FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
IMPROVEMENTS RELATING TO PERFUMES
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 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
IMPROVEMENTS RELATING TO ERFUMES
Technical Field:
5
The present invention concerns improvements relating to perfumes and particularly to the in-situ generation of perfume components by laundry treatment compositions.
10
Background of the Invention:
Perfume is one of the most expensive components of many cleaning compositions. In order to effectively deliver 15 perfume it is necessary to ensure that perfume is not lost during storage or products and that perfume is effectively deposited during the cleaning process. Many bleach components of laundry and other cleaning compositions are known to interact with perfume components as a consequence 20 it has been suggested to either select bleach components and perfumes which do not react or to separate perfume components from bleach components in many products.
It has therefore been suggested that perfume components for 25 use in formulations with those catalysts which make use
(either directly or indirectly) of atmospheric oxygen should be selected so as to minimise interaction between the perfume components and the bleach catalyst. In laundry tablets for example, any bleaching agents present and any

perfume components can be placed in different layers of the tablets.
Other approaches have been taken to ensuring that perfumes 5 deposit and /or are released at the appropriate time.
WO 2002/038120 (P&G) relates to photo-labile pro-fragrance conjugates which upon exposure to electromagnetic radiation are capable of releasing a fragrant species. By the use of 10 these pro-fragrances it is believed possible to delay
perfume release (and hence perfume loss). Other proposals for controlling deposition and release of perfumes have included the use of deposition aids and/or encapsulation.
15 W099/60990 (P&G) discloses other photo-labile pro-
fragrances. The pro-fragrances disclosed may have photosensitive structures including, alpha-keto esters related to acetophenone (see structures I and II). It is believed that the mechanism by which the fragrance is released involves 2 0 the formation of a hydrogen radical at, for example a 2- alkanoyl benzoate or 2-benzoyl benzoate and a subsequent intra-molecular reaction resulting in the cleavage of an ester-bond to release an alcohol perfume component. It is also suggested that radicals can transfer from pro-fragrance 25 molecule to pro-fragrance molecule.
Brief Description of the Invention;
We have now determined that a broad class of pro-fragrances can be converted to volatile odoriferous species by separate 5 photo-bleaches and that this can be used both to provide inexpensive perfumes and improve perfume delivery.
According to the present invention there is provided a laundry cleaning and/or care composition comprising, 10 separately, a photo-bleach and a pro-fragrance wherein the pro-fragrance comprises at least one, non-aromatic C-C double bond, more preferably at least two C-C double bonds, wherein the pro-fragrance comprises a plant oil and wherein the plant oil comprises a mono-, di- or triacyl-glycerol, 15 phospholipid, glycolipid. diol lipid, wax, sterol ester or tocopherol.
In the context of the present invention a "photo-bleach" is any chemical species {other than a pro-fragrance) which 20 forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction. Preferred photo-bleaches include radical photo-bleaches and, more preferably, singlet oxygen photo-bleaches. Suitable photo-bleaches are described in more detail below.
25
In the context of the present invention a pro-fragrance is any chemical species {other than a photo-bleach) which is a precursor of a volatile odoriferous compound and may be converted into the volatile odoriferous compound (or a
further precursor thereof) by the presence of an active photo-bleach.
Use of a photo-bleach to transform a pro-fragrance into a 5 fragrance enables relatively inexpensive and commonplace
materials to be used as the pro-fragrance, and avoid the necessity of including both a photo-responsive centre (such as one related to acetophenone) and a labile fragrance component in the same molecule. Advantageously, the use of 5 a separate photo-bleach, as opposed to a pro-fragrance which comprises a photo-sensitive portion, reduces the level of photo-sensitive materials which need be incorporated in the formulation. This is of particular benefit where the photo- bleach imparts a colour on the material being treated.
10
In a preferred case, the pro-fragrance is one which upon exposure to the photo-bleach is converted into one or more volatile odoriferous components with a lower olfactive perception threshold than the lipid: i.e. it can be detected 15 by the human nose at a lower level at a temperature of 20° C.
Preferred lipids contain mono- or di-unsaturated fatty acids (or their salts), Surprisingly, oxidation by photo-bleach appears to reduce the production of a rancid, oily "off" 20 odour. For example, oleic acid oxidises to produce nonanal (described as fruity), decanal (waxy orange), 2-undecenal (orange) and 2tr-decenal (orange peel). Linoleic acid
produces 3-nonelanl (cucumber like), hexanal (powerful fruity, green), heptanal (powerful, fruity vinous), octenal (orange) and 2c-octenal (walnut). Linolenic acid produces 2tr-pentenal (apple), 2,4,7-decatrienal (green, leafy), and 5 3c-hexenal (green, leafy).
It is believed that the compounds initially formed during the low temperature oxidation of lipids differ (either in kind or level) from those produced at higher temperatures or 10 from prolonged oxidation. Hexanal (powerful fruity, green) dominates the volatile composition in low temperature oxidation of linoleates, whereas at higher temperatures 2,4- decadienal dominates.
15 Plant oils contain small level of sterols (for example
peanut oil contains 6.2 mg/kg of cholesterol but the major component is beta-sistestrol- 1.145 g/kg in peanut, 1.317 g/kg in soya), carotenoids which play an important antioxidant role in fat and oils, some tocopherol (wheat 20 germ oil has the largest level 133 mg/kg) and vitamins/provitamins other than those already mentioned. These can also be oxidised to aroma chemicals.
For example, the oxidative degradation of carotenoids gives 25 rise to useful aroma compounds. Alpha-carotene generates
alpha-ionone as found in raspberry, beta-carotene generates beta-ionone found in rasberry, passion fruit and black tea, and neoxathin generates beta-damascenone found in coffee, beer, honey, wine and apple.
Preferred levels of photo-bleach present in the composition are from 0.00001 to 0.05 wt% preferably 0.00005 to 0.01%. Generally, a lower level of photo-bleach is used than would be used in practice where the objective of the photo-bleach 5 was simply stain removal.
Preferred levels of lipid present in the composition are from 0.01 to 5 wt% preferably from 0.05 to 1.0 % in fabric washing applications. All percentages used anywhere in this 10 specification being in wt% unless otherwise stated.
Headspace analysis of cotton cloth which has been laundered and dried indoors as opposed to cloth dried outdoors in sunlight shows that many natural odours, particularly 15 aldehydes, which can be obtained by the reaction of photo-
bleaches with plant oils can be recovered at low levels from the outdoor sun-dried cloth but not from the indoor dried cloth. It is believed that this may be due to the natural action of sunlight on cotton cloth. Ensuring that these 20 aldehydes are produced, or increasing the level of their production, provides a strong olfactive cue to users.
As noted above, some of the photo-bleaches impart colour to the fabric. To give the clothes an appealing white hue, it 25 is preferred if shading dyes are used in combination with
the photo-bleaches. Suitable shading dyes are those with a blue or violet hue, or those which when used in combination with photo-bleaches give a blue or violet hue. In the alternative a combination of photo-bleaches is used to generate a white hue. Preferred overall hue angles are 250 and 320, preferably 270 to 300.
Preferred dyes are as described in W02005/003274 (Unilever) 5 and W02005/003277 (Unilever). Particularly preferred
shading dyes are bis azo direct dyes, particularly those of the direct violet 9, 35 and 99 type and acid azine dyes such as acid violet 50 and acid blue 98. Alternative shading dyes are described below.
10
The present invention also provides a method of laundering fabrics which comprises the step of treating the fabrics with a composition according to the present invention.
15 The present invention also extends to the use of a photo- bleach to convert a 'pro-fragrance, and in particular a lipid, into a perfume component during either use or storage of a laundry product.
20
Detailed Description of the Invention:
In order that the present invention may be further understood it is described below with reference to various 25 preferred features.
Bleach catalysts
As noted above the photo-bleaches suitable for use in the present invention include singlet oxygen photo-bleaches and 5 radical photo-bleaches. Singlet oxygen photo-bleaches are preferred as these are believed to be less likely to engage in side-reactions.
Singlet Oxygen Photo-bleaches:
10
Singlet oxygen photo-bleaches (PB) function as follows:
PB + light - PB* 15 PB* + 302 — PB + l02
The photo-bleach molecule absorbs light and attains an electronical excited state, PB*. This electronically excited state is quenched by triplet oxygen, 3O2, in the 20 surroundings to form singlet 1O2 Singlet oxygen is a highly reactive bleach.
Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly 25 metallated phthalocyanine compounds where the metal is Zn or Al-Zl where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has 1-4 S03X groups covalently bonded to it where X is an alkali
metal or ammonium ion. Such compounds are described in W02005/014769 (Ciba).
Xanthene type dyes are preferred, particularly based on the 5 structure:

