CA2353958A1 - Detergent compositions - Google Patents

Abstract

A non-bleaching laundry detergent composition comprises surfactant, builder, and optionally other non-bleach detergent ingredients, and also contains from 0.05 to 2.5 wt.% of iminodisuccinate (IDS) or hydroxyiminodisuccinate (HIDS).
The composition provides improved maintenance and/or restoration of colour fidelity during the wash, especially at low wash pH. The IDS or HIDS is also an effective chlorine scavenger, reducing the in-wash fading of chlorine-sensitive dyes. In addition, the incorporation of the IDS or HIDS improves the stain removal performance of the composition.

Description

WO 00/34427 ' PCT/GB99/04139 DETERGENT COMPOS:LTIONS
TECHNICAL FIELD
The present invention relates to Iau.ndry detergent compositions suitable for washing both white and coloured fabrics. The compositions of the invention, which contain a sequestrant, iminodisuccinate or hydroxyiminodisuccinate, in controlled amounts, have been found to give improved maintenance and/or restoration of colour fidelity during the wash. The presence of the sequestrant also reduces dye fading due to chlorine in water, and in addition provides improved stain removal.
BACKGROUND
Certain colours used in the textile :i.ndustry have the tendency to degrade during the laundry process. Coloured articles may become darker or the co_Lour may change as a result of laundering, thus changing t:he appearance and shortening the useful life of the articles. White articles may also become discoloured, for exannple, yellowed, with time.
It has now been found that new fabric's may be protected against such colour degradation, and the colour fidelity of previously washed fabrics may be restored (ie the degradation reversed), if the fabrics are laundered using non-bleaching detergent compositions containing controlled amounts of iminodisuccinic acid or its water-soluble salts.

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CA 02353958 2001-06-05 ~ ~ - - __ 16-11-2000 gcl GB 009904139 The benefits are especially marked if the wash is carried out at low pH.
Fading of colouxed fabrics in the wash because of the presence of sodium hypochlorite and other chlorine compounds in crater ~.s also a known problem. It has been found that iminodisucc~.nic acid and a.tg salts are also effective ch7.orine scavengers and the inclusion of these compounds also mitigates this problem.
1~
Additionally, the inclcxsion of these ~~ompounds also gives improved removal of certain stains, e:3peCially red mud.
Z~ FRI(3R ART
Iminodisuccinate (IDS) is known as a deL~ergenay builder and, in bleaching detergent compositia~s~ e~s a stabiliser far peraxy bleach precursors.
US 3 6~7 453 (Pfiaer) discloses detexc~ent compos~_t.ions having a pH of from 9 to 12, containing iminodisuccinate as a detergency bualdEr, Cased together w3.th detergent surfactant in a weight ratio o~ 0.25:2, to 7.0;1. IDS as a detergency builder is a2so disclosed i,n EP 757 094A (Bayer).
US 5 S18 ?26 (Fienkel) disc~.oses deterg~era.t compositions containing hydroxy~.~ninodisucGinate (H1DS) as a detexgency builder or bleach stabiliser.
3o IDS and hydroxyiminodisuccinate are also disclosed in JP 09 110 B~.3A (lVippon Shck~,zbai) and JP D9 104 897A (Nippar.
Shokubai3.
AMENDED SHEET

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16-11 _2000 pal GB 009904139 4 311 444A (Henkel) disa3.dses terra-phosphate detergent compositions oontainir_g a builder syF~tem comprising zeolite, RIDS and silicate.
GB 47a 0$2 (IG Farbenindustrie) discloses the use of aminopalycarboxylic acids, including IDS, in textile treatment processes or washing procesvses, tt~ delay the precipitation of metal salts or to re~dissolve such .
precipitates.
EP 509 382A (W R Grace & Cv/Harnpshire Chemical Corporation) discloses a bleaching detergent composition comprising a bleaching agent and a bleach stabi7.iser of defined formula which includes IDS. The use of IDS as a bleach stabiliser ? 5 is also disclosed in WO 9'7 20907A tpr~dcter & Gamble) .
JP 09 249 895A (Lion) and JP 09 310 0'9'7A (Lion) disclose detergent compositions containing 3 to 2o wt% iDS or HZDS to improve the stability or fabric subst<~ntivity of fluorescers 2o (opta.cal brighteners).
Tl-le use of IDS as a processing aid foz: detergent powders and detergent powder ingredients is disclc>sed i.n JP 09 100 497A
(Lion) arid Jp 09 Z79 L88A (Lion) . JP 07 411294A (Kao) 25 disclosed high bulk density granular detergent compvsition9 containing aminoprslycarboxylic acids (:eg IDS or RIDS) to improve foaming behaviour and rinsabil.ity.
WO 98 38276A (PraCter & Gamble) di.sclc~se~s laundry detergent 30 Compositions containing 0.1-50 wt% of a colour care agent.
The colour care agents are amines substituted with, for exanzpl.e, hydroxyalkyl groups. The preferred material is N,N,N',Nt--tatrak.is-(2-hydroxypropyl)athylenediamine.
AMENDED SHEET

_.. _ __. ... - ~ 02353958 2001-06-05 - - ' ._ _ - _ _ .~- .,.. --".~. -_ __._ ~-16-11-2000 pG3 GB 009904139 WO 9~. 17234A (Procter & Gamble) di.acl.oses low-pH granular laundry detergent compositions contai~r~ing chlorine scavengers which minimise the fading flf pH-sensitive and chlorine-sensitive fabric dyes during; laundering. Preferred chlorine scavengers are ammonium salts, for example, ammonium sulphate.
DEFIN;ITI4N OF TF~E INVENTxGN
to The present invention accordingly' provides a non-bleaching laundry detergent composition provid~:ng improved maintenance and/or restoration of colour fidelity during the wash, the composition comprising surfactant, builder, and optionally other non-bleach detergent ingre3ients, and also containing from .fly to 1.5 wt~ of a compound of the formula (T):
Y - CH - c~3 - NH - CFA - CHZ ( 1 ?
I i I I
COOX COOX v00X COOX
wherein Y is ~H or OH and ,X is H or a ~3o~.ubilising ration.
A further subject of th$ invent~.or. is a process for laundering white or coloured textile j:abrics while maintaining and/or restoring the colour fidelity of the fabrics, which process comprises laLnciering the fabrics by hand r~r machine in a wash liquor containing a detergent composition as defined previously.
A further subject of the invention is a method of protecting new white or coloured textile fabrics from colour ' degradation on 7.aundPriag, which aompzvises~laundering the fabrics by hand or machi.n~: in a wash liquor containing a detergent composition as defined above:.
AMENDED SHEET

