CN1434853A

CN1434853A - Fabric care composition

Info

Publication number: CN1434853A
Application number: CN 00818988
Authority: CN
Inventors: S·N·巴特彻洛尔; D·A·卡尔; R·J·克劳福德; L·费尔克拉夫
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 1999-12-15
Filing date: 2000-11-14
Publication date: 2003-08-06
Also published as: BR0016437A; TR200201562T2; EP1242571A1; CA2394128A1; AU1702101A; GB9929693D0; WO2001044424A1

Abstract

A fabric care system comprising a radical initiator, which is preferably a photoinitiator and preferably selected from hydrogen abstraction photoinitiators, bond cleavage radical photoinitiators or mixtures thereof and a radical terminator 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 compositions

The present invention relates to fabric care compositions containing novel color care and stain treatment systems. The present invention also relates to a method of treating fabrics using this novel color care and stain treatment system. The present invention also relates to the use of the novel color care and stain treatment system in fabric care treatments.

Background of the invention

The present invention relates to fabric treatment of fabrics after use, and in particular to the elimination of degradation of the fabric such as staining and staining which occurs as a result of use of the fabric, such treatments being referred to herein as fabric care. Fabric care treatments include laundering and application of non-detergent based fabric care products, such as spray products. Attention is particularly focused on the components included in the fabric care compositions, particularly components specifically for color care. For example, these components may include dye transfer inhibitors, stain removers, photobleaching inhibitors, and fluorescence inhibitors.

European patent application No. 97200107.7 discloses a fabric detergent composition comprising a specific polymer system which provides stain removal benefits. International patent application No. PCT/EP97/07289 discloses fabric treatment compositions comprising sunscreen materials for the protection against sun damage. WO 95/13354 discloses compositions containing polymers such as PVPNO and N-vinylpyrrolidone/N-vinylimidazole copolymers as dye transfer inhibitors. EP-A-0035470 discloses ｃA textile treatment composition comprising ｃA photobleaching component. Photobleaching materials have some stain-proofing effect, but can also chemically attack dyes.

Fabric care compositions containing a free radical photoinhibitor system that functions with a hydrogen abstraction mechanism or a bond cleavage mechanism are described in our co-pending UK patent application No. 9917451.8. If the photoinhibitor has a high log P value (where P is the octanol-water partition coefficient), i.e., it is relatively hydrophobic, then the composition will cause little, but in other cases, may cause dye damage when applied to colored fabrics.

It is an object of the present invention to provide color care and stain treatment compositions which contain free radical inhibitors. It is also an object of the present invention to reduce the possibility of damaging the dye in coloured fabrics when the composition is used to treat such fabrics.

Free-radical photoinhibitors are well known per se and are used in unrelated areas of polymerization, polymer crosslinking and curing reactions in materials. Radical terminators are also known in these and other unrelated technical fields.

Definition of the invention

Accordingly, the present invention provides a fabric care composition comprising at least one free radical initiator and at least one free radical terminator.

The present invention also provides a fabric care treatment process comprising treating a fabric with at least one free radical initiator in the presence of at least one free radical terminator.

The invention also provides the use of a composition comprising at least one free radical initiator and at least one free radical terminator in a fabric care treatment process.

It has also been found that the free radical photoinitiators of the present invention act on stains without the need for agitation. The advantage of this is that they can be used with simple coating methods. In addition, damage to the fabric, such as fibrillation, can be avoided.

The free radical initiator system of the present invention is found to be soluble or dispersible in media other than water and can be used for dry cleaning only garments.

The compositions of the present invention have the surprising advantage that they reduce damage to coloured fabric dyes whilst also retaining the properties of an effective bleaching stain relative to corresponding compositions which do not contain any free radical terminators. Unexpectedly, when the free radical initiator and the free radical terminator are used together in a composition, they do not simply cancel each other out, thereby being substantially free of any stain bleaching properties.

Detailed description of the invention

Free radical initiators

Preferably, the free radical initiator is a free radical photoinitiator. Chemical and thermal free radical initiators are not preferred.

It has been found that the free radical photoinitiators of the present invention have the advantage that they are stable in solution if stored in the substantial absence of light. They do not degrade spontaneously on storage.

Preferably, these free radical initiators are selected from hydrogen abstraction reaction photoinitiators, bond cleavage free radical photoinitiators and mixtures thereof.

The radical initiator preferably used in the present invention is a component which generates radicals which attack stains on fabrics upon photoexcitation energy through one of the following paths:

hydrogen abstraction reaction

The hydrogen abstraction reaction radical photoinitiator is carried out according to the following reaction:

wherein X is a radical photoinitiator and R-H are hydrogen donor compounds.

