P
allo-Ocimene 192 4.362 Allyl Heptoate 210 3.301 Anethol 236 3.314 Benzyl Butyrate 240 3.698 Cainphene 159 4.192 Carvacrol 238 3.401 beta-Caryophyllene 256 6.333 cis-3-Hexenyl Tiglate 101 3.700 Citral (Neral) 228 3.120 Citronellol 225 3.193 Citronellyl Acetate 229 3.670 Citronellyl Isobutyrate 249 4.937 Citronellyl Nitrile 225 3.094 Citronellyl Propionate 242 4.628 Cyclohexyl Ethyl Acetate 187 3.321 Decyl Aldehyde 209 4.008 Dihydro Myrcenol 208 3.030 Dihydromyrcenyl Acetate 225 3.879 DimethylOctanol 213 3.737 DiphenylOxide 252 4.240 Dodecalactone 258 4.359 Ethyl Methyl Phenyl Glycidate 260 3.165 Fenchyl Acetate 220 3.485 gamma Methyl lonone 230 4.089 gamma-n-MethylIonone 252 4.309 gamma-Nonalactone 243 3.140 Geranyl Acetate 245 3.715 Geranyl Formate 216 3.269 Geranyl Isobutyrate 245 4.393 Geranyl Nitrile 222 3.139 HexenylIsobutyrate 182 3.181 Hexyl Neopentanoate 224 4.374 Hexyl Tiglate 231 3.800 alpha-Ionone 237 3.381 beta-Ionone 239 3.960 gamma-Ionone 240 3.780 alpha-Irone 250 3.820 Isobomyl Acetate 227 3.485 Isobutyl Benzoate 242 3.028 Isononyl Acetate 200 3.984 Isononyl Alcohol 194 3.078 5 Isobutyl Quinoline 252 4.193 Isomenthol 219 3.030 para-Isopropyl Phenylacetaldehyde 243 3.211 Isopulegol 212 3.330 Lauric Aldehyde (Dodecanal) 249 5.066 10 Lilial (p-t-Bucinal) 258 3.858 d-Limonene 177 4.232 Linalyl Acetate 220 3.500 Menthyl Acetate 227 3.210 Methyl Chavicol 216 3.074 alpha-iso "gamma" Methyl lonone 230 4.209 Methyl Nonyl Acetaldehyde 232 4.846 Methyl Octyl Acetaldehyde 228 4.317 Myrcene 167 4.272 Neral 228 3.120 Neryl Acetate 231 3.555 Nonyl Acetate 212 4.374 Nonyl Aldehyde 212 3.479 Octyl Aldehyde 223 3.845 Orange Terpenes (d-Limonene) 177 4.232 para-Cymene 179 4.068 Phenyl Heptanol 261 3.478 Phenyl Hexanol 258 3.299 alpha-Pinene 157 4.122 beta-Pinene 166 4.182 alpha-Terpinene 176 4.412 gamma-Terpinene 183 4.232 Terpinolene 184 4.232 Terpinyl acetate 220 3.475 Tetrahydro Linalool 191 3.517 Tetrahydro Myrcenol 208 3.517 Tonalid 246 6.247 Undecenal 223 4.053 Veratrol 206 3.140 Verdox 221 4.059 Vertenex 232 4.060 The perfume oil in the encapsulated perfume particle may be adsorbed or absorbed onto a carrier prior to encapsulation. Suitable carriers are described in W097/11151. A
particularly preferred carrier is zeolite.

The detergent compositions herein comprise from about 0.01 % to 50% of the encapsulated perfume particle. More preferably, the detergent compositions herein comprise from 0.05% to 8.0% of the perfume particle, even more preferably from 0.5% to 3.0%. Most preferably, the detergent coinpositions herein contain from 0.05%
to 1.0% of the encapsulated perfume particle. The encapsulated perfume particles preferably have size of from 1 micron to 1000 microns, more preferably from 50 microns to 500 microns.
The perfume oil and/or perfume composition is generally present in the detergent compositions of the invention in amounts of from 0.001% to about 5%, preferably fioin 0.01% to 5%, and more usually from 0.05% to 3%. Where present in the detergent compositions of the present invention, the preferred perfume ingredients may comprise 100% of the perfume oil, but is more usually used in addition to other perfume ingredients. A mixture of more than one of the preferred perfume ingredients may be present for example, at least 2 or even at least 5 or 6 or 7 different preferred perfume ingredients. Furthermore, the encapsulated perfume particles may contain at least 1 Or 5 or 10 wt% or even at least 20, 30, 40, 50, 60, 70, 80 or 90 wt% of such preferred perfuine ingredients.

Most common perfume ingredients which are derived from natural or synthetic sources are composed of a multitude of components. For example, orange terpenes contain about 90% to about 95% d-limonene, but also contain many other nziiior ingredients. When each such material is used in the formulation of the perfume oils in the present invention, it is counted as one ingredient, for the purpose of defining the invention.

The detergent compositions may comprise in addition to the encapsulated perfume oil, additional perfume oil forming part of the total perfume coinposition in the detergent composition. The additional perfiune oil may be incorporated into the detergent composition by any other delivery method, for example, simply by spraying onto the finished detergent composition or onto a component thereof, prior to mixing to form the finished detergent composition.

The encapsulated perfume particles also may comprise perfiune oil comprising esters derived from fatty acids having 1 to 7 carbon atoms. Where the detergent composition additionally comprises additional perfume oil, preferably at least 60 wt%, or at least 80 or 90 or substantially all the ester derived from fatty acid having from 1 to 7 carbon atoms will be present in the encapsulated perfume particles.