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CA 02353958 2001-06-05 "' - - ~ - --A Eur~.her 9ubj ect of the in~xention i~~ a method of restoring colour fidelit~r in white or caZoured textile fabrics that have been laundered, which comprises laundering the fabrics by hand ~r machi.ne ~.n a wash liquor containing a 3etergent composition a~ defined above.
A further subject of the invention is a method of removing stains fror;i textile fabr~.cs, which comprises laundering the fabrics bar hand or machine in a wash liquor containing a detergent composition as defined above.
~ further subject of the invention is the use of the compound of the formula I above in an amount of 0.45 to 1.5 ~.~t% in a laundry detergent oompasitio;n to protect nec~ white or coloured text~.le fabrics from colour degradation on laundering, or to restore aalour fide;l.ity in white or coloured textile fabrics that have been laundered.
The term ~~colour Fidelity~~ is used herein to include bath the true colour of coloured fabrics azzd the whiteness of white fabrics.
A furtb.er subject of xhe, invention is the use of a compound of the ~farmula I above, in an amount c>f from 0.0~ to 1.5 wt%, in a laundry deterctent compo.aition as a chlorine scavenger to prevent the fad~.ng o~ ahl.orine-sensitive dyes or coloured textile fabrics during laundering.
A further subject of the invention is the use of a compound 34 of the formula I above, in an amount of from fl.05 to s.5 wt%, in a laundry detergent compo~~itian to i.rnprove its stain rarncaval. performance.
AMENDED SHEET

DETAILED DESCRIPTION OF THE TNVENTION
The compound of formula I

The detergent compositions of the invention contain, as an essential ingredient, a compound of 'the formula I:
Y - CH - CH - NH - CH - CHZ ( I ) COOX COOX COOX COOX
wherein Y is H or OH, preferably H; and X is H or a solubilising canon, preferably a sodium ion.
If Y is a hydrogen atom, the formula I represents iminodisuccinic acid or a water-soluble salt thereof.
Iminodisuccinic acid, also known as Df-(1,2-carboxyethyl)D,L-aspartic acid, has the formula (Ia) wherein X = H:
CH2 - CH - NH - CH - CH2 ( I a ) COOX COOX COOX COOX
In the following description, the abbreviation "IDS" will be used to denote this material whether in acid or salt form.
IDS is commercially available from Bayer AG, Leverkusen, Germany, and from Nippon Shokubai KK, Japan.
If Y is a hydroxyl group, the formula I represents hydroxyiminodisuccinic acid or a water-soluble salt thereof.

' - . _ ~ 1 V - ~ t -..... . . ~ _ _=~~~m._y=_ . U1JLU-1~i LLSI !"i t CA02353958 2001-06-05 - _- _ _ _ '~~1 rf~ 'W~,~q.~.E» : #t is 16-11 2000 pCx GB 009904139 Hydrvxyirninodisuccinic ac~.d has the f.'orrnula (Ib) w3~erein X
H:
HO - CHI - CH - NH - CH - CHI (Ib) coox coox ~oox coox 1o In Lhe following description, the abbreviation "RIDS" Will be used to denote this matexial whether in acid or salt form. HILLS is commercially ava~.lable from Ni.ppon Shokubai KK, Japan.
For the puzpoeea of the present invention, the zDS or RIDS
may be, and preferably is, in then form of a ga7.t, ie X in the formula I is a stable solubilisin~~ canon, preferably an alkali metal cation, more preferably »odium.
Zn the la~.l.ndry detergent compositions of the invention, IDS
or HZDS is preaen4 in an amount of from 0.05 to 1.5 wt%, prefera#aly from 0.2 to 1.5 wt%, more preferably from 0.3 to 1.5 wt% and most preferably frog 0.5 t:o ~..0 wt%. The lower levels appear to prcwide the greatest benefit axxd~no additional benefit is observed if higher amounts, greater than 2.5 wt%, are used.
The preferred matez~ial is IDS, moat pz-eferably in sodium 9a1~ form.
AMENDED SHEET ~ ~ ~

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CA~02353958- 2001-06-05 - __ _ _ T-k~;a t5<i '.::S~~IH~'l~tiv : ii ~S

PCl GB 009904139 g _ Detergent composz~ione The composition of the ~nvent~cn also contains other cozl~entional detergent ingredients, other than bleaching ingredients. Essential. ingredients a,re surfactants (detergent-active compounds; and detergency buz~.ders, and other norz-bleach ingredients may optionally be present.
~ preferred detergent ~tornposi.tion according to the invention 1D comprises:
(a) from S to 60 wt~ of one car more detergent surfactants, (b) from 10 to 8o wt% of ore or more detergency builders, ~.5 (c) from o.05 to ::.5 wt~, preferably from X0.2 to 1.5 wt%, more prAferably from 0.3 to 1.5 wt% and most preferably from f~.5 to 1.D wt~, of IDS or HTD~, ZO (d) optior~al.Iy other non-bleach detergent ingredients to ioo wt,~.
The detergent compositions of the inve,rztian may be of any 25 physical Earn.
Surfactante~ (detergent-aotive compounds) 3o The detergent compositions will contain, as essential ingredients, ane or more detergent acxive compounds (surfactants) which c~ay be chaser. Ercm soap and non--soap AMENDED SHEET