Suitable examples of the hydrogen abstraction radical photoinitiator X include benzophenone, acetophenone, pyrazine, benzoquinone and benzil.

Suitable examples of hydrogen donor compounds R-H include, for example, organic molecules containing aliphatic C-H groups and include propan-2-ol, and compounds including cellulose, polyesters, or nylon backbones.

k1 is a rate constant of hydrogen abstraction reaction. Preferably, when RH is propan-2-ol, the rate constant k1 is greater than 10⁴Mol/sec.

Bond-cleavage radical photoinitiators

The bond-cleaving radical photoinitiator is carried out according to the following reaction:

k2 is the rate constant for the bond-cleavage reaction. Preferably, k2 is greater than 10⁶In seconds.

Suitable bond-breaking free radical initiators may be selected from the following groups:

(a) α -aminoketones, especially α -aminoketones containing a benzoyl moiety, or α -aminoacetophenone as such, as 2-solved-1- [ 4-phenyl]-2-morpholinopropan-1-one (trade mark, Irgacure907), (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade mark, Irgacure 369);

(b) α -hydroxyketones, in particular α -hydroxyacetophenones, such as (1- [4- (2-hydroxyethoxy) -phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade mark, Irgacure2959), 1-hydroxy-cyclohexyl-phenyl-one(trade mark, Irgacure 184);

(c) phosphorus-containing photoinitiators including monoacyl and bisacylphosphine oxides and sulphides, such as 2-4-6- (trimethylbenzoyl) diphenyl-phosphine oxide, bis (2-4-6-trimethylbenzoyl) -phenyl-phosphine oxide (trade mark, Irgacure819), (2-4-6-trimethylbenzoyl) -phenyl-phosphonic acid ethyl ester (Lucerin TPO-L (trade mark), available from BASF);

(d) dialkoxyacetophenones;

(e) α -haloacetophenone;

(f) a triacylphosphine oxide, and

(g) benzoin and a photoinitiator containing benzoin as a main component.

Suitable free-radical photoinitiators are disclosed in WO 9607662 (triacylphosphine oxide), U.S. Pat. No. 3, 5399782 (phosphine sulfide), U.S. Pat. No. 5410060, EP-A-57474, EP-A-73413 (phosphine oxide), EP-A-088050, EP-A-0117233, EP-A-0138754, EP-A-0446175 and U.S. Pat. No. 3, 4559371.

Suitable photoinitiators are disclosed, for example, in EP-A-0003002 under the name CibｃA Geigy, EP-A-0446175 under the name CibｃA Geigy, GB 2259704 under the name CibｃA Geigy (alkyldiacyl phosphine oxides), US 4792632 (diacyl phosphine oxides), US 5554663 under the name CibｃA Geigy (α -aminoacetophenone), US 5767169 (alkoxyphenyl-substituted diacyl phosphine oxides) and US 1924797 (acylphosphine compounds).

Free radical photoinitiators are generally discussed in A.F. Cunningham, V.Desorby, K.Dietliker, R.Husler and D.G.Leppard, Chemia 48(1994) 423-. Free radical photoinitiators are also discussed in H.F.Gruber "Advance in Polymer science (prog.Polym.Sci.)17(1992) 953-1044.

Without wishing to be bound by theory, it is preferred that the free radical photoinitiators all react through their excited triplet states to reduce the effects of the cage-closure effect.

The free radical photoinitiator suitably undergoes one of the reactions previously set forth when excited with radiation, typically 290 nm and 800 nm. For example, natural sunlight, including light in this wavelength band, would be suitable to cause the free radical photoinitiator to undergo one of the aforementioned reactions. Preferably, the maximum extinction coefficient of the free radical photoinitiator in the ultraviolet band (290-400 nm) is greater than 100 mol^-11 cm^-1. Suitably, the free radical photoinitiator is a solid or a liquid at room temperature. Preferably, the treated fabric is exposed to light until the stain is removed or all of the free radical photoinitiator has reacted. It will be appreciated that the time taken to remove the stain and/or substantially complete the reaction of the free radical photoinitiator will depend on the intensity of the light. The exposure time may be, for example, a few seconds to a few days, preferably 1 second to 6 hours, under typical terrestrial light conditions.

The method of the present invention preferably comprises the step of exposing the treated fabric to light, more preferably to sunlight, even more preferably to direct sunlight. When the process is carried out as part of a laundering process, light exposure conveniently involves drying the fabric in the sun. However, other means are possible, such as for example a fabric that has been exposed to light using an artificial light source.