10
where the dye may be substituted by halogens and other elements/groups. Particularly preferred examples are Food Red 14 (Acid Red 51), Rose Bengal, Phloxin B and Eosin Y.
15 Quantum yields for photosensitized formation of singlet
oxygen may be found in J.Phys.Chem.Ref. Data 1993, vol 22, nol ppl13-262. It is preferred if the quantum yield for singlet oxygen formation measured in an organic solvent or D20 is greater than 0.05, more preferably greater than 0.1.
20
Other singlet oxygen producing compound? include chlorophyll, coumarin, porphyrins, myoglobin, riboflavin, bilirubin, and methylene blue.
25 The singlet oxygen photo-bleaches generally impart some colour to the fabric. To give the clothes an appealing
white hue, it is preferred if blue or violet shading dyes are used. As noted above, preferred overall hue angles are between 250 and 320, preferably 270 to 300 for the combination of the photo-bleach and the shading dye on the 5 cloth.
Preferably the photo-bleaches are used in combination with the shading dyes as described in W02005/003274 (Unilever) and W02005/003277 (Unilever). Particularly preferred 10 shading dyes are bis azo direct dyes of the direct violet 9, 35 and 99 type and acid azine dyes such as acid violet 50 and acid blue 98.
In the alternative, combination of photo-bleaches can be 15 employed to give an appropriate hue. Particularly
advantageous results are obtained by use of the combination of a xanthene and a phthalocyanine photo-bleach. In particular, excellent results are obtained with a combination of an acid red xanthene photo-bleach a green- 20 blue sulphonated Zn/Al phthalocyanine photo-bleach.
Radical Photo-bleaches:
25 Radical photo-bleaches (radical photo-initiators) are well known chemicals in the plastics and curing industry. These application have been widely discussed in the literature see e.g. H.F. Gruber Prog. Polym. Sci. 17 (1992), 953-1044 and references therein. They are organic chemicals which on exposure to light react to form neutral radicals that may initiate the polymerization of alkenes. Recently they have been found to be effective laundry photo-bleaches: UK patent application 9917451.8 teaches their use from main wash 5 detergent powders and liquids, where the photo-initiators are intimately mixed into the powder or liquids.
Radical photo-bleaches are molecules that absorb light (typically 290-400nm) to produce organic carbon-centered 10 radicals.
Radica1 photo-bleaches way function by intermolecular: hydrogen abstraction or by intramolecular alpha or beta bond cleavage.
15
Suitable radical photo-bleaches may be selected from quinones, ketones, aldehydes, and phosphine oxides. Preferably the maximum extinction coefficient is between 2 90 and 4 00 nm (measured in ethanol) is greater 10, more 20 preferably greater than 100 mol-1 L cm-1.
A particularly preferred class of radical photo-bleaches are based on the structure:
5 Where
R1 may be H, OH, Oalkyl preferably methoxy or ethoxy
R2 may be H, C1- C9 alkyl branched or linear
R3 may be H, C1- C9 alkyl
10 Preferably Rl, R2 and R3 are hydrogen
The phenyl ring, A, may be substitute at the 3,4 and 5 position by:
C1-C9 allkyl branched of linear, preferably methyl, ethyl, 15 CR4 where R4 may be C1- C9 alkyl branched of linear, preferably methyl, ethyl,
Preferred examples of this type are acetophenone, 4 methyl acetophenone, 4 methoxy acetophenone. Benzophenone and 20 vitamin K3 are also preferred radical photo-bleach.
Other suitable bond cleavage radical photo initiators may be selected from the following groups:
(a) alpha amino ketones, particularly those containing a benzoyl moiety, otherwise called alpha-amino acetophenones, for example 2-methyl 1-[4-phenyl]-2- morpholinopropan-l-one (Irgacure 907, trade mark),
5 (2-benzyl-2-dimethyl amino-1-(4-morpholinophenyl)-
butan-l-one (Irgacure 369, trade mark);
(b) alphahydroxy ketones, particularly alpha-hydroxy acetophenones, eg (1-[4-(2-hydroxyethoxy)-phenyl]-2-
10 hydroxy-2-methyl-l-propan-l-one) (Irgacure 2959, trade
mark), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, trade mark);
(c) phosphorus-containing photoinitiators, including
15 monoacyl and bisacyl phosphine oxide and sulphides, for
example 2-4-6-(trimethylbenzoyl)diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (Irgacure 819, trade mark), (2,4,6- trimethylbenzoyl)phenyl phosphinic acid ethyl ester
20 (Lucerin TPO-L (trade mark) ex BASF);
(d) dialkoxy acetophenones;
(e) alpha-haloacetophenones; and
25
(f) trisacyl phosphine oxides.
(g) benzoin and benzoin based photoinitiators
(h) thioxanthene based photoinitiators
Further suitable radical photo-bleaches are disclosed in WO 9607662 (trisacyl phosphine oxides), Us 5399782 5 (phosphine sulphides), US 5410060, EP-A-57474, EP-A-73413
(phosphine oxides), EP-A-088050, EP-A-0117233, EP-A-0138754, EP-A-0446175 and US 4559371.
Yet further suitable photo-bleaches are disclosed for 10 example in EP-A-0003002 in the name of Ciba Geigy,
EP-A-0446175 in the name of Ciba Geigy, GB 2259704 in the name of" Ciba Geigy (alkyl bisacyl phosphine oxides) , US 4792632 (bisacyl phosphine oxides), US 5554663 in the name of Ciba Geigy (alpha amino acetopheiiones) , US 5767169 15 (alkoxy phenyl substituted bisacyl phosphine oxides) and US 4719297 (acylphosphine compounds).
Radical photo-bleaches are discussed in general in A.F. Cunningham, V. Desorby, K. Dietliket, R. Husler and 20 D.G. Leppard, Chemia 48 (1994) 423-426. They are discussed in H. F. Gruber Prog. Polym. Sci. 17(1992) 953-1044.
Inorganic photo-bleaches, including titanium dioxide are not excluded, but are less preferred.
25
In the context of the present invention the photo-bleach will typically have a cleaning function well as reacting with the pro-fragrance. However, as noted above, the level
of the photo-bleach can be such that the cleaning effect per-se is small.
5 Pro-fragrance:
The pro-fragrances used in the present invention may themselves have a characteristic odour or may not. Generally, they will be materials with a low odour or no 10 perceivable odour and the levels used.
The reaction of the pro-fragrance with the activated photo- bleach may be a single step reaction which produces the volatile odoriferous component directly or may be one step 15 in a multi-step reaction. A pro-fragrance may produce a single volatile odoriferous component or it may produce a mixture of components. Preferably, the volatile odoriferous component comprises an aldehyde.
20 Aldehydes used in perfumes include but are not limited to
phenylacetaldehyde, p-methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methyinonyl acetaldehyde, phenylpropanal, 3- (4-t-butylphenyl)-2-methyl propanal, 3- (4-t-butylphenyl)- propanal, 3- (4-methoxyphenyl)-2- 25 methylpropanal, 3- (4-isopropylphenyl)-2- methylpropanal, 3- (3, 4-methylenedioxyphenyl)-2-methylpropanal, 3- (4- ethylpheny)-2, 2-dimethylpropanal, phenylbutanal, 3-methyl- 5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-enal, heptanal, cis-4-heptenal, 2-ethyl-2- heptenal, 2,6-dimethyl- 5-heptenal, 2,4-heptadienal, octanal, 2-octenal, 3,7- dimethyloctanal, 3,7-dimethyl-2,6-octadien-l-al, 3,7- dimethyl-1,6-octadien-3-al, 3,7-dimethyl-6-octenal, 3,7- dimethyl-7-hydroxyoctan-l-al, nonanal, 6-nonenal, 2,45 nonadienal, 2, 6-nonadienal, decanal, 2-methyl decanal, 4- decenal, 9- decenal, 2,4-decadienal, undecanal, 2- methyldecanal, 2-methylundecanal, 2, 6,10-trimethyl-9- undecenal, undec-10-enyl aldehyde, und^c-8-enanal, dodecanal, tridecanal, tetradecanal, anisaldehyde, 10 bourgenonal, cinnamic aldehyde, a-amylcinnam-aldehyde, a- hexyl cinnamaldehyde, methoxy- cinnamaldehyde, citronellal, hydroxy-citronellal, isocyclocitral, citronellyl oxyacet- aldehyde, cortexaldehyde, cumminic aldehyde, cyclamen aldehyde, florhydral, heliotropin, hydrotropic aldehyde, 15 lilial, vanillin, ethyl vanillin, benzaldehyde, p- methyl benzaldehyde, 3,4-dimethoxybenzaldehyd^, 3-and 4- (4- hydroxy-4- methyl-pentyl)-3-cyclohexen§-i-carboxaldehyde, 2,4-dimethyl-3-cyclohexene-1- carboxaldehyde, l-methyl-3- (4-methylpentyl) -3-cyclohexen-carboxalciehyde, p- 20 methylphenoxyacetaldehyde, and mixtures thereof.
Particularly preferred pro-fragrances Comprise the structure (I) below:
5 It is believed that this structure is the site of the
reaction with the photo-bleach, Rx and R2 are selected such that fragmentation of the molecule following exposure to the photo-bleach leads to the production of an odoriferous compound.
10
In their natural state, plant lipids comprise antioxidants to prevent their oxidation. While these may be at least in part removed during the isolation of oils from plants some antioxidants may remain. These antioxidants can be pro-
15 fragrances. In particular, the carotenoids and related
compounds including vitamin A, retinol, retinal, retinoic acid and provitamin A are capable of being converted into fragrant species including the ionones, damascones and damscenones as mentioned above.
20
Preferred food lipids include olive oil, palm oil, canola oil, squalene, sunflower seed oil, wheat germ oil, almond oil, coconut oil, grape seed oil, rapeseed oil, castor oil, corn oil, cottonseed oil, safflower oil, groundnut oil, 5 poppy seed oil, palm kernel oil, rice bran oil, sesame oil, soybean oil, pumpkin seed oil. jojoba oil and mustard seed oil.
Preferred food lipids also include oils and fats of animal 10 source including butter, ghee, and squalene. To avoid allergic reaction, certain nut oils (peanut oil, for example) are less preferred.
The most preferred pro-fragrance contain at least 20 wt% of 15 a compound which comprises the moiety
Where R1 and R2 are organic groups containing carbon, 20 hydrogen and oxygen. A preferred example is linoleic acid.
Particularly preferred lipids contain 10 wt% or less of moieties containing three double bonds, (such as linolenic acid). Also the most preferred lipids contain less than 15 25 wt% saturated acids and less than 15 wt% of acids with less than 14 carbon atoms. Within these preferred limits branched-chain and hydroxyl acid moieties are included
Most preferred oils exclude those of high linolenic content (preferred < 10%), such as hemp oil (~25%wt linolenic acid), and oils of nut origin.
5 Particularly preferred pro-fragrances are olive oil, sunflower oil, soybean oil, palm oil, rapeseed oil, squalene, and mixtures thereof.
While some non-soap surfactants may contain very low levels 10 of compounds derived from unsaturated alkyl chains, it is not intended that the present invention should extend to such compositions.
15 Shading Dyes:
As noted above an optional shading dye can be used to counteract the tendency of the photo-bleach to move the hue of fabrics away from white. Preferred dyes are violet or 20 blue, or in combination with the photo-bleach yield a violet or blue shade. Suitable and preferred classes of dyes are discussed below.
Direct Dyes:
25
Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
Preferably the dye are bis-azo or tris-azo dyes are used.
Most preferably, the direct dye is a direct violet of the following structures:

wherein:
ring D and E may be independently naphthyl or phenyl as 15 shown;
R1 is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;
R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted 2 0 naphthyl, preferably phenyl;
R3 and R4 are independently selected from: hydrogen and Cl- C4-alkyl, preferably hydrogen or methyl;
X and Y are independently selected from: hydrogen, C1-C4- alkyl and Cl-C4-alkoxy; preferably the dye has X= methyl; 5 and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, 10 and direct violet 99,. Bis-azo copper containing dyes such as direct violet 66 may be used.
The benzidene based dyes are less preferred.
15 Preferably the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
In another embodiment the direct dye may be covalently linked to the photo-bleach, for example as described in 20 W02006/024612 .
An alternative to the azo dyes are the blue or violet triphenodioxazine direct dyes.
25 A suitable example of this is the the triphenodioxazine direct dye is of the form:
wherein the dye is substituted by 1 to 4 sulphonate groups 5 and X is independently selected from: Cl-C6-alkyl, alkyl ester, benzyl, F, Cl, Br and I.
Acid dyes:
10
Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:
15 (i) azine dyes, wherein the dye is of the following core structure:
2 0 wherein Ra, Rb, Rc and Rd are selected from: H, an branched or linear Cl to C7-alkyl chain, benzyl a phenyl, and a naphthyl;
the dye is substituted with at least one SO3" or -COO" group; the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups 5 selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.
Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 10 98.
Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
15 Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
Hydrophobic dyes
2 0 The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising 2 5 group. Hydrophobic dyes may be selected from the groups of
disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
5 Preferably the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
Basic dyes:
10 Basic dyes are organic dyes which carry a net positive
charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly
cationic surfactants. Dyes may be selected from the basic
violet and basic blue dyes listed in the Colour Index 15 International. .
Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 71, basic blue 159, basic violet 19, basic violet 20 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141. Thiazolium dyes may also be used, examples are basic blue 41, 54, 65, 66, 67, 162 and 164.
25 Reactive dyes
Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this s species. Dyes may be selected from the reactive violet and 5 reactive blue dyes listed in the Colour Index International.
Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
10 Dye conjugates:
Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
15 Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in W02006/055787. They are not preferred.
Particularly preferred dyes are: direct violet 7, direct 20 violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 54, direct violet 99,, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 25 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.
In a particularly preferred embodiment, the compositions of the present invention comprise:
a) photo-bleach, preferably comprising at least one phthalocyanine, preferably at a level of 0.00001-lwt%
b) pro-fragrance, preferably at a level of 0.1-10%wt and
5
c) a blue violet dye, preferably with an optical adsorption peak in the range 540-600nm, preferably a bis-azo direct dye, preferably at a level of 0.000001- lwt%
10
Fluorescent Agents:
In order to further improve whiteness, especially in the presence of both the photo-bleach and the shading dye, but 15 also in the absence of the shading dye it is convenient and advantageous to include a fluorescer in the compositions of the invention. The composition therefore preferably further comprises a fluorescent agent (optical brightener).
20 Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
25 The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal {Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline 5 compounds, e.g. Blankophor SN.
Preferred fluorescers are: sodium 2 (4-styryl-3- sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'- bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,510 triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium
4,4'-bis{ [ (4-anilino-6-morpholino-l, 3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2- sulfoslyryl)biphenyl.
15 In a particularly preferred embodiment, the compositions of the present invention comprise:
a) photo-bleach, preferably comprising at least one phthalocyanine, preferably at 0.00001-lwt%
20
b) pro-fragrance, preferably at 0.1-10%wt and
c) fluorescer, preferably at a level of 0.005 to 2 wt %
25 It is preferred to use a shading dye in combination with a fluorescer in order to reduce yellowing due to chemical changes in adsorbed fluorescer.
Polymers:
The composition may comprise one or more polymers. Examples are carboxymethylcellulose, poly (vinylpyrrolidone), poly 5 (ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine- N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
10 Modern detergent compositions typically employ polymers as
so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times. Any suitable dye-transfer inhibition agents may be used in accordance with the present invention. Generally, such dye-transfer
15 inhibiting agents include polyvinyl pyrrolidone polymers,
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof.
20 Nitrogen-containing, dye binding, DTI polymers are
preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone, and/or vinyl imidazole are preferred.
25 Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-0 group can form part of the polymerizable unit; A is one of the following structures: -
NC(0)-, -C(0)0-, -S-, -0-, -N=; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or combination thereof to which the nitrogen of the N-0 group can be attached or the N-0 group is part of 5 these groups, or the N-0 group can be attached to both units.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, 10 pyrrolidine, piperidine and derivatives thereof. The N-0 group can be represented by the following general structures: N{O)(R')0-3 , or =N(O){R')0-i , wherein each R' independently represents an aliphatic, aromatic, heterocyclic or alicylic group or combination thereof; and 15 the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa<10, preferably pKa<7, more preferably pKa< 6.
2 0 Any polymer backbone can be used provided the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and 25 mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N- oxide of 10:1 to 1:1,000,000. However, the number of amine
oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the 5 average molecular weight is within the range of 500 to
1,000,000; more preferably 1,000 to 500,000; most preferably 5,000 to 100,000. This preferred class of materials is referred to herein as "PVNO". A preferred polyamine N-oxide is poly (4-vinylpyridine-N-oxide) which as an average 10 molecular weight of about 50,000 and an amine to amine N- oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (as a class, referred to as "PVPVI") are also 15 preferred. Preferably the PVPVI has an average molecular weight range from 5, 000 to 1, 000, 000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000, as determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. "Modern Methods of Polymer 20 Characterization". The preferred PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These Copolymers can be either linear or branched. Suitable PVPVl polymers include 25 Sokalan1™' HP56, available commercially from BASF, Ludwigshafen, Germany.
Also preferred as dye transfer inhibition agents are polyvinylpyrrolidone polymers ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 2000,000, and more preferably from about 5,000 to about 50,000. PVP's are disclosed for example in EP-A-262,897 and EP-A-256,696.
5 Suitable PVP polymers include Sokalan'™' HP50, available commercially from BASF. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of 10 PEG to PVP on a ppm basis delivered in wash solutions is
from about 2:1 to about 50:1, and more preferably from about 3:1 to- about
Also suitable as dye transfer inhibiting agents are those 15 from the class of modified polyethyleneimine polymers, as disclosed for example in WO-A-0005334. These modified polyethyleneimine polymers are water-soluble or dispersible, modified polyamines. Modified polyamine^ are further disclosed in US-A-4,548,744; US-A-4,597,898; 20 US-A- 4,877,896; US-A- 4,891, 160; US-A- 4,976,879; US-A-5,415,807; GB-A-1,537,288; GB-A-1,498,520; DE-A-28 29022; and JP-A-06313271.
Preferably the composition according to the present 25 invention comprises a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI)„ copolymers thereof, and mixtures thereof.
The amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10 %, preferably from 0.02 to 5 %, more preferably from 0.03 to 2 %, by weight of the composition. It will be 5 appreciated that the dye transfer inhibition agents will assist in the preservation of whiteness by preventing the migration of dyes from coloured articles to white ones.
Other polymers used in laundry compositions include soil- 10 release and anti-redeposition polymers as well as polymers which improve powder properties.
Polymeric dispersing agents can advantageously be utilized in the compositions herein, especially in the presence of 15 layered silicate builders. Suitable polymeric dispersing agents include polycarboxylates and polyethylene glycols, although others known in the art can also be used.
It is also believed that polymeric dispersing agents enhance 20 overall detergent builder performance, when used in
combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release, peptization, and anti- redeposition.
25
Polycarboxylate materials, which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are preferably admixed in their acid form. Unsaturated monomeric acids that can be polymerized to form
suitable polycarb oxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polycarboxylates herein of 5 rnonomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
10 Particularly suitable polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 15 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of 20 polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. In the present invention, the preferred polycarboxylate is sodium polyacrylate.
25 Acrylic/maleic-based copolymers may also be used as a
preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form
preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 5 30:1 to about 1: 1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials 10 which are described in European Patent Application No.
66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep. 3, 1986/ which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol 15 terpolymers. Such materials are also disclosed in
EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Polyethylene glycol (PEG) can exhibit dispersing agent 20 performance as well as act as a clay soil removal-
antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 3,000 to about 10,000. Polyaspartate and 25 polyglutamate dispersing agents may also be used.
Dispersing agents such as polyaspartate preferably have an average molecular weight of about 10,000.
Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to 5 hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable 10 stains occurring subsequent to treatment with the soil
release agent to be more easily cleaned in later washing procedures.
Generally the soil release polymers will comprise polymers 15 of aromatic dicarboxylic acids and alkylene glycols
(including polymers containing polyalkylene glycols).
The polymeric soil release agents useful herein especially include those soil release agents having:
20
(a) one or more nonionic hydrophilic components consisting essentially of:
(i) polyoxyethylene segments with a degree of 25 polymerization of at least 2, or
(ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10,
wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or
5
(iii) a mixture of oxyalkylene units comprising
oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the 10 hydrophile component has hydrophilicity great
enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably 15 comprising at least about 25% oxyethylene units
and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
2 0 (b) one or more hydrophobe components comprising:
(i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of
25 oxyethylene terephthalate:C3 oxyalkylene
terephthalate units is about 2:1 or lower,
(ii) C4 -Cs alkylene or oxy C4 -C6 alkylene segments, or mixtures therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C1 -C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures 5 therein, wherein said substituents are present in
the form of C1 -C4 alkyl ether or hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1 -C4 10 alkyl ether and/or C4 hydroxyalkyl ether units to
deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hyclroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber 15 surface hydrophilicity, or a combination of (a)
ana (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although 20 higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4 -C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3 S(CH2)n OCH2 CHi 0--, where M is sodium and n is an integer 25 from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with 5 polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1 -C4 alkyl and 10 C4 hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093, issued Dec. 28, 1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl 15 ester), e.g., C1 -C6 vinyl esters, preferably poly(vinyl
acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published Apr. 22, 1987 by Kud, et al. Commercially available soil release agents of this kind 20 include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and 25 polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene 5 terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
10
Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties 15 covalently attached to the backbone. These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J.J. Scheibel and E. P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued 20 Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
25
Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
If utilised, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
5
Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units,
sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2- propylene units. The repeat units form the backbone of the 10 oligomer and are preferably terminated with modified
isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2- propyleneoxy units in a ratio of from about 1.7 to about 15 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-
ethanesulfonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, 20 toluene sulfonate, and mixtures thereof.
It is believed that those polymers which deposit on cloth as a part of their activity may assist in the deposition of the pro-fragrance, perfume generated from the pro-fragrance 25 and/or other perfume components present. Other types of polymeric deposition aid may also be used. These include cationic polymeric deposition aids. Suitable cationic polymeric deposition aids include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids). Cationic polymeric aids are particularly 5 preferred in the absence of any other cationic material in the composition.
Particularly preferred compositions according to the present invention comprise:
10
a) at least one photo-bleach, preferably a phthalocyanine photo-bleach, preferably at level of 0.00001-lwt%;
b) at least one pro-fragrance, preferably at a level of
15 0.001 to 10wt%, more preferably 0.1 to 2 wt%
c) at least one shading dye, preferably a bis-azo direct dye, preferably with an optical adsorption peak in the range 540-600nm, preferably at a level of 0.000001-lwt%
2 0
d) at least one fluorescer, preferably selected from the group comprising: di-styryl biphenyl compounds, diamine stilbene di-sulphonic acid compounds and
25 pyrazoline compounds, preferably at a level of 0.005 to
2 wt %; and,
e) optionally, a polymeric deposition aid for the pro- fragrance and/or perfume, which, when present is
preferably a soil release polymer comprising residues of aromatic dicarboxylic acids and alkylene glycols.
5 Other Components:
In a preferred embodiment a composition of the invention also contains one or more surfactants and/or optionally other ingredients such that the composition is fully 10 functional as a laundry cleaning and/or care composition. A composition of the invention may be in dry solid or liquid form. The composition may be a concentrate to be diluted, rehydrated and/or dissolved in a solvent, including water, before use. The composition may also be a ready-to-use (in- 15 use) composition.
The present invention is suitable for use in industrial or domestic fabric wash compositions, fabric conditioning compositions and compositions for both washing and 20 conditioning fabrics (so-called through the wash conditioner compositions). The present invention can also be applied to industrial or domestic non-detergent based fabric care compositions, for example spray-on compositions.
25 Fabric wash compositions according to the present invention may be in any suitable form, for example powdered, tableted powders, liquid or solid detergent bars.
Other contemplated ingredients including surfactants, hydrotropes, preservatives, fillers, builders, complexing agents, stabilizers, perfumes per se, other conventional detergent ingredients, or combinations of one or more 5 thereof are discussed below. The composition may also
contain other conventional detergent ingredients such as e.g. fabric conditioners including clays, foam boosters, suds suppressors (anti-foams), anti-corrosion agents, antimicrobials or tarnish inhibitors.
10
Surfactants:
Fabric wash compositions according to the present invention comprise a fabric wash detergent material selected from non- 15 soap anionic surfactant, nonionic surfactants, soap, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.
Detergent compositions suitable for use in domestic or 20 industrial automatic fabric washing machines generally
contain anionic non-soap surfactant or nonionic surfactant, or combinations of the two in suitable ratio, as will be known to the person skilled in the art, optionally together with soap.
25
Many suitable detergent-active compounds are available and fully described in the literature, for example in "Surface- Active Agents and Detergents", Volumes I and II, by Schwartz, Perry & Berch.
The surfactants may be present in the composition at a level of from 0.1% to 60% by weight.
Suitable anionic surfactants are well known to the person 5 skilled in the art and include alkyl benzene sulphonate, primary and secondary alkyl sulphates, particularly C8—C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl sulphosuccinates; ether carboxylates; isethionates; 10 sarcosinates; fatty acid ester sulphonates and mixtures thereof. The sodium salts are generally preferred. When included therein the composition usually contains from about 1% to about 50%, preferably 10 wt%-40 wt% based on the fabric treatment composition of an anionic surfactant such 15 as linear alkylbenzenesulfonate, alpha-olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap. Preferred surfactants are alkyl ether sulphates and blends 20 of alkoxylated alkyl nonionic surfactants with either alkyl sulphonates or alkyl ether sulphates.
Preferred alkyl ether sulphates are C8-C15 alkyl and have 210 moles of ethoxlation. Preferred alkyl sulphates are 25 alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8—C15. The counter ion for anionic surfactants is typically sodium, although other counter-ions such as TEA or ammonium can be used. Suitable anionic surfactant materials are available in the marketplace as the 'Genapol'™ range from Clariant.
Nonionic surfactants are also well known to the person 5 skilled in the art and include primary and secondary alcohol ethoxylates, especially C8—C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of 10 from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used. When included therein the composition usually contains from 15 about 0.2% to about 40%, preferably 1 to 20 wt%, more
preferably 5 to 15 wt% of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, 20 polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 25 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
Higher levels of surfactant may be employed (up to almost 100%) but this can leave little space in the formulation for builders and other components and may lead to a sticky product which requires special processing.
5
Hydrotropes:
The term "hydrotrope" generally means a compound with the ability to increase the solubilities, preferably aqueous 10 solubilities, of certain slightly soluble organic compounds. Examples of hydrotropes include sodium xylene sulfonate, SCM.
Solvents:
15
The composition may comprise a solvent such as water or an organic solvent such as isopropyl alcohol or glycol ethers. Solvents are typically present in liquid or gel compositions.
20
Metal chelation agents:
The composition may contain a metal chelating agent such as carbonates, bicarbonates, and sesquicarbonates. The metal 25 chelating agent can be a bleach stabiliser (i.e. heavy metal sequestrant). Suitable metal chelation agents include ethylenediamine tetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and the polyphosphonates such as the Dequests (Trade Mark),
ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).
Builders or Complexing agents:
5
Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
10 Examples of calcium sequestrant builder materials include
alkali metal polyphosphates, such as sodium tripolyphosphat and organic sequestrants, such as ethylene diamine tetra- acetic acid.
15 Examples of precipitating builder materials include sodium orttiophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or
20 amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also knovi as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
25 The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach- stabilising agents by virtue of their ability to complex metal ions.
Where builder is present, the compositions may suitably 5 contain less than 20%wt, preferably less than 10% by weight, and most preferably less than 10%wt of detergency builder.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, 10 more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula:
0.8-1.5 M20. A12O3. 0 . 8-6 SiO2
15
where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO2 20 units' in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
25
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
For low cost formulations carbonate (including bicarbonate 5 and sesquicarbonate) and/or citrate may be employed as builders.
Enzymes:
10 One or more enzymes may be present in a composition of the invention and when practicing a method of the invention.
Especially contemplated enzymes include proteases, alpha- amylases, cellulases, lipases, peroxidases/oxidases, pectate 15 lyases, and mannanases, or mixtures thereof.
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases 20 from Humicola (synonym Thermomyces) , e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. 25 stutzeri (GB 1,372,034), P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, e.g. from B. svbtilis (Dartois et al. (1993), Biochemica et Biophysica
Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).
Other examples are lipase variants such as those described 5 in WO 92/05249, WO 94/01541, EP 407 225, EP 260 105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202.
Preferred commercially available lipase enzymes include 10 Lipolase™ and Lipolase Ultra™, Lipex™ (Novozymes A/S).
The method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an 15 enzyme which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric 20 acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2 which hydrolyze one fatty acyl group (in the sn-1 and 25 sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
The enzyme and the pro-fragance may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme and pro-fragrance 5 and/or other segregation within the product.
Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The 10 protease may be a serine protease or a metallo protease,
preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, (Novozymes 15 A/S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect GxP™, FN2™, and FN3™ (Genencor International Inc.).
The method of the invention may be carried, out in the presence of cutinase. classified in EC 3.1.1.74. The 20 cutinase used according to the invention may be of any
origin. Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
Suitable amylases (alpha and/or beta) include those of 25 bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839, or the Bacillus sp. strains disclosed in
WO95/026397 or WO 00/060060 . Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).
5
Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, 10 Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307. Commercially 15 available cellulases include Celluzyme™, Carezyme01,
Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation).
20 Suitable peroxidases/oxidases include those of plant,
bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in 25 WO 93/24618, WO 95/10602, and WO 98/15257. Commercially
available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).
Enzyme Stabilizers:
Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such 5 as propylene glycol or glycerol, a sugar" or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. 10 WO 92/19709 and WO 92/19708.
Perfumes per se:
15 Compositions according to the present invention will preferably also comprise some perfume per se. Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found 20 in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to 25 the person skilled in the art of perfuming, flavouring,
and/or aromatizing consumer products, i.e., of imparting an odor and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.
By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
5
Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top 10 notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
15 Some or all of the perfume or pro-fragrance may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100—250 Celsius and pro—fragrances 20 which can produce such components.
It is also advantageous to encapsulate perfume components which have a low Log P (ie. those which will be partitioned into water), preferably with a Log P of less than 3.0. These 25 materials, of relatively low boiling point and relatively low Log P have been called the "delayed blooming"' perfume ingredients and include the following materials:
Allyl Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisole, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Iso Valerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor 5 Gum, Laevo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formate, Cis-Jasmone, cis-3-Hexenyl Acetate, Cuminic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Aceto Acetate, Ethyl Amyl Ketone, Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl 10 Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (tricyclo Decenyl Acetate), Frutene (tricyclco Decenyl Propionate), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydratropic Alcohol, Hydroxycitronellal, Indone, Isoamyl Alcohol, Iso Menthone, 15 Isopulegyl Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Formate, Menthone, Menthyl Acetphenone, Methyl Amyl Ketone, Methyl Anthranilate, Methyl Benzoate, Methyl Benyl Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptine Carbonate, Methyl Heptyl Ketone, 20 Methyl Hexyl Ketone, Methyl Phenyl Carbinyl Acetate, Methyl Salicylate, Methyl-N-Methy1 Anthranilate, Nerol, Octalactone, octyl Alcohol, p-Cresol, p-Cresol Methyl Ether, p-Methoxy Acetophenone, p-Methyl Acetophenone, Phenoxy Ethanol, Phenyl Acetaldehyde, Phenyl Ethyl Acetate, Phenyl 25 Ethyl Alcohol, Phenyl Ethyl Dimethyl Carbinol, Prenyl
Acetate, Propyl Bornate, Pulegone, Rose Oxide, Safrole, 4- Terpinenol, Alpha-Terpinenol, and /or Viridine
It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more 5 or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the perfume.
Another group of perfumes with which the present invention 10 can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. By means 15 of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed- linen) .
20 In order that the invention will be further understood it is described below with reference to the following examples:
Table 1: Fatty acid composition (wt%) of some food lipids.
4:0 to 12:0 14:0 16:0 16:1 18:0 18:1 18:2 1B:3J^18:1 (OH) 20:0 20:1 22:0 22:1 24:0)
Ghee
(butter fat) 6-17 5-15 25-41 2-6 6-11 18-33 0-4 i
0 I 0-2 0-2 0-2
Grapeseed oil 7 0 3 22 67 0.9 ! 0.1
Hemp seed oil 6 2 12 55 25 !
Sunflower oil H 6 0.1 5.6 j 17.fi 68. 7 0.2 \ 0.3 0.8 0.1
Rapeseed oil
(high erucic acid rape) 3 1 16 14 10 ; 1 6 4 9.
(low erucic acid rape) 4 2 56 26 1
io ! 2 0.2
Cocoa butter 0.1 26 i 0.3 34.4 34.8 3 0.2 ; 1
Castor oil 1 1 3 4 0 90
Olive oil 10 0.7 2.3 78.1 7.3 0.6 0.4 0.3
Palm j 0-2 32-45 2-7 38-52 5-11 j
Soy oil | 11 0.5 4 22 53 7.5 i 1