_ g _ anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
Many suitable detergent active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes L and II, by Schwartz, Perry and Berch.
The preferred detergent active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-Cls; primary and secondary alkylsulphates, particularly CB-Cls primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Sodium salts are generally preferred.
Nonionic surfactants that may be used. include the primary and secondary alcohol ethoxylates, especially the C$-C2o aliphatic alcohols ethaxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Clo-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to IO moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (gl~ucamide?.
Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N+ X- wherein the R groups are long or short hydroc<~rbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which R1 is a Ca-Ca2 alkyl group, preferably a C8-C1« or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4; which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
In an especially preferred cationic :surfactant of the general formula R1R2R3R4N+ X-, R1 represents a C$-Clo or C12-C14 alkyl group, R2 and R3 represent methvyl groups, and R4 presents a hydroxyethyl group.
Amphoteric surfactants, for example, amine oxides, and zwitterionic surfactants, for example:; betaines, may also be present.
Preferably, the quantity of anionic surfactant is in the range of from 5 to 50% by weight of the total composition.
More preferably, the quantity of anionic surfactant is in the range of from 8 to 35% by weight.
Nonionic surfactant, if present, is preferably used in an amount within the range of from 1 to 20% by weight.
The total amount of surfactant present is preferably within the range of from 5 to 60 wt%.
Detergency builders The compositions may suitably contain from 10 to 80%, preferably from 15 to 70% by weight, of detergency builder.

Preferably, the quantity of builder is in the range of from 15 to 50% by weight.
The detergent compositions may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a ~oodium aluminosilicate (zeolite).
The zeolite used as a builder may bE: the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders. Alternatively, th.e zeolite may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever), and commercially available as Doucil (Trade Mark) A24 from Crosfield Chemicals Ltd, UK.
Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, 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 particle size of the zeolite is not critical.
Zeolite A or zeolite MAP of any suitable particle size may be used.
Also preferred according to the present invention are phosphate builders, especially sodium tripolyphosphate.
This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate.
Other inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate, amorphous aluminosilicates.

Organic builders that may be present: include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates; monomez-ic polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di-and trisuccinates, carboxymethyloxy~>uccinates, carboxy-methyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
Organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites.
Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from l to 10 wt%.
Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
Other ingredients The detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
Preferred proteolytic enzymes (prote.ases) are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric .stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.

Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available. Proteases of both high and low isoelectric point are suitable.
Other enzymes that may suitably be present include lipases, amylases, and cellulases including high-activity cellulases such as "Carezyme ~' ) .
In particulate detergent compositions, detergency enzymes are commonly employed in granular farm in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
Antiredeposition agents, for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present:
The compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, <~nd polyethylene glycol/polyvinyl alcohol,graft copol~,rmers such as Sokolan (Trade Mark) HP22.
Especially preferred soil release po7.ymers are the sulphonated non-end-capped polyester~~ described and claimed in WO 95 32997A (Rhodia Chimie)_ Other ingredients that may be present include solvents, hydrotropes, fluorescers, photobleach.es, foam boosters or foam controllers (antifoams) as appropriate, sodium carbonate, sodium bicarbonate, sodium. silicate, sodium WO 00/3442? PCT/GB99/04139 sulphate, calcium chloride, other inorganic salts, fabric conditioning compounds, and perfumes.
Product form As previously indicated, the compositions of the invention may be of any suitable physical form,, for example, particulates (powders, granules, tab_Lets), liquids; pastes, gels or bars.
According to one especially preferred embodiment of the invention, the detergent composition is in particulate form.
It necessary, the IDS may be incorporated in particulate compositions in the form of granules containing an inert carrier material.
Compositions in powder form may be of°_ any bulk density and may be prepared by spray-drying, non-tower granulation, or any combination of these techniques.
According to another especially preferred embodiment of the invention, the detergent composition is in liquid form.
Liquid detergent compositions may be prepared by admixing the essential and optional ingredients in any desired order to provide compositions containing the ingredients in the the requisite concentrations.

The colour care benefit The colour benefit associated with the compositions of the invention is twofold: protection (maintenance) of the colour or whiteness of new fabrics, and restoration (recovery) of the colour or whiteness of previously washed fabrics.
New fabrics, when washed with the compositions of the invention, show reduced colour degradation as compared with fabrics washed in control formulatiOTls Without IDS. The fabrics maintain a new appearance even after multiple washing. This protection or maintenance benefit has been found to apply both to white and to coloured fabrics., Previously washed fabrics which have already undergone colour degradation show significant improvements in colour fidelity when washed using compositions according to the invention. Thus colour damage that has already occurred can be reversed and the new appearance of the fabrics restored.
It is believed that a cause of the colour degradation resulting from the laundry process may be heavy metal ions, especially iron but also copper, zinc and manganese: these may originate from the water or water pipes, from washing machine parts, from the detergent composition used, or from the soil present on the fabric.
Without wishing to be bound by theory, it is believed that the colour care benefit obtained according to the present invention may be attributed to the sequestration by the IDS
of any heavy metal ions present in the wash liquor.

- 1s -However, it is not known why IDS should be especially effective in this regard. In particular, it is surprising that IDS should be significantly more effective that the more common detergent and highly effective sequestrant, nitrilotriacetate (NTA).
pH of composition According to a preferred embodiment of the invention, the composition has a 0.250 aqueous solution pH (in demineralised water at 30°C) not exceeding 10.5, preferably not exceeding 10Ø The preferred ;pH range is from 8.0 to 10.5, more preferably from 8.5 to 10Ø
The colour care benefits of the invention have been found to be especially marked under low-pH conditions.
The wash process As indicated previously, a further subject of the invention is a process in which white or coloured fabrics are laundered using the composition of the invention. According to a preferred embodiment of the invE~ntion, the process is carried out in a wash liquor having a pH not exceeding 10.5, more preferably not exceeding 10Ø
It has been found that the colour cax-e benefits of the invention, both protection and recovery, are especially marked when the wash liquor pH is low.