In a further aspect of the invention, the encapsulated perfume oil and/or the perfume composition in the detergent composition coinprises at least 10 % , 20%, 30%, 40%, 50%, 60%, 70%, 80%, or even 90% of one or more perfume ingredients having a molecular weight of greater than 0 but less than or equal to 350 daltons, from about 100 daltons to about 350 daltons, from about 130 daltons to about 270 daltons, or even from about 140 daltons to about 230 daltons; at least 80%, 85%, 90% or even 95% of said one or more perfume ingredients having a cLogP of at least 2.4, from about 2.75 to about 8.0 or even from about 2.9 to about 6.0, said perfume composition comprising at least 5%, 15%, 25%, 35%, 45 10, 55%, 65%, 75%, 85%, or even 95% of said one or more perfume ingredients having a cLogP in the range of at least 2.4, from about 2.75 to about 8.0 or even from about 2.9 to about 6Ø In said aspect of the invention said one or more perfunle ingredients may be selected from the group consisting of a Schiff's base, ether, phenol, ketone, alcohol, ester, lactone, aldehyde, nitrile, natural oil or mixtures thereof.
Schiff's base and nitriles may be least preferred. In certain aspects of the invention as recited above, said one or more perfume ingredients may include Table 2 Perfume Ingredients or mixtures thereof or even Table 2 Perfume Ingredients 1 through 28 or mixtures thereof. It may be preferred for ketones and aldehydes to have a molecular weight of below 200 daltons.
In another aspect of the invention said perfume composition coinprises at least 10 % , 20%, 30%, 40%, 50%, 60%, 70%, 80%, or even 90% of a perfuine ingredient selected from the group consisting of the ingredients listed in Table 2 below and mixtures thereof.

