WO2000065015A2

WO2000065015A2 - Surface care compositions and methods for treating surfaces

Info

Publication number: WO2000065015A2
Application number: PCT/US2000/011056
Authority: WO
Inventors: Jean-Luc Philippe Bettiol; Ann Katrien Marie Agnes Verschuere; Andre Cesar Baeck; Johan Smets; Alfred Busch; Steven Paul Georges Cooremans
Original assignee: The Procter & Gamble Company
Priority date: 1999-04-27
Filing date: 2000-04-25
Publication date: 2000-11-02
Also published as: WO2000065015A3; AU4660700A

Abstract

The present invention relates to a surface care composition, preferably a fabric care composition to be applied on a new and/or clean surface, preferably fabric surface, fully or in discrete regions thereof, comprising a film-forming polymer and providing superior soil removal performance while maintaining the particulate stain removal performance. The present invention further relates to a process of treating a new and/or clean surface, preferably fabric surface, fully or in discrete regions thereof with such composition, to impart soil release properties thereto.

Description

SURFACE CARE COMPOSITIONS AND METHODS FOR TREATING SURFACES

Field of the Invention

The present invention relates to a process of treating a new and/or cleaned surface, preferably fabπc surface, to impart soil release properties thereto and to the corresponding surface care, preferably fabπc care treatment compositions.

Background of the invention

Treatments of fibers and fabπcs compπsed of fibers pπor to or after cleaning (washing, dry cleaning, etc.) of such fibers and/or fabπcs are known m the textile and fϊber/fabπc-treatmg industries. Examples of such known treatments are sizing treatments, which are typically applied to fibers pπor to being woven mto fabπc, and finishing treatments, which are typically applied to fabπcs (woven fabπcs) or already processed textiles.

Finishing treatments can be permanent, semi-permanent (i.e., more than one, typically more than 2 domestic wash cycles are needed to substantially remove the finishing treatment, m other words reapphcation of the finishing treatment is not necessary after each wash) or non- permanent (temporary) (i.e., one domestic wash cycle substantially removes the finishing treatment, m other words, reapphcation of the finishing treatment is necessary after each wash). Permanent and or semi-permanent finishing treatments typically compπse resms. Examples of permanent finishing treatments are permanent press, flame retardation and/or water resistance. Typical permanent finishing treatments Examples of non-permanent finishing treatments include softening treatments applied to fabπcs and/or starching (stiffening) treatments applied to fabπcs.

Conventional soil/stam release treatments applied to fabπcs have been less than completely effective Regardless of the cleaning process used (conventional home washing in washing machine, dry-cleaning, etc.) to clean a fabπc in need of cleaning, it is not always possible to entirely remove all of the soils and/or stains from the fabπc being cleaned. This problem is even more present with today's trend to move to lower wash temperature, lower water consumption and shorter wash cycles, mamly for economic and environmental reasons.

As a result, a frequently observed problem of today's cleaning processes is the incomplete soil and/or stam removal. Some visible examples of such incomplete soil and/or stam removal include, but are not limited to, soil lines, m particular, of body soil and airborne dust left on collars and cuffs of shirts, blouses, T-shirts, soil (e.g., clay) patches on socks (e.g., sports socks), tough food stains (e.g., bacon grease, tomato sauce, meat sauce, etc.), particulate (clay) stains, grass stains, ground soil, and body soil on underwear mateπal. Once the stams and/or soils have not been completely removed from the fabπc after the cleaning process (i.e., they have been set on the surface of the fabπc or have penetrated the porous regions of the fabπc), they are more difficult to remove due to the ageing effect. Therefore, fabπcs tend to grey and/or yellow due to the soil deposited and remaining on the fabπc. Repetitive use and cleaning of the garment under these conventional cleaning processes increases the intensity of the greying / yellowing to the point ultimately that the garment is unacceptable to the consumer for further use due to its discoloration and/or fading.

Current attempts to solve this problem are frequent re-washmg; additional pre-, post-treatment with extra mechanical action or detergent quantity, the use of solvent and/or dry cleaning However, these soluttons result in increased fabπc deteπoration and/or are more time-consuming and/or less environmentally friendly.

Detergent composition formulators have unsuccessfully attempted to address this problem by formulating detergent compositions with soil release polymers. Such soil release polymers do not wholly prevent the attachment of soil to the fabπc but hinder such attachment and renders the cleaning operation more successful. As a result of this hindrance rather than prevention, it is a logical step to increase the level of the soil release polymers in the detergent compositions However, by increasing the level of soil release polymers in the detergent compositions, the fabπc has a tendency to become stiffer, less desirable m appearance and handfeel characteπstics Thus the upper limit on the amount of soil release polymer is determined by economics and the resulting adverse effect on fabrics, 1 e., the appearance and handfeel of the fabric Fabπcs with a relatively heavy application of soil release polymer do not have the same desirable appearance and handfeel as fabπcs without soil release polymers Moreover, it is recognized in the art that the efficiency of soil release polymers differs with fabπc type.

Conventionally, fabπc care/softness formulators have been more concerned about the "feel", softness and physical properties of the fabπcs rather than soil release properties of the fabπcs. For example, such formulators have looked at fabπc care compositions compnsmg starch, polyvmyl alcohol and/or cellulose deπvatives in combination with other ingredients to impart a smooth surface (i.e , reduced friction) to fabπcs duπng ironing, a moderate feeling and/or skin touch to fabπcs, a reduction or depression of wrinkles after washing or drying fabπcs, improved tightening of fabπcs, body and/or stiffness to the fabπcs, and anti-redeposition properties to fabπcs.