_ 17 _ Particularly good results are obtained at pH values of from 8.0 to 10.5, preferably from 8.5 to 10Ø
Whilst the invention is also applicable to the machine wash, the two preferred conditions previously mentioned - very low pH, and low sequestrant level - have especial relevance to the handwash as carried out, for example, in South East Asia. In that region, it is a common habit to presoak or prerinse the fabrics in water, without detergent, to remove gross soiling. At this stage the wash liquor pH
may be as low as 6.0 to 7Ø The wet fabrics are then immersed in the main wash liquor (detergent solution). The additional water imported into the wash liquor from the wet fabrics has the dual effect of diluting the wash liquor (and thus lowering the sequestrant level) and lowering the pH.
Under these conditions, especially significant colour care benefits according to the present imrention have been observed.
The chlorine scavenging benefit The incorporation of IDS has also beE:n found to reduce the fading upon laundering of chlorine-sE:nsitive dyes. This fading occurs due to the presence of sodium hypochlorite, which is routinely put into supply water for hygiene purposes: levels of 0.5 ppm are typical. This causes fading of dyes of a wide range of colours. The incorporation of IDS in accordance with the present invention can significantly reduce the amount of fading attributable to chlorine in the wash water.

The stain removal benefit A further benefit for the incorporation of IDS has unexpectedly been observed: a significant improval in the removal of certain highly coloured stains, notably red mud.
Better removal of blood and tea stains is also observed.
~''YTMDT.L~C
The invention will now be illustrated in further detail by means of the following Examples, in which parts and percentages are by weight unless otherwise stated. Examples designated with a number illustrate the invention, while examples designated with a letter az-e comparative.

WO 00/34427 PCTlGB99/04139 EXAMPLE 1, COMPARATIVE EXAMPLES A TO G
Protection of new coloured fabrics from colour degradation by Cu2+ ions using sequestrants In these experiments, the protective>, effect of IDS on cotton fabrics dyed with Direct Red 80 against colour degradation in the presence of copper ions was demonstrated and compared with other sequestrants.
The sequestrants used were as follows:
IDS: iminodisuccinate, tetrasod.ium salt, ex Bayer NTA: nitrilotriacetate, trisodium salt, ex Aldrich EDTMP: ethylenediaminetetramethylene phosphonate, calcium salt (bequest {Trade Mark) 2047 ex Monsanto) EDDS: ethylenediamine disuccinate, tetrasodium salt (Octaquest (Trade Mark) E30 ex Associated Octel) STP: sodium tripolyphosphate (Polyphos technical grade ex Thai Polyphosphate and ~~hemicals) Magnesium silicate: Macrosorb (Trade Mark) MS33 ex Crosfield Chemicals, UK.
The fabrics were washed in demineral:ised water containing 3 0 copper ions ( 0 . 5 ppm Cu2+ ex CuCl2 ) ate a liquor to cloth ratio of 200:1 in tergotometers for 30 minutes at 30°C at 90 rpm.

Experiments were carried out at two different pH values, 9.5 and 6.5, the pH adjustment being made by adding sodium hydroxide (the addition of the copper salt having caused a slight drop in pH).
At each pH, experiments were carried out at two different sequestrant levels:
(i) a sequestrant level of 0.00286 g/1, calculated as equivalent to the concentration in the final rinse when using a detergent composition conta_~ning 0.5 wt% of the sequestrant; and (ii) a sequestrant level of 0.00572 g/1, calculated as equivalent to the concentration in t:he final rinse when using a detergent composition containing 1.0 wt% of the sequestrant.
Control runs containing no sequestra.nt, and containing neither copper ions nor sequestrant, were also carried out at each pH. No detergent ingredients were present in these experiments.
Colour changes were monitored as reflectances differences at 620 nm. Two different effects are in operation here: dye fading, which leads to a generally small reflectance increase; and dye darkening (colour degradation) resulting from the presence of the copper ions, leading to a rather larger reflectance decrease. Both effects are undesirable and result in deterioration of the appearance of the fabric.
Ideally the reflectance difference observed should be close to zero or a small increase (not gre<~ter than 3 units, and preferably not greater than 2 units).

WO 00/34427 PCTlC899/04139 The results were as shown in the Table below.
Example Sequestrant Lower sequestrant Higher level (0.5%) sequestrant level (1.0%) pH 9.5 pH 6.5 pH 9.5 pH 6.5 A Water alone + 2.40 + 2.49 + 2.40 + 2.49 B Water + Cu'+ - 5.62 -20.00 - 5.62 -20.00 1 IDS + 1.04 + 0.95 + 2.64 + 1.22 C NTA + 4.05 + :3.38 + 4.95 + 4.11 D EDTMP + 0.87 -10.23 + 1.06 - 6.10 E EDDS + 4.43 - 4.35 + 4.91 + 3.98 F STP - 6.03 -20.90 -15.72 -15.71 G ~ Mg silicate - 3.88 -15.40 - 4.18 -13.27 It will be seen that only IDS gave reflectance differences within the 0 to +3 range under all four conditions. EDTMP
performed well at pH 9.5 but not at :pH 6.5. With NTA, dye fading predominated. This also occurred with EDDS under most conditions. The inorganic sequ~estrants, sodium tripolyphosphate and magnesium silicate, had only an insignificantly small protective effect against darkening.