Table 2 Chemical Name CAS Functionality M Wt clogP
1 2-Methoxynaphthalene 93-04-9 Ether 158 3.24 2 Diphenyl ether 101-84-8 Ether 170 4.24 2-methoxy-4-propenyl 120-11-6 Phenol 164 4.63 3 phenol 4 2-Methoxy-4 allyl phenol 97-53-0 Phenol 164 2.40 4-Penten- 1 -one, 1-(5,5- 56973-85-4 Ketone 192 4.0 dimethyl-l-cyclohexen-1-yl) (lalpha (E),2 beta) - 1- 71048-82-3 Ketone 192 3.62 (2,6,6-Trimethyl-cyclohex-3-en-1-yl)but-2-6 en-l-one 3-Buten-2-one, 3-Methyl-4- 127-51-5 Ketone 206 4.0 (2,6,6-Trimethyl-2-7 Cyclohexen-1-yl) 2-(2-(4-methyl-3- 95962-14-4 Ketone 220 4.44 cyclohexen-1-8 yl)propyl)cyclopentanone 4-[(2,6,6-trimethyl-l- 127-41-3 Ketone 192 3.71 cyclohex-2-enyl)]but-3-en-9 2-one 1Buten-l-ol,2ethyl-4-(2,2,3- 28219-61-6 Alcohol 208 4.43 trimethyl-3 - cyclop entyl-l-yl)-2-Ethyl-4-(2,2,3- 28219-61-6 Alcohol 208 4.43 trimethylcyclopent-3 -enyl-11 1)-2-buten-l-ol Cyclopentaneacetic 24851-98-7 , Ester 226 2.42 acid,3 oxo-2-pentyl-methyl 12 ester Methyl 2-hexyl-3-oxo- 37172-53-5 Ester 226 3.09 13 cyclopentanecarboxylate 14 Tricyclodecenyl Propionate 17511-60-3 Ester 206 2.89 Tricyclo Decenyl Acetate 2500-83-6 Ester 190 2.36 16 n-pentyl salicylate 2050-08-0 Ester 208 4.56 chromen-2-one or 1,2- 91-64-5 Lactone 146 1.41 17 benzopyrone 4- 30168-23-1 Aldehyde 204 3.63 (tricycle(5,2,1,0)decylidene-18 8)butanal 3-(3- 125109-85- Aldehyde 190 3.55 19 isopropylphenyl)butanal 5 p-tert.Butyl-alpha- 80-54-6 Aldehyde 204 3.86 methyldihydrocinnamic aldehyde 21 alpha-Hexylcinnamaldehyde 101-86-0 Aldehyde 216 4.85 22 n-octanal 124-13-0 Aldehyde 128 2.95 23 n-nonanal 124-19-6 Aldehyde 142 3.98 24 n-decanal 10486-19-8 Aldehyde 156 5.60 dodecanal 112-54-9 Aldehyde 184 5.07 Benzene propane nitrile 97384-48-0 Nitrile 171 2.31 26 alpha-ethenyl-alpha-methyl 2-cyclohexylidene-2- 104621-98- Nitrile 197 n/a 27 phenylacetonitrile 0 28 Patchouli n/a Natural Oil n/a n/a Naphtho[2,1-b]furan, 3738-00-9 Ether 236 5.26 dodecahydro-3a,6,6,9a-29 tetramethyl-30 Cyclopentanone, 2-pentyl- 4819-67-4 Ketone 154 2.94 Ethanone, 1-(1,2,3,4,5,6,7,8- 54464-57-2 Ketone 234 4.84 octahydro-2,3,8,8-tetramethyl-2-31 naphthalenyl)-3-methyl-4(5)- 82356-51-2 Ketone 236 5.60 32 cyclopentadecenone 2(3H)-Furanone, 5- 104-67-6 Lactone 184 3.83 33 heptyldihydro-34 Methyl ionone (mixture) 1335-46-2 Ketone 206 4.23 Spiro[1,3-dioxolane- 154171-77- Ketone n/a 5.67 2,8'(5'H)-[2H- 4 2,4a]methanonaphthalene], hexahydro-1',1',5',5'-tetrainethyl-, [2'S-(2'. alpha.,4'a. alpha., 8'a. alpha 35 .)]-36 Undecanal, 2-methyl- 110-41-8 Aldehyde 184 4.85 37 10-Undecenal 112-45-8 Aldehyde 168 4.05 38 4-Methyl-3-decen-5-ol 81782-77-6 Alcohol 170 Benzoic acid, 2-hydroxy-, 25485-88- Ester 220 4.48 39 cyclohexyl ester 5 4H-Inden-4-one, 1,2,3,5,6,7- 33704-61- Ketone 206 3.99 hexahydro-1,1,2,3,3- 9 40 pentamethyl-N-2,4-Dimethyl-3- 68738-99- Schiffs base n/a 4.78 cyclohexenemethylene 8 41 methyl anthranilate 2-Buten-l-ol, 2-ethyl-4- 28219-61- Alcohol 208 4.43 (2,2,3-trimethyl-3- 6 42 cyclopenten-l-yl)-43 Acetic acid, hexyl ester 142-92-7 Ester 144 2.83 1,6-Octadien-3-ol, 3,7- 78-70-6 Alcohol 154 2.55 44 dimethyl-Cyclohexanol, 2-(1,1- 88-41-5 Ester 198 4.06 45 dimethylethyl)-, acetate 2-Butanone, 4-(4- 5471-51-2 Ketone 164 1.07 46 hydroxyphenyl)-Ethanone, 1-(2,3,4,7,8,8a- 32388-55-9 Ketone 246 4.75 hexahydro-3,6,8,8-tetramethyl-lH-3a,7-methanoazulen-5-yl)-, [3R-(3.alpha.,3 a.beta.,7.beta.,8a.
47 alpha.)]-Cyclododecane, 58567-11- Ether 242 5.48 48 (ethoxymethoxy)- 6 Cyclohexane, 3-ethoxy- 24691-15- Ether 156 3.93 49 1,1,5-trimethyl-, cis- 4 1,3-Benzodioxole-5- 120-57-0 Ether/aldehy 150 1.14 50 carboxaldehyde de Benzoic acid, 2-hydroxy-, 118-58-1 Ester 228 4.22 51 phenylmethyl ester 2-Cyclopenten-l-one, 2- 1105062-7 Ketone 164 2.64 52 methyl-3-(2-pentenyl)-53 Oxacyclohexadecen-2-one 34902-57-3 Lactone 238 5.40 4-Cyclopentadecen-l-one, 0014595- Ketone 222 n/a 54 (Z)- 54-1 Benzoic acid, 2-[(7- 89-43-0 Schiffs base 305 4.17 hydroxy-3,7-dimethyloctylidene)amino]-, 55 methyl 4,7-Methano-3aH-indene- 80623-07- Ester 209 3.37 3a-carboxylic acid, 0 octahydro-, ethyl ester, (3 a. alpha.,4.beta.,7.beta.,7 a.
56 alpha.)-Benzoic acid, 2-hydroxy-, 3- 65405-77- Ester 220 4.61 57 hexenyl ester, (Z)- 8 Benzoic acid, 2-amino-, 134-20-3 Ester 151 2.02 58 methyl ester Benzoic acid, 2-hydroxy-, 6259-76-3 Ester 222 5.09 59 hexyl ester Carbonic acid, 4-cycloocten- 87731-18- Ester 184 2.77 60 1-yl methyl ester 8 37609-25- Ketone 236 5.97 5-Cyclohexadecen-l-one Cyclohexanepropanoic acid, 705-87-5 Ester 196 3.93 62 2-propenyl ester Pentanoic acid, 2-methyl-, 28959-02- Ester 144 2.61 63 ethyl ester, (S)- 6 3-Buten-2-one, 4-(2,6,6- 79-77-6 Ketone 192 3.77 trimethyl-l-cyclohexen-l-64 yl)-, (E)-1,3-Dioxolane, 2,4- 131812-51- Ether 288 6.27 dimethyl-2-(5,6,7,8- 6 tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-65 , cis-2,6-Octadienenitrile, 3,7- 5146-66-7 Nitrile 227 3.25 66 dimethyl-2,6-Nonadienenitrile, 3,7- 61792-11- Nitrile 163 3.78 67 dimethyl- 8 3-Cyclohexene-l- 27939-60-2 Aldehyde 138 2.53 68 carboxaldehyde, dimetllyl-69 Oxacyclohexadecan-2-one 106-02-5 Lactone 240 6.29 Methy-2-methyl-3-(4-tert 91-51-0 Schiffs base 337 6.31 butylphenyl)propylidenanthr 70 anilate Acetic acid, (3- 67634-00-8 Ester 186 2.38 methylbutoxy)-, 2-propenyl 71 ester 9-Undecenal, 2,6,10- 141-13-9 Aldehyde 210 5.16 72 trimethyl-Cyclopentanone, 3-methyl- 13074-63- Ketone 168 3.46 73 2-pentyl- 0 In any of the aforementioned aspects, if the perfume oil or composition comprises an ester perfume ingredient, when said perfume oil or composition comprises an ester perfume component said ester perfuine may have one or more of the following characteristics: branching or pendant rings in at least one of the alpha, beta or garrnna positions; branching or pendant rings in at least one of the alpha or beta positions; or at least one tertiary carbon atom in the alpha position. While not being bound by theory, it is believed that the aforementioned perfume ester characteristics result in increased perfume ester stability, and thus perfume composition stability, when said perfume ester in is the presence of an enzyme that can hydrolyze ester bonds, for exainple, enzymes classed in EC 3.1.1, such as lipases.
In any of the aforementioned aspects of the invention, said perfume oil or composition typically contains no more than about 5 %, or even none of the perfume coinponents selected from the group consisting of Acetic acid, phenylmethyl ester;
Benzene ethanol; Butanoic acid, 2-methyl-, etliyl ester; 4H-Pyran-4-one, 2-ethyl-3-hydroxy-; Benzaldehyde, 4-hydroxy-3-methoxy-; Benzaldehyde, 3-ethoxy-4-hydroxy-; 3-Hexen-l-o1, acetate, (Z)-; Butanoic acid, 2-methyl-, 1-; methylethyl ester; 3-Decanone, 1-hydroxy-; 2-Heptanone; Benzaldehyde; Propanenitrile, 3-(3-hexenyloxy)-, (Z)-;

Butanone, 4-phenyl-; 2-Hexen-l-ol; 2(3H)-Furanone, 5-butyldihydro-.

