CA2206260A1 - Detergent composition containing combination of nonionic polysaccharide ether with synthetic oxyalkylene-containing soil release agent - Google Patents

Abstract

The present invention relates to detergent compositions comprising the combination of nonionic polysaccharide ethers having an average degree of polymerisation of 100 or more with a synthetic soil release agent having a molecular weight of less than 10000. Said combination provides improved soil release performance and clay soil removal and antiredeposition performance.

Description

CA 02206260 1997-0~-28 W 096/17048 PCTrUS95/15547 DETERGENT COMPOSITION CONTAINING COMBINATION OF
NONIONIC POLYSACCHARIDE ETHER WITH SYNTHETIC
OXYALKYLENE-CONTAINING SOIL RELEASE AGENT

Technical Field of the Invention The present invention relates to detergellt compositions comprising soil release agents in combination with nonionic polysaccharide ethers.

Back~round to the Invention During the l~lln~ering operation of fabrics it is highly desirable to provide the fabric, particularly man-made fabrics produced from synthetic fibres, with soil release properties.

Due to the hydrophobic nature of fabrics composed of partially ~ or completely synthetic fibres, the removal of greasy soils and stai~s therefiolll is particularly difficult. In order to address this problem, ~ soil release polymers may be incorporated into the detergent composition. During l~un~lering the soil release agents are adsorbed onto the surface of the fabric, thereby inducing greater hydrophobicity to the fabric surface. Once the fabric is treated with a soil release CA 02206260 1997-0~-28 W O 96/17048 PCTrUS95/15547 agent, the ease of removal of greasy soil and stains from the surface of the fabric is considerably improved.

The main types of soil release agents incorporated into detergent compositions, which provide benefits to primarily hydrophobic synthetic fabrics include synthetic soil release agents, preferably terephth~l~te based and polysaccharide ethers. Polymeric soil release agents are described in the art, for example US 4 795 584 and EPO-253 567 disclose soil release polymers comprising ethyleneoxy terephth~l~te and polyethyleneo~y terephth~l~te units having a molecular weight of 900 to 9000.

Polysaccharide ethers such as cellulose ethers have bee~
described for example in EPO 054 325 which discloses a detergent composition having re~ ce~ soil redeposition effects comprising carboxymethyl cellulose, a linear polycarbo~ylate and a cellulose ether having a degree of substitution (ds) of at least 0.5 and a degree of polymerisation (dp) of less than 300. GB 1 534 641 discloses nonionic surfactant deter~ent compositions comprising cellulose ether soil release agents such as alkyl and hydro~yalkyl cellulose ethers. US 4 441 881 discloses detergellt compositions comprising modified cellulose ethers such as alkyl and hydro~yaL~yl cellulose ethers having a molecular weight of 19000 to 185000 and a degree of substitution up to 3.

The soil release pelrormance of the polysaccharide ethers may be subst~nti~lly im~ro~ed upon greasy/oily stains by increasing the amount of ether used or by increasing the molecular weight or degree of polymerisation of the ether. However, such higher molecular weight polysaccharide ethers are known to have detrim~nt~l effects on the clay soil removal and anti-redeposition pel~l~ance of the detergent composition in which they are incorporated. This is particularly evident on fabrics after a number of repeated washing cycles or when high dosage or concentrations of detergellt composition are lltili.~e~ to clean heavily soiled fabrics. This problem is also acute on fabrics which contain a high percentage of synthetic fibres.

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CA 02206260 1997-0~-28 Synthetic soil release agents, particularly those soil release agents having a significantly lower molecular weight than the polysaccharide ethers have been used to address this problem. The clay soil removal performance of the detergent composition is not as detrimentally affected by the use of synthetic soil release agents in comparison with compositions comprising poylsaccharide ether. Thus, synthetic soil release agents tend to be preferred. In particular those having a low molecular weight are preferred for solubility requirements and ease of manufacture.

Thus, it is an aim of the present invention to provide a deter~ ent composition providing increased soil removal performance without negatively affecting the particulate/clay soil removal performance.

It has now been determined that this aim can be achieved by the use of the combination of a synthetic soil release agent having a molecular weight of less than 10000 with a nonionic polysaccharide ether having an average degree of polymerisation of 100 or more.

An additional advantage of the present invention is that this combination of synthetic soil release agent and polysaccharide ether provides improved overall cle~ning performance, particularly on greasy food soils, mechanical oil stains and clay.

A further advantage of the present invention is that the improved c!e~nin.~ pelrollllance, especially of clay soil is achieved on a broad range of fabric types, such as synthetics for e~cample polyester and additionally on natural/synthetic blend fabrics such as polycottons.

Synthetic soil release agents and polysaccharide ethers have been described for e~ample in US 4 740 326 which discloses a laundry product comprising a sul.sllate material coated with a soil release polymer for e~ample dryer added sheets. The soil release polymers are selected from i) alkyl or hydro~yalkyl cellulose ethers having a molar degree of substitution (ds) of from 1.5 to 2.7 and average molecular weight of from 2000 to 100000 or ii) various ethylene terephth~l~te CA 02206260 1997-0~-28 W O96/17048 PCT~US95/15547 and polyethylene o~cide tereph~h~l~te polymers having an average molecular weight of from 1000 to 100000 and mi~tures of i) and ii).

US 4 770 666 discloses laundry detergent compositions comprising peroxyacid bleach and soil release polymers. The soil release polymers are selected from i) alkyl or hydroxyalkyl cellulose ethers having a ds of 1.5 to 2.7 and an average molar weight of 2000 to 100000 and ii) various ethylene terephth~l~te and polyethylene oxide terephth~l~te polymers having an average molecular weight of from 1000 to 100000 and mixtures of i) and ii). However, the art does not suggest the synergic effect of the combination of synthetic soil release agents with polysaccharide ethers.

Sllmm~ry of the Invention The present invention relates to a delergcl,t composition comprising the combination of a nonionic polysaccharide ether having a degree of polymerisation of 100 or more with a soil release agent comprising at least one oxyaL~ylene unit and having a molecular weight of less than 10000.

All weights, ratios and percentages are given as a % weight of the total composition unless otherwise stated.

Detailed Description of the Invention The present invention is a detergcnt composition comprising the combination of a nonionic polysaccharide ether with a soil release agent comprising at least one o~yalkylene unit.

Soil Release A~ent Thus, an essential ingredient of the present invention is a soil release agent. Any polymeric soil release agent known to those skilled in the art are employed in the compositions and processes of this invention. Polymeric soil release agents are characterised in that they impart hydrophilicity to the surface of hydrophobic fibres, such as CA 02206260 1997-0~-28 W O96/17048 PCTrUS95/1~547 polyester and nylon, and hydrophobic segments, to facilitate the attraction of the soil release agent to the synthetic fibres.

The soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of at least one o~yalkylene unit, preferably having a degree of polymerisation of at least 2, more preferably 2 to 10. Pre~erably the soil release agent further comprises at least one terephth~l~te or substituted terephth~l~te unit, preferably the soil release agent further comprises a polyester backbone comprising at least one terephth~l~te unit and at least one sulphoisophth~l~te unit and at least one end capping unit.