EXAMPLE 2, COMPARATIVE EXAMPLES H TO P
Protection of new white fabrics frorn discolouration by mixed heavy metal ions The procedure of Example 1 was repeated at pH 6.5 using white cotton fabrics and a "cocktail." of heavy metal ions:
Cu2+ 0.5 ppm Fe3+ 2.5 ppm Mn2+ 2.0 ppm Zn2+ 5.0 ppm For the white fabrics, discolouration was monitored by means of reflectance changes at 450 nm. F'or white fabrics there is no colour fading to consider, and the ideal here is for a result as close as possible to zero.
Example Sequestrant 0.5% 1.0%

H Water alone - 0.20 - 0.20 i J Water + ions -'1.66 - 1.66 2 IDS - 0.32 - 0.38 K NTA - 1.62 - 1.30 L EDTMP - 0.54 - 0.54 M EDDS - 2.37 - 2.03 N STP - 0.89 - 0.71 P Mg silicate - 2.23 - 1.71 EXAMPLE 3, COMPARATIVE EXAMPLE Q
Protection of new white silk fabric .from colour degradation by mixed heavy metal ions using sequestrants in. detergent powder compositions A detergent powder formulation was prepared by conventional spray-drying and postdosing techniqufss to the following formulation:
wt%

Sodium linear alkylbenzene sulphonate (NaLAS) 22.92 Sodium silicate (anhydrous) 4.67 Sodium tripolyphosphate - 18.67 Sodium carboxymethyl cellulose 0.25 Polyacrylate polymer 0,70 Calcite 10.00 Sodium sulphate, water, impurities, to 100 sequestrant if present Comparative Example Q: no sequestrant Example 3: plus 1.25 wto IDS
The fabrics were washed five times in. a wash liquor comprising 20/6° FH (Ca/Mg) water containing a "cocktail" of heavy metal ions and 2.5 g/litre of the detergent composition, and with the pH adjusted. to 9.5 using dilute sulphuric acid. The washes were carried out in tergotometers at a liquor to cloth ratio of 200:1 for 30 minutes at 30°C and 90 rpm. After a<~ch wash, two rinses were carried out at a liquor to cloth ratio of 200:1 and the fabrics were line dried.
The "cocktails" of heavy metal ions were as follows:
Wash Rinse 2+
Cu 0.5 ppm 0.05 ppm 3+
Fe 2.5 ppm 0.1 ppm Mn2+ 2.0 ppm 2.0 ppm Zn2+ 5 . 0 ppm 1 . Z ppm The results (0R at 450 nm) were as follows:
Example Sequestrant OR (450 nm) after l wash after 5 washes Q None - 1.71 - 2.60 3 IDS - 1.25 - 1.63 The reduced yellowing of the fabrics washed with the composition of Example 3 was visually apparent.

EXAMPLE 4, COMPARATIVE EXAMPLES R and S
Protection of new white silk from co:Lour degradation by mixed heavy metal ions using sequest_rants in detergent powder compositions The procedure of Example 3 was repeated using the same powder formulation but the pH was adjusted to the lower value of 8.5, and a total of 10 washes per example were carried out. Reflectances were measured after 5 and l0 washes.
The sequestrants used were TDS (invention) and NTA
(comparative) , at a level of 1.25 wt='s.
Example Sequestrant aR {450 nm) after 5 washes after 1.0 washes 'R None - 0.85 - 1.72 4 IDS + 0.42 + 0.66 S NTA - 0.11 - 0.57 WO 0013442'7 PCTJGB99/04I39 EXAMPLE 5, COMPARATIVE EXAMPLE T
Protection of new coloured fabrics from colour degradation by mixed heavy metal ions (2.5 ppm Fe:3+ and 0.5 ppm Cu2+) using sequestrants in detergent powdESr compositions A mufti-wash experiment using panellists and handwash conditions was carried out. The colour care benefit was determined using coloured monitors.
A detergent powder composition was pi°epared by conventional spray-drying and postdosing technique's to the following formulation:
- wt%

Sodium linear alkylbenzene sulphonate~ (NaLAS) 22.92 Sodium silicate (anhydrous) 5.37 Sodium tripolyphosphate 18.67 Sodium carboxymethyl cellulose 0.25 Polyacrylate polymer 0,70 Calcite 10.00 Sodium sulphate, fluoresces, zeolite, perfume, to 100 enzymes, water, impurities, sequestra.nt if present Comparative Example T: no sequestran.t Example 5: IDS at 0.6250 of the farmmlation.
12 wash cycles in total were carried out using the following conditions:
- Trace levels of iron (2.5 ppm) and copper (0.5 ppm) - Product dosage : 5 g/1 (formulai:.ion below) - Water hardness: 10 °FH Ca - Liquor to cloth ratio in the ma_Ln wash: 6 to 1 - Liquor to cloth ratio in the rinse: 20 to 1 - Number of rinses: 2 Rubbing time: 30 seconds per p~~ece.
- Wash temperature: 30 °C.
- Total washload weight: 1 kg.
The coloured monitors were line-dried in the shade.
Colour care benefits were determined both instrumentally (reflectance, ~E) and by visual asse~~sment.
Instrumental measurements The reflectance change DE, indicative of total colour change across the whole visible spectrum, was measured. The lower the figure, the better the result.
Fabric ,,~E
-(no sequestrant) (IDS 0.6250) Red linen Yellow cotton 7:3 6.2 Deep green cotton 2.0 1,g Light blue 7.7 6.8 Cotton ( Lavender cotton 4.3 3.9 WO 00/34427 PCT/GB99104t39 Visual assessment by panellists Visual assessment was carried out by experienced panellists using the universal grey scale [ISO 105-A02: 1993, BS EN
20105-A02: 1995, BS 1006-A02: 1990, Society of Dyers and Colourists Standard Methods 5th Edii~ion A02]:

5 = no colour change from original fabric colour 1 - large change from original fabric colour Therefore, the higher the visual assessment score, the nearer the test fabric is to the new (unwashed) fabric.
Fabric Visual assessment~~(grey scale, 1-5) No sequestrant IDS 0.625%

