FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
DYE RADICAL INITIATORS
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

DYE RADICAL INITIATORS
FIELD OF INVENTION 5
The present invention relates to the delivery of dyes to fabrics.
BACKGROUND OF INVENTION
10
Organic radicals are carbon containing compounds that are paramagnetic. Most organic radicals are unstable and rapidly decay to non-paramagnetic compounds. Unstable organic radicals are useful reactive intermediates that may be used
15 for a number of valuable chemical and biological processes. Unstable Organic radicals are well known to initiate polymerisation reactions that lead to technically useful polymers. WO 01/44127 and WO 01/44424 (both Unilever) teach the use of unstable organic radical to bleach substrates. WO
20 04/072217 (Unilever) teaches the use of photolytically
generated unstable organic radicals to kill mammalian cells.
Radical photoinitiators are widely used to efficiently produce unstable organic radicals. Photoinitiators absorb UV 25 light and then undergo cleavage or abstraction reaction to
yield radicals. Photoinitiators are difficult to use on many heterogeneous substrates due to low substantivity.
WO2006/024612, to CIBA, discloses dyes linked to 30 phthalocyanine compounds that act as singlet oxygen generators in the presence of light.

Summary of the Invention
Radical photoinitiators are difficult to target to textiles. We have found that linking radical initiators to a fabric 5 substantive dye permits targeting of the radical initiator to a textile. We have observed photobleaching and shading of textiles treated with the dye radical photoinitiators. We have also observed that the dye does not show substantial fading due to the radical production but fabric stains are 10 bleached.
In one aspect the present invention provides a detergent composition comprising from 2 to 70 wt % of a surfactant together with a ketonic radical photoinitiator dye of the 15 following structure (I):

wherein, the carbonyl shown in the structure is non-enolizable, and the ketonic radical photoinitiator dye is comprised of an aromatic group, Arl, and the Ari is directly
20 covalently bound to an azo group, the azo group directly
covalently bound to a second aromatic, Ar2, and R is selected
from:
a group having from 3 to 30, preferably 3 to 24, carbon
atoms having from: 0 to 2 phosphorous atoms, from 0 to 3
25 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3 nitrogen atoms;
a group having from 3 to 30, preferably 3 to 24, carbon atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3

nitrogen atoms and forms a six or five membered ring by being covalently bound to Ari.
In another aspect the present invention provides a domestic 5 method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of the ketonic radical photoinitiator dye, the aqueous solution comprising from 1 ppb to 1 ppm of the ketonic radical 10 photoinitiator dye; and, from 0.0 g/L to 3 g/L of a surfactant;
(ii) optionally rinsing; and,
(iii) drying the textile in the presence of natural sunlight. 15
It is preferred that the aqueous solution used in the method has a fluorescer present and/or perfume.
The present invention also extends to the ketonic radical 20 photoinitiator dye. Preferred ketonic radical photoinitiator dyes are detailed immediately below.
In a further aspect the present invention also provides a ketonic radical photoinitiator dye of the form:


wherein, the carbonyl bound directly to R shown in the
structure is non-enolizable, and:
X is para and/or ortho and X is selected from: -H; -CN; -F; 5 -CI; -Br; -N02; -CH2C1; -CF3; -NHC(0)CH3; -N+(Me)3 ; -N+(Et)3;
and, -N+(Pr)3; and,
R is selected from:
a group having from 3 to 30, preferably 3 to 24, carbon
atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 10 sulphur atoms, from 0 to 3 oxygen atoms, and from 0 to 3
nitrogen atoms;
a group having from 3 to 30, preferably 3 to 24, carbon
atoms having from: 0 to 2 phosphorous atoms, from 0 to 3
sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3 15 nitrogen atoms and forms a six membered ring by being
covalently bound at the position indicated by the arrow.
Preferably the ketonic radical photoinitiator dye is present in the detergent composition from 0.00001 to 1 wt%, most 20 preferably 0.0001 to 0.01 wt%.