The following structure is illustrative, but by no means limiting, of preferred structures of ester soil release agents of the invention:

NaO3SCH2CH2 ~CH2CH2o ~ 0cH2cH2ocH2cH2so3Na Also encompassed are certain stabilisers which reduce the crys~ tion problems encountered during m~n~lf~cture and storage of the soil release agents as well as when introduced to the wash liquor. The stab~lisers are especially useful in compositions with high ratios of o~yethyleneoxy to o~y-1,2-o~ypropylene in the "backbone"
structure of the agent.

The esters herein can be simply characterised as soil release agents which comprise a subst~nti~lly linear ester "backbone" and end-capping units which are derived from sulfonated monohydroxy polyetho~y/propo~y monomers, especially 2-(2-hydroxyetho~y)eth~nesulfonate. Proper selection of the structural units which comprise the ester backbone and use of sufficient amounts of the charged end-capping units results in the desired soil-release properties of these materials. The integration of stabilisers into the agent reduces CA 02206260 1997-0~-28 the cryst~lli7~tion of the agent during manufacture and when introduced into the wash liquor, thereby enhancing the dissolution/dispersion and the soil release performance.

Oli~omeric Esters - It is to be understood that the compositions herein are not resinous, high molecular weight, macromolecular or fibre-forming polyesters but, in~te~(l are relatively low molecular weight and contain species more a~ro~liately described as oligomers rather than as polymers. Individual ester molecules herein, including the end-capping units, can have molecular weights r~nging from 500 to about 8,000. Relevant for purposes of comparison with glycol-terephth~l~te ~Ibrous polyesters (typically averaging 15,000 or more in molecular wei~ht) is the molecular weight range from about 500 to about 5,000, within which molecules of the prefelred esters of the invention which incorporate the essential uni~s and 5-sulfoisophth~l~te are generally found.

Molecular Geometry - The soil release agents employed herein are all "subst~nti~lly linear" in the sense that they are not significantly branched or crosslinked by virtue of the incorporation into their structure of units having more than two ester-bond forming sites. A
typical example of polyester branching or crosslinking of this type is exemplified in Sinker et al, U.S. Patent 4,554,328, issued November 19, 1985.) Furthermore, no cyclic esters are essential for the purposes of the invention but may be present in the compositions of the invention at low levels as a result of side-reactions during ester synthesis. Prererably, cyclic esters will not exceed about 2% by weight of the compositions; most pre~lably, they will be entirely absent from the compositions.

Contrasting with the above, the term "subst~nti~lly linear" as applied to the esters herein does, however, e~cpressly encompass materials which contain side-chains which are unreactive in ester-forn~illg or transesterification reactions. Thus, oxy-1,2-propyleneo~cy units are of an unsymmetrically substit~1te-1 type; their methyl groups do not constitute what is conventionally regarded as "branching" in polymer technology (see Odian, Principles of Polymerisation, Wiley, W O96/17048 PCTrUS95/15547 N.Y., 1981, pages 18-19, with which the present definitions are fully consistent) and are unreactive in ester-forming reactions. Optional units in the esters of the invention can likewise have side-chains, provided that they conform with the same nonreactivity criterion.

Molecular Structures - The following structures are illustrative of structures of ester molecules falling within the foregoing preferred embodiments, and demonstrate how the units are connected:
a) doubly end-capped ester unit;

N~3scH2a~2xH2a~2o~ ~ ~2a~2~~H2a~2S~3Na b) singly end-capped ester units;

3 2 2 2 2 ~ 2 2 c) doubly end-capped ester unit(termed a "hybrid backbone" ester molecule herein) may be comprised of a mixture of oxyethyleneoxy and o~y-1,2-propyleneo~y units, in the example shown below at a 2:1 mole ratio (on average, in ester compositions as a whole in contrast to i~dividual molecules such as illustrated here, ratios r~ngin~: from about 1:1 to about 10:1 are the most highly ~left;rled.

N~l~2a~ 2a~2CC~I2al25~)3 CA 02206260 1997-0~-28 W O96/17048 PCT~US95/15547 d) doubly end-capped ester units. On average, in ester compositions as a whole in contrast to individual molecules such as illustrated below, the most highly l~refelled ratios of oxyethyleneo~cy to oxy-1,2-propyleneoxy units range from about 0.5:1 to 1:0.
NaO3SCH2CH20CH2CH2O~ LOCH2CH(CH3)0 o o o o --~CH(CH3)CH2 ~ ~Q~L OCH2CH20 ~[~ OCH2CH20 ~L~,~IL

SO Na OCH2CH20~0CH2CH20 L OCH2CH20CH2CH2S03Na In addition the moelcular structures of the ester molecules may also include singly or doubly-endcapped ester molecules having alkyl branching or having polyethyleneglycol e~ctensions.

In the context of the structures of ester molecules disclosed herein it should be recognised that the present invention encompasses not only the arrangement of units at the molecular level but also the gross mi~tures of esters which result from the reaction schemes herein and which have the desired range of composition and properties.
Accordingly, when the number of monomer units or ratios of units are given, the numbers refer to an average quantity of monomer units present in oligomers of the composition.

Ester Backbone - As illustrated in the structures shown above, in the esters of this invention, the backbone is formed by o~yethyleneo~y and terephthaloyl units connected in alternation. Optionally, the backbone is formed by S-sulfoisophthaloyl units, terephthaloyl units, o~cyethyleneoxy or mi~ctures of oxyethyleneo~cy, o~cypropyleneo~cy and poly(o~cyethyleneo~cy) units connecte~l with alternation of ~he aryldicarbonyl and oxyalkyleneo~y units.

Groups at the Termini of the Ester Backbone - Likewise, the "polyester backbone of the invention" is a term which encompasses CA 02206260 1997-0~-28 W O96/17048 PCTrUS95/15547 doubly and singly end-capped compounds disclosed herein, mi~tures thereof, and mi~tures of said end-capped materials which may unavoidably contain some non-capped species. Although, levels of the latter will be zero or at a minimum in all of the highly preferred compositions. Thus, when referred to herein, it is intended to refer, by definition, collectively to the mi~cture of capped and uncapped ester molecules resulting from any single preparation.

Any soil release molecules which are present in compositions of the invention which are not fully, i.e., doubly, end-capped by the end-capping units must termin~te with units which are not sulfonated poly-etko~y/propoxy end-capping units. These termini will typically be hydro~yl groups or other groups attributable to the unit-formin~
reactant. In other structures which may be constructed, units such as -(O)CC6H4C(O)-OCH3 may be found in terminal positions. All the most highly preferred ester molecules herein will, however, as indicated above, have two sulfonated end-capping units and no backbone units OCCUpyihg terminal positions.