Red linen 1.9 2.5 Yellow 2.3 2.8 cotton Deep green 2.9 3.1 cotton Light blue 2.5 2.9 Cotton Lavender 3.1 3.3 cotton Light blue 2.9 3.1 poly-cotton - 2g _ EXAMPLE 6, COMPARATTVE EXAMPLES U to X

Restoration/recovery of coloured fabrics that have been colour-damaged by exposure to co pez- ions These experiments demonstrate the bE;nefits of IDS in restoring colour-damaged coloured fabrics.
The fabrics used were cotton dyed with Direct Red 80. They were pre-treated with demineralised water containing 0.5 ppm Cu2+ ions and having the pH adjusted to 6.5 by means of sodium hydroxide. The pretreatment was carried out using tergotometers at 30°C, 90 rpm and a .Liquor to cloth ratio of 200:1, then the fabrics were line dried.
The fabrics were then washed in a wash liquor containing 2.5 g/1 of the detergent composition used in Example 3, and 0.5 ppm Cu2+, in 20/6° Ca/Mg French hard water) : the pH was adjusted from 9.9 to 9.5 using dilutca sulphuric acid. The washes were carried out in tergotomei~ers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1. '.Che washes were followed by two rinses in 20/6° Ca/Mg French hard water containing 0.05 ppm Cu2+ at a liquor to cloth ratio of 200:1, and the fabrics were then line dried.
The sequestrants, where present, werE; dosed directly into the wash liquor in the amounts indicated in the table below (percentages based on the detergent composition).
The procedure was also repeated using' 15-minute handwashes (using a strictly controlled protocol) at liquor to cloth ratios of 25:1 and 7:1 instead of the tergotometer washes at 200:1.

Colour changes were monitored by reflectance changes at 620 nm, the standard being the fabrics prior to pretreatment. All values were negative, the ideal being the smallest possible negative value.
The results are shown in the Table below.
Example 200::1 25:1 7:1 tergca handwash handwash U After pretreatment -19.;3 -19.93 -19.93 V Detergent composition -11.98 - 8.51 - 6.86 without sequestrant 6 IDS 1.250 - 3.50 - 2.64 - 0.31 W NTA 1.71s - 6.44 - 4.42 - 1.50 X STP 3.85% -12.32 - 9.55 - 3.18 Similar results were obtained in a repeat experiment in which the fabrics were not dried between washes.

EXAMPLES 7 and 8, COMPARATTVE EXAMPhES Y and Z
The procedure of Example 6 was repeated at a 200:1 liquor to cloth ratio using both IDS and HIDS, and gave similar results:
Example 200:1 tergo Y After pretreatment -23.68 Z Detergent composition -13.40 without sequestrant 7 IDS 1.25% - 5.69 ~

8 HIDS 1.25% - 5.28 EXAMPLE 9, COMPARATIVE EXAMPLES AA to DD
Restoration/recovery of coloured fabrics that have been colour-damaged by exposure to mixed heavy metal ions The procedure of Example 6 was repeated using, instead of copper ions alone, the "cocktails" of heavy metal ions (different for wash and for rinse) used in Example 3. For the pretreatment step the same "cock.tail" was used as for the wash.
Similar results to those of Example 6 were obtained, as shown in the Table below.
Example 200:7. 25:1 7:1 tergo handwash handwash AA After pretreatment -18. -18.08 -18.08 C)8 BB Detergent composition -10.E>1 -14.83 -14.10 without sequestrant 9 IDS 1.25% - 2.59 - 7.59 - 7.73 ICC NTA 1.71% - 3,38 - 8.22 -11.50 DD STP 3.85% - 7. -15.69 -13.11 i'6 Restoration/recovery of coloured fabrics that have been colour-damaged by exposure to copper ions, using a wider range of formulations The procedure of Example 6 was repeated using six different formulations of varying pH. The tergotameter method of previous examples was used. For each formulation, the initial pH was adjusted slightly downwards, using dilute sulphuric acid, to mimic the effect of soil on wash pH.
The washing and rinsing regime was as described in Example 6, and colour changes were monitored as reflectance changes (ORS at 620 nm.
The formulations, and the reflectancE: results, are shown in the following Tables.

Formulations 11 _12 13 NaLAS 10.00 22.00 28.00 15.00 NaPAS 15.00 Nonionic C12-15 7E0 1.00 Na silicate(anhydr) 6.00 8.00 15.00 Na sulphate 19.29 37.:90 15.16 23.90 Na tripolyphosphate 30.00 20.00 23.49 SCMC 0.75 0.'70 0.65 0.40 Polymer** 0.50 0.50 Calcite 10.00 3.64 Zeolite (78%) 20.00 Citric acid 1.50 Na carbonate 1.00 Na bicarbonate 10.00 16.00 Enzyme 2* 0.25 Enzyme 3* 0.53 0.81 0.49 Enzyme 5 * 0 . 7_ 6 0 . 19 Water, impurities, to 100 to 7.00 to 100 to 100 sequestrant (if present) pH 8.8 9.9: 9.6 9.6 adjusted pH 8.6 8.9 9.1 9.1 14 is is .
NaLAS 22.92 20.00 16.80 Nonionic Clz-is 7E0 2.50 Na silicate(anhydr) 5.36 12.00 8.22 Na sulphate 28.71 39.12 20.17 Na tripolyphosphate 18.67 12.00 24.00 SCMC 0.25 0..50 1.00 Polymer** 0.70 0.:50 O.SO