Processes of Making Perfume Compositions Perfume compositions of the present invention may be made by ad-mixing of perfume raw niaterials, which are typically liquids. Certain perfume raw materials are solid materials and can require gentle heat to homogenise with the rest of the perfume.
The perfume blend can also comprise a significant proportion of a diluent (e.g dipropylene glycol), an antioxidant or a solubilising material. Solubilisers can be particularly advantageous where the surfactant level is low in order to disperse the perfume in a predominantly hydrophilic matrix such as aqueous liquid cleaners.
Perfume Delivery Methods Any of the aforementioned aspects of the perfume compositions may be combined with other materials to produce any of the following deliveiy systems for delivering additional perfume oils into the detergent composition: spray-on perfume oils, sprayed directly onto detergent composition or components thereof, starch encapsulate delivery systems, porous carrier material delivery systems, coated porous carrier material delivery systems, microencapsulate delivery systems. Preferably, detergent comopositions of the invention will comprise encapsulates and spray-on perfume. Suitable methods of producing the aforementioned delivery systems may be found in one or more of the following U.S. patents 6,458,754; 5,656,584; 6,172,037; 5,955,419 and 5,691,383 and WIPO publications WO 94/28017, WO 98/41607, WO 98/52527. Such delivery systeins may be used alone, in combination with other or even in combination with the neat 5 sprayed on or admixed perfume compositions of the present invention in a consumer product.

In addition to the lipase enzyme and encapsulated perfume particles, the detergent compositions of the invention will also contain one or more conventional detergent 10 ingredients and/or detergent adjunct ingredients.

Optional Detersive Adjuncts The detergent compositions of the invention may be in any convenient form such as powdered or granular solids, bars, tablets or non-aqueous liquids, including gel and 15 paste forms. Other forins of cleaning composition include other institutional and/or household cleaning compositions such as liquid or solid cleaning and disinfecting agents, including antibacterial cleaners car or carpet shampoos, denture cleaners, hard surface cleaners, for example for kitchen and/or bathroom use optionally for cleaning metal, hair shainpoos, shower gels, bath foam as well as cleaning auxiliaries such as bleach additives 20 and "stain stick" or pre-treat types. When present in the granular form the detergent compositions of the present invention are preferably those having an overall bulk density of from 350 to 1200 g/l, more preferably 450 to 1000g/l or even 500 to 900g/l.
Preferably, the detergent particles of the detergent composition in a granular form have a size average particle size of from 200 m to 2000 m, preferably from 350 m to 600 m.
Generally the detergent compositions of the invention will be mixed with other detergent particles including combinations of agglomerates, spray-dried powders and/or dry added materials such as bleaching agents, enzymes etc.

As a preferred embodiment, the conventional detergent ingredients are selected from typical detergent composition components such as detersive surfactants and detersive builders. Optionally, the detergent ingredients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition. Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. and in Great Britain Patent Application No. 9705617.0, Trinh et al., published Septeinber 24, 1997.
Such adjuncts are included in detergent compositions at their conventional art-established levels of use, generally from 0% to about 80% of the detergent ingredients, preferably from about 0.5% to about 20% and can include color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, solvents, solubilizing agents, chelating agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, bleaching agents, bleaching activators, bleach stabilizers, etc.
As described above, detergent compositions comprising the particles of the invention will comprise at least some of the usual detergent adjunct materials, such as agglomerates, extrudates, other spray dried particles having different composition to those of the invention, or dry added materials. Conventionally, surfactants are incorporated into agglomerates, extrudates or spray dried particles along with solid materials, usually builders, and these may be admixed with the spray dried particles of the invention. However, as described above some or all of the solid material may be replaced with the particles of the invention.
The detergent adjunct materials are typically selected from the group consisting of detersive surfactants, builders, polymeric co-builders, bleach, chelants, enzymes, anti-redeposition polymers, soil-release polymers, polymeric soil-dispersing and/or soil-suspending agents, dye-transfer inhibitors, fabric-integrity agents, suds suppressors, fabric-softeners, flocculants, perfumes, whitening agents, photobleach and combinations thereof.
The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.

