CA2372289C - Fabric care treatment composition and a method of treating fabric - Google Patents

Abstract

A fabric care system comprising a bond cleavage radical photoinitiators is used to treat fabric, for example as a stain removal system in the washing or rinsing of fabric in a laundry process. The fabric treatment system can be incorporated into a fabric washing composition or a conditioner composition.

Description

Fabric Care Treatment Composition and a Method of Treating Fabric The present invention relates to a fabric care treatment composition comprising a novel colour care and stain treatment system. The present invention also relates to a method of treating fabric using the novel colour care and stain treatment system. The present invention further relates to the use of the novel.colour care and stain treatment system in fabric care treatment.
Background of the Invention The present invention is concerned with fabric treatment that takes place after use of the fabric, in particular to reverse degradation of fabric that occurs as a result of that use, for example soiling and staining. Such treatments are referred to herein as fabric care. Fabric care treatments include laundering and the application of non-detergent-based fabric'care products, such as spray-on products. Considerable attention has been focused on components for inclusion in fabric care compositions which are specifically intended for colour care. For example, these components may comprise dye transfer inhibitors, stain removers, photofading inhibitors, and fluorescence inhibitors.

EP 0 786 517 discloses a fabric wash detergent composition in which a specific polymer system is included to provide stain removal benefits. International patent application no. PCT/EP

~~~q.3 tC) WO
Amended 22 August 2001 _ 2 _ -~
97/07289 discloses fabric treatment compositions comprising a sunscreen material for preventing sun damage to colour.
WO 95/13354 discloses compositions comprising polymers such as PVPNO and N-vinyl pyrollidone/N-vinyl imidazole copolymers as dye transfer inhibitors. EP-A-0035470 discloses a textile treatment-composition which comprises a photobleaching component. The photobleach material has some effect against stains, but can also attack dye.

The present inventors have sought further colour care and stain treatment components which are suitable for incorporation into fabric care compositions.

The present inventors have discovered that radical photoinitiator systems that operate by bond cleavage mechanism can act as colour care and stain removal components in fabric care compositions.

WO 96 12785, US-A-3915974 and JP 08 239700A, each disclose the use of materials which have radical initiating properties as perfume ingredients. All of these materials function by a hydrogen-abstraction mechanism rather than a bond-cleavage mechanism."

Radical photoinitiators themselves are well known and used in the unrelated fields of polymerisation, polymer cross linking and curing reactions in materials.

AMENDED SHEET

- 2a -Definition of the Invention The present invention'accordingly provides a fabric care composition, comprising a bond-cleavage radical photoinitiator.

More specifically, the present invention provides a fabric care composition, chosen from a fabric conditioner composition or a fabric wash composition comprising a bond-cleavage radical photoinitiator, wherein the composition being a fabric wash composition, the composition further comprises fabric wash detergent, and wherein the composition being a fabric conditioner composition, the composition further comprises fabric conditioner.

- 3 - ~
The present invention further provides a fabric care treatment method, comprising treating the fabric with a bond cleavage radical photoinitiator.

The present invention further provides use of a bond-cleavage radical photoinitiator in a fabric care treatment method.

It has also been found that the radical photoinitiators of the present invention have the advantage that they are stable in solution if kept in the dark. It is found that they do not degrade spontaneously on storage.

Further, it has been found that the radical photoinitiators of the present invention will act on stains without the need for agitation. This has the advantage that they can be used in simple application me-thods. Further, damage to fabrics, such as fibrillation can be avoided.

The radical photoinitiator systems according to the present invention are found to be soluble or dispersible in other media than water and can be used on dry-clean only garments.
Finally, it is found that the radical photoinitiators of the present invention can have a bactericidal effect.

1..3743 (l;) WO Amended 22 August 2001 - 4 - ~
Detailed Description of the Invention Radical Photoinitiators Radical photoinitiators suitable for use in the present invention are components which produce radicals capable of attacking stains on fabric, on photoexcitation.