Moreover, it has been surpπsmgly found that most of the pπor art carbohydrate finishes commonly used in the textile industry or detergent industry m a laundry process or finishing treatment, impart a particulate stain removal negative leading to an actual fixation of stains rather than improved removal. Indeed, without wishing to be bound by theory, it is believed that such conventional carbohydrate finishes have a high affinity for fabπc, especially cotton but as well for clay. Such high affinity results in particulate stam removal negative performance.

However, the pπor art fails to teach or suggest a sihcone- and starch-free fabπc care composition and treating process whereby a layer of film-forming polymer with a low affinity for the fabπc or other surface is deposited on the fabπc surface or other surface (e.g., clothing, fabπc curtains, fabπc wall papers, fabπc tablecloths, fabπc napkins, fabπc-covered furniture, carpet, upholstery, bed linens, etc ) fully or in discrete regions thereof, pπor to and/or after the fabπc is cleaned by a conventional cleaning process, and subsequently easily removed by any conventional cleaning process, such as washing and/or dry cleaning.

Accordingly, there is a need for a sihcone- and starch-free fabπc care composition and treating process employing the fabric care composition whereby a layer of film-forming polymer with a low affinity for the fabric is deposited on the fabπc surface fully or in discrete regions thereof, pπor to and/or after the fabπc is cleaned by a conventional cleaning process, and subsequently easily removed by any conventional cleaning process, such as washing and/or dry cleaning so that the fabπc is protected from stams which would otherwise come into contact with the fabπc surface but for the layer of film-forming polymer; a fabπc cleaning process that provides superior stam removal performance compared to conventional cleaning processes; a fabπc treating process whereby the fabπc is imparted soil release properties supeπor to conventional fabric treating processes; a fabπc care composition that provides supeπor stam removal perfomance compared to conventional stam removal compositions.

Summary of the invention

The present invention meets and satisfies the needs identified above. The present invention relates to surface care compositions, preferably fabπc care compositions, more preferably sihcone- and starch-free fabπc care compositions to be applied on a new and/or clean surfaces, preferably fabπc surfaces, fully or in discrete regions thereof, compnsmg a film-forming polymer which provides supeπor soil removal performance without detracting from the particulate stain removal performance, as determined by the Test Protocol descπbed hereinafter, treating processes employing such surface care compositions, preferably fabπc care compositions to impart soil release properties to new and/or clean surfaces, preferably fabnc surfaces.

It has now been discovered that an excellent soil removal performance can be achieved in a fabπc treatment process whereby a new and/or clean fabπc is treated fully or in discrete regions thereof, by a sihcone- and starch-free fabnc care composition compnsmg a polymer forming a film on the surface of the fabπc and having a low affinity for the fabnc surface. The film produced by the film-forming polymer of the present invention, is more easily removed in a subsequent conventional cleaning process. The fabπc treating process of the present invention provides supenor stam removal while not impacting the particulate stain removal performance of the fabπc care composition.

Although the surface care compositions of the present invention are directed mamly to treating fabπc surfaces, namely garments and clothing, other fabπc surfaces such as carpets, upholstery, fabπc curtains, fabπc wall papers, fabπc tablecloths, fabric napkins, fabπc-covered furniture, bed linens, and non-fabπc surfaces such as hardwood floors, tile floors, linoleum floors, jewelry, wallpaper coverings can also be treated with the surface care compositions of the present invention under the methods of the present invention.

In one aspect of the present invention, a surface care composition, preferably a fabπc care composition, more preferably a sihcone- and starch-free fabπc care composition compnsmg a film-forming polymer is provided.

In yet another aspect of the present invention, a fabπc care composition, preferably a sihcone- and starch-free fabπc care composition compnsmg a film-forming polymer and a quaternary ammonium compound, preferably a biodegrabable quaternary ammonium compound is provided.

In still yet another aspect of the present invention, a method for treating a surface in need of treatment, preferably a fabnc in need of treatment compnsmg contacting the surface, preferably the fabπc surface with the surface care composition, preferably the fabnc care composition, more preferably the sihcone- and starch-free fabnc care composition compnsmg a film-forming polymer of the present invention is provided.

In even still yet another aspect of the present invention, a method for treating a fabnc m need of treatment compnsmg contacting the fabπc with the fabπc care composition, preferably the sihcone- and starch-free fabnc care composition compnsmg a film-forming polymer and a quaternary ammonium compound, preferably a biodegradable quaternary ammonium compound of the present invention is provided.

In still yet another aspect of the present invention, a method for protecting a surface against soiling, said method compnsmg the step of contacting said surface with a surface care composition compnsmg a film-forming polymer that forms a temporary film on said surface such that stams that come into contact with said temporary film can be removed from said surface upon washing.

In even still yet another aspect of the present invention, a method for protecting a fabπc surface against soiling, said method compnsmg the step of contacting said fabπc surface with a fabπc care composition compnsmg a film-forming polymer that forms a temporary film on said fabπc surface such that stams that come into contact with said temporary film can be removed from said fabπc surface upon washing.