Suitably, the free radical photoinitiator is substantially colourless, giving a colourless photoproduct on performance of one of the reactions set out above.

Optionally, the composition includes ｃA sensitizer photosensitizer as described in EP-A-0088050, EP-A-0138754, such as thioxanthone.

Preferred free radical photoinitiator systems

The inventors have found that radical photoinitiators having a specific hydrophobicity, which can be determined by their logP value, have a particularly preferred effect. All materials that remove stains also have a tendency to attack dyes. Preferred free radical photoinitiator systems have a particularly beneficial balance between stain removal and tendency to attack dyes.

Preferably, the free radical photoinitiator has a high logP value, wherein logP is the octanol-water partition coefficient. It is preferred that the free radical photoinitiator has a logP, measured at 25 ℃, of more than 2.5, more preferably more than 4.0.

Radical terminator

The radical terminators used in the compositions and methods of the present invention react rapidly with reactive radicals to yield non-reactive products. "reactive free radicals" are free radicals generated by free radical initiators or by reaction of these free radicals with molecules present in the environment in the confines of the stain.

The reaction of the radical terminator (T) with the reactive radical (R) to give the non-reactive product can be briefly represented by the following equation:

the non-reactive product may be, for example, a relatively stable (and relatively non-reactive) radical or non-radical molecule or ion.

The rate constant k3 for the above reaction is preferably greater than 10⁴Mole of^-1Second of^-1More preferably greater than 10⁶Mole of^-1Second of^-1Or even more preferably at or near the diffusion control limit (i.e., near the diffusion control limit)Where T is the temperature, R is the gas constant,is viscosity).

Suitable radical terminators include, for example, stable (i.e., non-reactive) radicals such as nitroxide (N-O.) radical containing compounds, i.e., compounds containing radicals derived from hindered semibenzoquinones or radicals derived from hindered phenols. These radicals act as radical terminators by reacting with reactive radicals to form non-radical molecules or ions.

Suitable radical terminators also include, for example, compounds which react with reactive radicals to form the stable radicals mentioned in the preceding paragraph. Thus, hindered amines (HALS; hindered amine light stabilizers), hindered phenols and hindered hydroquinones capable of forming nitroxide radicals may also function as effective terminators.

Preferred radical terminators for use in the present invention include ascorbic acid (vitamin C) and chromanols such as vitamin E.

The chemistry of free radical terminators is well known and is described, for example, in Pospisil et al, "Oxidation Inhibition in organic materials", volumes I and II, CRC Press, 1990. The rate constant k3 for the Reaction of the Radical terminator with the reactive free Radical is given, for example, in Landolt-Bornstein, free Radical Reaction rates in liquids (radial Reaction rates), Fisher H, Hellwege K-H, (Springer-Verlag), 1963-1997.

The radical terminators which may be used in the compositions and methods of the present invention may be a single radical terminator compound or a mixture containing two or more different radical terminators.

Surprisingly, when a radical terminator is used in combination with a radical initiator in the present invention, the two not only cancel each other but also give an effective stain bleaching effect with reduced dye damage in colored fabrics. When the radical terminator is water-soluble, particularly, although such an advantage is not exclusively observed, therefore, it is preferable to use a water-soluble radical terminator.

The ratio of the amount of free radical terminator to free radical initiator (by weight) used in the compositions and methods of the present invention may be, for example, 100: 1 to 1: 100, preferably 10: 1 to 1: 10, more preferably 5: 1 to 1: 5.

Fabric care compositions

The invention is applicable to industrial and domestic fabric washing compositions, fabric conditioning compositions and compositions for fabric washing and conditioning (so-called direct wash conditioner compositions). The invention may also be applied to non-detergent based fabric care compositions, such as spray compositions, for industrial or domestic use.

Fabric cleaning composition

The fabric washing compositions of the invention may be in any suitable form, for example as a powder, liquid or solid detergent bar, in powder or tablet form.

The fabric washing compositions of the present invention comprise a fabric detergent material selected from the group consisting of non-soap anionic surfactants, nonionic surfactants, soaps, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.

Suitable anionic surfactants are well known to those skilled in the art and include alkyl benzene sulfonates, primary and secondary alkyl sulfates, especially sulfuric acid C₈-C₁₅A primary alkyl ester; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonate, dialkyl sulfosuccinic acidSalt; an etherate salt; isethionate; a sarcosinate salt; fatty acid ester sulfonates and mixtures thereof. Sodium salts are generally preferred.