AMENDED SHEET

~.. ~~ k %.I) WO
Amended 22 August 2001 - 5 - z Bond cleavage radical photoinitiators operate according to=
the following reaction:

light k2 = =
y Y* R1 + R2 k(2) is the rate constant of the bond-cleavage reaction.
Preferably, k(2) is greater than 106 s"1 .

Suitable bond cleavage radical initiators may be selected from the following groups.

(a) alpha amino ketones, particuarly those containing a benzoyl moiety, otherwise called alpha-amino acetophenones, for example 2-methyl 1-[4-phenylJ-2-morpholinopropane-l-one (Irgacure 907, trade mark), (2-benzyl-2-dimethyl amino-l-(4-morpholinophenyl)-butan-l-one (Irgacure 369, trade mark).
(b) alphahydroxy ketones, particuarly alpha-hydroxy acetophenones, eg (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l-propane-i-one) (Irgacure 2959, trade mark), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, trade mark).
(c) phosphorus containing photoinitiators, including monoacyl and bisacyl phosphine oxide and sulphides, for AMENDED SHEET

28_08_2001 CA 02372289 2001-10-24 U,sy4.s (C) WO
Amended 22 August 2001 example 2-4-6-(trimethylbenzoyl)diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (Irgacure 819, trade mark).

(d) dialkoxy acetophenones.
(e) alpha-haloacetophenones.
(f) trisacyl phosphine oxides.
Suitable radical photoinitiators are disclosed in WO 9607662 (trisacyl phosphine oxides), US 5399782 (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.

Suitable photoinitiators are disclosed for 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 acetophenones) and US
5767169 (alkoxy phenyl substituted bisacyl phosphine oxides).

Radical photoinitiators are all discussed in A.F.
Cunningham, V. Desorby, K. Di-e-tliker, R. Husler and D.G.
Leppard, Chemia 48 (1994) 423-426.

AMENDED SHEET

~~} WO
Amended 22 August 2001 - 7 - ~
Without wishing to be bound by theory, it is preferred that the radical photoinitiators all react through their excited triplet state, to reduce the influence of the cage effect.

The radical photoinitiator suitably undergoes the reactions set out above when excited by radiation falling generally in the range 290-800 nm. For example, natural sunlight, which comprises light in this region, will be suitable for causing the radical photoinitiator to undergo the reactions described above. Preferably, the radical photoinitiator has a maximum extinction coefficient in the ultraviolet range (290-400 nm) which is greater than 100 mol'1 lcml. Suitably, the radical photoinitiator is a solid or a liquid at room temperature.
Suitably, the radical photoinitiator is substantially colourless and gives non-coloured photo products upon undergoing one of the reactions set out above.

Preferably, the compositions comprise sensitisers such as thioxanthones, for example as described in EP-A-0088050, EP-A-0138754.

Preferred Radical Photoinitiator Systems The present inventors have discovered that radical photoinitiators having a spec_i_f.i-ed_hydrophobicity, measured by their log P value, have a particularly preferred effect.
All materials for the removal -of stains also have a tendency to attack dye. The preferred radical photoinitiator systems AMENDED SHEET

have a particularly beneficial balance of stain removal versus dye attack tendency.

Preferably, the radical photoinitiators have a high log P
value, where log P is the octanol-water partition coefficient. It is preferred that the radical photoinitiators have a log P measured at 25 C in excess of 2.5 and more preferably in excess of 4Ø

= 10 Fabric Care Compositions The present invention is suitable for use in industrial or domestic fabric wash compositions, fabric conditioning compositions and compositions for both washing and 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.

Fabric Wash Compositions Fabric wash compositions according to the present invention may be in any suitable form, for example powdered, tableted powders, liquid or solid detergent bars.

Fabric wash compositions according to the present invention comprise a fabric wash detergent-4naterial selected from non-soap anionic surfactant, nonionic surfactants, soap, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.