In even still yet another aspect of the present invention, an article compnsmg the surface care composition, preferably the fabric care composition, more preferably the sihcone- and starch-free fabπc care composition of the present invention and instructions for using the surface care composition, preferably the fabnc care composition, more preferably the silicon- and starch-free fabnc care composition of the present invention to protect surfaces, preferably fabπc surfaces from stams is provided.

Accordingly, the present invention provides a surface care composition, preferably a fabπc care composition, more preferably a sihcone- and starch-free fabnc care composition and surface treating process, more preferably fabnc surface treating process employing such composition that imparts to new and/or clean surfaces, preferably fabπc surfaces supeπor soil/stam removal properties.

These and other aspects, objects, features and advantages will be clear from the following detailed descπption, examples and appended claims.

All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference.

Detailed description of the invention

The fabnc post-treatment compositions of the present invention compnses as an essential element a film-forming polymer and provide supeπor soil removal performance without detracting from the particulate stam removal performance.

Fabric Care Compositions

The fabnc care compositions of the present invention compnse a film-forming polymer. Preferably, the fabπc care compositions further compπse a quaternary ammonium compound. It is desirable that the fabπc care compositions of the present invention are free one or more of the following

1) resms; n) sihcone; in) compounds having a molecular weight of from 4,500 to 12,000 and selected from the group consisting of the ethylene oxide adducts of Cj2 - Ci g fatty alcohols, Cj2 - Ci g saturated fatty alcohols, and Ci 4 - Cι g alkyl phenols;

IV) quaternary ammonium compounds of the formula:

wherein one or two of R - R^ are Cg - C25 alkyl groups or alkenyl groups and the others are Ci - C3 alkyl groups or hydroxyalkyl groups; and X^" is an anion group; v) nomonic surfactants having an HLB of 2-16; vi) ionic surfactants having a cπtical micelle concentration of less than 1.0 mmol, vn) water-soluble inorganic salts; vui) quaternary ammonium compounds of the formula:

R

Θ 4

R— N I— R⁴ #

wherein R^ and R^ are C12 - C22 alkyl groups or alkenyl groups, R⁸CONHC_mH2_m, R⁹NHCOC_mH_2m, or R⁹OC_mH_2m wherein R⁸ is C_j 1 - C21 alkyl or alkenyl groups, R⁹ is Ci 2 - C22 alkyl or alkenyl groups and m is 1-5; R^ and R^ are H, Ci - C4 alkyl groups or (CHY- CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X^" is H, CH3SO4, C₂H₅S0₄, ^lA SO4, HC0₂, CH₃C0₂ or HOCH₂COO and p is 1-5; ix) compounds of the formula:

wherein R^ and R > are Ci 1 - C21 alkyl groups or alkenyl groups, R⁸COOC_mH_2m, R⁹OCOC_mH_2m, R⁸CONHC_mH_2m, R⁹NHCOC_mH_2m or R⁹OC_mH2_m wherein R⁸ is Ci \ - C₂\ alkyl or alkenyl groups, R⁹ is Cj2 - C22 alkyl or alkenyl groups and m is 1-5; R³ is H, Ci - C alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X" is H, CH3SO4, C₂H₅SO₄, Vz SO₄, HCO₂, CH3CO2 or HOCH₂COO and p is 1-5; Q is O or NH; and n is 1-3; x) compounds of the formula:

wherein R³, R⁴and R⁷ are H, Ci - C alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X- is H, CH3SO4, C₂H₅SO₄, 5 SO₄, HC0₂, CH₃CO₂ or HOCH₂COO and p is 1-5; R⁵ and R⁶ are C\ \ - C21 alkyl groups or alkenyl groups, R⁸COOC_mH_2m, R⁹OCOC_mH_2m, R⁸CONHC_mH_2m, R⁹NHCOC_mH_2m or R⁹OC_mH2_m wherein R⁸ is Ci \ - C₂ι alkyl or alkenyl groups, R⁹ is Cj2 - 22 alkyl or alkenyl groups and m is 1-5; R³ is H, Ci - C₄ alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X" is H, CH3SO4, C₂H₅S0₄, 14 SO4, HC0₂, CH3CO2 or HOCH₂COO and p is 1-5, xi) compounds of the formula:

wherein R* and R^ are C12 - C22 alkyl groups or alkenyl groups, R⁸CONHC_mH_2m, R⁹NHCOC_mH _m, or R⁹OC_mH_2m wherein R° is C\ 1 - C21 alkyl or alkenyl groups, R⁹ is C12 - C22 alkyl or alkenyl groups and m is 1-5; ? and R⁴ are H, C\ - C4 alkyl groups or (CHY- CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X" is H, CH3SO4, C2H5SO4, V₂ SO4, HCO₂, CH₃C0₂ or HOCH₂COO and p ιs l-5; xn) compounds of the formula:

wherein R^ and R > are Ci 1 - C21 alkyl groups or alkenyl groups, R⁸COOC_mH2_m, R⁹OCOC_mH_2m, R⁸CONHC_mH_2m, R⁹NHCOC_mH2_m or R⁹OC_mH2_m wherein R⁸ is C! 1 - C₂\ alkyl or alkenyl groups, R⁹ is Cj2 - C22 lkyl °^r alkenyl groups and m is 1-5; R-¹ is H, C! - C₄ alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X" is H, CH3SO4, C2H5SO4, ^l/ι SO₄, HC0₂, CH3CO2 or HOCH₂COO and p is 1-5; Q is O or NH, and n is 1-3, xiπ) water repellents; xiv) at least one of: a) lipophihc surfactants having a HLB of 6 or less; and b) propellants; xv) at least one of: a) polymers or their salts prepared by polymeπzation of a monomer having at least a vmyl group and/or an aromatic πng, a sulfonic group and an average molecular weight of 10,000 to 500,000; and b) carboxyhc acid-contammg polymers or salts thereof having recurnng units of the formula [I] :