DETAILED DESCRIPTION OF THE INVENTION
The R (and Arl) group of the ketonic radical photoinitiator dye is non-enolisable with the ketone (bridging ketone) 5 directly bound to Arl (and R). That is to say that the R group does not carry a hydrogen alpha to the ketone. The process of keto-enol tautomerism is shown directly below in the schematic.

10 Preferably, the ketonic radical photoinitiator dye is blue or violet in colour. Preferably the ketonic radical photoinitiator dye gives a blue or violet colour to the cloth with a hue angle of 250-345, more preferably 265 to 330, most preferably 270 to 300. The cloth used to determine
15 the hue angle is white bleached non-mercerised woven cotton sheeting.
It is preferred that Ari and Ar2 are independently selected
from: phenyl; naphthyl; pyridinyl; pyrimidinyl; pyrazinyl, 20 triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl;
isoquinolinyl; quino.xalinyl; imidazolyl; pyrazolyl;
benzimidazolyl; isothiazolyl; oxazolidinyl; pyrrolyl;
carbazolyl; indolyl; isoindolyl; furanyl; benzofuranyl;
isobenzofuranyl; isoindolyl; thiophenyl; benzothiophenyl; 25 benzo[c]thiophenyl; imidazolyl; purinyl; indazolyl;
oxazolyl; benzoxazolyl; isoxazolyl; benzisoxazolyl;

thiazolyl; benzothiazolyl; naphthalenyl; quinolinyl; isoquinolinyl; pyrazinyl; quinoxalinyl; pyrimidinyl; quinazolinyl; pyridazinyl; and, cinnolinyl, and wherein nitrogen containing hetrocycles are neutral or quaternized 5 by alkyl groups. The alkyl groups of the quaternized
nitrogen containing hetrocycles are preferably methyl or ethyl.
It is more preferred that Ari and Ar2 are independently 10 selected from: phenyl; and, naphthyl.
Ar2 is preferably substituted by an amine group, most preferably -NH2.
15 The ketonic radical photoinitiator dye is preferably of the form:

Ar3 may substituted by a further azo group which is covalently bound to an aromatic or an hetroaromatic group
20 which in turn may also be substituted by a further azo group which is covalently bound to an aromatic or an hetroaromatic group; these further aromatic or an hetroaromatic group are selected from Ari (Ar2) as defined herein. The groups Arl, Ar2, (and if present) Ar3 and further aromatic are all
25 independently selected.
The ketonic radical photoinitiator dye is most preferably of
the form:


wherein, the carbonyl bound directly to R shown in the structure is non-enolizable, and:
X is para and/or ortho and is H or an electron withdrawing 5 group; and,
R is selected from:
a group having from 3 to 30, preferably 3 to 24, carbon atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3
10 nitrogen atoms;
a group having from 3 to 30, preferably 3 to 24, carbon atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3 nitrogen atoms and forms a six membered ring by being
15 covalently bound at the position indicated by the arrow. The X substituent is most preferably para. X is more preferably selected from: -CN; -F; CI; -Br; -N02; -CH2C1; -CF3; -NHC(0)CH3; -N+(Me)3; -N+(Et)3; and, -N+(Pr)3.
20 R is preferably selected from: phenyl; 2,4,6-
trimethylphenyl; a phosphine oxide; a phosphinate; -CR2R3R4, wherein R2, R3, R4 may be independently selected from -C1-C8-

alkyl; -0Cl-C8-alkyl; phenyl; -OH; amine, CN, halogen, and -S02-phenyl, with the proviso that not more than one of R2, R3, R4 is -OH, phenyl; amine, CN, halogen, and -S02-phenyl and no more than two of R2, R3, R4 are -OCl-C8-alkyl; and, a group 5 such that RCOAri forms a group selected from: a quinone,
thioxanthone and xanthone. A preferred class of dye radical photoinitiator are those in which RCOAri forms a group selected from: a quinone, thioxanthone and xanthone; these structures are found in some of the preferred examples of 10 the ketonic radical initiator below.
Preferred groups for R are those selected from: C6H5-;2,4,6-