EXAMPLES: Example 1:
5 20% emulsions of the lipids were prepared in a bench-top
jacketed mixer using a three-blade impeller at 500 RPM and a process temperature of 50 °C. The lipids were heated to -50°C and added drop-wise into a 1% solution of non-ionic surfactant (Genapol LA 070, ex Clariant). After sufficient
10 mixing the batch was cooled slowly to room temperature and
the emulsion decanted into a bottle and further treated in a Silverson high shear homogeniser (one minute mixing at the lowest speed setting).
15 Cotton sheeting monitors roughly 20x20 cm were padded with these emulsions in the following manner. A 500 ml glass bottle filled with 200 g of tap water to which 20 or 10 g of the above 20% emulsion was weighed in and shaken. To this a fixed level of photo-bleach was weighed in and shaken. Then two monitors were added and agitated on a roller for some 30 minutes. The monitors then removed and spin dried. From the monitor's dry and wet weight and the concentration of emulsion the amount of lipid (emulsion) could be calculated.
Table 2: Amount of lipid picked up by monitors for 20 g of emulsion and an average 0.090 mg of Acid Red 51 per g of fabric.
Lipids dry weight/g padded weight/g pick up/g Mg oil/g fabric
Soy oil 12.56 27.37 14. 81 21.44
Ryoto sugar ester ER2 90 12.52 27.24 14 .72 21.31
Soy oil sugar ester 12.44 27.06 14. 62 21.16
Estol 1476 12.7 27. 62 14 . 92 21. 60
Sirius M40 13.09 28.03 14. 94 21.63
Extra virgin olive oil 15. 08 32.51 17.43 25.23
Palm and Canola oil 15. 63 32.51 16.88 24.44
Coconut oil 15.18 32.64 17.46 25.28
Squalene 15.16 31.83 16. 67 24.13