X Z

[I]

wherein X, Y and Z are each H, CH3, COOH or CH2COOH; and n is 10 to 2000; or of the formula [II]:

H

I 1 (— C-O— )m

COOH

[1TJ

wherein m is 10-200; xv) swelling clay matenals; xvi) alkalis; xvπ) gelatinous materials; xvπi) at least one of: a) benzoic acid; b) fluroescent brightening agents; and c) perfumes; xix) starch and starch derivatives.

A more preferred fabric care composition in accordance with the present invention is a si cone- and starch-free fabric care composition compnsmg: a) from about 0.02% to about 5% of a film-forming polymer; b) from about 0.01% to about 5% of a quaternary ammonium compound; c) optionally, from about 0.01% to 80% adjunct matenals; and d) balance solvent wherein said solvent is selected from the group consisting of water, alcohol, polyethylene glycol and mixtures thereof; wherein said weight ratio of said film-forming polymer to quaternary ammonium compound is from about 50: 1 to about 1:5.

The film-forming polymer of the present invention are preferably present m the fabnc care compositions of the present invention at a level of from about 0.001% to about 20%, more preferably 0.02% to about 5%, most preferably from about 0.05% to about 2% by weight of the fabric care composition.

Quaternary ammonium compounds, preferably biodegradable quaternary ammonium compounds, when present in the fabnc care compositions of the present invention, are preferably present at a level of from about 0.01% to about 5%, more preferably from about 0.01% to about 2% by weight of the fabnc care composition.

Noniomc surfactants, preferably nomonic surfactants having an HLB value of from 8-14, when present in the fabnc care compositions of the present invention are preferably present at a level of from about 0.01% to about 5%, more preferably from about 0.5% to about 2% by weight of the fabπc care composition.

Perfumes, when present in the fabπc care compositions of the present invention are preferably present at a level of from about 0.001% to about 1%, more preferably from about 0.1% to about 0.5% by weight of the fabπc care composition. When the fabπc care composition of the present invention includes both a film-forming polymer and a quaternary ammonium compound, the film-forming polymer and quaternary ammonium compound are preferably present in a weight ratio of from about 50: 1 to about 1:5, more preferably from about 10: 1 to about 1: 1

In addition to the film-forming polymer, the fabπc care composition of the present invention preferably includes one or more adjunct matenals as fully descπbed hereinafter, preferably one or more of the following quaternary ammonium compounds (preferably biodegradable quaternary ammonium compounds), noniomc surfactants having an HLB value of from 8-14, and perfumes. The precise nature of these adjunct mateπals, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.

The preferred viscosity of the film-forming polymers in a 2% by weight aqueous solution is at least 5 Cp, more preferably at least 10 Cp.

The preferred level of fabπc care composition applied to the surface of a fabπc in need of treatment in accordance with the methods of the present invention is preferably from about 0.05 g/m^ to about 10 g/m^, more preferably from about 0.1 g/m^ to about 5 g/w .

After the cleaning process the composition of the present invention is applied, preferably by spraying, on clean fabπcs, m particular onto the problem areas where stains and soils may appear (collars, cuffs, sock heals, etc).

Form of Fabric Care Composition

The fabπc care compositions of the present invention can be m solid (powder, granules, bars, tablets), dimple tablets, liquid, paste, gel, spray, stick, or foam forms. Liquid, gel, spray, stick, foam, paste forms are preferred. Liquid and spray forms are highly preferred.

The liquid forms, can also be m a "concentrated" form which are diluted to form compositions with the usage concentrations, as given herembelow, for use in the "usage conditions" Concentrated compositions compπse a higher level of film-forming polymer, typically from about 1% to about 99%, preferably from about 2% to about 65%, more preferably from about 3% to about 25%, by weight of the concentrated fabπc care composition. Concentrated compositions are used in order to provide a less expensive product When a concentrated product is used, i.e., when the film-forming polymer is from about 1% to about 99%, by weight of the concentrated composition, it is preferable to dilute the composition, preferably with water, before treating a fabric m need of treatment. Preferably, the water content of the "concentrated" form is less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.

The present invention also relates to film-formmg polymer-containmg fabnc care compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabnc articles and/or surfaces with said compositions containing the film-formmg polymer and other optional ingredients at a level that is effective, yet is not discernible when dned on the surfaces. The spray dispenser compnses manually activated and non-manual powered (operated) spray means and a container containing the fabπc care composition. The articles of manufacture preferably are in association with instructions for use to ensure that the consumer applies sufficient film-formmg polymer to provide the desired benefit.

Preferably the articles of manufacture are in association with instructions for how to use the composition to treat fabncs correctly, to obtain the desirable fabπc care results, for example, improved color appearance and/or pill prevention and/or abrasion resistance, while at the same time providing improved cleaning benefits, including, e.g., the manner and/or amount of composition to be used, and the preferred ways of stretching and/or smoothing, if any, the fabncs. It is important that the instructions be as simple and clear as possible. Accordingly, the use of pictures and/or icons to assist in explaining the instructions is desirable.