Nonionic surfactants are well known to those skilled in the art and include primary and secondary alcohol ethoxylates, particularly C wherein an average of from 1 to 20 moles of ethylene oxide is ethoxylated per mole of alcohol₈-C₂₀Aliphatic alcohols, more particularly those in which the average is from 1 to 10 moles of ethylene oxide ethoxylated per mole of alcohol, C₁₀-C₁₅Primary and secondary aliphatic alcohols. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamides). Mixtures of nonionic surfactants may be used.

Detergent compositions suitable for use in domestic or industrial automatic washing machines generally contain anionic non-soap surfactant or nonionic surfactant, or, as will be appreciated by those skilled in the art, a combination of the two in appropriate proportions, may also be used with soap.

Many suitable detergent-active compounds are available and are fully described in the literature, for example, by Schwartz, Perry&Berch in surfactants and Detergents, volumes I and II. The anionic surfactant is suitably present in an amount of from 5 to 50 wt%, preferably from 10 to 40 wt%, based on the fabric treatment composition. The nonionic surfactant content is suitably from 1 to 20% by weight, preferably from 5 to 15% by weight.

The total amount of surfactant will depend on the intended end use, for example in a composition for washing fabrics by hand, and may be as high as 60% by weight. In washing machine compositions amounts of from 5 to 40% by weight are generally suitable.

Washing assistant

The detergent compositions of the present invention typically also contain one or more detergency builders. The total amount of detergency builder in the composition is suitably from 5 to 80 wt%, preferably from 10 to60 wt%.

Inorganic adjuvants which may be used include sodium carbonate, if desired in combination with calcium carbonate seeds, as disclosed in GB 1437950 (Unilever); crystalline and amorphous aluminosilicates, such as the zeolites disclosed in GB 1473202 (Henkel), mixed crystalline/amorphous aluminosilicates as disclosed in GB 1470250 (Procter&Gamble); and layered silicates as disclosed in EP 164514 b (hoechst). Inorganic phosphate builders, such as sodium orthophosphate, pyrophosphate and tripolyphosphate, are also suitable for use in the present invention.

The detergent compositions of the present invention preferably contain an alkali metal aluminosilicate, preferably sodium aluminosilicate builder. Sodium aluminosilicate is generally added in an amount of 10 to 70% by weight (on a water-free basis), preferably 25 to 50% by weight.

The alkali metal aluminosilicates may be crystalline or amorphous or mixtures thereof, and have the following general formula:

0.8-1.5Na₂O.Al₂O₃.0.8-6SiO₂

these materials contain some bound water and also need to have a calcium ion exchange capacity of at least 50 mg CaO/g. Preferred sodium aluminosilicates contain 1.5-3.5SiO₂Units (according to the above formula). Both amorphous and crystalline materials are readily prepared from the reaction of sodium silicate with sodium aluminate as described by ampliy in the literature.

Suitable crystalline sodium aluminosilicate ion exchange detergency builders are described, for example, in GB 1429143 (Procter&Gamble). Such preferred sodium aluminosilicates are the well known commercially available zeolites a and X and mixtures thereof.

The zeolite may be a commercially available 4A zeolite, which is now widely used in laundry detergents. The zeolite builder added to the composition of the invention may be, at most, a P-aluminium zeolite (MAP zeolite) as described in EP 384070A (Unilever) and claimed. MAP zeolites are defined as alkali metal aluminosilicates of the P zeolite class having a silicon to aluminium ratio not exceeding 1.33, preferably from 0.90 to 1.33, more preferably from 0.90 to 1.20.

Particularly preferred is a MAP zeolite having a silicon to aluminum ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of MAP zeolites is typically at least 150 mg CaO per gram of amorphous material.

Organic adjuvants that may be used include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers and acrylic phosphonates; monomeric polycarboxylates, such as citrates, gluconates, oxydisuccinates, mono-, di-and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, pyridinedicarboxylates, hydroxyethyliminodiacetates, alkyl-and alkenylmalonates and succinates; and sulfonated fatty acid salts. The auxiliaries listed here are not intended to be exhaustive.

A particularly preferred organic adjuvant is citrate, suitably used in an amount of from 5 to 30% by weight, preferably from 10 to 25% by weight; and acrylic polymers, more preferably acrylic/maleic copolymers, suitably used in amounts of 0.5-15 wt%, preferably 1-10 wt%.

Both inorganic and organic auxiliaries are preferably present in the form of alkali metal salts, in particular sodium salts.

Bleaching component

The detergent compositions of the present invention may also suitably contain a peroxygen bleach system capable of generating hydrogen peroxide in aqueous solution, for example an inorganic persalt or an organic peroxyacid.

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.

Particularly 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 2123044 b (kao).