Calcite 10.00 Zeolite (anhydr) 1.56 Zeolite (78%) 4,93 Na carbonate 8 . ()0 15. 00 Enzyme 1* 0.16 Enzyme 4 * 0 . S ~_ 0 . 5 6 Water, impurities, to 100 to L00 to 100 sequestrant (if present) PH 9.9 10.3 10.5 adjusted pH ~ 9.4 9.8 10.0 *Enzyme l: protease (Purafect 21006) *Enzyme 2: protease (Savinase 12T) *Enzyme 3: protease/lipase/amyla~,e (60/15/15):
Savinase/Lipolase/Termamyl *Enzyme 4: protease/lipase (80/20):
Savinase/Lipolase *Enzyme 5: cellulase: Clazinase 70006 All specific enzyme names are Trade Marks **polyacrylate, or acrylate/maleate copolymer wo 0o1344z~
PCTIGB99/04t39 Reflectance results Ex. pH OR at 620 nm Initial Adjusted After 1Vo IDS NTA
pretreat- aequest- 1.25% 1.71%
ment .rant 8.8 - 8.6 -20.31 --8.52 -3.11 -4.37 11 9.4 8.9 -19.97 --8.55 --2.40 -3.59 12 9.6 9.1 -19.99 --7.37 -1.80 -2.30 13 9.6 9.1 -18.50 --4.23 -2.14 -3.30 -14 9.9 9.4 _19.72 --7.83 -2.27 -3.52 10.3 9.8 -19.27 -4.13 -2.14 -3.30 ~1~ 10.5 ~ 10.0 ~~ -19.50 -3.47 -1.60 -1.92 EXAMPLE 17, COMPARATIVE EXAMPLE EE
Prevention of dye fading from chlorine using sequestrants in detergent powder formulations (chlor-i.ne scavenging) A mufti-wash tergotometer experiment was carried aut using the detergent composition of Example 3, without sequestrant (Comparative Example EE) or containing 1 wt% of IDS {Example 17). The colour care benefit was determined using a range of coloured cotton monitors.

The wash conditions were as follows:
- Trace levels of metal ions:
Fe = 2.5 ppm, Cu = 0.5 ppm, Zn = 5 ppm, Mn = 2 ppm - Trace level of NaOCl: 0.5 ppm - Product dosage: 2.5 g/1 (formulation below) - Water hardness (wash and rinsei~: 26 °FH Ca - Liquor to cloth ratio in the wash and rinse: 200 to 1 - Wash time: 20 minutes - Number of rinses: 2 - Agitation: 75 rpm - Wash temperature: 40 °C.
The washed fabrics were line-dried ~_n the shade.
Reflectance results The lower the figure, the better the result.
Colour of Wavelength Reflectance change cotton measured monitor Example EE Example 17 (No sequestrant ) ( TDS 1. 0 0 ) Yellow 460 nm 13.59 0.51 Orange 510 nm 3.25 0.72 Navy 620 nm 2.97 0.79 EXAMPLE 18, COMPARATIVE EXAMPLES FF ,AND GG
Stain removal from fabrics using sequestrants in detergent powder formulations Stain removal was assessed using a h<~ndwash methodology and the following detergent powder formulation:
wt~

Sodium linear alkylbenzene sulphonate~ (NaLAS) ~ 23.71 Sodium silicate (anhydrous) 7.37 Sodium tripolyphosphate 18.77 Sodium carbonate 7.00 Sodium carboxymethyl cellulose 0.52 Polyacrylate 0.54 polymer Calcite g.88 Sodium to 100 sulphate, fluorescer, zeolite, perfume, enzymes, water, impurities, sequestrant if present Comparative Example FF: no sequestrant Comparative Example GG: 1 wto NTA
Example 18: 1 wt°s IDS
The wash conditions were as follows:
- Trace levels of metal ions: Fe :- 0.1 ppm, Cu = 0.01 ppm, Zn = 0.1 ppm, Mn :- 0.2 ppm - Product dosage: 2 g/1 - Water hardness:
- Wash : 4 5 °FH ( Ca : Mg 3 : 1 ) Rinse: 25 °FH (Ca:Mg 3:1) - Liquor to cloth ratio in the soak and wash: 7 to 1 - Liquor to cloth ratio in the r~_nse: 3 to 1 - Soak time: 20 minutes - Number of rinses: 2 - Rubbing time: 30 seconds per piece - Wash temperature: 22°C
- Total load weight: ca. 700 g.
The washed fabrics were line-dried in the shade.
to Reflectance results (DE) were as follows. These represent residual stain and therefore the lower the figure, the better the results. The results on red mud were significant to 95%, while directional improvements were observed on blood and tea.
Example Sequestrant pE (residual stain) Blood Tea Red mud FF None 7.84 30.13 19.66 18 IDS 7.20 28.90 14.98 GG NTA 7.62 30.00 19.86 EXAMPLE 19, COMPARATIVE EXAMPLE HH
Stain removal from fabrics using se~uestrants in deter ent_ powder formulations (tergotometer methodology) Stain removal was also assessed using a tergotometer method, and the formulation of Example 3.

Comparative Example HH contained no sequestrant, while Example 3 contained 1 wt% of IDS.
Wash conditions:
- Trace levels of metal ions:
Fe = 2.5 ppm, Cu = 0.5 ppm, Zn = 5 ppm, Mn = 2 ppm - Product dosage: 2.5 g/1 - Water hardness (wash and rinse): 26 °FH Ca - Liquor to cloth ratio in the wash and rinse: 200 to 1 - Wash time: 20 minutes - Number of rinses: 2 - Agitation: 75 rpm - Wash temperature: 40°C.
The washed fabrics were line-dried in the shade.
Stain removal results are shown below. These are a measure of the stain removed so the larger the figure, the better the result. The improvement here was statistically significant and visually apparent.
Example Sequestrant QR 580 (Stain removal) Red wine (Empa 114) '~HH None 12.67 I