Liquid or solid, preferably powder, film-formmg polymer-containmg fabπc care composition for treating fabnc in accordance with the present invention compnse an effective amount of the film- formmg polymer of the present invention, and optionally, fabπc softener actives, perfume, electrolytes, chlonne scavenging agents, dye transfer inhibiting agents, dye fixative agents, phase stabilizers, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, chelatmg agents, aminocarboxylate chelatmg agents, colorants, enzymes, bnghteners, soil release agents, anti-encrustation agents, builders and/or mixtures thereof. Again, the composition is preferably packaged in association with instructions for use to ensure that the consumer knows what benefits can be achieved Yet another liquid or solid, preferably powder or granular, fabric care composition m accordance with the present invention comprises an effective amount of one or more Film-formmg polymers, and optionally, surfactants, builders, perfume, chlonne scavenging agents, dye transfer inhibiting agents, dye fixative agents, dispersants, detergent enzymes, heavy metal chelatmg agents, suds suppressors, fabπc softener actives, chemical stabilizers including antioxidants, sihcones, antimicrobial actives and/or preservatives, soil suspending agents, soil release agents, optical bnghteners, colorants, and the like, or mixtures thereof. Again, the composition is preferably packaged in association with instructions for use to ensure that the consumer knows what benefits can be achieved.

A preferred fabnc care composition for treating fabnc compnses an effective amount of one or more film-forming polymers, and optionally, perfume, fabnc lubπcants, adjunct fabπc shape retention polymers, lithium salts, hydrophilic plasticizers, odor control agents, antimicrobial actives and/or preservatives, surfactants, enzymes, or mixtures thereof. Other optional ingredients can also be added, e.g., antioxidants, chelatmg agents, e.g., aminocarboxylate chelatmg agents, heavy metal chelatmg agents, antistatic agents, insect and moth repelling agents, dye transfer inhibiting agents, dye fixative agents, colorants, suds suppressors, and the like, and mixtures thereof. The composition is typically applied to fabnc via a, e.g., dipping, soaking and/or spraying process followed by a drying step, including the process compnsmg a step of treating or spraying the fabπc with the fabnc care composition either outside or inside an automatic clothes dryer followed by, or concurrently with, the drying step in said clothes dryer. However, the composition may be applied by spraying the fabπc with the fabnc care composition pπor to and/or dunng ironing, if needed. The application can be done industnally by large scale processes on textiles and/or finished garments and clothings, or in consumer's home by the use of commercial product.

The fabnc care compositions herein can be made by any suitable process known in the art. Examples of such processes are descπbed in U.S. Pat. No. 5,576,282.

The fabnc care compositions of the present invention can be incorporated into a spray dispenser, or concentrated stick form that can create an article of manufacture that can facilitate the cleaning and/or fabπc care or conditioning of fabπc. If the spray treatment is a "pre-treat", which is followed by a wash cycle, then the spray treatment fabπc care compositions preferably compnse from about 0.01% to about 50% of film-formmg polymer by weight the of total fabnc care composition, more preferably from about 0 1% to about 3% of film-formmg polymer by weight of the total fabric care composition. If the spray treatment compositions are desired to do the cleaning, as in the case of wash, then the spray treatment compositions preferably compπse from about 2 ppm to about 10000 ppm of the film-formmg polymer by weight of the total fabπc care composition, more preferably from about 200 ppm to about 5000 ppm of the film-formmg polymer by weight of the total fabπc care composition. In the latter case, a bπef nnse, not a full wash cycle, is desirable after treatment. Such spray treatment compositions are typically packaged m a spray dispenser.

The spray-treatment compositions herein are typically packaged m spray dispensers. The spray dispensers can be any of the manually activated means for producing a spray of liquid droplets as is known m the art, e.g. tπgger-type, pump-type, non-aerosol self-pressuπzed, and aerosol-type spray means. It is preferred that at least about 70%, more preferably, at least about 80%, most preferably at least about 90% of the droplets have a particle size of smaller than about 200 microns.

The spray dispenser can be an aerosol dispenser. Said aerosol dispenser compnses a container which can be constructed of any of the conventional matenals employed in fabπcatmg aerosol containers. The dispenser must be capable of withstanding internal pressure in the range of from about 20 to about 110 p.s.i.g., more preferably from about 20 to about 70 p.s.i.g. The one important requirement concerning the dispenser is that it be provided with a valve member which will permit the wnnkle reducing composition contained in the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets. The aerosol dispenser utilizes a pressunzed sealed container from which the wnnkle reducing composition is dispensed through a special actuator/valve assembly under pressure. The aerosol dispenser is pressunzed by incorporating therein a gaseous component generally known as a propellant. Common aerosol propellants, e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated hydrocarbons, are not preferred. Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to contnbute to environmental problems Preferred propellants are compressed air, nitrogen, inert gases, carbon dioxide, etc. A more complete descnption of commercially available aerosol spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbms, issued Apr.8, 1969; and 3,600,325, Kaufman et al., issued Aug. 17, 1971; both of said references are incoφorated herein by reference Preferably the spray dispenser can be a self-pressuπzed non-aerosol container having a convoluted lmer and an elastomeπc sleeve. Said self-pressuπzed dispenser compnses a liner/sleeve assembly containing a thm, flexible radially expandable convoluted plastic liner of from about 0.010 to about 0.020 inch thick, mside an essentially cyhndncal elastomeπc sleeve The lmer/sleeve is capable of holding a substantial quantity of odor-absorbmg fluid product and of causing said product to be dispensed. A more complete descnption of self-pressuπzed spray dispensers can be found in U.S. Pat. Nos.: 5,111,971, Winer, issued May 12, 1992; and 5,232,126, Winer, issued Aug. 3, 1993; both of said references are herein incorporated by reference. Another type of aerosol spray dispenser is one wherein a barπer separates the wnnkle reducing composition from the propellant (preferably compressed air or nitrogen), as is disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981, incorporated herein by reference. Such a dispenser is available from EP Spray Systems, East Hanover, N.J.