The compositions also contain ｃA photobleaching system as described, for example, in EP-A-0035470.

Fabric softening composition

The fabric treatment composition of the invention may be a fabric conditioning composition or it may contain a fabric conditioning agent.

Fabric softening compounds

The fabric softening compound is preferably a cationic, nonionic or anionic fabric softening compound.

The fabric softening compound may be a quaternary ammonium material containing polar end groups 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 a sugar ester.

It is particularly preferred that the fabric softening compound has two long alkyl or alkenyl chains with an average chain length greater than C₁₄More preferably each chain has an average chain length greater than C₁₄More preferably at least 50% of the alkyl or alkenyl groups of each long chain have C₁₈Chain length.

Preferably, the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.

It is particularly preferred that the fabric softening compound is substantially water insoluble. Within the scope of the inventionSubstantially insoluble fabric softening compound is defined as having a solubility in demineralized water at 20 ℃ of less than 1X 10^-3Weight% of a fabric softening compound, preferably a fabric softening compound having a solubility of less than 1 x 10^-4More preferably, the solubility of the fabric softening compound in demineralized water at 20 ℃ is 1X 10^-3To 1X 10^-6And (3) weight percent.

The well known species of substantially water insoluble quaternary ammonium compounds having the formula:

in the formula R¹And R²Represents a hydrocarbon group having 12 to 24 carbon atoms; r³And R⁴Represents a compound containing 1 to 4A hydrocarbon group of carbon atoms; x is an anion, preferably selected from the group consisting of halide, methyl sulfate and ethyl sulfate.

Representative examples of such quaternary ammonium softeners include di (tallow alkyl) dimethyl ammonium methyl sulfate; dicetyl dimethyl ammonium chloride; di (hydrogenated tallow alkyl) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; di (hydrogenated tallow alkyl) dimethyl ammonium methyl sulfate; dicetyl diethylammonium chloride; di (coconut oil alkyl) dimethyl ammonium chloride, ditalloalkyl dimethyl ammonium chloride and di (hydrogenated tallow alkyl) dimethyl ammonium chloride (trade mark, Arquard 2 HT).

Other preferred softeners contain ester or amide linkages, such as those available under the trademarks Accosoft 580, Varisoft 222 and Stepandex.

Particularly preferred fabric softening compounds are water insoluble quaternary ammoniummaterials comprising a quaternary ammonium material having two C' s_12-18Compounds of alkyl or alkenyl groups which are linked to the molecule by at least one ester bond. More preferably, the quaternary ammonium material has two ester linkages present. Preferred ester-bonded quaternary ammonium materials for use in the present invention can be represented by the formula:wherein each R is¹The radicals are independently selected from C_1-4Alkyl, hydroxyalkyl or C_2-4An alkenyl group; wherein each R is²The radicals are independently selected from C_8-28An alkyl or alkenyl group; t is-C (O)-O-or-O-c (O) -; x^-Is any suitable anion and n is an integer from 0 to 5. Particularly preferred is di (ethyl) dimethylammonium chloride (deemac).

A second class of preferred quaternary ammonium materials can be represented by the following formula:in the formula R₁、n、X^-And R₂As previously defined.

For environmental reasons, it is advantageous that the quaternary ammonium material is biodegradable.

Preferred materials of this type, for example 1, 2-bis [ hindered tallowoyloxy]-3-trimethylpropane ammonium chloride and processes for their preparation, are described, for example, in U.S. Pat. No. 4,137,180 (lever Brothers). Preferably, these materials contain small amounts of the corresponding monoester as described in US 4137180, for example 1-hindered tallowoyloxy-2-hydroxytrimethylpropane ammonium chloride.

The fabric softener may also be a polyol ester quat (peq) as described in EP 0638639 (Akzo).

Other Components

The compositions of the present invention may also contain one or more optional components selected from pH buffers, perfume carriers, optical brighteners, colorants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brighteners, opacifiers, shrink proofing agents, anti-wrinkle agents, anti-spotting agents, bactericides, fungicides, anti-corrosion agents, fabric drape agents, antistatic agents and ironing aids.

The invention may be in the form of a dilute or concentrated aqueous solution or suspension, for example as described in WO97/15651, WO 95/27769. Additionally, 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 tablet containing the fabric conditioning composition for use in a tumble dryer, for example as disclosed in WO 95/27777. Additionally, the fabric conditioning composition may be in the form of a substantially non-aqueous concentrate, as described in International patent application No. PCT/EP 99/00497.

The fabric detergent compositions of the present invention may also comprise direct wash softening materials, such as cationic fabric softeners.