AMENDED SHEET

.C3943 Suitable anionic surfactants are well known to the person skilled in the art and include alkyl benzene suiphonate, primary and secondary alkyl sulphates, particularly C8-C,5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl sulphosuccinates; ether carboxylates; isethionates;
sarcosinates; fatty acid ester sulphonates and mixtures thereof. The sodium salts are generally preferred.

Nonionic surfactants are also well known to the person skilled in the art and include primary and secondary alcohol ethoxylates, especially C8-C2Q aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Clo-C15 primary and secondary aliphatic alcohols ethoxylated with an average of 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.

Detergent compositions suitable for use in domestic or 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.

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.
AMENDED SHEET

Anionic surfactant is suitably present at a level of from 5 wt% to 50 wt%, preferably 10 wt%-40 wt% based on the fabric treatment composition. Nonionic surfactant is suitably present at a level of 1-20 wt%, preferably 5-15 wtt.

The total amount of surfactant present will depend upon the intended end use and may be as high as 60 wt% for example in a composition for washing fabrics by hand. In compositions for machine washing of fabric, an amount of from 5 to 40 wt%
is generally appropriate.

Detergency Builder The detergent compositions of the invention will generally also contain one or more detergency builders. The total amount of detergency builder in the compositions will suitably range from 5 to 80 wtt, preferably from 10 to 60 wt%.

Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437,950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoeehst-)-: Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and .tripolyphosphate are also 'suitable for use with this invention.

AMENDED SHEET

The detergent compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70t by weight (anhydrous basis), preferably from 25 to 50 wt%.

The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general : formula:

0. 8-1. 5 Na20. A1203. 0-8-6 S i 02 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 Si02 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily be reaction between sodium silicate and sodium aluminate, as amply described in the literature.

~ 20 Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. The zeolite builder incorporated in the compositions of the invention may be maximum aluminiuin zeolite P (zeolite MAP) as AMENDED SHEET

described and claimed in EP 384 070A (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.

Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di-and trisuccinates, carboyxmethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroyxethyliminodiacetates, alkyl- and alkenylmalonates and = 20 succinates,; and sulphonated fatty acid salts. This list is -not intended to be exhaustive.

Especially preferred organic builders are citrates, suitable used in amounts of from 5 to 30 wtt, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts'of from 0.5 to 15 wtt, preferably from 1 to 10 wt%-. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
AMENDED SHEET

Bleach Components Detergent compositions according to the invention may also suitably contain a peroxy bleach system for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.

Suitable peroxy bleach compounds include organic peroxides , such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.

Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) .
, 20 The compositions may further comprise a photobleach system as described, for example, in EP-A-0035470.

Fabric Softening Composition The fabric treatment composition of the present invention may be a fabric conditioning_oamposition or it may comprise fabric conditioner.

AMENDED SHEET

Fabric Softening Compound The fabric softening compound is preferably a cationic nonionic or anionic fabric softening compound.

The fabric softening compound may be a quaternary ammonium material comprising a polar head group and one or two alkyl or alkenyl chains. The fabric softening compound may also be a nonionic fabric softening compound such as a fabric softening oil, a fabric softening silicone composition or a fabric softening ester composition such as sugar esters.

Particularly preferably, the fabric softening compound has two long chain alkyl or alkenyl chains with an average chain length greater than C14, more preferably each chain has an average chain length greater than C14, more .
preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of Cls.
. 20 It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
It is highly preferred if the fabric softening compounds are substantially water-insoluble. Substantially insoluble fabric softening compounds in the context of this invention are defined as--fabric softening compounds having a solubility less than 1 x 10-3 wt* in demineralised water at 20 C, preferably the fabric softening compounds have a solubility less than 1 x 10'4, most preferably the AMENDED SHEET

fabric softening compounds have a solubility at 20 C in demineralised water from 1 x 10'3 to 1 x 10-6.