Svmmetry - It is to be appreciated that in esters in which oxy-1 ,2-propyleneo~cy units are also present, the o~y-1 ,2-propyleneo~cy units can have the methyl groups randomly alternating with one of the adjacent -CH2-hydrogen atoms, thereby lowering the symmetry of the ester chain. Thus, the oxy-1,2-propyleneo~y unit can be depicted as having either the -OCH2CH(CH3)0- orientation or as having the opposite -OCH(CH3)CH20- orientation. Carbon atoms in the o~y-1,2-propylene units to which the methyl gruu~s are ~tt~çhe~l are, furthermore, asymmetric, i.e., chiral; they have four non-equivalent chemical entities attached.

In contrast to the o~y-1,2-propyleneo~y units, oxyethyleneoxy units cannot be used herein as a sole source of o~y-1,2-alkyleneoxy units without the addition of stabilisers since they lack the needed ~ unsymmetrical character. It is the presence of the unsymmetrical units and/or of the stabilisers that inhibit the cryst~ tion of the oligomer during m~nllf~ct~re and later when added to the wash liquor. The use of oxyethyleneo~y units or high ratios of oxyethyleneoxy to CA 02206260 1997-0~-28 oxypropyleneoxy units, therefore, must be accompanied by the use of stabilisers to retard the formation of crystals. Accordingly, such compositions herein contain sulfonate-type hydrotropes, linear or branched alkylbenzenesulfonates, paraffin sulfonates, and mixtures thereof integrated into the oligomer composition.

Preferably, various optional units of a hydrophilicity enhancing and nonpolyester substantive type can be incorporated into the esters.
The pattern of such incorporation will generally be random. Preferred optional units are anionic hydrophiles, such as S-sulfoisophthaloyl or ~imil~r units. Such units will, when incorporated into the ester backbone, generally divide it into two or more hydrophobic moieties separated by one or more hydrophilic moieties.

It should also be noted that the essential non-charged aryldicarbonyl units herein need not e~clusively be terephthaloyl units, provided that the polyester fabric-sub~ltivity of the ester is not harmed to a significant e~tent. Thus, for e~ample, minor amounts of isomeric non-charged dicarbonyl units, such as isophthaloyl or the like, are acceptable for incorporation into the esters.

Poly(o~yethylene)o~y units - The optional poly(oxyethylene)o~y units comprising the esters of the present invention have a degree of polymerization of from 2 to 4 and can constitute from O to about 25 mole percent of the total o~yalkyleneo~y units present. rLefe-~bly, poly(o~yethylene)o~y units are present when the backbone unit comprises 8 or more terephthaloyl units; however, at least some poly(oxyethylene)oxy units are present in esters with as few an average 1.5 terephthaloyl units. The poly(o~yethylene)o~y units, especially in esters with 8 or more terephthaloyl units, aid in the rate of dissolution of the soil release agent into the wash liquor.

The amount of poly(oxyethylene)o~cy units present in the backbone is related to its degree of polymerisation. For example, oxyethyleneo~cyethyleneo~y units (formed from diethylene glycol), which have a degree of polymerisation of two, can constitute from O to 25 mole percent of the total oxyalkyleneo~y units in the backbone.

CA 02206260 1997-0~-28 O~cyethyleneo~yethyleneo~yethyleneoxyethyleneoxy units (formed from tetraethylene glycol), which have a degree of polymerisation of four, can constitute from 0 to 12 mole percent of the total o~yalkyleneo~y units present in the backbone.

Cappin~ units - According to the present invention at least 50%, of said soil release agent comprises at least one terminal capping unit selected from anionic, nonionic, cationic capping units and mixtures thereof.

Suitable anionic capping unit for use herein are according to the formula (M03S)(CH2)m(CH2CH20)(RO)n, wherein M is a salt forming cation such as sodium or tetraalkylammonium, m is 0 or 1, is ethylene, propylene or a mi~ture thereof and n is from 0 to 2.
Preferably said end capping unit is derived from sulphobenzoic acid or derivatives thereof. These end-cap units provide anionic charged sites when the esters are dispersed in aqueous media, such as a laundry liquor. It is not intended to exclude the acid form, but most generally the esters herein are used as sodium salts, as salts of other alkali metals as salts with nitrogen-cont~inin~ cations (especially tetraalkylammonium), or as the disassociated ions in a aqueous environment.

E~amples of end-capping groups include sodium isethionate, sodium 2-(2-hydro~cyetho~cy) eth~nesulfonate, sodium 2-[2-(2-hydroxyethoxy)etho~y] ethanesulfonate, sodium 5-hydro~y-4-methyl-3-oxa-pent~nesulfonate, sodium alpha-3-sulr~ropyl-omega-hydro~y-poly-(o~cy-1,2-ethanediyl) (with average degree of etho~ylation of 1-2), sodium 5-hydro~y-3-oxa-he~canesulfonate, and mi~ctures thereof.

On a mole basis, the compositions herein will preferably comprise from about one to about two moles of the sulfonated end-capping units per mole of the ester. Most preferably, the esters are doubly end-capped; i.e., there will be two moles of end-capping units present per mole of the ester. From the viewpoint of weight composition, it will be clear that the fractional contribution of end-CA 02206260 1997-0~-28 W ~96/17048 PCT/US95/15547 capping units to the molecular weight of the esters will decrease as the molecular weight of the ester backbone increases.

Suitable nonionic endcapping units are consecutive polyethylene glycol units, preferably from 2 to 20 consecutive polyethylene glycol units.

Suitable cationic end capping units are quaternary ammonium or quaternary ammonium salts according to the formula R4N+, wherein each R is independently selected from C1-C4 alkyl groups, C1-C4 hydroxyalkyl groups, C2-C4 alkylene groups, C2-C4 oxyalkylene groups, phenyl, phenyl C1-C4 alkyl groups, hydrogen and wherein two R groups can be joined to form cyclic structures. Suitable cationi~
end capped soil release polymers for use herein are described in EPO-398 133.

Stabilisers - Stabilisers useful in this invention should be water soluble or water dispersible. The stabilising agents that are useful herein include sulfonate-type hydrotropes, linear or branched alkylbenzenesulfonates, paraffin sulfonates, and other thermally-stable alkyl sulfonate variations with from about 4 to about 20 carbon atoms.
Prererled agents include sodium dodecylbenzenesulfonate, sodium cumenesulfonate, sodium toluenesulfonate, sodium ~cylenesulfonate, and mi~ res thereof. When higher levels of stabilisers are used, mi~chlres of hydrotropes and/or other stabilisers are prefel-led over pure components to insure full integration into the oligomer and to reduce the possibility of cryst~ tion of the stabiliser.

In general, the level of such agents should be kept as low as possible while providing the primary benefit, i.e., the reduction in the amount of cryst~ tion that the soil release agent undergoes during m~nl~f~cture, storage and when introduced to the wash liquor. The composition may comprise from about 0.5% to about 20% stabiliser.
Most ~rere.ably, these ester compositions comprise an amount sufficient to reduce the cryst~ tion of the oligomer during m~mlf~ct~lre and when introduced to the wash liguor, i.e., at least 3%
by weight.