Fabric care product based on non-detergent

The invention may also be used in fabric care products based on non-detergent ingredients. For example, the product may contain a stain removal system as an essential component. For example, a non-detergent based composition may comprise a solution of the stain removal system of the present invention in a suitable solvent (e.g., isopropanol, etc.). The composition may comprise an aerosol or spray composition. They may be in the form of sticks, coating compositions adsorbed on sponges, for example for application to a surface, and the like.

The invention is further described, by way of example only, with reference to the following examples.

Examples

All amounts are expressed in weight percent or parts by weight unless otherwise indicated.

The following free radical initiators were used in these examples. They are commercially available as initiators for free radical polymerization under the trademarks Ciba Specialty Chemicals mentioned below.

Irgacure 184- α -hydroxyacetophenone photoinitiator.

Irgacure 819-bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (logP ═ 5.8, determined at 25 ℃).

The radical terminator used was 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinyloxy (TEMPOL from Aldrich).

Example 1

Cotton stained with curry, chilies, bolo, bologes and β carotenes was purchased from Equest (aged for 3 days, packaged under nitrogen.) the amounts listed in the table Irgacure184 and TEMPOL were dissolved in ethanol and reapplied to the stained cotton cloth after the cloth was dried and irradiated in a Weatherometer (WOM) for 12 minutes, which was operated at outdoor Florida sunlight settings.

Bleaching and protection of the stain cloths was also observed when exposed to ambient light in the uk.

TABLE 1 values for dry cloth, calculated Δ E vs. original white cloth

184	TEMPOL	Stain or soil	Before treatment Δ E	After treatment,. DELTA.E
184	TEMPOL	Stain or soil	Before treatment Δ E	After treatment,. DELTA.E	0.1	0	β A carotene	50.3	7.6
0.1	0	Bolognese	9.8	8.5	0.1	0	β A carotene	50.3	7.6
0.1	0	Bolognese	9.8	8.5	0.1	0	Chili pepper	31.8	25.7
0.1	0	Curry powder	47.1	31.7	0.1	0	Chili pepper	31.8	25.7

0.1	0	Mean value of	34.9	18.4
0.1	0	Mean value of	34.9	18.4	0.1	0.1	β A carotene	52.5	9.3
0.1	0.1	Bolognese	10.7	9.0	0.1	0.1	β A carotene	52.5	9.3
0.1	0.1	Bolognese	10.7	9.0	0.1	0.1	Chili pepper	31.2	24.9
0.1	0.1	Curry powder	46.3	30.2	0.1	0.1	Chili pepper	31.2	24.9
0.1	0.1	Curry powder	46.3	30.2	0.1	0.1	Mean value of	35.2	18.4

TABLE 2 Dry cloth number

184	TEMPOL	Stain or soil	Before treatment Δ E	After treatment,. DELTA.E
184	TEMPOL	Stain or soil	Before treatment Δ E	After treatment,. DELTA.E	0.1	0	β A carotene	50.5	3.5
0.1	0	Bolognese	10.7	7.1	0.1	0	β A carotene	50.5	3.5
0.1	0	Bolognese	10.7	7.1	0.1	0	Chili pepper	33.0	23.2
0.1	0	Curry powder	48.3	26.2	0.1	0	Chili pepper	33.0	23.2
0.1	0	Curry powder	48.3	26.2	0.1	0	Mean value of	35.6	14.3
0.1	0.1	β A carotene	52.5	4.9	0.1	0	Mean value of	35.6	14.3
0.1	0.1	β A carotene	52.5	4.9	0.1	0.1	Bolognese	10.7	7.1
0.1	0.1	Chili pepper	31.2	19.1	0.1	0.1	Bolognese	10.7	7.1
0.1	0.1	Chili pepper	31.2	19.1	0.1	0.1	Curry powder	46.3	25.9
0.1	0.1	Mean value of	35.2	14.3	0.1	0.1	Curry powder	46.3	25.9

The padding procedure described above was repeated with cloths dyed with the dyes listed in table 4 (cloths from Veebee Tech, haromen, uk). Dye damage was measured with a reflectometer and expressed as CIELAB Δ E values compared to the original values. The results are shown in table 3 and show that dye damage is significantly reduced in the presence of TEMPOL. Thus, the combination of the free radical initiator with TEMPOL provides a relatively good cleaning action in the care action.