Acid Red 51 is erythrosine B (ex Aldrich). Ryoto sucrose ester is a food grade oil based on erucate (22:1) lipid 10 source (ex Mitsubishi). Soy oil sucrose ester is touch hardened oil (ex Clariant). The sucrose esters have an average of 4 ester linkage. Estol 1476 is isobutyl stearate (ex Uniqema). Sirius M40 is a mainly C12-C20 light mineral oil (ex Silkolene) Squalene is a polyunsaturated triterpene 15 (C30) oil (ex Sigma). The remaining oils were purchased off the shelf from supermarkets (Tesco).
Table 3. Amount of lipid picked up by monitors for 10 g of emulsion for two photobleach treatments of an average of 0.090 mg of Acid Red 51 and an average of 0.246 mg of pentyl-phenyl ketone per g of 5 fabric.

dry padded mg oil/g
Lipids weight/g weight/g pick up/g fabric
Ghee 12.74 27.76 15.02 11.23
Grapeseed oil 12.72 27.59 14.87 11.13
Hemp oil 12. 11 26.11 14 . 00 11.01
Sunflower oil 12 . 08 26. 05 13. 97 11. 01
Rapeseed oil 12.04 26.62 14 . 58 11.53
Cocoa Soft 12.26 27.73 15.47 12.02
Pumpkin oil 12. 16 27 . 98 15. 82 12.39
Sweet almond
oil 12.31 26.79 14.48 11.20
Castor oil 12.32 27 . 60 15.28 11. 81
Jojoba oil 12.10 26.26 14.16 11.15