CA 02206260 1997-0~-28 WO 9~/17048 PCTtUS95/1~547 The stabilisers may be added to the soil release agent in various ways. Preferably, the stabilisers are added to the oligomer reagents in the initial stages prior to full oligomerization. The stabilisers thereby integrate uniformly into the oligomer. Another method would entail first melting the pre-formed oligomer and then uniformly mixing the stabiliser into the molten oligomer.

Alkylbenzenesulfonates when used as surfactants in detergent compositions do not provide the stabilising and cryst~ tion reducing effect, even during dissolution of the soil release agent in the laundry liquor, that the stabiliser does when it is added as directed above.

A preferred polymeric soil release agent is a polyester with repeat units of ethylene terephth~l~te units contains 10-155~o by weight of ethylene terephth~l~te units together with 90-80% by weight of polyoxyethylene terephth~l~te units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated product of a subst~nti~lly linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and o~yalkyleneo~y repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephth~l~te polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sul-foarolyl, end-capped terephth~l~te esters.

CA 02206260 1997-0~-28 According to the present invention the soil release agent has a molecular weight of less than 10000, preferably less than 5000 According to the present invention the detergent compositions comprise from 0.01% to 5%, typically from 0.01% to 3%, preferably from 0.01 % to 1.0% .

Methods of m~kin~ soil release a~ents The soil release agents of the present invention can be prepared using any one of combination of several alternative general reaction types, each being well known in the art. Types of synthetic and analytical methods useful herein are illustrated in EPO 185 427 and i~
"Principles of polymerisation", Odien, Wiley, NY, 1981. The general types of reactions suitable for preparing the soil release agents of the present invention include those classifiable as:
1. alcoholysis of acyl halides 2. esterification of organic acids 3. alcoholysis of esters(transesterification) and 4. reaction of alkylene carbonates with organic acids.

Reaction types 2-4, prefelably 3-4 are preferred.

Polysaccharide ethers According to the present invention an essential component of the detergent composition is a nonionic polysaccharide ether. Chemically, the polysaccharides are composed of pentoses or he~coses. Suitable polysaccharide ethers for use herein are selected from cellulose ethers, starch ethers, de~tran ethers and mi~tures thereof. Preferably said nonionic polysaccharide ether is a cellulose ether. Cellulose ethers are generally obtained from vegetable tissues and fibres, including cotton and wood pulp.

The hydro~cy group of the anhydro glucose unit of cellulose can be reacted with various reagents thereby replacing the hydrogen of the hydro~yl group with other chemical groups. Various alkylating and CA 02206260 1997-0~-28 W O 96/17048 PCTrUS95/15547 hydroxyalkylating agents can be reacted with cellulose ethers to produce either alkyl-, hydroxyalkyl- or alkylhydro~yalkyl-cellulose ethers or mixtures thereof. The most preferred for use in the present invention are C1-C4 alkyl cellulose ether or a C1-C4 hydroxyalkyl cellulose ether or a C 1 -C4 alkylhydroxy alkyl cellulose ether or mi~tures thereof. Preferably the polysaccharides of the present invention have a degree of substitution of up to 3, preferably from 0.5 to 2.5, most preferably from 0.5 to 2.2 inclusive.

Suitable cellulose ethers include methylcellulose ether, hydroxypropyl methylcellulose ether, hydroxyethyl methylcellulose ether, hydroxypropyl cellulose ether, hydroxybutyl methylcellulose ether, ethylhydroxy ethylcellulose ether, ethylcellulose ether and hydroxy ethylcellulose elher. Most preferably said polysaccharide is a methylcellulose ether. Such agents are commercially available such as METHOCEL (Dow Chemicals).

According to the present invention said polysaccharide ether has a degree of polymerisation of more than 100, preferably from 100 to 10000. As used herein the term degree of polymerisation (dp) is the ratio of the weight average molecular weight on average molecular unit weight, i.e. dp=MWW/MUW. The weight average molecular weight (MWW) is obtained by st~n~l~rd analytical methods as described in Polymer handbooks. A prerelled method is light scattering from polymer solutions as originally defined by Debye.

For e~ample the average molecular unit weight (MUW) for methylcellulose ether may be determined from the sum of the molecular weight of the unsubst~ tell cellulose unit and the product of the degree of polymerisation and the molecular weight of the substituent less the hydrogen mass (1).
i.e. MUW= 162 + (15-1)* ds -for methyl substituents found in methyl cellulose ethers.
MUW may also be determined from the "% methoxyl content"
value (mc) also used by m~nl~ctures of methyl cellulose ethers instead of the degree of substitution, such that;

CA 02206260 1997-0~-28 WO 96/17048 PCT/US95/15~47 MUW= 100 - [(mol. wt. of CH2/mol. wt. of OCH3)*mc]

The compositions of the present invention comprise from 0.01%
to 10%, preferably from 0.01% to 3% of said nonionic polysaccharide ethers. According to the present invention the detergent compositions comprise said polysaccharide and soil release polymer in a ratio of from 0.1:1 to 20:1, preferably from 0.5:1 to 10:1.

According to the present invention the detergent compositions may comprise additional ingredients such as surfactants, other anti-redeposition agents, builders, chelants, bleaches and the like.

Clay Soil Removal/Anti-redeposition A~ents The compositions of the present invention can also optionally contain clay soil removal and antiredeposition agents. Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of said agents, liquid detergent compositions typically contain 0.01% to 5%. Suitable clay soil removal and/or anti redeposition agents known in the art includes the carbo~y methyl cellulose (CMC) materials.

Detersive Surfactants According to the present invention the detergent composition may pl-efel~lby comprise surfactants. Surfactants useful herein include the conventional C11-C1g alkyl benzene sulphonates ("LAS") and primary, branched-chain and random C1o-C20 alkyl sulphates ("AS"), the C1o-C1g secondary (2,3) alkyl sulphates of the formula CH3(CH2),~(CHOS03-M+) CH3 and CH3 (CH2)y(CHOS03~M+) CH2CH3 where x and (y + 1) are integers of at least about 7, ~r~f~rably at least about 9, and M is a water-solubilizing cation, especially sodium, lln~lrated sulphates such as oleyl sulphate, the C1o-C1g alkyl alko~cy sulphates ("AE,~S"; especially EO 1-7 ethoxy sulphates), C1o-C1g alkyl alko~y carbo~ylates (especially the EO 1-5 etho~ycarboxylates), the C10-l8 glycerol ethers, the C10-cl8 alkyl =~ =
CA 02206260 1997-0~-28 W O96/17048 PCTrUS95/15547 polyglycosides and their corresponding sulphated polyglycosides, and C12-C1g alpha-sulphonated fatty acid esters.

If desired, the conventional nonionic and amphoteric surfactants such as the C12-C1g alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl etho~ylates and C6-C12 alkyl phenol alko~ylates (especially etho~ylates and mixed etho~y/propo~y), C12-(~1g betaines and sulphobetaines ("sultaines"), C1o-C1g amine oxides, and the like, can also be included in the overall compositions. The C1o-C1g N-alkyl polyhydro~y fatty acid amides can also be used. Typical examples include the C12-C1g N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1o-C1g N-(3-methoxypropyl) ghlc~mi(le. The N-propyl through N-hexyl C12-C1g glllc~micles can be used for low sudsing. C 10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C1o-C16 soaps may be used.
Mi~tures of anionic and nonionic surf~ct~nts are especially useful.
Other conventional useful surfactants such as cationics are listed in standard te~ts.