Electron-withdrawing groups used herein are groups having a Hammett substituent constant op value of at least 0.1, more preferably at least 0.30.
20 Specific examples of the electron-withdrawing group having a op value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a
25 diarylphosphinyl group, an alkylsulfinyl group, an
arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl

group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanato group, a thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a 5 halogenated alkylthio group, an aryl group substituted by other electron-withdrawing group having a op value of 0.20 or more, a heterocyclic group, a halogen atom, an azo group.
The ketonic radical photoinitiator dye may be further substituted by uncharged organic groups having a total 10 molecular weight of less than 400. Preferred uncharged
organic groups are selected from: NHCOCH3, CH3, C2H5, CH30, C2H50, amine, Cl, F, Br, I, N02, CH3S02, and CN.
Preferred examples of the ketonic radical photoinitiator dye 15 are:

OTHER DYES 5 In a preferred embodiment of the invention, other shading colourants may be present that build up over multiple washes, thereby counteracting long term yellowing and greying effect. They are preferably selected from blue and violet pigment such as pigment violet 23, solvent and 10 disperse dyes such as solvent violet 13, disperse violet 28, bis-azo direct dyes such as direct violet 9, 35, 51 and 99, and triphenodioxazine direct dyes such as direct violet 54.
Even more preferred is the presence of acid azine dyes as 15 described in WO 2008/017570; the level of the acid azine dyes should be in the range from 0.0001 to 0.1 wt%.
Additional Photobleaches such as sulphonated Zn/Al phthalocyanins may be present. 20
For addition to granular formulation the ketonic radical photoinitiator dye may be added to the slurry to be spray dried or added via post-dosed granules.

In granular formulation the dye ketonic radical photoinitiator dye may be granulated with an acidic component to reduce hydrolysis on storage as discussed in WO2007/039042 (Unilever). 5
In a preferred embodiment the ketonic radical photoinitiator dye powder obtained from the ketonic radical photoinitiator dye synthesis is mixed with a Na2So4 or NaCl or pre-prepared granular base or full detergent formulation to give a 0.1 to
10 5 dye wt% mixture. This ketonic radical photoinitiator dye mix is then mixed into the granular formulation. The ketonic radical photoinitiator dye powder is preferably formed by drying a liquid slurry or solution of the ketonic radical photoinitiator dye, for example by vacuum drying, freeze
15 drying, drying in drum dryers, Spin Flash © (Anhydro), but most preferably by spray drying. The ketonic radical photoinitiator dye powder may be ground before, during or after the making of the slurry. This grinding is preferably accomplished in mills, such as for example ball, swing, bead
20 or sand mills, or in kneaders.
Other ingredients such as dispersants or alkali metal salts may be added to the liquid slurry. The ketonic radical photoinitiator dye powder preferably contains 20 to 100 wt% 25 of the dye.
Preferably, the ketonic radical photoinitiator dye powder has an average particle size, APS, from 0.1 to 300 microns, preferably 10 to 100 microns. Preferably this is as measured 30 by a laser diffraction particle size analyser, preferably a Malvern HP with 100 mm lens.

SURFACTANT
The composition comprises between 2 to 70 wt % of a surfactant, most preferably 10 to 30 wt %. In general, the nonionic and anionic surfactants of the surfactant system 5 may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in 10 "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser
Verlag, 1981. Preferably the surfactants used are saturated.
Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds
15 having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol-ethylene oxide
20 condensates, generally 5 to 25 EO, i.e. 5 to 25 units of
ethylene oxide per molecule, and the condensation products of aliphatic C6 to C18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO,
25 Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
30 Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those

obtained by sulphating higher Cs to Cia alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and 5 sodium alkyl glyceryl ether sulphates, especially those
ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cn to Ci5 alkyl benzene sulphonates and sodium C12 to C13 alkyl 10 sulphates. Also applicable are surfactants such as those
described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.
15 Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali metal
20 salt of a C-i6 to Cia primary alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate.
The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant 25 system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 4 0 wt % of the surfactant system.
In another aspect which is also preferred the surfactant may 30 be a cationic such that the formulation is a fabric conditioner.