A highly preferred adjunct component is a surfactant. Preferably, the detergent composition comprises one or more surfactants. Typically, the detergent composition comprises (by weight of the composition) from 0% to 50%, preferably from 5%
and more preferably from 10 or even 15 wt% to 40%, or to 30%, or to 20% one or more surfactants. Preferred surfactants are anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof.
Preferred anionic surfactants comprise one or more moieties selected from the group consisting of carbonate, phosphate, sulphate, sulphonate and mixtures thereof.
Preferred anionic surfactants are C$_lg alkyl sulphates and C8_18 alkyl sulphonates.
Suitable anionic surfactants incorporated alone or in mixtures in the compositions of the invention are also the C8_18 alkyl sulphates and/or C8_18 alkyl sulphonates optionally condensed with from 1 to 9 moles of C1_4 alkylene oxide per mole of C8_18 alkyl sulphate and/or C8_1$ alkyl sulphonate. The alkyl chain of the C8_1$ alkyl sulphates and/or C8_1$
alkyl sulphonates may be linear or branched, preferred branched alkyl chains comprise one or more branched moieties that are C1_6 alkyl groups. Other preferred anionic surfactants are C8_1$ alkyl benzene sulphates and/or C$_18 alkyl benzene sulphonates. The alkyl chain of the C$_I$ alkyl benzene sulphates and/or C8_1$ alkyl benzene sulphonates may be linear or branched, preferred branched alkyl chains comprise one or more branched moieties that are C1_6 alkyl groups.
Other prefeiTed anionic surfactants are selected from the group consisting of:
C8_18 alkenyl sulphates, C$_18 alkenyl sulphonates, C$_1$ allcenyl benzene sulphates, C8_18 alkenyl benzene sulphonates, C8_18 alkyl di-methyl benzene sulphate, C$_18 alkyl di-methyl benzene sulphonate, fatty acid ester sulphonates, di-alkyl sulphosuccinates, and combinations thereof. The anionic surfactants may be present in the salt form.
For example, the anionic surfactant may be an alkali metal salt of one or more of the compounds selected from the group consisting of: C8_18 alkyl sulphate, C8_1$
alkyl sulphonate, C8_18 alkyl benzene sulphate, C$-C1$ alkyl benzene sulphonate, and combinations thereof. Preferred alkali metals are sodium, potassium and mixtures thereof.
Typically, the detergent composition comprises from 10% to 30wt% anionic surfactant.

Preferred non-ionic surfactants are selected from the group consisting of C$_18 alcohols condensed with from 1 to 9 of Cl-C4 alkylene oxide per mole of C8_1$
alcohol, C8_18 alkyl N-CI_4 alkyl glucamides, C$_18 amido CI_4 dimethyl amines, C$_18 alkyl polyglycosides, glycerol monoethers, polyhydroxyamides, and combinations thereof.
Typically the detergent compositions of the invention comprises from 0 to 15, preferably from 2 to 10 wt% non-ionic surfactant.

Preferred cationic surfactants are quaternary ammonium compounds. Preferred quaternary aminonium compounds comprise a mixture of long and short hydrocarbon chains, typically alkyl and/or hydroxyalkyl and/or alkoxylated alkyl chains.
Typically, long hydrocarbon chains are C$_I$ alkyl chains and/or Cs_I$ hydroxyalkyl chains and/or C$_rg alkoxylated alkyl chains. Typically, short hydrocarbon chains are C1_4 alky chains and/or C1_4 hydroxyalkyl chains and/or C1_4 alkoxylated alkyl chains.
Typically, the detergent composition comprises (by weight of the composition) from 0% to 20%
cationic surfactant.

Preferred zwitterionic surfactants comprise one or more quaternized nitrogen atoms and one or more moieties selected from the group consisting of carbonate, phosphate, sulphate, sulphonate, and combinations thereof. Preferred zwitterionic surfactants are alkyl betaines. Other preferred zwitterionic surfactants are alkyl amine oxides. Catanionic surfactants which are complexes comprising a cationic surfactant and an anionic surfactant may also be included. Typically, the molar ratio of the cationic surfactant to anionic surfactant in the complex is greater than 1:1, so that the complex has a net positive charge.

A further preferred adjunct component is a builder. Preferably, the detergent composition comprises (by weight of the composition and on an anhydrous basis) from 20% to 50% builder. Preferred builders are selected from the group consisting of:
inorganic phosphates and salts thereof, preferably orthophosphate, pyrophosphate, tri-poly-phosphate, alkali metal salts thereof, and combinations thereof;
polycarboxylic acids and salts thereof, preferably citric acid, alkali metal salts of thereof, and combinations thereof; aluminosilicates, salts thereof, and combinations thereof, preferably amorphous aluminosilicates, crystalline aluminosilicates, mixed amorphous/crystalline aluminosilicates, alkali metal salts thereof, and combinations thereof, most preferably zeolite A, zeolite P, zeolite MAP, salts thereof, and combinations thereof;
silicates such as layered silicates, salts thereof, and combinations thereof, preferably sodium layered silicate; and combinations thereof.

A preferred adjunct component is a bleaching agent. Preferably, the detergent composition comprises one or more bleaching agents. Typically, the composition comprises (by weight of the composition) from 1% to 50% of one or more bleaching agent. Preferred bleaching agents are selected from the group consisting of sources of peroxide, sources of peracid, bleach boosters, bleach catalysts, photo-bleaches, and combinations thereof. Preferred sources of peroxide are selected from the group consisting of: perborate monohydrate, perborate tetra-hydrate, percarbonate, salts thereof, and coinbinations thereof. Preferred sources of peracid are selected from the group consisting of: bleach activator typically with a peroxide source such as perborate or percarbonate, preformed peracids, and combinations thereof. Preferred bleach activators are selected from the group consisting of: oxy-benzene-sulphonate bleach activators, lactam bleach activators, imide bleach activators, and combinations thereof. A
preferred source of peracid is tetra-acetyl ethylene diamine (TAED)and peroxide source such as percarbonate. Preferred oxy-benzene-sulphonate bleach activators are selected from the group consisting of: nonanoyl-oxy-benzene-sulponate, 6-nonamido-caproyl-oxy-benzene-sulphonate, salts thereof, and combinations thereof. Preferred lactam bleach activators are acyl-caprolactams and/or acyl-valerolactams. A preferred imide bleach activator is N-nonanoyl-N-methyl-acetamide.
Preferred preformed peracids are selected from the group consisting of N,N-pthaloyl-amino-peroxycaproic acid, nonyl-amido-peroxyadipic acid, salts thereof, and combinations thereof. Preferably, the STW-composition comprises one or more sources of peroxide and one or more sources of peracid. Preferred bleach catalysts comprise one or more transition metal ions. Other preferred bleaching agents are di-acyl peroxides.
Preferred bleach boosters are selected from the group consisting of:
zwitterionic imines, anionic imine polyions, quaternary oxaziridiniuin salts, and combinations thereof. Highly preferred bleach boosters are selected from the group consisting of aryliminium zwitterions, aryliminium polyions, and combinations thereof. Suitable bleach boosters are described in US360565, US5360569 and US5370826.