According to the present invention the compositions comprise from 15~ to 80~, preferably from 5% to 50%, most preferably from 10% to 40% of a surfactant. Prefefled surf~ct~nts for use herein are linear alkyl benzene sulphonate, alkyl sulphates and alkyl alko~ylated nonionics or mi~tures thereof.

Builders Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric l~lnrltoring compositions to assist in the removal of particulate soils.
.

The level of builder can vary widely depenflin~ upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. Liquid -CA 02206260 1997-0~-28 W O 96/17048 PCTrUS9SllSS47 formulations typically comprise from 5% to 50%, more typically about 5~ to 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15 % to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

Inorganic or P-cont~inin~ detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates (see, for example, U.S. Patents 3,1~9,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

However, non-phosphate builders are required in some locales.
Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

E~amples of silicate builders are the aL~ali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain alllminl~m. NaSKS-6 has the delta-Na2Si2Os morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly prefelled layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi~02~ + 1 ~yH20 wherein M is sodium or hydrogen, ~c is a number from 1.9 to 4, ~refeiably 2, and y is a number from 0 to 20, ~referably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and ~~mm~ forms. As noted above, the CA 02206260 1997-0~-28 delta-Na2Si2Os (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for example m~gnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

E~amples of carbonate builders are the ~lk~line earth and alkali metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15, 1973.

Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently marketed heavy duty grallular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
MZ[(sio2)w(zAlo2)y] ~H2o wherein w, z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and ~ is an integer from about 15 to about 264.

Useful aluminosilicate ion e~change materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring ~hlminosilicates or synthetically derived. A method for producing aluminosilicate ion e~change materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Pleferred synthetic cryst~llin.o.
~lnminosilicate ion e~cchange materials useful herein are available under the de~i~n~tions Zeolite A, Zeolite P (13), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion e~change material has the formula:
Na12[(AlO2)12(siO2)l2] ~~H2O
wherein ~ is from aboul: 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Prei~erably, the ~lllminosilicate has a particle size of about 0.1-10 microns in diameter.

CA 02206260 1997-0~-28 W O96/17048 PCTrUS95/15547 Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarbo~ylate" refers to compounds having a plurality of carbo~ylate groups, preferably at least 3 carbo~ylates. Polycarbo~ylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates~
including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarbo~cylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydro~ypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydro~y benzene-2, 4, 6-trisulphonic acid, and carbo~ymethylo~ysuccinic acid, the various aL~ali metal, ammonium and substitnte~ ammonium salts of polyacetic acids such as ethylene~ mine tetraacetic acid and nitrilotriacetic acid, as well as polycarbo~ylates such as mellitic acid, succinic acid, o~ydisuccinic acid, polymaleic acid, ben~ene 1,3,5-tricarbo~ylic acid, carbo~ymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarbo~ylate builders of particular importance for heavy duty liquid detergellt formulations due to their availability from renewable resources and their biodegradability.
Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.

CA 02206260 1997-0~-28 W O96/17048 PCT~USg5/15547 O~ydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-o~a-1,6-he~anedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et: al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.

Fatty acids, e.g., C12-C18 monocarbo~cylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a ~limimltion of sudsing, which should be taken into account by the form~ tQr.

CA 02206260 1997-0~-28 W O96/17048 PCTrUS95/15547 Chelating Agents The detergent compositions herein may also optionally contain one or more iron and/or m~n~nese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and m~n~nese ions from washing solutions by formation of soluble chelates.

Amino carbo~ylates useful as optional chelating agents includ~
ethylene~ minetetracetates, N-hydro~yethylethylen~Ai~minetriacetates, nitrilotriacetates, ethylenefli~mine tetraproprionates, triethylenetetra-aminehe~acetates, diethylenetri~minepent~cetates, and ethanoldi-glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylene~ minetetrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-subst~ te~l aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. P1eft;rled compounds of this type in acid form are dihydro~ydisulfobenzenes such as 1,2-dihydro~y-3,5-disulfobenzene.

A ~l~fe~led biodegradable chelator for use herein is ethylene~ mine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

CA 02206260 1997-0~-28 WO 96/17048 PCTIUS95/lS547 If utilized, these chelating agents will generally comprise from .1~ to 10% more preferably, from 0.1% to 3.0% by weight of such compositions.

Bleachin~ Compounds - Bleaching A~ents and Bleach Activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions cont~ining a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from 1% to 40%, more typically from 5% to 30%, of the detergent composition, especially for fabric ln-lering. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleachin~
composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in te~tile cle~ning, hard surface cleaning, or other cle~nin~ purposes that are now known or become known. These include o~ygen bleaches as well as other bleaching agents.

Pero~cygen bleaching agents can also be used. Suitable pero~cygen bleaching compounds include sodium carbonate pero~cyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate pero~yhydrate, urea pero~cyhydrate, and sodium pero~cide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.

A ~referred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. rreferled co~tin~ are based on carbonate/sulphate mi~ctures. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

CA 02206260 l997-0~-28 W O 9G/17048 PCT~US95/15547 Another category of bleaching agent that can be used without restriction encompasses percarbo~ylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include m~gn~sium monoperoxyphth~l~te he~ahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxopero~ybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonyl~mino-6-oxopero~ycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

Mixtures of bleaching agents can also be used. Pero~ygen bleaching agents, the perborates, e.g., sodium perborate (e.g., mono-or tetra-hydrate), the percarbonates, etc., are preferably combined with bleach activators, which lead to the in sin~ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach aclivator. Various nonlimiting examples of aclivato~s are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoylo~yben~ene sulfonate (NOBS) and tetraacetyl ethylene ~i~mine CrAED) activators are typical, and mi~tures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Highly ~refelled amido-derived bleach activators are those of the formulae:
R1N(R5)C(o)R2C(o)L or R1C(O)N(R5)R2C(o)L
wherein R1 is an alkyl group cont~ining from about 6 to about 12 carbon atoms, R2 is an alkylene cont~inin~ from 1 to about 6 carbon atoms, R~ is H or alkyl, aryl, or alkaryl cont~inin~ from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a -CA 02206260 1997-0~-28 consequence of the nucleophilic attack on the bleach activator by the perhydroxyl anion. ~ preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include (6-oct~n~mido-caproyl)o~ybenzenesulfonate, (6-non~n~mi~ocaproyl)- oxybenzenesulfonate, (6-dec~n~mido-caproyl)o~ybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by refelence. A highly preferred activator of the benzo~azin-type is:

~ C~
Still another class of preferled bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerol~ct~m.
of the formulae:
1~l 1~l Cl--CH2--CH

o wherein R6 is H or an alkyl, aryl, aL~oxyaryl, or aL~aryl group cont~ininp from 1 to about 12 carbon atoms. Highly prerelled lactam activators include benzoyl caprolactam, octanoyl caprol~ct~m, 3,5,5-trimethylhe~canoyl caprol~ct~m, nonanoyl caprolactam, ~lec~noyl caprolactam, ~lntlecenoyl caprolactam, benzoyl valerol~c~m, octanoyl valerolactam, decanoyl valerol~ct~m, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerol~ct~m and mi~tures thereof. See also U.S. Patent 4,545,784, issued to CA 02206260 1997-0~-28 W O 96/17048 PCTrUS95/15547 Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, adsorbed into sodium perborate. Other preferred activators are cationic bleach activators.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be lltili~etl herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or al~minllm phthalocyanines.
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25 %, by weight, of such bleaches, especially sulfonate zinc phthalocyanine .