CATIONIC COMPOUND
When the present invention is used as a fabric conditioner it needs to contain a cationic compound.
5 Most preferred are quaternary ammonium compounds.
It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C12 to C22 alkyl chain. 10
It is preferred if the quaternary ammonium compound has the following formula:

in which R1 is a CL2 to C22 alkyl or alkenyl chain; R2, R3 and 15 R4 are independently selected from C1 to C4 alkyl chains and X" is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
20 A second class of materials for use with the present
invention are the quaternary ammonium of the above structure in which R1 and R2 are independently selected from C12 to C22 alkyl or alkenyl chain; RJ and R4 are independently selected from C1 to C4 alkyl chains and X" is a compatible anion.
25
A detergent composition according to claim 1 in which the ratio of (ii) cationic material to (iv) anionic surfactant is at least 2:1.

Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble).
It is preferred if the ratio of cationic to nonionic 5 surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.
The cationic compound may be present from 1.5 wt % to 50 wt % of the total weight of the composition. Preferably the 10 cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.
The softening material is preferably present in an amount of from 2 to 60% by weight of the total composition, more 15 preferably from 2 to 40%, most preferably from 3 to 30% by weight.
The composition optionally comprises a silicone.
20 BUILDERS OR COMPLEXING AGENTS
Builder materials may be selected from 1) calcium
sequestrant materials, 2) precipitating materials,
3) calcium ion-exchange materials and 4) mixtures thereof.
25 Examples of calcium sequestrant builder materials include
alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
30 Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.

Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known 5 as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid,
10 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.
15
Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders.
The composition may contain as builder a crystalline 20 aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula:
25 0.8-1.5 M20. A1203. 0.8-6 Si02
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. 30 The preferred sodium aluminosilicates contain 1.5-3.5 Si02
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. 5
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 10 silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., 15 contains less than 1 wt% of phosphate.
FLUORESCENT AGENT
The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and
20 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. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2
25 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 compounds, e.g. Blankophor SN.
30 Preferred fluorescers are: sodium 2 (4-styryl-3-
sulfophenyl)-2H-napthol[1,2-d]triazole, drsodium 4,4'-

bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[ (4-anilino-6-morpholino-l,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis (2-5 sulfostyryl)biphenyl.
It is preferred that the aqueous solution used in the method has a fluorescer present. When a fluorescer is present in the aqueous solution used in the method it is preferably in 10 the range from 0.0001 g/1 to 0.1 g/1, preferably 0.001 to 0.02 g/1.
PERFUME
Preferably the composition comprises a perfume. The perfume
15 is preferably in the range from 0.001 to 3 wt %, most
preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory
20 80th Annual Edition, published by Schnell Publishing Co.
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 25 more, preferably five or more, more preferably six or more or even seven or more different perfume components.
In perfume mixtures preferably 15 to 25 wt% are top notes. Top notes are defined by Poucher (Journal of the Society of 30 Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are

selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
Perfume and top note may be used to cue the whiteness 5 benefit of the invention.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
10
POLYMERS
The composition may comprise one or more polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates,
15 maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Polymers present to prevent dye deposition, for example poly(vinylpyrrolidone), poly (vinylpyridine-N-oxide), and 20 poly(vinylimidazole), are preferably absent from the formulation.
ENZYMES
The laundry treatment composition may contain an enzyme. 25 Examples
Example 1: Synthesis
Azo coupling reactions are well discussed in the literature, for example Industrial Dyes, K.Hunger ed., Wiley VCH 2003 30 ISBN 3-527-30426-6.