19 IDS 14.59 EXAMPLES 20 to 22 Concentrated (high bulk density) detergent compositions contairiing IDS
Phosphate-built and zeolite-built dE=_tergent powder formulations of high bulk density (850-900 g/1) containing IDS were prepared to the following :Formulations:
_.__ _ 2 0 21 2 2 _ _ NaLAS 15.63 22.82 18.00 Nonionic Clz-15 7E0 7.00 3.25 Na sulphate 1.30 Na tripolyphosphate 30.57 SCMC 0.60 0.77 1.00 Polymer** 1.96 2.00 Zeolite (78%) 44.65 23.13 50.00 Na carbonate 12.12 6.73 19.00 Na bicarbonate 17.77 5.87 Enzyme &* 2.00 Enzyme 7* 0.51 Enzyme 4 0.45 IDS 1.25 1.25 1.25 Fluorescer, to 100 to 100 to 100 perfume, speckles, water _ _ 0.25% solution pH ~ 9.8 10.0 10.6 *Enzyme 6: protease/lipase (72/28):
Savinase/Lipolase *Enzyme 7: protease/cellulase (50/50):
Purafect 2100G/Clazinase 70006 WO 00/3442'7 EXAMPLES 23 and 24 Liquid detergent com ositions conta-Lning IDS

Liquid detergent compositions were prepared to the following formulations:

NaLAS 12.50 10.50 Nonionic C12-is 7E0 2.25 SLES 6.66 2.25 Na tripolyphosphate 15.00 Mg sulphate (7H20) 2.50 Na tetraborate 4.00 Boric acid 0.50 Glycerine CP 6.00 Polymer 0.12 Preservatives O,pg Blue dye 0.02 IDS 1.25 1.:Z5 Perfume 0. 15 0.40 Water - to .I00 to :L00 ~

~ 6.5 9,0 0.25% solution pH

Liquid detergent com osition containing IDS
A liquiid detergent composition containing a lower level of IDS was prepared to the following formulation. The IDS was incorporated in liquid form (30% act.ive).
Ingredient Weight -~

Sodium linear alkylbenze g.655' --onat~e ne sulph Nonionic surfactant 7E0 2.gg5 Zeolite 20.000 Glycerol 4.000 Borax 3:200 Citric acid 2.500 Sodium hydroxide 1.719 IDS (sodium salt) 0.667 Silicone oil/silica 0.200 Sodium xylene sulphc~nate 0.200 Calcium chloride dehydrate 0.150 Soil release polymer {PET/POET) 0.100 Sodium polyacrylate (Sokalan PA50) 0.100 Protease 0.100 Amylase 0.100 Fluorescer 0.025 Perfume 0.250 Preservative 0.016 Water to 100% 42.378 30 '

Claims

-44-1 A non-bleaching laundry detergent composition comprising Surfactant, builder, and optionally other non-bleach detergent ingredients, and also containing from 0.05 to 1.5 wt% of a compound the the formula I:
wherein Y is H or OH, and X is H or a solubilising canon.
2 A detergent composition as claimed in claim 1, characterised in that it comprises:
(a) from 5 to 60 wt% of one or more detergent surfactants, (b) from 10 to 80 wt% of one or more detergency builders, (c) from 0.05 to 1.5 wt% of a compound of the formula I, (d) optionally other non-bleach detergent ingredients to 100 wt%.
3 A detergent composition as claimed in claim 1 or claim 2, characterised in that it comprises from 0.2 to 1.5 wt% of the compound of the formula I.

4 A detergent composition as claimed in any preceding claim, characterised in that the compound of the formula I
is iminodisuccinic acid or a salt, preferably the sodium salt, thereof.
A detergent composition as claimed in any preceding claim, characterised in that it has an 0.25% aqueous solution pH (in demineralised water at 30°C) not exceeding 10.5, preferably not exceeding 10.0,, more preferably not exceeding 9.5.
6 A detergent composition as claimed in any preceding claim, characterised in that it is in particulate form.
7 A detergent composition as claimed in any one of claims 1 to 5, characterised in that it is in liquid form.
8 A process for laundering white or coloured textile fabrics while maintaining and/or restoring the colour fidelity of the fabrics, which process comprises laundering the fabrics by hand or machine in a wash liquor containing a detergent composition as claimed in claim 1.
9 A process as claimed in claim 8, characterised in that the laundering process is carried outs at a wash liquor pH
not exceeding 10.5, preferably not exceeding 10Ø

A process as claimed in claim 8 or claim 9, characterised in that the laundering process is carried out by hand.
12 A method of protecting new white or coloured textile fabrics from colour degradation on laundering, which comprises laundering the fabrics by hand or machine in a wash liquor containing a detergent composition as claimed in any one of claims 1 to 7.
13 A method of restoring colour fidelity in white or coloured textile fabrics that have been laundered, which comprises laundering the fabrics by hand or machine in a wash liquor containing a detergent composition as claimed in any one of claims 1 to 7.
13 A method of removing stains from textile fabrics, which comprises laundering the fabrics by hand or machine in a wash liquor containing a detergent composition as claimed in any one of claims 1 to 7.

14 Use of a compound of the formula I:
wherein Y is H or OH, and X is H or a solubilising cation, in an amount of from 0.05 to 1.5 wt%, in a laundry detergent composition to protect new white or coloured textile fabrics from colour degradation on laundering.
15 Use of a compound of the formula I:
wherein Y is H or OH, and X is H or a solubilising cation, in an amount of from 0.05 to s.5 wt%, in a laundry detergent composition to restore colour fidelity in white or coloured textile fabrics that have been laundered.
16 Use of a compound of the formula I:
wherein Y is H or OH, and X is H or a solubilising cation, in an amount of from 0.05 to 1.5 wt%, in a laundry detergent composition as a chlorine scavenger to prevent the fading of chlorine-sensitive dyes an coloured textile fabrics during laundering.

17 Use of a compound of the formula I:
wherein Y is H or OH, and X is H or a solubilising cation, in an amount of from 0.05 to 1.5 wt%, in a laundry detergent composition to improve its stain removal performance.