If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the m~ng~nese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S.
Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred e~amples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4~7-triazacyclononane)2-(clo4)2~ MnIV4(u-0)6(1,4,7-triazacyclononane)4(Cl04)4, MnIIIMnIV4(u-0)1(u-OAC)2-(1 ~4~7~
trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mi~ctures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of m~ng~nese with various comple~ ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612;

5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;

Polymeric Dispersing Agents Polymeric dispersing agents can advantageously be lltili7etl at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silic~te builders.
Suitable polymeric dispersing agents include polymeric CA 02206260 1997-0~-28 WO 96/170~8 PCT/US95/15547 polycarbo~ylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarbo~ylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable lln~hlrated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mes~conic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, cont~inin~ no carbo~ylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such se~ments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarbo~cylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more ~reîerably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for e~ample, the alkali metal, ~mmonium and subst~ te~l ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for ea~ample, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.

Acrylic/maleic-based copolymers may also be used as a L~reÇelled component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form L)referably ranges from about 2,000 to 100,000, more CA 02206260 1997-0~-28 W O96/17048 PCTrUS95/15547 preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 70:30 to 30:70. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for e~cample, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known mate~ials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydro~ypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol or acetate terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can e~chibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyamino acid dispersing agents such as polyaspartate and polygl~lt~m~temay also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate prefelably have a molecular weight (avg.) of about 10,000.

Dye Transfer Inhib;tin~ Agents The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cle~ninP process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-o~ide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, m~ng~nese phthalocyanine, pero~idases, and mi~tures thereof. If used, these agents typically comprise from 0.01 %

CA 02206260 1997-0~-28 to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.

More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A~-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, etho~ylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O
group can be attached or the N-O group is part of these groups.
Preferred polyamine N-o~ides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imi~l~7ole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures:
~x 7 (R2)y; =N (Rl)x (R3)z wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; ~c, y and z are 0 or 1; and the nitrogen of the N-O group can Ibe attached or form part of any of the aforementioned groups. The amine o~ide unit of the polyamine N-o~cides has a pKa < 10, pleferably pKa ~7, more prefelled pKa <6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mi~tures thereof. These polymers include random or block copolymers where one monomer type is an amine N-o~cide and the other monomer type is an N-o~cide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine o~ide groups present in CA 02206260 1997-0~-28 W O 96/170q8 PCTrUS9~/15547 the polyamine o~ide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine o~ides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of S00 to 1,000,000; more preferred 1,000 to S00,000; most preferred S,000 to 100,000. This preferred class of materials can be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about S0,000 and an amine to amine N-oxide ratio of about 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimid~7ole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more yrdf~lably from 5,000 to 200,000, and most pler~rably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimi(l~7ole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.
These copolymers can be either linear or br~nch~l.

The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about S,000 to about 400,000, prdfe.ably from about S,000 to about 200,000, and more prdferably from about S,000 to about S0,000.
PVP's are known to persons skilled in the detergent field; see, for e~ample, EP-A-262,897 and EP-A-256,696, incorporated herein by referd~ce. Compositions cont~ining PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about S00 to about 100,000, ~ref~rably from about 1,000 to about 10,000.
Pref~rably, the ratio of PEG to PVP on a ppm basis delivered in wash CA 02206260 1997-0~-28 solutions is from about 2:1 to about 50:1, and more preferably from about 3 :1 to about 10:1.

The detergent compositions herein may also optionally contain from 0.0055~ to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
Rl R2 N~O~ H IH~ I ~(~N

R2 SO3M SO3M Rl wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydro~yethyl, N-2-hydroxyethyl-N-methyl~mino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)~mino]-2,2 '-stilbenedisulfonic acid and disodium salt. This particular brightenerspecies is commercially marketed under the tr~le.n~me Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the plefel~ed hydrophilic optical brightener useful in the delergent compositions herein.

When in the above formula, R1 is ~nilino, R2 is N-2-hydro~yethyl-N-2-methylamino and M is a cation such as sodium, the bri~ht~ner is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brighte~or species is commercially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.

CA 02206260 1997-0~-28 When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone.
Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and thereforc deposit relatively quick on these fabrics. The e~tent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "e~haustion coefficient". The e~haustion coef~lcient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightPner concentration in the wash liquor. Brighteners with relatively high exhaustion coef~cients are the most suitable for inhibiting dye transfer in the conte~t of the present invention.

Of course, it will be appreciated that other, conventional optical bri htener types of compounds can optionally be used in the present compositions to provide conventional fabric "bri~htne~s" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detelgent formulations.

According to the present invention the detergent composition may comprise any other ingre~lient~ commonly employed in conventional detergent compositions such as soaps, suds ~u~ressors, dye transfer inhibitors, perfumes, softeners, brighteners, enzymes and enzyme stabilisers.

CA 02206260 1997-0~-28 W ~96/17048 PCTrUS95/15547 Use of the combination of soil release agents and polysaccharide ethers The compositions of the present invention may be used in laundry detergent compositions, fabric treatment compositions and fabric softening compositions in addition to hard surface cleaners. The compositions may be form~ te~l as conventional granules, bars, pastes or powder or non aqueous liquid forms or as part of a dryer added sheet. The detergent compositions are m~nllf~ctured in conventional manner, for example in the case of powdered detergent compositions, spray drying or spray mixing processes may be utilised.

The polysaccharide ether and soil release agent combination of the present invention are present at aqueous concentrations of from lppm to 300ppm, ~referably from Sppm to lOOppm in the wash solution, l,rarerably at a pH of from 7 to 11, preferably from 9 to 10.5.

The present invention also relates to a method of laundering fabrics and concurrently providing a soil release finish thereto. The method comprises contacting said fabric with an aqueous laundry liquor cont~inin~: conventional detersive ingre~lient~ described herein in addition to the soil release agent and polysaccharide ether of the present invention. In a ~refe~,ed method polyester and polyester-cotton blends and other synthetic fabrics are used. The most ~refel~ed method for simultaneously cle~nin~ and soil release tre~tn~ent is a "multi-cycle" method, whereby the best results are obtained after two or more cycles comprising the steps of:
a) cont~rtinP: said fabric with said aqueous laundry liquor in a conventional automatic washing machine or by hand washing for periods of from about 5 minutes to about 1 hour;
b) rinsing said fabrics with water c) line- or tumble drying said fabrics; and d) exposing said fabrics to soiling through normal wear or domestic use.