Well known species of substantially water-insoluble quaternary ammonium compounds having the formula:

. N +

R2 Ra wherein R' and R2 represent hydrocarbyl groups having from 12 to 24 carbon atoms; R3 and R4 represent hydrocarbyl groups containing 1 to 4 carbon atoms; and X is an anion, preferably selected from halide, methyl sulphate and ethyl sulphate groups are preferred.

Representative examples of these quaternary softeners include di(tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride;
di(hydrogenated tallow alkyl) dimethyl ammonium chloride;
dioctadecyl dimethyl ammonium chloride; di(hydrogenated tallow alkyl) ditnethyl ammonium methyl sulphate;
dihexadecyl diethyl ammonium chloride; di(coconut alkyl) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride and di (hydrtsgerna't-ed tallow alkyl) dimethyl ammonium chloride (Arquad 2HT Trade Mark).
AMENDED SHEET

Other preferred softeners contain esters or amide links, for example those available under the trade names Accosoft 580, Varisoft 222, and Stepantex.

Particularly preferred fabric softening compounds are water-insoluble quaternary ammonium materials which comprise-a compound having two C12_la alkyl or alkenyl groups connected to the molecule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present. The preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula:

FZl (CHZ) n-T-R2 X"
(CH2) n-T-RZ

wherein each Rl group is independently selected from Cl-4 alkyl, hydroxyalkyl or Ca_4 alkenyl groups; and wherein each R2 group is independently selected from Ce_28 alkyl or alkenyl groups;

T is --C-O- or -0-C-; X' is any suitable anion and n is an integer from 0-5. Particularly preferred is di(ethyl ester) dimethyl ammonium chloride (DEEDMAC).

AMENDED SHEET

A second preferred type of quaternary ammonium material can be represented by the formula:

(RI) aN +- ( CH2 ) a CH X-CHzO0CR2 i 10- wherein Rt, n, X- and R2 are as def ined above.

It is advantageous for environmental reasons if the quaternary ammonium material is biologically degradable.
Preferred materials of this class such as 1,2 bis[hardened tallowoyloxy]-3-trimethylammonium propane chloride and their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers). Preferably these materials comprise small amounts of the corresponding monoester as . 20 described in US 4 137 180 for example 1-hardened tallowoyloxy-2-hydroxy trimethylamrnonium propane chloride.
The fabric softening agent may also be a polyol ester quat (PEQ). as described in EP 0 638 639 (Akzo).

Other Ingredients The compositions of the invention can also contain one or more optional ingredients, selected from pH buffering agents, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, AMENDED SHEET
_._..~,~.._ enzymes, optical brightening agents, opacifiers, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.
The present inverition may be in the form of a dilute or concentrated aqueous solution or suspension, for example as described in WO 97/15651, WO 95/27769. Alternatively, the fabric softening composition may be in the form of a powder for use in the rinse cycle of an automatic washing machine.
Alternatively, the fabric softening composition may be in the -form-of a sheet comprising fabric conditioning compositions for use in a tumble dryer, for example as disclosed in WO 95/27777. Alternatively, the fabric conditioning composition may be in the form of a substantially non-aqueous concentrate as described in international patent application no. PCT/EP99/00497.

Fabric wash detergent compositions according to the present ~ 20 invention may further include through the wash softening material, such as-cationic fabric softener.
Non-Detergent-Based Fabric Care Products The present invention can also be used in non-detergent-based fabric care products. For example, the product may comprise the stain removal systenr-as the principal ingredient. For exainple, non-detergent based compositions may comprise solutions of the stain removal system of the present invention in a suitable solvent, such as isopropanol, alcohol etc. The compositions may comprise AMENDED SHEET

aerosol or spray-on compositions. They may be in the form of sticks, bars, dab-on compositions, for example absorbed into sponges for application to the surface etc.

The present invention will be further described by way of example only with reference to the following examples.
Examples All quantities are in percent or parts by weight unless indicated otherwise.