TABLE 3 Effect of TEMPOL on dye damage

184	TEMPOL	Dye bleach-wet	Dye bleach-dry
184	TEMPOL	Dye bleach-wet	Dye bleach-dry	0.1	0	4.3	2.1
0.1	0.1	1.0	1.3	0.1	0	4.3	2.1

Table 4 dye set used

Serial number	Name (R)	Type (B)	G/kg
Serial number	Name (R)	Type (B)	G/kg		Pusha' an
1	Red HE-7B	Hydrazone(s)	0.5		Pusha' an
1	Red HE-7B	Hydrazone(s)	0.5	2	Scarlet HE-3G	Hydrazones and azones	0.5
3	Crimson HE-XL	Hydrazone(s)	0.5	2	Scarlet HE-3G	Hydrazones and azones	0.5
3	Crimson HE-XL	Hydrazone(s)	0.5	4	Yellow HE-6G	Azo compounds	1.0
5	Red HE-GXL	Hydrazone(s)	0.5	4	Yellow HE-6G	Azo compounds	1.0
5	Red HE-GXL	Hydrazone(s)	0.5	6	Blue HE-XL	Anthraquinones and hydrazones	2.0
7	Turquoise H-A	Phthalocyanine dyes	5.0	6	Blue HE-XL	Anthraquinones and hydrazones	2.0
7	Turquoise H-A	Phthalocyanine dyes	5.0	8	Navy HE-XL	Hydrazone(s)	1.0
	Lemaconazole			8	Navy HE-XL	Hydrazone(s)	1.0
	Lemaconazole			9	Red RB	Hydrazone(s)	1.0
10	Golden Yellow RNL	Azo compounds	1.0	9	Red RB	Hydrazone(s)	1.0
10	Golden Yellow RNL	Azo compounds	1.0	11	Brill Red RBS	Hydrazone(s)	2.0
12	Yellow FG	Azo compounds	1.0	11	Brill Red RBS	Hydrazone(s)	2.0
12	Yellow FG	Azo compounds	1.0	13	Orange FR	Hydrazone(s)	2.0
14	Navy GG	Hydrazone(s)	2.0	13	Orange FR	Hydrazone(s)	2.0
14	Navy GG	Hydrazone(s)	2.0	15	Turquoise G	Phthalocyanine dyes	2.0
16	Black B	Hydrazone(s)	1.0	15	Turquoise G	Phthalocyanine dyes	2.0

Example 2

The experimental procedure of example 1 was repeated using Irgacure 819. The results are summarized in Table 5, and stain reduction and dye damage are expressed as Δ E. In addition, there is little effect on bleaching, but dye damage is greatly reduced, i.e. better cleaning/care conditions. The starting average stain was 40 Δ E units and irradiation was performed while wet.

TABLE 5

819	TEMPOL	Average stain reduction^*	Average dye bleaching
819	TEMPOL	Average stain reduction^*	Average dye bleaching	0.1	0	18.5	3.5
0.1	0.1	14.9	0.5	0.1	0	18.5	3.5

^*Quoted values are radiation values without initiator

Example 3

The experiment was repeated using Irgacure184 instead of TEMPOL, vitamin C (ascorbic acid, Sigma). In addition, dye damage is reduced, but stain-free bleaching action. (in this case, Irgacure184 was coated with ethanol, dried, and then vitamin C was coated with water). Thus, 0.1% 184 and 0.1% vitamin C gave an average stain reduction of 19.6 and a dye damage of 1.1 when exposed to moisture for 12minutes.

Example 4

The experiment was repeated using vitamin e (sigma) and Irgacure 184. Dye damage is also reduced, however, in this case stain bleaching is somewhat reduced. Vitamin E is insoluble in water.

Example 5

The following rinse conditioner formulation was prepared:

HEQ¹-4％

0.3 percent of spice

Ascorbic acid-0.66%

Irgacure819 (trade Mark) -0.66%

Water-to 100%.

1 HEQ ═ 1, 2 bis [ hindered tallowacyloxy]-3-trimethylpropane ammonium chloride, available from Hoechst.

3 grams of this rinse conditioner was dissolved in 600 grams of cold water. 18 g of cotton cloth were placed in it for 5 minutes. Then, the cotton cloth was taken out and dried. The reflectance spectrum of the cotton cloth was studied at 320 nm using a Spectraflash SF60 (trade mark) reflectometer.

Calculated from the reflectance results, about 0.003% free radical photoinitiator (by weight of cloth) was provided.

Example 6

The white cloth was coated with an oily tomato paste (available from Sacla, component: rehydrated sun-dried tomatoes, sunflower oil, white wine vinegar, salt, sugar, spices, garlic, black pepper powder and lactic acid). After application of the sauce, it is left for 30 minutes and then washed with a bleach-or optical brightener-free detergent (Persil Colour (trade mark) powder) at 20 ℃ and rinsed. (all water has softened). Washing does not remove all of the stain.