E~amples WO 96/17048 PCI/US9Stl5547 Abbreviations used in Examples In the detergent compositions, the abbreviated component identifications have the following me~nin~.c:

XYAS : Sodium Clx - Cly alkyl sulphate 25EY : A C12 15 predomin~ntly linear primary alcohol condensed with an average of Y moles of ethylene oxide XYEZ . : : A Clx - Cly predomin~ntly linear primary alcohol condensed with an average of Z moles of ethylene o~ide XYEZS : Clx - Cly sodium alkyl sulphate contle~.ee~l with an average of Z moles of ethylene o~ide per mole TFAA : C16-C1g alkyl N-methyl glllc~mi(le.

Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0) NaSKS-6 : Crystalline layered siliç~te of formula ~-Na2Si20s Carbonate : Anhydrous sodium carbonate MA/AA : Copolymer of 30:70 maleic/acrylic acid, average molecular weight about 70,000.

CA 02206260 1997-0~-28 W O 96/17048 PCTrUS95/1~547 Zeolite A : Hydrated Sodium Aluminosilicate of formula Na12(A1~2Si~2)12- 27H20 having a primary particle size in the range from 1 to 10 micrometers Citrate : Tri-sodium citrate dihydrate Percarbonate : Anhydrous sodiumpercarbonate bleach coated with a coating of sodium silicate (Si2O:Na2O
ratio = 2:1) at a weight ratio of percarbonate to sodium silicate of 39:1 CMC : Sodium carbo~cymethyl cellulose DETPMP : Diethylene tri~mine penta (Methylene phosphonic acid), marketed by Monsanto under the Tr~len~me Dequest 2060 PVNO : Poly (4-vinylpyridine)-N-o~ide copolymer of vinylimid~ole and vinylpyrrolidone having an average molecular weight of 10,000.

Smectite Clay : Calcium montmorillonite ex. Colin Stewart Minchem Ltd.

SRA 1~ : Soil release agent comprising a backbone of 4( o~cyalkylene trephth~l~te units) and 1( sulpoisoterephth~l~te unit) end capped with sulphonated glycol based end caps having an ethylene to propylene ratio of 1.7 and an average molecular weight of less than 3000.

CA 02206260 1997-0~-28 SRA 2* : Soil release agent comprising a backbone of 11(o~yalkylene trephth~l~te units) and 2( sulpoisoterephth~ e unit) end capped with sulphobenzoyl units and an average weight of less than 3000.

Granular Suds : 12% Silicone/silica, 18% stearyl alcohol,70%
Suppressor starch in granular form LAS : Sodium linear C12 alkyl benzene sulphonate TAS : Sodium tallow alkyl sulphate SS : Secondary soap surfactant of formula 2--butyl octanoic acid Phosphate : Sodium tripolyphosphate TAED : Tetraacetyl ethylene tli~mine PVP Polyvinyl pyrrolidone polymer HMWPEO : High molecular weight polyethylene o~ide MC1 : Methyl cellulose ether with dp = 650 available from Shin Etsu Chemicals MC2 : Methyl cellulose ether (Methol 60 HG) obtained from Fluka, with a % mole of 28-30 dp HPMC : Hydro~ypropyl methylcellulose ether with dp=

TAE 25 : Tallow alcohol etho~ylate (25) CA 02206260 1997-0~-28 WO 96/17048 PCT/US95tl5547 E~ample 1 The following laundry detergent compositions A, B, C, D and E were prepared. Compositions B and D represent the invention.

A B C D E
45AS/25AS (3:1) 9.1 9.1 9.1 9.1 9.1 35AE3S 2.3 2.3 2.3 2.3 2.3 24E5 4.5 4.5 4.5 4.5 4.5 TFAA 2.0 2.0 2.0 2.0 2.0 Zeolite A 10.2 10.2 10.2 10.2 10.2 SRA 1* 0.2 0.2 - - -SRA2* - - 0.27 0.27 Na SKS-6/citric acid 10.6 10.6 10.6 10.6 10.6 (79:21) Carbonate 7.6 7.6 7.6 7.6 7.6 TAED 5 6.67 6.67 6.67 6.67 Percarbonate ~.s 22.5 ~.5 22.5 22.5 DETPMP 0.5 0.5 0.5 0.5 0.5 Protease 0-55 0-55 0-55 0-55 0 55 Polycarboxylate 3.1 3.1 3.1 3.1 3.1 CMC 0.4 0.4 0.4 0.4 0.4 PVNO 0.03 0.03 0.03 0.03 0.03 Granular suds 1.5 1.5 1.5 1.5 1.5 ~ul)~ressor Minors~misc to 100%

CA 02206260 1997-0~-28 Clay soil removal performance of composition D was compared to the performance of reference compositions (C and E). The soil removal testing was carried out using a standard UK Hotpoint washing machine using city water at 12 ~H hardness (German hardness) at 400C. The polyester and polycotton unstained fabrics were prewashed for two cycles (long cycle setting) using a lkg. balast of housewife soiled cotton load with 100g of one of the product compositions, delivered via the dispensing drawer of the Hotpoint machine . lOg. of clay sampled from the Newcastle area, UK, was added to lOml. of tilled water to form a slurry, which was brushed homogeneously onto the fabric samples. The fabric samples were dried overnight at ambient temperatures and subsequently washed under the same conditions described herein above. The test was repeated four times for each soil test.

The difference in soil removal pelrollllance using the well known Scheffe scale was recorded in panel score units (psu), positive values indicating a better performance than the referellce products. The following grading was used:
psu 0 = e~ual 1 = I think this one is better 2 = I know this one is better 3 = This one is a lot better 4 = This one is a whole lot better The grading was carried out under controlled standard northern european lif~htin~ by four trained graders. The average score is given below.

Composition C E D LSD
PSU
Polyester Ref -1.8s +0.8s 0.7 Polycotton Ref -1.9s ~1.5s 1.

(65/35 polyester/cotton ) The 's' PSU values denotes that the score was significant on a 95~Yo confidence limit. The results clearly show the synergistic effect of the combination of the invention.