The following radical initiators are used in the present examples. They-are available commercially under the trade marks set out below from Ciba Specialty Chemicals.

Irgacure 369 - 1-[4-(2-hydroxy ethoxy)-phenyl]-2-hydroxy-2-methyl-l-propane-i-one (log P = 2.9, measured at 25 C).

Irgacure 819 - bis(2,4,6-trimethyl benzoyl) - phenyl phosphine oxide (log P = 5.8, measured at 25 C).

Irgacure 2959 - (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l-propane-l-one (log P 0.84, measured at 25 C).
Example 1 Cloths heavily stained with stains set out in Table 1 were obtained from a commercial supplier (Equest, stains aged for three days then sealed). The stained cloths were then treated with solutions of ethanol containing various radical AMENDED SHEET
~_ _ _ photoinitiators and then placed in an Atlas S3000 Weatherometer WOM (trade mark) for 12 minutes (at a power level of 0.35 w/m2 at 340 nm). The results in the change in reflectance at 460 nm (R(460 nm)) measured using a Spectraflash SF60 (trade mark) reflectometer are set out in table 4.

The following treatment regimes were used:
Treatment 1 - no immersion.

Treatment 2 - place stained cloth in ethanol, remove and dry, wet with water, placed in Weatherometer for 12 minutes.
Treatment 3 - place in ethanol containing 0.20% by weight Irgacure 2959 (trade mark), remove and dry, wet with water, place in WOM for 12 minutes.

Treatment 4 - place in ethanol containing 0.20% Irgacure 819 (trade mark), remove and dry, wet with water, place in Weatherometer for 12 minutes.

The results are shown in Table 1.
AMENDED SHEET

Table 1 R(460 nm) stain 1 2 3 4 chilli 42.7 52.7 61.5 72.6 bolognese. 33.8 40.1 48.2 67.8 curry 43.2 55.9 55.9 84.5 baby food 50.6 71.3 79.9 84.8 P-carotene 23.8 24.5 43.0 87.5 grass 18.8 2=2.4 26.8 32.6 blood 8.1 5.8 6.8 5.7 wine 60.4 59.9 61.2 63.2 In general, the radical initiators lead to an increase in reflectance at 460 nm for a variety of stains. That is, the radical initiators effectively bleach the stains from the fabric.

Example 2 The method of Example 1 was repeated, using treatment 1, 2 and 4 except that the quantity of Irgacure 819 (trade mark) in the ethanol was varied. The results are shown in Table 2.

Table 2 Stain Treatment ~ Ir acure 0 0 0.01 0.02 0.05 0.1 bolognese 38.3 38.7 48.9 50.3 52.8 55.1 13-carotene 32 30.6 65.3 76 82.1 curry 31 29.1 44.7 50.2 55.4 57.5 The results show that the bleaching of stains can be obtained at very low on-weight-fabric levels of radical photoinitiator.

annFNDFD ,SHEET

Example 3 The following experiment was conducted to compare the effect of different radical initiator systems on stains and on dye.
A variety of stained cotton cloths were purchased from Equest as above. Photoinitiators at various levels on-weight-fabric (owf) were padded onto the stained cloths from ethanol. The ethanol was then evaporated, the cloths wetted with demineralised water and placed in an Atlas S3000 Weatherometer (trade mark) for 12 minutes of irradiation (power = 0.35W/mz at 340 nm Reflectance at 460 nm was measured for the stained cloths and for a piece of unstained fabric to yield.AE values. The values were compared to a Control where the stains had followed the same treatment, except that the ethanol contained no radical initiator. It was found, as in Example 1, that the initiators were particularly good at bleaching curry, bologonese, b-carotene and chilli. Table 3 and 4 give the average reduction in AE
above the control found for these four stains for Irgacure 2959 and 819 (trade mark) at various levels on weight of fabric.