A preferred adjunct component is an anti-redeposition agent. Preferably, the detergent composition comprises one or more anti-redeposition agents.
Preferred anti-redeposition agents are cellulosic polymeric components, most preferably carboxymethyl celluloses.
5 A preferred adjunct component is a chelant. Preferably, the detergent composition comprises one or more chelants. Preferably, the detergent composition comprises (by weight of the composition) from 0.01% to 10% chelant. Preferred chelants are selected from the group consisting of: hydroxyethane-dimethylene-phosphonic acid, ethylene diamine tetra(methylene phosphonic) acid, diethylene triamine pentacetate, ethylene 10 diamine tetraacetate, diethylene triamine penta(methyl phosphonic) acid, ethylene diamine disuccinic acid, and combinations thereof.
A preferred adjunct component is a dye transfer inhibitor. Preferably, the detergent composition comprises one or more dye transfer inhibitors.
Typically, dye transfer inhibitors are polymeric components that trap dye molecules and retain the dye 15 molecules by suspending them in the wash liquor. Preferred dye transfer inhibitors are selected from the group consisting of: polyvinylpyrrolidones, polyvinylpyridine N-oxides, polyvinylpyrrolidone-polyvinylimidazole copolymers, and combinations thereof.
Preferred adjunct components include other enzymes. Preferably, the detergent composition comprises one or more additional enzymes. Preferred enzymes are selected 20 from then group consisting of: amylases, arabinosidases, carbohydrases, cellulases, chondroitinases, cutinases, dextranases, esterases, B-glucanases, gluco-amylases, hyaluronidases, keratanases, laccases, ligninases, lipoxygenases, malanases, mannanases, oxidases, pectinases, pentosanases, peroxidases, phenoloxidases, phospholipases, proteases, pullulanases, reductases, tannases, transferases, xylanases, xyloglucanases, and 25 combinations thereof. Preferred additional enzymes are selected from the group consisting of: amylases, carbohydrases, cellulases, proteases, and combinations thereof.
A preferred adjunct component is a fabric integrity agent. Preferably, the detergent composition comprises one or more fabric integrity agents.
Typically, fabric integrity agents are polymeric components that deposit on the fabric surface and prevent fabric damage during the laundering process. Preferred fabric integrity agents are hydrophobically modified celluloses. These hydrophobically modified celluloses reduce fabric abrasion, enhance fibre-fibre interactions and reduce dye loss from the fabric. A
preferred hydrophobically modified cellulose is described in W099/14245. Other preferred fabric integrity agents are polymeric components and/or oligomeric components that are obtainable, preferably obtained, by a process comprising the step of condensing imidazole and epichlorhydrin.
A preferred adjunct component is a salt. Preferably, the detergent composition comprises one or more salts. The salts can act as alkalinity agents, buffers, builders, co-builders, encrustation inhibitors, fillers, pH regulators, stability agents, and combinations thereof. Typically, the detergent composition comprises (by weight of the composition) from 5% to 60% salt. Preferred salts are alkali metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulphate, and combinations thereof.
Other preferred salts are alkaline earth metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulphate, and combinations thereof.
Especially preferred salts are sodium sulphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, and combinations thereof. Optionally, the alkali metal salts and/or alkaline earth metal salts may be anhydrous.
A preferred adjunct component is a soil release agent. Preferably, the detergent composition comprises one or more soil release agents. Typically, soil release agents are polyineric compounds that modify the fabric surface and prevent the redeposition of soil on the fabric. Preferred soil release agents are copolymers, preferably block copolyiners, comprising one or more terephthalate unit. Preferred soil release agents are copolymers that are synthesised from dimethylterephthalate, 1,2-propyl glycol and methyl capped polyethyleneglycol. Other preferred soil release agents are anionically end capped polyesters.
A preferred adjunct component is a soil suspension agent. Preferably, the detergent composition comprises one or more soil suspension agents. Preferred soil suspension agents are polymeric polycarboxylates. Especially preferred are polymers derived from acrylic acid, polymers derived from maleic acid, and co-polymers derived from maleic acid and acrylic acid. In addition to their soil suspension properties, polymeric polycarboxylates are also useful co-builders for laundry detergents.
Other preferred soil suspension agents are alkoxylated polyalkylene imines.
Especially preferred alkoxylated polyalkylene imines are ethoxylated polyethylene imines, or ethoxylated-propoxylated polyethylene imine. Other preferred soil suspension agents are represented by the formula:

bis((C2Hs0)(C2H40)õ(CH3)-N+-CXH2X N+-(CH3)-bis((C2H4O)õ(C2H50)), wherein, n=from 10 to 50 and x=from 1 to 20. Optionally, the soil suspension agents represented by the above formula can be sulphated and/or sulphonated.

Softening system The detergent compositions of the invention may comprise softening agents for softening through the wash such as clay optionally also with flocculant and enzymes.
Further more specific description of suitable detergent components can be found in WO97/11151.