More preferably, the spray dispenser is a non-aerosol, manually activated, pump-spray dispenser. Said pump-spray dispenser compnses a container and a pump mechanism which securely screws or snaps onto the container. The container compnses a vessel for containing the wnnkle reducing composition to be dispensed.

The pump mechanism compnses a pump chamber of substantially fixed, volume, having an opening at the inner end thereof. Within the pump chamber is located a pump stem having a piston on the end thereof disposed for reciprocal motion m the pump chamber. The pump stem has a passageway there through with a dispensing outlet at the outer end of the passageway and an axial mlet port located inwardly thereof.

The container and the pump mechanism can be constructed of any conventional matenal employed in fabricating pump-spray dispensers, including, but not limited to: polyethylene; polypropylene, polyethlyleneterephthalate; blends of polyethylene, vmyl acetate, and rubber elastomer. Other matenals can include stainless steel. A more complete disclosure of commercially available dispensing devices appears m: U.S. Pat. Nos.. 4,895,279, Schultz, issued Jan. 23, 1990; 4,735,347, Schultz et al, issued Apr. 5, 1988; and 4,274,560, Carter, issued Jun 23, 1981; all of said references are herein incorporated by reference. Most preferably, the spray dispenser is a manually activated trigger-spray dispenser Said tπgger- spray dispenser comprises a container and a tngger both of which can be constructed of any of the conventional material employed m fabπcatmg tπgger-spray dispensers, including, but not limited to : polyethylene, polypropylene, polyacetal, polycarbonste, polyethylene-terephthalate , polyvmyl chloride, polystyrene, blends of polyethylene, vmyl acetate, and rubber elastomer Other matenals can include stainless steel and glass. The trigger-spray dispenser does not incorporate a propellant gas. The tπgger-spray dispenser herein is typically one which acts upon a discrete amount of the wnnkle reducing composition itself, typically by means of a piston or a collapsing bellows that displaces the composition through a nozzle to create a spray of thin liquid. Said tngger-spray dispenser typically compnses a pump chamber having either a piston or bellows which is movable through a limited stroke response to the tngger for varying the volume of said pump chamber. This pump chamber or bellows chamber collects and holds the product for dispensing. The tngger spray dispenser typically has an outlet check valve for blocking communication and flow of fluid through the nozzle and is responsive to the pressure mside the chamber. For the piston type tngger sprayers, as the tngger is compressed, it acts on the fluid in the chamber and the spnng, increasing the pressure on the fluid. For the bellows spray dispenser, as the bellows is compressed, the pressure increases on the fluid. The increase m fluid pressure m either tngger-spray dispenser acts to open the top outlet check valve. The top valve allows the product to be forced through the swirl chamber and out the nozzle to form a discharge pattern. An adjustable nozzle cap can be used to vary the pattern of the fluid dispensed.

For the piston spray dispenser, as the tngger is released, the spnng acts on the piston to return to its oπginal position. For the bellows spray dispenser, the bellows acts as the spnng to return to its onginal position. This action causes a vacuum m the chamber. The responding fluid acts to close the outlet valve while opening the inlet valve drawing product up the chamber from the reservoir.

A more complete disclosure of commercially available dispensing devices appears in U.S. Pat. Nos.: 4,082,223, Nozawa, issued Apr. 4, 1978, 4,161,288, McKinney, issued Jul. 7, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19, 1994, all of said references are incorporated herein by reference. A broad array of trigger sprayers or finger pump sprayers are suitable for use with the compositions of this invention These are readily available from suppliers such as Calmar, Inc., City of Industry, California, CSI (Continental Sprayers, Inc.), St. Peters, Missouπ; Berry Plastics Corp , Evansville, Indiana - a distributor of Guala ® sprayers; or Seaquest Dispensing, Cary, 111.

For smaller four fl-oz size (about 118 ml), a finger pump can be used with canister or cyhndncal bottle. The preferred pump for this application is the cyhndncal Euromist π® from Seaquest Dispensing.

It has been found that film-formmg polymers impart to the fabπc improved color appearance and or pill prevention and/or abrasion resistance. These benefits provided by the film-forming polymer improve the appearance of the fabπc.

Film-Forming Polymers

Film-formmg polymers suitable for the fabπc care compositions and treating processes of the present invention preferably have the following charactenstics of film forming and of providing supenor soil removal without detracting from the particulate stain removal performance of a subsequent cleaning process.