To gauge how badly the initiators damage dyes, the above experiments were repeated except printed cloth purchased from Veebee The of Harrogate England,was used instead of stained fabric. In this case, the AE values represent dye damage. 16 different dyes were tested and the average dye damage measured is given in Tables 3 and 4.

The dyes were as follows:
AMENDED SHEET

Dye Level on weight fabric (g/kg) on dyed side Procion Red HE-7B 0.5 Scarlet HE-XL 0.5 Yellow HE-6G 1.0 Red HE-GXL 0.5 Blue HE-GXL 2.0 Turquoise H-A 5.0 Navy HE-XL 1.0 Remazol Red RB 1.0 Golden Yellow RNL 1.0 Brill Red RBS 2.0 Yellow FG 1.0 Orange FR 2.0 Navy GG 2.0 Turquoise G 2.0 Black B 1.0 The measurement of stain removal was divided by the measurement of dye damage to give a value of benefit/damage which is a measure of how specific the initiator is to the stains rather than the dye. It can be seen that Irgacure 819 (trade mark) which has a log P above 2.5 is much more stain specific than Irgacure 2953--{=trade mark) which has a log P below 2.5. This is particularly true at low levels (0-0.02% owf), where Irgacure 819 (trade mark) give large stain bleaching benefits but only very small dye damage.
AnnFNnFp PHEET

Table 3 wt% Irgacure 819 average stain average dye benefit (trade mark) owf removal, DE damage, AE damage 0.01 11.5 0.31 37.1 0.02 14 0.62 22.6 0.05 16.9 1.85 9.1 0.1 18.5 3.53 5.2 0.2 17.4 3.9 4.5 Table 4 wtt Irgacure 2959 average stain average dye benefit (trade mark) owf removal, AE damage, AE damage 0.05 2.3 3.5 0.66 0.1 3.9 5.3 0.74 0.2 4.9 9.9 0.49 , It should be noted that when the experiments were repeated using dry cloth much less dye damage was observed. However, the stain bleaching was also reduced.

Examples 4 and 5 The following base powder was prepared:

linear sodium alkyl-benzene sulphonate (LAS) 23.60%
sodium tripolyphosphate - 19.22%
sodium silicate - 4.81%
sodium sulphate - 28.59%
~AIIFNf1Frl ~HF~T

calcite - 10.30%

minors - 1.08%
water - 12.49%

In Example 4, 1 gram of this base powder was intimately mixed with 0.024 g of Irgacure 819. The final product contains 2.3% by weight of Irgacure 819. In Example 5, 1 gram of base powder was intimately mixed with 0.024 g of Irgacure 369. The final product thus contains 2.3% by weight Irgacure 369.

In each example, the mixture of base powder and radical photoinitiator was dissolved in 400 grams water at 40 C.
Three lots of cotton cloth were prepared. Each contained sheets weighing 16.1 grams in total and brushed cotton weighing 10 grams in total. All cloth was white. For each lot, both types of cloth were cut into four pieces. The lots were then washed in the solution prepared above for 5 minutes. One piece of cotton sheeting and one piece of brushed cotton was removed and dried. The wash solution was discarded and the cotton rinsed in 600 grams of cold water.
One piece of the cotton sheeting and brushed cotton was removed and dried. The first.rinse solution was then discarded. A second rinse was then conducted with a further 600 grams of water. Again, one piece of cotton sheeting and one piece of brushed cotton were removed.

The pieces of cotton sheeting and brushed cotton removed at each step were tested to see how much initiator had deposited onto the cloth. This was measured by measuring the reflectance of the dried cloths at 320 nm using a anncnin~n cN~~-r Spectraflash SF60 (trade mark) reflectance spectrometer.