The ketonic radical photoinitiator dye below (BPCN) was synthesised according to the 2 stage scheme:

BPCN
5 In the first stage, conducted at pH=l-2 H-acid was coupled with a diazonium salt to form an "acid coupled" monoazo derivative in which coupling had taken place ortho to the amino group of H-acid (l-Amino-8-naphthol-3,6-disulphonic acid). In the second stage conducted at pH=7, the coupling 10 of the diazonium salt took place ortho to the hydroxyl group.
The diazonium salts were prepared following standard procedure from the amine in HCl/ice with sodium nitrate. 15 Sulphamic acid was added until a negative starch iodide test was obtained. Once prepared the diazonium salts were immediately used for the coupling reactions.
The final product was purified by dissolving in water and 20 adding acetone until precipitation occurs. The precipitate was then collected as final product and dried. The structure was confirmed by Mass spectroscopy (negative ion electrospray). The spectrum showed a large ion at m/z 655, which is consistent with the pseudo molecular ion (M-H)~ 25 for the proposed formula. HPLC revealed the product to be of high purity (>95%).

In this structure R and Ar1 are both phenyl and Ar2 is a naphthol. The naphthol carrying a further aromatic Ar3 via an azo group which is p-cyanophenyl.
5 Example 2: UV-VIS Spectrum
The UV-VIS spectrum of the ketonic radical photoinitiator dye of example 1 was recorded in water, and the following results obtained in the range 300-800nm. 10

Xmax / nm e / L mol-1cm-1 Xmax /
nm £ / L mol-1cm-1
607 47000 600 47000
398 12600 395 13200
323 27800 313 30200
Example 3: Radical Generation
Generation of unstable organic radicals from the compound of Example 1 (BPCN) was shown by mean of a photo-CIDNP
15 experiment. The CIDNP technique is described in detail in J.Phys.Chem. 1996, 100, 556-564. Observation of polarized (non-Boltzmann) resonance in NMR signals, following light excitation of the sample indicate the presence of photoinitiated radicals and their subsequent reaction
20 products.

Steady state CIDNP experiments were done using a 200W High-pressure mercury lamp (Hamamatsu LC4) as the irradiation source. After presaturation and a 300ms lamp flash, the 5 observing radiofrequency pulse (1.5US, 30°) was applied to record CIDNP spectra. A lamp pulse was used to avoid depletion of sample. All samples were bubbled with argon and kept in dark at room temperature prior to use.
10 The sample was dissolved in deuterated methanol. When the
CIDNP experiment was run in the absence of a lamp flash, no NMR signals were observed due to the presaturation pulse. In the presence of a lamp flash Absorptive polarised NMR signals were observed at the following ppm, 7.53, 7.57,
15 7.70, 7.72, 7.75, 7.79, 7.82, 7.86, 7.91, 8.2.
In a comparative example the photoinitiator benzophenone also gave polarized NMR signals.
20 The compound, EPCN, produces unstable organic radical under UV irradiation.
Example 4: deposition
0.003wt% of the ketonic radical photoinitiator dye of 25 example 1 (BPCN) was added to ECE ref detergent A. This was used to wash a piece of woven cotton. After rinsing and drying the cotton, the cloth was clearly blue indicating the deposition of the initiator. The %reflectance of the cloth measured on a reflectometer at 570nm was 83.4 compared to 30 8 9.9 for cloth washed in ECE detergent without dye. The drop in % reflectance indicates deposition to the cloth.

In a comparative example the photoinitiator benzophenone showed no deposition to the cotton cloth.
5 Example 5 Bleaching benefit
0, 0.005 and 0.01 wt% of the radical initiator of Example 1 (BPCN) was added to were added to a washing powder. The washing powder contained 20% LAS surfactant, 30% Na2C03, 40% NaCl, remainder minors included calcite and fluorescer and
10 moisture. The washing powders was used to wash together 4 white woven cotton cloth, and 4 model cotton tea stain monitor (BC1). Washes were conducted in 26° French Hard water at 293K with a liquor to cloth ratio of 10:1 and 4g/L powder. Washes took 30 minutes and were followed by 2, 1
15 minute rinsed in 26° French Hard water at 293K. Following the wash half the fabrics were tumble dried in the dark and half the monitors were irradiated in a weatherometer (20% RH, simulated florida sunlight, 0.35 W/m2 @ 340nm) for 2 hours. After drying the reflectance spectra of the clothes were
20 measured (UV-excluded). The additional stain removal on the BC1 monitor caused, by the light irradiation was calculated as 5AR46o such that:
5AR46o = AR450 (irradiated) - AR46o (tumble dried) and
25 AR460 = R460 (after wash) -R460 (before wash)
where R4eo is the % reflectance at 460nm. The more +ve AR460 is the greater the stain removal. Results are given in the table below.