10 Pentyl-phenyl ketone or hexanophenone is a radical photo- bleach (ex Aldrich). Cocoa Soft was Lipex Cococasoft (ex AAK). Castor oil was a pure grade (ex Now). Jojoba oil was (ex Henry Lamotte). The Sweet almond oil was (ex Provital SA). The remaining oils purchased off the shelf from a 15 supermarket (Tesco).
The two monitors treated for each lipid and each photo- bleach were dried one on line (inside) and one in Weather-o- meter™ (WOM) for 30 minutes. WOM produces artificial
sunlight and was set up to give 385 W/m2 in the UV-visible range (290-750nm).
Monitor 1 was the line dried control (C)) against which the 5 Weather-o-rneter monitor 2 (W) was judged. The monitors were kept in closed top bottles under florescent light condition to be presented to panel members to evaluate the quality of the odours in the headspace and on the monitors. The odour descriptors used were based on those known in the art. The 10 panel members described the odour and assigned a number to quantify the intensity of the odour they perceived.
The odour comparison between the saturated oil Estol 1476 and Sirius M40 and the oils containing unsaturation revealed 15 that the Weather-o-meter irradiated samples of the
unsaturated lipids from the start had developed a sharp "ozonic", bleach type penetrating odour labelled as "pungent". It is not necessarily an unpleasant odour and most of the time connoted a 'clean' fabric note not 20 dissimilar to outside line dried laundried fabrics.
Table 4. Odour description of oils same day for line dried (C) and weather-o-meter dried (W).
Pleasant —h. Odour Olive oil Palm & Canola Coconut oil Squalene
treatment C w C W c w C w
Fruity 1 2 honey caramel
Greein 1 2
Clean 1 1 1 1
Soapy 1 1 1
Dairy
Pungent 2 2 1
Oily 1 1 2 2 2 1
Tallowy 1
Frying oil 1 2
Stale nut
Fishy

Table 5: Odour description after one day standing under fluorescent light.
Odour Olive oil Palm & Coconut Squalene
1 Canola oil
treatment C W C w C w C W
-w
c Fruity 1 1
sweet 2 honey caramel
CU Clean 1 1 1 1 1
Soapy 1 1 1 1 1 1
Dairy
Pungent 3 1 1.5
Oily 2 1 1 1 1 0.5 1
Tallowy 1 1 1 0.5
Frying
oil
Stale nut 1 1
Fishy

The light induced oxidation products of squalene were particularly noteworthy in their distinct and unmistakable 10 potent perfume quality.
Table 6. Odour description and intensity of oils with Red Acid 51 photo bleach first day.
t Odour Ghee Grapeseed oil Hemp oil Sunflower Oil Rapeseed oil
treatment C w C w C W C W C w
Fruity 1 1
a Green 2
CO Clean 1
P-l Soapy 1 1 1
Dairy 2
Pungent 2 1
Oily 1 2 1 1 1 1
Tallowy
Frying oil
Stale nut 2
Fishy 2 3

Table 6 (continued). Odour description and intensity of oils
with Red Acid 51 photo bleach first day.

Pumpkin Sweet Castor Joj oba
Cocoasoft oil Almond oil oil
C W C W C W C W C w
Fruit 0.5 0.5 0 . 5
Green 0.5 0.5 1.5 1. 5 0.5
Clean 0.5 1 1 1. 5 1 1.5 2
Soap 0.5 0.5 1 1.5
Dairy 1
Pungent 0.5 1.5 1 0.5 1.5
Oily 0.5 0.5 0.5
Tallowy 0.5
Frying
oil 1 2 2 . 5 1
Stale
nut 0.5 1.5 2
Fish

Table 7 Odour description and intensity of oils with of
0.246 mg of phentyl-phenyl ketone per g of fabric.

5
Ghee Grapeseed Hemp Sunflower Rapeseed
C W C W C W C W C W
Fruity 1 1 1 1
Green 1 2 1
Clean 1 2
Soapy 1 2 1
Dairy 1 2.5 0 1 1 1.5
Pungent
Oily 1
Tallowy
Frying oil 2
Stale Nut
Fish 2 2

Pentyl-phenyl ketone has a fruity green smell by itself and the control C and W monitors of this photo-bleach on its own 10 were used for comparison in Table 6. The control C had an intensity of 1 fruity and 1 green. The control W on the other lost the fruity green and a pungent note of intensity 1 emerged. This fruity green note of the photo-bleach itself was perceivable on line dried treated monitors for 15 grape seed, hemp, sunflower and rapeseed, cocoa soft,
pumpkin, almond and jojoba (as indicated by an intensity of 1) .
Table 7 (continued). Odour description and intensity of
oils with of 0.246 mg of pentyl-phenyl ketone per g of fabric.
5
Cocoasoft Pumpkin oil Sweet Almond Castor oil Jojoba oil
C W C W C W C w C W
Fruity 1 1 1 1
Green 1 2
Clean 1
Soapy 1 2 2
Dairy 2 2
Pungent
Oily 1 1 1
Tallowy
Frying oil 2
Stale Nut
Fish

To determine the volatile aromas of the fatty acids 10 themselves 20% emulsions of oleic, linoleic and linolenic
acids where prepared as described for oils above and cotton sheeti ngs padded to the levels seen in Table 3 with and without Acid Red 51 photo-bleach at a 0.0 606mg/g fabric level. The panel assessment of the odours is summarised in 15 Table 8.
It is clear that linolenic acid with three double bonds results in a fishy off-odour which can and be detrimental to the overall perfume impact of the laundry composition..
5
Table 8. Aromas generated (after one day at 20C) on cotton sheeting treated by fatty acid emulsions.
Fatty acid* Without Acid Red 51 With Acid Red 51
C W C w
Control (non-ionic and water) Laundry
died
inside
with stale
slightly
fishy
smell Clean laundry Slightly oily Laundry
died
inside
with stale
slightly
fishy
smell Clean laundry
Oleic Clean laundry Green cucumber Clean
laundry
Green
cucumber
and
volatile Ozonic Clean
fresh
pleasant
laundry
dried
outside Clean fresh Sweet perfume smell of caramel/honey
Linoleic Clean laundry Green cucumber Clean Green slightly oily Clean Green cucumber Clean fresh sweet
caramel/honey
smell
Ozonic
pungent
volatiles
Linolenic Strong fishy Less fishy
Pungent
Oily Strong fishy Slight green Less fishy Some Green Pungent Slightly sweet caramel