The following results were obtained:

Table 5 - Cloth Sheeting Wash First Second rinse Rinse Powder without radical 39.0 38.5 38.5 photoinitiator Powder with 2.3% Irgacure 369 35.0 36.0 37.5 (trade mark) Powder with 2.3% Irgacure 819 34.7 35.5 36.0 (trade mark) Table 6 - Brushed Cotton Wash First Second rinse Rinse Powder without radical 20.0 16.4 17.3 initiator . Powder with 2.3% Irgacure 369 17.0 13.5 14.0 (trade mark) Powder with 2.3* Irgacure 819 14.0 15.0 16.1 (trade mark) In all cases, the reflectance of the cloth washed with powder compositions containing radical initiator is lower than the control composition which contains no radical initiator. This is because the Irgacure radical initiator absorbs strongly at 320 nm reducing the reflectance. The changes in reflectance measured were significantly above the n nnCnrnCn cl-IC:CT

1.1) 7`1J ~l) WO
Amended 22 August 2001 - 27 - ~
noise level for this type of measurement and confirm the deposition of the initiators.

Examples 4 and 5 demonstrate that radical photoinitiators may be deposited onto fabric from a laundry composition.
Example 6 The following rinse conditioner formulation was prepared:
HEQ ~ - 4%
Perfume - 0.3%

Irgacure 819 (trade mark) - 0.66%
Water - to 100%

1 HEQ = 1,2 bis [hardened tallowoyloxy)-3-trimethylammonium propanechloride, ex Hoechst.

3 grams of this rinse conditiorier were dissolved in 600 grams of cold water. 18 grams of cotton sheeting were placed in it for 5 minutes. At the end of this time, the cotton was removed and dried. The reflectance spectrum of the cotton sheeting was studied at 320 nm using a Spectraflash SF60 (trade mark) reflectometer.

It was calculated from the reflectance results that approximately 0.003% of radical photoinitiator (based on the weight of the cloth) had been delivered.

n n nC~nmcn QUCCT

1.J743 (l'.) WO
Amended 22 August 2001 Example 8 The following experiment carried out to test the effect of pH on the effects of radical photoinitiators.

The procedure of Example 7 was repeated except that Irgacure 819 (trade mark) was padded from ethanol onto stained cloths at 0.1% on-weight-fabric. For each stain, separate samples were taken and then wetted with buffer solution of varying pH. The resulting cloths were irradiated for 12 minutes in the Atlas S3000 (trade mark) Weatherometer. The variation in average reflectance at 460 nm after treatment is shown in the table. The average reflectance at 460 nm for the four A IICN I-'1CI'1 0 I_1CCT

treatments was 46.5. It can be seen that the radical photoinitiators give a substantial improvement in reflectance over a wide range of pH.

Table 7 pH

~ average R460 77.0 78.8. 76.5 68.4 Example 9 The experiments of example 3 were repeated, using Lucerin TPO-L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, ex BASF) and, separately Irgacure 184 (1-hydroxy-cyclohexyl-phenyl-ketone ex Ciba) at 0.02 and 0.2% owf. The results are shown in table 8 below:-Table 8 chemical wt% owf average average benefit/
stain dye damage damage removal Lucerin 0.02 12.5 1.3 9.6 TPO-L
Lucerin 0.2 15.1 2.0 7.6 TPO-L
Irgacure 0.02 8.0 0.9 8.9 Irgacure 0.2 13.3 4.6 2.9 n n nrrn I rN rn C+i_J1777 rT

Example 10 Stained white polyester cloth (Veebee Tech) was treated with Initiators as in previous examples and good cleaning effect found, above control. Little damage was found on dyed polyester cloth.

Example 11 An oily tomato stains were created by smearing a tomato paste ( Traditional Ragu Recipe Van den Bergh foods, ingredients: Tomatoes, sunflower oil, onion, salt, sugar, dextrose, garlic powder, basil, parsley, spice extract, citric acid, basil, parsley, CaCla) onto cotton sheeting and then ageing in air for 1 day. The stained cloths were washed in a linitest under the following conditions: each pot contained 12g cloths, (of which 6g were stained), 240ml of water, 0.34g Borax, 1.44g of liquid detergent. 40 degrees C, minutes, and no rinse. Cloths were dried in the tumble 20 drier, then placed in a WOM for 6 minutes.