Containing 0.0019 mol/l Irgacure819 (trade mark) and:

(a) without any other substances

(b)0.0035 mol/l TEMPOL

(c)0.0037 moles/liter 10-DOXYL nonadecane (Sigma) solution was dip-dyed onto stains and dyed cotton (according to the procedure set forth in example 1); the cloth was dried, moistened with water and irradiated in WOM for 6 minutes. The results are summarized in the table below.

Treatment of	Reduction of soiling,. DELTA.E	Average dye damage, Δ E
Treatment of	Reduction of soiling,. DELTA.E	Average dye damage, Δ E	(a)	19.2	3.5
(b)	19.3	0.5	(a)	19.2	3.5
(b)	19.3	0.5	(c)	17.8	2.5

Although less water soluble 10-DOXYL nonadecane did reduce dye damage, it was not as effective as TEMPOL.

Example 7

Producing a base detergent powder comprising:

of chemical origin	Measurement of
of chemical origin	Measurement of	Sodium linear alkyl benzene sulfonate (LAS) Sodium tripolyphosphate Sodium silicate Sodium sulfate Calcite Small amount of Water (W)	23.60％ 19.22％ 4.81％ 28.59％ 10.30％ 1.08％ 12.49％

Also as before a powder containing 9.5% Irgacure819 (trade mark) and 9.5% Irgacure819 (trade mark) with 10% TEMPOL was produced. The three powders were dissolved in water for washing cotton stained with oily ketchup stain (as per example 5), and cotton dyed with 0.1% by weight of fabric of cibacron red dye and cibacron turquoise dye. After washing, the cloth was exposed to wetradiation in WOM for 6 minutes. Both Irgacure819 (trade mark) containing formulations gave better cleaning than the control. Formulations containing TEMPOL gave less dye damage.

Claims

1. A fabric care composition comprising at least one free radical initiator and at least one free radical terminator.

2. The composition of claim 1, wherein the rate constant for the reaction of the radical terminator with the reactive radical is at least 10⁴Mole of^-1Second of^-1。

3. The composition of claim 2, wherein the rate constant for the reaction of the radical terminator with the reactive radical is at least 10⁶Mole of^-1Second of^-1。

4. The composition of any of the above claims wherein the free radical initiator is a free radical photoinitiator.

5. The composition of claim 4 wherein the free radical initiator is selected from the group consisting of a hydrogen abstraction reaction photoinitiator, a bond cleavage free radical photoinitiator, and mixtures thereof.

6. The composition of claim 5, wherein the radical terminator is selected from the group consisting of hindered amines, nitroxides generated from the hindered amines, hindered phenols and hindered hydroquinones, radicals generated from the phenols or hydroquinones, and mixtures thereof.

7. The composition of claim 1, wherein the radical terminator is ascorbic acid.

8. The composition of claim 1, wherein the radical terminator is a chromanol.

9. The composition of claim 8, wherein the free radical terminator is vitamin E.

10. A composition according to any preceding claim which is a fabric conditioner composition, the composition further comprising a fabric conditioner.

11. The composition of claim 10 which is a rinse conditioner.

12. A composition according to any preceding claim which is a fabric washing composition further comprising a fabric detergent.

13. The composition of claim 12, wherein the fabric detergent is selected from the group consisting of non-soap anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof.

14. The composition of claim 1, further comprising an adjuvant.

15. The composition of any of the above claims wherein the free radical photoinitiator is a hydrogen abstraction free radical photoinitiator selected from the group consisting of benzophenones, acetophenones, pyrazines, benzoquinones, benzils and mixtures thereof.

16. The composition of any of the preceding claims wherein the free radical photoinitiator is selected from the group consisting of α -amino ketones, preferably α -aminoacetophenones, α -hydroxyketones, preferably α -hydroxyacetophenones, mono-and bisacylphosphine oxides and sulfides, dialkoxyacetophenones, α -haloacetophenones, triacylphosphine oxides, benzoin and benzoin based photoinitiators and mixtures thereof.

17. The composition of any of the above claims wherein the radical initiator is a photoinitiator excitable with light predominantly in the 290-460 nm band.

18. A method of treating a fabric, the method comprising treating the fabric with a composition according to any preceding claim.

19. The method of claim 18, wherein the fabric treatment is performed during a fabric washing step.

20. The method of claim 18, wherein the fabric treatment is performed in the presence of a fabric conditioner during the fabric rinsing step.

21. Use of a composition according to any one of claims 1 to 17 in a fabric care treatment process.