Nonhmiting examples of film-formmg polymers include agar, algm, amylopectm, carboxymethylcellulose (CMC), dextrans, dextπns, ethylhydroxyethylcellulose (EHEC), guar, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxybutylcellulose (HBC), karaya, larch, methylcellulose (MC), tamannd, scleroglucan, xanthan, carboxymethylhydroxyethylcellulose (CMHEC), methoxypropyl methyl cellulose (MPMC), hexylcarboxymethyl cellulose, C\₂ - C₂Q alkyl carboxymethylcellulose, methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC), hydroxyethylmethylcellulose (HEMC), hydroxypropylmethylcellulose (HPMC), hydroxybutylmethylcellulose (HBMC) and mixtures thereof.

A preferred film-formmg polymer is a water-soluble cellulose deπvative.

A more preferred film-formmg polymer is selected from the group consisting of substituted β- 1 ,4-glucans and denvatives thereof as represented by formula [I] ^■ WO 00/65015 PCT/USOO/l 1056

19

wherein R is selected from H, C_vH2_v+ι with v being 1-18, C_wH2_wOH with w being 1-18, CH₂OC(O)CH₃, (CH )_xCOOCH₃ with x being 1-10, CH₂COOM with M being Na or K, and wherein the degree of polymerisation as represented by n is from 50 to 10,000. In the glucose unit, positions 2, 3, and/or 6 can be substituted independently by R, and in the end glucose units, positions 1 and/or 4 can also be substituted. The degree of substitution is preferably no more than 3, more preferably from about 0.5 to about 3.

Even more preferred film-forming polymers are the substituted β-l,4-glucans selected from the group consisting of carboxymethylcellulose, ethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxybutylcellulose, methylcellulose, methoxypropyl methyl cellulose, carboxymethylhydroxyethylcellulose, hexylcarboxymethyl cellulose, C\ - C20 alkyl carboxymethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose and mixtures thereof.

Highly preferred film-forming polymers are selected from the group consisting of: hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hexylcarboxymethyl cellulose, C\ - C₂Q alkyl carboxymethylcellulose and mixtures thereof.

Examples of such film-forming polymers are commercially available from the following companies: Aqualon, Dow Chemical, ShimEtsu, MetsaSeila, Akzo Nobel, Zoltak, Nippon Soda, Sigma. In particular, Hydroxypropyl-cellulose (HPC): Klucel from Aqualon; Hydroxypropylmethylcellulose (HPMC): e.g. Metolose SH from ShinEtsu Chemical co, Ltd; Carboxymethylcellulose (CMC): Blanose from Aqualon; Methylcellulose (MC): e.g. Metolose SM from ShmEtsu Chemical Co., Ltd, Benecel from Aqualon; Methylhydroxyethylcellulose (HEMC): e.g. Metolose SE from Shin Etsu Chemical Co., Ltd; Hydroxyethylcellulose (HEC): Natrosol from Aqualon; Carbomethylhydroxyethylcellulose; Ethylhydroxyethylcellulose: Aqualon from Aqualon.

Without wishing to be bound by theory, it is believed that the selected polymer of the present invention demonstrate relatively low affinity to the fiber surface in a cleaning situation and low soil permeability properties. Moreover, it is believed that compounds with no or little film forming properties and high surface affinity show poor stam release and a negative for particulate stam removal.

The selected film-forming polymer of the present invention, upon naturally drying, tumble drying and/or ironing forms a protective film on the fiber surface that provides a barner against stam and soil penetration into the fiber, incrustation, improves feel, helps ironing, and protects against wear and colour damage. Dunng the subsequent cleaning process, e.g. wash cycle and/or dry cleaning, the polymeπc film dissolves and loosens the soil/stain from the fabnc fiber. Such polymeπc film dissolution greatly facilitates the cleaning and provide supenor cleaning.

Quaternary Ammonium Compounds

Suitable quaternary ammonium compounds for use in the present invention include, but are not limited to, catiomc surfactants, catiomc softeners, biodegradable quaternary ammonium compounds and mixtures thereof. The preferred quaternary ammonium compounds for use m the fabπc care compositions and methods of the present invention are biodegradable quaternary ammonium compounds.

Catiomc Surfactants - Catiomc detersive surfactants suitable for use in the compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such catiomc surfactants include the ammonium surfactants such as alkyltπmethylammonium halogemdes, and those surfactants having the formula :

[R²(OR³)_y][R⁴(OR3)_y]₂R5N+X-

wherein R² IS an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, - CH2CH(CH2θH)-, -CH2CH2CH2-, and mixtures thereof, each R⁴ is selected from the group consisting of C1 -C4 alkyl, C1-C4 hydroxyalkyl, benzyl πng structures formed by joining the two R⁴ groups, -CH₂CHOH-CHOHCOR⁶CHOHCH OH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R^ is the same as R or is an alkyl chain wherein the total number of carbon atoms of R² plus R^ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Quaternary ammonium surfactant suitable for the present invention has the formula (I):

Formula I

whereby RI is a short chain length alkyl (C6-C10) or alkylamidoalkyl of the formula (H)

Formula II

y is 2-4, preferably 3, whereby R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and R5 are either the same or different and can be either a short chain alkyl (Cl-

C3) or alkoxylated alkyl of the formula EQ,

whereby X" is a countenon, preferably a hahde, e.g. chloπde or methylsulfate.

Formula HI

Preferred quat ammonium surfactants are those as defined in formula I whereby Rj is Cg, C10 or mixtures thereof, x=o, R3, R4 = CH3 and R5 = CH2CH2OH.