Liquid detergents were created from, Coco5EO (ex Clariant -a non ionic surfactant), SDS (sodium dodecyl sulphate - an anionic surfactant), CTAC (cetyl trimethyl ammonium chloride -a cationic surfactant), Arquad 2HT (ex Akzo Nobel - a cationic surfactant), with 0.1* Lucerin TPO-L and 10t ethanol on weight of formulation; the remainder was water.
The amount of surfactant in each formulation is given in the table:

A n ncnmcn C+lJCC~' ingredients control L1 L2 L3 L4 Coco5E0 15.3 15.3 15.3 0 0 SDS 0 0 0 15.3 0 CTAC 1.7 1.7 0 0 0 Arquad 2HT 0 0 0 0 15.3 Lucerin 0 0.1 0.1 0.1 0.1 TPO-L

The results are shown below, in all cases the samples containing the initiator gave lower DE values (better stain removal) than the control.

AE value of stain compared to white original control 30.0 L1 16.0 L2 18.7 L3 11.3 L4 12.2 Example 12 Formulation Li of example 11 was made using Irgacure 819 instead of TPO-L. Good stain removal benefits above control were obtained.

Example 13 A detergent composition was created containing 15.3% of an anionic surfactant, 10% ethanol, 0.1% Lucerin TPO-L, remainder water. The anionic surfactants were LAS, and SDS.
nnncn1 t',\ rn 0 UCC-r tc) WO
Amended 22 August 2001 - 32 - z They were tested using the wash protocol of example 11, both showed large increased in stain removal benefit on irradiation, compared to a control of water only. This indicated that the initiator was effective from the wash.

Benefits were also found for a(3-carotene and a paprika stain.

Example 14 Persil liquid was purchased in Ireland and 0.01% on weight Lucerin TPO-L added to the product. On washing, rinsing and irradiating cloth stained with (,3-carotene, much greater stain removal was found when the initiator was present.

Example 15 The initiators, benzoin, dimethoxyphenylacetophenone, benzoin methyl ether, and benzoin ethyl ether (ex Aldrich) were seperately applied from ethanol to cotton cloth stained with P-carotene. All bleached the stain. As expected the initiators with higher logP value gave less dye damage.
n r. n~T nre~ nT}-'T

Claims (12)

1. A fabric care composition, chosen from a fabric conditioner composition or a fabric wash composition comprising a bond-cleavage radical photoinitiator, wherein when the composition is a fabric wash composition, the composition further comprises fabric wash detergent, and when the composition is a fabric conditioner composition, the composition further comprises fabric conditioner.

2. The composition of claim 1, wherein the fabric conditioner is a rinse conditioner.

3. The composition of claim 1, wherein the fabric wash detergent is selected from non-soap anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof.

4. The composition of claims 3, further comprising a builder material.

5. The composition of any one of claims 1 to 4, wherein the radical photoinitiator is selected from the group consisting of alpha amino ketones, alpha-hydroxy ketones, monoacyl and bisacyl phosphine oxides and sulphides, dialkoxy acetophenones, alphahalo acetyl phenones, tricacyl phosphine oxides and mixtures thereof.

6. The composition of any one of claims 1-5, wherein the radical photoinitiator is excitable by light substantially in the range of 296-460 nm.

7. A fabric care treatment method comprising treating the fabric with a bond cleavage radical photoinitiator.

8. A method according to claim 7, wherein the treatment of fabric takes place during a fabric washing step.

9. A method according to claim 7, wherein the treatment takes place during a fabric rinsing step, in the presence of fabric conditioner.

10. Use of a bond-cleavage radical photoinitiator in a fabric care treatment method.

11. The composition of claim 5 wherein the alpha amino ketones are alpha amino acetophenones.

12. The composition of claim 5 wherein the alpha-hydroxy ketones are alpha-hydroxy acetophenones.