3
*01eic acid was a 90% assay from Aldrich, linoleic was a 60% assay from Sigma and linolenic was a 70% assay with 25% linoleic and 5% oleic from Fluka.
Example II:
White woven cotton cloth was washed at 20°C in 2.0 g/L of a base washing powder containing: 18% NaLAS, 73% salts 5 (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3% minors including fluorescer and enzymes, remainder impurities and water. A liquor to cloth of 30:1 was used, each wash lasted for 30 mins, and was conducted with and without the addition of varying level of Tinolux BBS (a 10 green-blue sulphonated Zn/Al phthalocyanine ex Ciba
Speciality chemicals) and acid red 51. The level of dye was quantified by the optical absorption (5cm pathlength) at 528nm for acid red 51 and 670nm for the Tinolux BBS.
15 Following the wash, the cotton cloth was rinsed twice, dried and colour of the cloth was then assessed using a reflectometer (UV excluded for all measurements) and expressed as the hue angle. A hue angle of 180 corresponds to green, a hue angle of 270 to blue and a hue angle of 20 0/360 to red. The results are shown in Table 9 below:
Table 9
Absorption (AR51 Absorption Hue angle
at 528nm) (Tinolux BBS at
670nm)
0 1.2 209
0.03 1. 17 225
0 .06 1.14 243
0.09 1.11 258*
0.12 1.08 278**
0.15 1.05 295**
0.18 1. 02 301*
0 .21 0. 99 306*
0.24 0. 96 308*
0.3 0.9 322
0-6 0, 6 r 331
0.9 0.3 334
1.2 0 337

5 For whiteness preferred hue angles are between 250 and 320, preferably 270 to 300 (as marked with asterisks). As noted above, this may be provided by a mixture of an acid red xanthene photobleach and a green-blue sulphonated Zn/Al phthalocyanine photobleach.
10
Example III
Exemplary Granular Laundry Formulations A,B,C,D 5 Table 10
Formulation A B C D
NaLAS 15 20 10 14
NI(7E0) ■ - - - 10
Na tripolyphosphate 7 15 - - ■
Soap - - - 2
Zeolite A24 - - - 17
Sodium silicate 5 4 5 1
Sodium carbonate 25 20 30 20
Sodium sulphate 40 33 40 22
Carboxymethylcellulose 0.2 0.3 - 0.5
Sodium chloride - - - 5
Lipase 0.005 0.01 - 0.005
Protease 0.005 0.01 - 0.005
Amylase 0.001 0.003 - -
Cellulase - 0.003 - -
Fluorescer 0.1 0.15 0.05 0.3
Direct Violet 9 0.0002 0.00015 _ 0.0001
Solvent Violet 13 - 0.002 - 0.001
Acid red 51 0.002 0.002 0.0001 0.0003
Direct violet 54 - - 0.0001 -
Sulphonated Zn phthalocyanine photo- bleach 0.002 0.004 0.0004 0.0005
profragance 0.1 1.0 0.2 0.4
Water/impurities/minors remainde r remainder remainder remainder

Claims
1. A laundry cleaning and/or care composition comprising, separately, a photo-bleach and a pro-fragrance wherein the pro-fragrance comprises at least one, non-aromatic- C-C double bond, more preferably at least two C-C double bonds, wherein the pro-fragrance comprises a plant oil and wherein the plant oil comprises a mono-, di- or triacyl-glycerol, phospholipid, glycolipid. diol lipid, wax, sterol ester or tocopherol.
2. A composition according to claim 1, wherein the photobleach is a singlet oxygen photo-bleach or a radical photo-bleach.
3. A composition according to any preceding claim, wherein the photo-bleach comprises singlet oxygen photo bleach.
4. A composition according to claim 3wherein the photobleach comprises a water-soluble phthalocyanine compound.
5. A composition according to any of claims 1-2, wherein, the photo-bleach comprises a radical photo-bleach.
6. A composition according to claim 5, wherein the radical photo-bleach absorbs light to produce organic, carbon- centred radicals.
j 7. A composition according to claim 6, wherein the radical photo-bleach comprises the structure:

wherein: R1 may be H, OH, Cl- C9 oxy-alkyl, R2 and R3 are, independently, H, Cl- C9 alkyl branched or linear, .and, A is optionally substituted with C1-C9 alkyl or 15 oxyalkyl.
8. A composition according to any one of claims 1-7, wherein the pro-fragrance comprises the structure;

9. A composition according to claim 8, wherein the pro- fragrance comprises at least one of, olive oil, palm oil, canola oil, squalene, sunflower seed oil, wheat germ oil, almond' oil, coconut oil, grape seed oil,
5 rapeseed oil, castor oil, corn oil, cottonseed oil,
safflower oil, groundnut oil, poppy seed oil, palm kernel oil, rice bran oil, sesame oil, soybean oil, pumpkin seed oil. jojoba oil and mustard seed oil.
10 10. A composition according to claim 8, wherein the pro- fragrance comprises 10 wt% or less of moieties containing three double bonds.''
11.. A composition according to claim 8, wherein the pro- 15 fragrance comprises less than 15 wt% saturated fatty
acids. ...
12. A composition according to claim 8, wherein the pro- fragrance comprises less than 15 wt% of fatty acids 20 with less than 14 carbon atoms.
13.. A composition according to any preceding claim, further comprising a blue or violet shading dye.
25 14. A composition according to claim 13, wherein the shading-dye is a bis-azo or tris-azo dye.
15. .A composition according to claim 13- wherein the
Shading dye is a direct violet comprising the following structures:

15 wherein: ring D and E may be independently naphthyl or
phenyl as shown; Rr is selected from; hydrogen and Cl- C4 - alkyl, R2 is selected from: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl; R3 and R, are independently
20 selected from: hydrogen and Cl-C4-alkyl; X and Y are
independently selected from: hydrogen, C1-C4-alkyl and CI-C4-alkoxy and n is 0, 1 or 2.
16. A composition according to claim 13, wherein the dye is 5 selected from direct violet 7, direct violet 9, direct
violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 54, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, 10 acid black 1, acid blue 29, solvent violet 13, disperse
violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, 15 basic violet 38, basic violet 48; basic blue 3, basic
blue 75, basic blue 95, basic blue 122, basic blue-124, basic blue 141, reactive blue 19, reactive blue 163, reactive blue 182, reactive blue 96 and mixtures thereof.
20
17. A composition according to claim 13,- wherein the' shading dye is an azine dye comprising the following structure:

5 wherein Ra, Rb, Rc and Rd are selected from: H, an
branched or linear Cl to C7-alkyl chain, benzyl a
phenyl, and a naphthyl; the dye is substituted with at
least one S03" or -COO" group; the B ring does not carry
a negatively charged group or salt thereof; the A ring

10 is optionally substituted to form a naphthyl; and the
- ' structure is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy,
phenoxy, Cl, Br, I, F, N02 and mixtures thereof.
!
15 18. A composition according to any preceding claim, further comprising a fluorescer'.
19. A composition according to any preceding claim, further comprising a fabric-substantive polymer as a deposition
20 aid.

20. A composition according to any proceeding claims, comprising:
a) at. least one photo-bleach, preferably a 'phthalocyanine photo-bleach, preferably at level of 0.00001-lwt%;
1
b) at,least one pro-fragrance, preferably at a level of 5 0.001 to 10wt%, more preferably 0.1 to 2 wt%
c) at least one shading dye, preferably a bis-azo direct
dye, preferably with an optical adsorption peak in the
!
range 540-600nm, preferably at a level of 0.000001- 10 1wt %;
d) at least one fluorescer, preferably selected from the group comprising: di-styryl biphenyl compounds, diamine stilbene di-sulphonic acid compounds and
15 pyrazoline compounds, preferably at a level of 0.005 to
2 wt %; and,
e) optionally, a polymeric deposition aid for the pro- fragrance and/or perfume.
20
21. A method of laundering fabrics which comprises the step of treating the fabrics with a composition according to any1 one of claims 1-20.
25 22. Use of a composition according to any one of claims 120 to perfume fabric articles.