Wt% BPCN in formulation 5AR46o

0 1.9
0.005 2.5
0.01 2.9
The presence of BPCN increases the stain removal when
irradiated.
13 Example 6: Dye Photofading
The dyes listed in the table pelow were synthesised and deposited onto white cotton fabric from water containing Na2S04, such that the reflectance at 610nm lay in the range 45 to 55%. The fabric was dried and then irradiated in a 10 weatherometer (20% RH, simulated florida sunlight, 0.40 W/m2 @ 340nm) for 4 hours.
The reflectance spectra of the cloth were measured before and after irradiation and converted to the remission
15 function K/S such that K/S = (1-R2)/2R Where R = % reflectance/100.
To correct for the reflectance of the white cloth, the K/S values for white cloth were subtracted from the dyed cloth.
20 The K/S values are proportional to the dye loading on the cotton. Comparison of the values (550-700nm) before and after irradiation allows the adye loss due to photofading to be calculated. The results are summarised in the table below.
25
The ketonic radical photoinitiator dye X=PhCO and Y =CN (BPCN) with values given in italics shows similar or less photofading than comparison dyes.

X Y Lambda max in % dye
water photofaded
after 4
hours
irradiation
CN F 593 9
CN CN 600 10
PhCO CN 608 14
H NH2 599 16
H N02 619 19
F F 593 26
CH30 CN 633 33


We claim:
1. A detergent composition comprising from 2 to 70 wt % of a surfactant together with a ketonic radical photoinitiator 5 dye of the following structure (I):

wherein the carbonyl shown in the structure is non-enolizable and the ketonic radical photoinitiator dye is comprised of an aromatic group, Ari, and the Ari is directly
10 covalently bound to an azo group, the azo group directly
covalently bound to a second aromatic, Ar2, and R is selected
from:
a group having from 3 to 30, preferably 3 to 24, carbon
atoms having from: 0 to 2 phosphorous atoms, from 0 to 3
15 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3 nitrogen atoms;
a group having from 3 to 30, preferably 3 to 24, carbon atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3
20 nitrogen atoms and forms a six or five membered ring by being covalently bound to Ari.
2. A detergent composition according to claim 2, wherein Ari and Ar2 are independently selected from: phenyl; 25 naphthyl; pyridinyl; pyrimidinyl; pyrazinyl, triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; isothiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; isoindolyl; furanyl; benzofuranyl; isobenzofuranyl;

isoindolyl; thiophenyl; benzothiophenyl; benzo[c]thiophenyl; imidazolyl; purinyl; indazolyl; oxazolyl; benzoxazolyl; isoxazolyl; benzisoxazolyl; thiazolyl; benzothiazolyl; naphthalenyl; quinolinyl; isoquinolinyl; pyrazinyl; 5 guinoxalinyl; pyrimidinyl; quinazolinyl; pyridazinyl; and, cinnolinyl, and wherein nitrogen containing hetrocycles are neutral or quaternized by alkyl groups.
3. A detergent composition according to claim 2, wherein
10 Ari and Ar2 are independently selected from: phenyl; and,
naphthyl.
4. A detergent composition according to any preceding
claim, wherein Ar2 is substituted by an amine group.
15
5. A detergent composition according to any preceding
claim, wherein the dye radical initiator is of the form:

20 wherein Ari and Ar2 are independently selected and are as defined in any preceding claim and Ar3 is independently selected and takes a definition of Ari as defined in any preceding claim, and wherein Ar3 is optionally substituted by a further azo group which is covalently bound to a
25 aromatic or an hetroaromatic group.
6. A detergent composition according to claim 5, where: the dye radical initiator is of the form:


wherein:
X is para and/or ortho and is H or an electron withdrawing
group; and, 5 R is selected from:
a group having from 3 to 30, preferably 3 to 24, carbon atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3 nitrogen atoms;
10 a group having from 3 to 30, preferably 3 to 24, carbon atoms having from: 0 to 2 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3 oxygen atoms, and, from 0 to 3 nitrogen atoms and forms a six membered ring by being covalently bound at the position indicated by the arrow.
15
7. A detergent composition according to claim 6, wherein X is para.
8. A detergent composition according to claim 6 or 7,
20 wherein X is selected from: -CN; -F; CI; -Br; -N02; -CH2C1; -CF3; -NHC(0)CH3; -N+(Me)3; -N+(Et)3; and, -N+(Pr)3.

9. A detergent composition as defined in any preceding
claim, wherein:
R is selected from:
phenyl; 2,4,6-trimethylphenyl; a phosphine oxide; a 5 phosphinate; -CR2R3R4, wherein R2, R3, R4 may be independently selected from -Cl-C8-alkyl; -OCl-C8-alkyl; phenyl; -OH; amine, CN, halogen, and -S02-phenyl, with the proviso that not more than one of R2, R3, R4 is -OH, phenyl; -OH; amine, CN, halogen, and -S02~phenyi and no more than two of R2, R3, 10 R4 are -OCl-C8-alkyl; and,
a group such that RCOAri forms a group selected from: a quinone, thioxanthone and xanthone.
10. A detergent composition according to claim 9, wherein R
15 is selected from: C6H5-; 2,4,6-trimethylphenyl;

20 11. A detergent composition according to claim 10, wherein R is selected from: phenyl; and, 2,4,6-trimethylphenyl.
12. A detergent composition according to any preceding claims, wherein RCOAri forms a group selected from: a 25 quinone, thioxanthone and xanthone.

13. A detergent composition according to any preceding claims, wherein the dye radical initiator is a bis-azo compound.
5 14. A detergent composition according to any preceding
claim, wherein the dye radical initiator is blue or violet.
15. A dye radical initiator of the form:

10 wherein, the carbonyl bound directly to R shown in the
structure is non-enolizable, and:
X is para and/or ortho and X is selected from: H; -CN; -F;
Cl; -Br; -N02; -CH2C1; -CF3; -NHC(0)CH3; -N+(Me)3 ; -N+(Et)3;
and, -N+(Pr)3; and, 15 R is selected from:
a group having from 4 to 20 carbon atoms having from: 0 to 2
phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3
oxygen atoms, and, from 0 to 3 nitrogen atoms;
a group having 'from 4 to 20 carbon atoms having from: 0 to 2 20 phosphorous atoms, from 0 to 3 sulphur atoms, from 0 to 3
oxygen atoms, and, from 0 to 3 nitrogen atoms and forms a

six membered ring by being covalently bound at the position indicated by the arrow.
16. A dye radical initiator according to claim 15, wherein
5 X is para.
17. A dye radical initiator according to claim 15 or 16,
wherein:
R is selected from: 10 phenyl; 2, 4, 6-trimethylphenyl; -CR2R3R4, wherein R2, R3, R4 may
be independently selected from -Cl-C8-alkyl; -OCl-C8-alkyl;
phenyl; -OH; amine, CN, halogen, and -S02~phenyl, with the
proviso that not more than one of R2, R3, R4 is -OH, phenyl; -
OH; amine, CN, halogen, and -S02_phenyl and no more than two 15 of R2, R3, R4 and -0Cl-C8-alkyl; and,
a group such that RCOAri forms a group selected from: a
quinone, thioxanthone and xanthone.
18. A dye radical initiator according to claim 17, wherein 20 R is selected from; phenyl; and, 2,4,6-trimethylphenyl.
19. A dye radical initiator according to claim 17, wherein
R is selected from: C6HS p-Me-C6H4-S(0)2-
C{Me)2- ; Me2C(CN)- ; Me2C(OH)- ;; C6H5-
25 C(Me)2-; and, t-Bu-.

20. A dye radical initiator according to claim 17, wherein RCOAri forms a group selected from: a quinone; thioxanthone; and xanthone.