W O96tl7048 PCT~US95115547 Example 2 Granular fabric cle~nin.~ compositions in accord with the invention are prepared as follows:
II
SRA1* 0.14 0.14 SRA 2*
MC1 0.75 HPMC - 0.5 LAS 22.0 ~.o Phosphate 23.0 23.0 Carbonate 23.0 23.0 Silicate 14.0 14.0 Zeolite A 8.2 8.2 SodiumSulfate 5.5 5.5 Water/minors Up to 100%

E~ample 3 Granular fabric cle~nin~: compositions in accord with the invention are prepared as follows:
II

LAS 12.0 12.0 Zeolite A 26.0 26.0 SS 4.0 4.0 Citrate 5.0 5.0 Sodium Sulfate 17.0 17.0 Perborate 16.0 16.0 HPMC - 0.5 MC1 0.75 SRA1* 0.14 0.14 Water/minors Up to 100%

CA 02206260 1997-0~-28 WO96/17048 PCTrUS95/15547 Example 4 Granular fabric cleaning compositions in accord with the invention which are especially useful in the l~lln(lering of coloured fabrics are prepared as follows:
LAS 11.4 10.7 11.4 10.7 - -TAS 1.8 2.4 1.8 2.4 TFAA
45AS 3.0 3.1 3.0 3.1 10.0 10.0 45E7 4.0 4.0 4.0 4.0 25E3S - - - - 3.0 3.0 68E11 1.8 1.8 1.8 1.8 25E5 - - - - 8.0 8.0 Citrate 14.0 15.0 14.0 15.0 7.0 7.0 Carbonate - - - - 10 10 Citric acid 3.0 2.5 3.0 2.5 3.0 3.0 Zeolite A 32.5 32.1 32.5 32.1 25.0 25.0 Na-SKS-6 - - - - 9.0 9.0MA/AA 5.0 5.0 5.0 5.0 5.0 5.0 DETPMP 1.0 0.2 1.0 0.2 0.8 0.8 MCl 0.75 0.75 - 0.75 - 0.75 SRA 1* 0.14 0.14 0.14 0.14 0.14 0.14 Silicate 2.0 2.5 2.0 2.5 Sulphate 3.5 5.2 3.5 5.2 3.0 3.0 PVP 0.3 0.5 0.3 0.5 Poly(4-vinyl - - - - 0.2 0.2 pyridine)-N-o~cide/copolymer of vinyl-imi~ ole & vinyl-pyrrolidone Perborate 0.5 1.0 0.5 1.0 Phenol sulfonate 0.1 0.2 0.1 0.2 Water/Minors Up to 100%

-Example 5 Granular fabric cle~nin~ compositions in accord with the invention are prepared as follows:

LAS 6.5 8.0 Sulfate 15.0 18.0 Zeolite A 26.0 22.0 Sodium nitrilotri~cet~te 5.0 5.0 PVP 0.5 0.7 TAED 3.0 3.0 Boric acid 4.0 Perborate 0.5 1.0 Phenol sulphonate 0.1 HPMC 0.5 MC1 - 0.75 SRAlk 0.14 0.14 Silicate 5.0 5.0 Carbonate 15.0 15.0 Water/minors Up to 100%

-W O 96/17048 PCT~US95/15547 Example 6 A granular fabric cleaning compositions in accord with the invention which provide "softening through the wash" capability are prepared as follows:
45AS - - 10.0 10.0 LAS 7.6 7.6 - -68AS 1.3 1.3 45E7 4.0 4.0 25E3 - - 5.0 5.0 Coco-alkyl-dimethyl 1.4 1.4 1.0 1.0 hydroxy-ethyl ammonium chioride Citrate 5.0 5.0 3.0 3.0Na-SKS-6 - - 11.0 11.0 Zeolite A 15.0 15.0 15.0 15.0MA/AA 4.0 4.0 4.0 4.0DETPMP 0.4 0.4 0.4 0.4Perborate 15.0 15.0 Percarbonate - - 15.0 15.0 TAED 5 0 5.0 5 O 5 OSmectite clay 10.0 10.0 10.0 10.0HMWPEO - - 0.1 0.1 HPMC - 0.5 - 0.5 MC1 0.75 - 0.75 - =
SRA 1* 0.14 0.14 0.14 0.14Silicate 3.0 3.0 5.0 5.0Carbonate; 10.0 10.0 10.0 10.0Granular suds suppressor 1.0 1.0 4.0 4.0CMC 0.2 0.2 0.1 0.1Water/minors Up to 100%

Claims

1. A detergent composition comprising the combination of a nonionic polysaccharide ether having a degree of polymerisation of 100 or more with a soil release agent comprising at least one oxyalkylene unit and having a molecular weight of less than 10000.

2. A detergent composition according to claim 1, wherein said nonionic polysaccharide ether is selected from cellulose ethers, starch ethers, dextran ethers and mixtures thereof.

3. A detergent composition according to claim 1, wherein said polysaccharide ether has a degree of polymerisation of from 100 to 10000 and a degree of substitution of from 0.5 to 2.5 inclusive.

4. A detergent composition according to either of claims 2 or 3, wherein said cellulose ether is a C1-C4 alkyl cellulose ether, a C1-C4 hydroxyalkyl cellulose ether, a C1-C4 alkylhydroxy alkyl cellulose ether or mixtures thereof.

5. A detergent composition according to any of the preceding claims, wherein said polysaccharide is a methylcellulose ether.

6. A detergent composition according to any of the preceding claims, wherein said soil release agent further comprises at least one terephthalate or substituted terephthalate unit.

7. A detergent composition according to any of the preceding claims, wherein said soil release agent further comprises a polyester backbone comprising at least one dimethylterephthalate unit and at least one dimethylsulphoisophthalate unit.

8. A detergent composition according to any of the preceding claims, wherein at least 50% of said soil release agent comprises at least one terminal capping unit selected from anionic, nonionic, cationic capping units and mixtures thereof.

9. A detergent composition according to any of the preceding claims, wherein said terminal capping unit is an anionic capping unit.

10. A detergent composition according to claim 9, wherein said capping unit is according to the formula (MO3S)(CH2)m(CH2CH2O)(RO)n, wherein M is a salt forming cation such as sodium or tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or a mixture thereof and n is from 0 to 2.

11. A detergent composition according to claim 9, wherein said end capping unit is derived from sulphobenzoic acid or derivatives thereof.

12. A detergent composition according to claim 8, wherein said end capping unit is a nonionic capping unit comprising from 2 to 20 consecutive polyethylene glycol units.

13. A detergent composition according to claim 8, wherein said cationic end capping unit is a cationic unit is according to the formula R4N+, wherein each R is independently selected from C1-C4 alkyl groups, C1-C4 hydroxyalkyl groups, C2-C4 alkylene groups, C2-C4 oxyalkylene groups, phenyl, phenyl C1-C4 alkyl groups, hydrogen and wherein two R groups can be joined to form cyclic structures.

14. A detergent composition according to any of the preceding claims, wherein said soil release agent has a molecular weight of less than 5000.

15. A detergent composition according to any of the preceding claims, wherein the ratio of said polysaccharide ether to said soil release agent is from 0.1:1 to 20:1.

16. A detergent composition according to any of the preceding claims, comprising from 0.01% to 5% of said polymeric soil release agent and from 0.01% to 10% of said polysaccharide ether.

17. A detergent composition according to any of the preceding claims, further comprising a detergent adjunct selected from surfactants, chelants, builders and mixtures thereof.

18. A method of treating fabrics and providing a soil release finish thereto, comprising contacting said fabrics with an aqueous liquor containing from 1ppm to 300ppm of the combination of said nonionic polysaccharide and said soil release agent according to

claim 1.