Washing Method The invention also includes methods of washing textiles comprising cleaning, treating and/or masking the odour of a situs for example, a surface or fabric.
Such method comprises contacting the situs such as a textile with an aqueous solution comprising the detergent composition of the invention. The invention may be particularly beneficial at low water temperatures such as below 30 C or below 25 or 20 C.
Typically the aqueous wash liquor will comprise at least 100 ppm, or at least 500ppm of the detergent composition Example 1: Perfume Compositions Common Name CAS Composition Yara Yara 93-04-9 5 Diphenyl Oxide 101-84-8 2 7 5 Iso Eugenol 120-11-6 6 Eugenol 97-53-0 4 5 Dynascone 56973-85-4 1 1.5 Delta damascone 71048-82-3 2 4 Ionone Gamma 127-51-5 20 5 Methyl Nectaryl 95962-14-4 20 lonone alpha 127-41-3 4 Dartanol 28219-61-6 8 Levosandol 28219-61-6 8 Hedione 24851-98-7 25 40 Dihydro 37172-53-5 10 12 5 IsoJasmonate Frutene 17511-60-3 25 Flor Acetate 2500-83-6 25 Amyl Salicylate 2050-08-0 20 Coumarin 91-64-5 4 Dupical 30168-23-1 1 Florhydral 125109-85-5 2 Lilial 80-54-6 20 20 Hexyl Cinnamic 101-86-0 40 aldehyde Aldehyde C10 10486-19-8 5 Laurie Aldehyde 112-54-9 1.5 Peonile 104621-98-0 15 12 Patchouli 10 Balance 100 100 100 100 Example 2: Perfumes Made With Compositions from Example 1.
Perfume Exainple Common Name CAS A B C D
Composition 1 n/a 61 Composition 2 n/a 45 Composition 3 n/a 26 Composition 4 n/a 10 Cetalox 3738-00-9 0.5 Delphone 4819-67-4 2 Delta Muscenone 82356-51-2 1 Undecalactone Aldehyde MNA 110-41-8 2 Undecavertol 81782-77-6 2 Cyclohexyl salicylate 25485-88-5 3 Cashmeran 33704-61-9 1 Agrumea 6873 8-99-8 3 Hexyl Acetate 142-92-7 5 Verdox 88-41-5 10 Methyl Cedrylone 32388-55-9 2 Heliotropin 120-57-0 1 Benzyl Salicylate 118-58-1 4 Iso Jasmone 11050-62-7 1 Habanolide 34902-57-3 5 5 Aurantiol 89-43-0 1 Cis-3-hexenyl salicylate 65405-77-8 3 Methyl Anthranilate 134-20-3 1 Hexyl Salicylate 6259-76-3 4 Manzanate 28959-02-6 1 Geranyl Nitrile 5146-66-7 2 Ligustral 27939-60-2 1 2 Allyl Amyl Glycolate 67634-00-8 1 Adoxal 141-13-9 0.5 Jasmylone 13074-63-0 1 Benzyl Acetate 140-11-4 10 58 Phenyl Ethyl Alcohol 60-12-8 34 Vanillin 121-33-5 1 Ethyl Vanillin 121-32-4 0.5 Cis 3 hexenyl acetate 3681-71-8 1 Cinnamalva 1885-38-7 1 Benzyl Acetone 2550-26-7 20 20 Beta Gamma Hexenol 2305-21-7 1 2 1 Gamma Octalactone 104-50-7 0.5 1 D-Limonene 138-86-3 15 26 Total 100 100 100 100 In the following encapsulation and detergent compositions the perfume component is a perfume according to the present invention and/or Examples 1 and 2 above.

5 Manufacture of Modified Starch Encapsulated Perfume Particles Example 3 1. 225 g of CAPSUL modified starch (National Starch & Chemical) is added to 450 g of water at 24 C.
2. The mixture is agitated at 600 RPM (turbine impeller 2 inches in diameter) for 20 10 minutes.
3. 75 g perfume oil is added near the vortex of the starch solution.
4. The emulsion formed is agitated for an additiona120 minutes (at 600 RPM).
5. Upon achieving a perfume droplet size of less than 15 microns, the emulsion is pumped to a spray drying tower and atomized through a spinning disk with co-current 15 airflow for drying. The inlet air temperature is set at 205-210 C, the exit air temperature is stabilized at 98-103 C.
6. Dried particles of the starch encapsulated perfume oil are collected at the dryer outlet.
Analysis of the finished perfume particle (all % based on weight):
Total Perfume Oil 24.56%
20 Encapsulated Oil/ Free or Surface Oil 24.46%/0.10%
Starch 72.57%
Moisture 2.87%

Particle Size Distribution < 50 micrometers 16%
50-500 micrometers 83%
> 500 micrometers 1 %
Example 4 In a suitable container 500g of HiCap 100 modified starch (supplied by National Starch & Chemical) are dissolved into 1000g of deionised water. Once a homogenous solution is achieved, 40g of anhydrous citric acid is added to the starch solution. The mixture is agitated for 10 minutes to dissolve the citric acid. At this point, 600g of perfume is added to the mixture. The emulsion is then agitated with a high shear mixer (ARD-Barico) for 10 more minutes.
The mixture is then spray dried in a Production Minor cocurrent spray dryer manufactured by Niro A/S. A rotary atomising disc type FS 1, also from Niro A/S, is used. The air inlet teinperature is 200 C and the outlet temperature 90 C.
Disc speed is set at 28,500 rpm. The tower is stabilized at these conditions by spraying water for 30 minutes before spray drying the emulsion. The dried particles are collected in a cyclone.
Detergent compositions comprising the encapsulated perfumes of examples 3 and 4 are exemplified in Table 3 below:

Table 3 Ingredient A B C D E
Sodium linear C11_13 11% 12% 10% 18% 15%
alkylbenzene sulfonate R2N+(CH3)2(C2H4OH), wherein 0.6% 1% 0.6%
R2 = C12_14 alkyl group Mid chain methyl branched 1.4% 1.2% 1%
sodium C 12_C 14 linear alkyl sulfate Sodium C12_181inear alkyl 0.7% 0.5%

sulfate C12_18 linear alkyl ethoxylate 1% 4% 2% 3% 1%
condensed witli an average of 3-9 moles of ethylene oxide per mole of alkyl alcohol Citric acid 2% 1.5% 2%
Sodium tripolyphosphate 25% 22%
(anhydrous weight given) Sodium carboxymethyl 0.2% 0.2% 0.3%
cellulose Sodium polyacrylate polymer 2.0% 0.5% 1% 0.7%
having a weight average molecular weight of from 3000 to 5000 Copolymer of maleic/acrylic 2.1% 3.5% 7% 2.0% 2.1%
acid, having a weight average molecular weight of from 50,000 to 90,000, wherein the ratio of maleic to acrylic acid is from 1:3 to 1:4 (Sokalan CP5 from BASF) Diethylene triamine pentaacetic 0.2% 1.0% 0.2% 0.3%
acid Ethylene diamine disuccinic 0.5% 0.6% 0.5%
acid Proteolytic enzyme having an 0.2% 0.2% 0.5% 0.4% 0.3%
enzyme activity of from 15 mg/g to 70 mg/g Amyolitic enzyme having an 0.2% 0.2% 0.3% 0.4% 0.3%
enzyme activity of from 25 mg/g to 50 mg/g Lipex enzyme from 0.2% 0.5% 0.1% 0.5% 0.3%
Novozymes having an enzyme activity of 5 mg/g to 25 mg/g Anhydrous sodium perborate 20% 5% 8%
monohydrate Sodium percarbonate 10% 12%
Magnesium sulfate 0.1% 0.5%

Nonanoyl oxybenzene sulfonate 2% 1.2%
Tetraacetylethylenediamine 3% 4% 2% 0.6% 0.8%
Brightener 0.1% 0.1% 0.2% 0.1% 0.1%
Sodium carbonate 10% 10% 10% 19% 22%
Sodium sulfate 20% 15% 5% 5% 6%
Zeolite A 25% 20% 20% 17% 14%
Sodium silicate (2.0 R) 0.2% 1% 1%
Crystalline layered silicate 3% 5% 10%
Photobleach 0.002%
Polyethylene oxide having a 2% 1%
weight average molecular weight from 100 to 10,000 Perfume spray-on 0.2% 0.5% 0.25% 0.1%

Starch encapsulated perfume 0.4% 0.5% 1% 0.4% 1.5%
from example 1 or example 2 Silicone based suds suppressor 0.05% 0.05% 0.02%
Soap 1.2% 1.5% 1.0%
Miscellaneous and moisture To To To To To 100% 100% 100% 100% 100%

Claims (10)

1. A detergent composition comprising:
1. a lipase which is a polypeptide having an amino acid sequence which: (a) has at least 90% identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109; (b) compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid at the surface of the three-dimensional structure within 15Angstroms of El or Q249 with a positively charged amino acid; and (c) comprises a peptide addition at the C-terminal; and/or (d) comprises a peptide addition at the N-terminal and/or (e) meets the following limitations:
i) comprises a negative amino acid in position E210 of said wild-type lipase; ii) comprises a negatively charged amino acid in the region corresponding to positions 90-101 of said wild-type lipase; and iii) comprises a neutral or negative amino acid at a position corresponding to N94 or said wild-type lipase and/or has a negative or neutral net electric charge in the region corresponding to positions 90-101 of said wild-type lipase; and

2. an encapsulated perfume particle comprising (a) an at least partially water-soluble solid matrix comprising one or more water-soluble hydroxylic compounds, preferably starch; and (b) a perfume oil encapsulated by the solid matrix.

2. A detergent composition according to claim 1 in which the encapsulated perfume oil comprises at least 1%, or at least 5 % or at least 10% by weight, or even at least 40 % by weight of at least one perfume ingredient having a boiling point at 36KNm-2(760mmHg) of 260°C or lower and a calculated log10 of its octanol/water coefficient P(ClogP), of at least 3Ø

3. A detergent composition according to claim 1 or claim 2, wherein the encapsulated perfume oil comprises an ester derived from a fatty acid having from 1 to 7 carbon atoms.

4. A detergent composition according to any preceding claim in which in addition to the encapsulated perfume oil additional perfume oil is present as a sprayed-on component.

5. A detergent composition according to claim 4 in which the perfume oil comprises an ester derived from a fatty acid having from 1 to 7 carbon atoms and at least 90 wt% of the ester derived from a fatty acid having from 1 to 7 carbon atoms is present in the encapsulated perfume particle.

6. A detergent composition according to any preceding claim in which the encapsulated perfume particle comprises benzyl acetate and/or phenylethyl acetate.

7. A detergent composition according to any preceding claim in which the perfume oil in the encapsulated perfume particle is absorbed or adsorbed onto a carrier and both perfume oil and carrier are encapsulated.

8. A detergent composition according to any preceding claim in which the perfume oil in the encapsulated perfume particle and any optional additional perfume oil in the detergent composition comprise a perfume composition, said perfume composition comprising at least 1% or at least 5 wt% or even at least 10% of one or more perfume ingredients having a molecular weight of greater than 0 but less than or equal to 350 daltons, at least 80% of said one or more perfume ingredients having a cLogP
of at least 2.4, said perfume composition comprising at least 1% or even at least 5% of said one or more perfume ingredients having a cLogP of at least 2.4.

9. A washing process comprising laundering textile articles in an aqueous solution comprising the detergent composition according to any preceding claim.

10. A washing process according to claim 9 in which the aqueous solution is at a temperature below 30°C.