More preferred catiomc surfactants are the water-soluble quaternary ammonium compounds useful m the present composition having the formula :

RiR₂R3R4N⁺X- (1)

wherein Rj is Cg-Ci g alkyl, each of R2, R3 and R4 is independently -C4 alkyl, C1 -C4 hydroxy alkyl, benzyl, and -(C2H4Q)_XH where x has a value from 2 to 5, and X is an amon. Not more than one of R2, R3 or R4 should be benzyl.

The preferred alkyl chain length for Ri is C12-C15 particularly where the alkyl group is a mixture of chain lengths deπved from coconut or palm kernel fat or is deπved synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the amon X may be selected from ha de, methosulphate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (1) for use herein are :

coconut tπmethyl ammonium chlonde or bromide; coconut methyl dihydroxyethyl ammonium chlonde or bromide; decyl tnethyl ammonium chlonde; decyl dimethyl hydroxyethyl ammonium chlonde or bromide;

C 12-15 dimethyl hydroxyethyl ammonium chlonde or bromide; coconut dimethyl hydroxyethyl ammonium chlonde or bromide; mynstyl tπmethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chlonde or bromide, lauryl dimethyl (ethenoxy)4 ammonium chlonde or bromide; cholme esters (compounds of formula (1) wherein R is CH2-CH2-O-C-C12-I4 alkyl and R2R3R4 are methyl)

O di-alkyl lmidazolmes [compounds of formula (1)]

Other catiomc surfactants useful herein are also descnbed m U.S. Patent 4,228,044, Cambre, issued October 14, 1980 and in European Patent Application EP 000,224.

Catiomc Softeners - Typical catiomc fabπc softening components include the water-msoluble quaternary-ammonium fabπc softening actives or their corresponding amme precursor, the most commonly used having been di-long alkyl chain ammonium chlonde or methyl sulfate.

Preferred catiomc softeners among these include the following:

1) ditallow dimethylammonium chlonde (DTDMAC);

2) dihydrogenated tallow dimethylammonium chlonde;

3) dihydrogenated tallow dimethylammonium methylsulfate;

4) distearyl dimethylammonium chlonde;

5) dioleyl dimethylammonium chlonde;

6) dipalmityl hydroxyethyl methylammonium chlonde;

7) stearyl benzyl dimethylammonium chlonde;

8) tallow tπmethylammonium chlonde;

9) hydrogenated tallow tπmethylammonium chlonde;

10) Ci 2"i4 alkyl hydroxyethyl dimethylammonium chlonde;

11) C12-I8 alkyl dihydroxyethyl methylammonium chlonde;

12) dι(stearoyloxyethyl) dimethylammonium chlonde (DSOEDMAC);

13) dι(tallowyl-oxy-ethyl) dimethylammonium chlonde;

14) ditallow lmidazohnium methylsulfate;

15) 1 -(2-tallowylamιdoethyl)-2-tallowyl lmidazohnium methylsulfate.

Biodegradable Quaternary Ammonium Compounds - Highly preferred quaternary ammonium compounds for use m the fabnc care compositions and methods of the present invention are biodegradable quaternary ammonium compounds Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups. Said matenals and fabπc softening compositions containing them are disclosed m numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.

The biodegradable quaternary ammonium compounds and amme precursors herein have the formula (I) or (II), below :

(I) (H) wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR⁴-C(O)-, -C(O)-NR⁴-;

Rl ιs (CH₂)_n-Q-T² or T3;

R² is (CH₂)m-Q-T⁴ or ≠ or R³;

R3 is Ci -C4 alkyl or C1 -C4 hydroxyalkyl or H;

R⁴ is H or C1-C4 alkyl or C1-C4 hydroxyalkyl;

T*, T², T³, T⁴, T^ are independently Cj 1-C22 alkyl or alkenyl; n and m are integers from 1 to 4; and

X" is a softener-compatible amon.

Non-limiting examples of softener-compatible anions include chlonde or methyl sulfate. The alkyl, or alkenyl, chain T , T², T³, T⁴, T^ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl mateπal. The compounds wherein T^, T², T³, T⁴, T^ represents the mixture of long chain mateπals typical for tallow are particularly preferred.

Specific examples of biodegradable quaternary ammonium compounds suitable for use in the fabπc care compositions and methods of the present invention include : 1) N,N-dι(tallowyl-oxy-ethyl)-N,N-dιmefhyl ammonium chlonde;

2) N,N-dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;

3) N,N-dι(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dιmethyl ammonium chlonde;

4) N,N-dι(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dιmethyl ammonium chlonde;

5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dιmethyl ammonium chlonde;

6) N,N,N-tπ(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;

7) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dιmethyl-ammonιum chlonde; and

8) l,2-dιtallowyl-oxy-3-tπmethylammomopropane chlonde; and mixtures of any of the above matenals.

Test Protocol

To determine whether a film-forming polymer can provide supenor stain/soil removal performance without detracting from the particulate stam removal performance, such as clay stain removal performance, the following Test Protocols should be used.

PROTOCOL SEBUM STAIN MAKING

Fabnc: - Muslm cotton ( 197 g / m² )

Soil: Sebum ( ex WFK )

Synthetic pigment wfk-09N ( ex WFK )

Soiling procedure Weigh 8 g sebum

Weigh 2 g pigment

Homogenize

Apply soil with brush [ evenly and consistently from πght to left and from left to nght to cover a surface of 8 cm x 2 cm ]

Ageing: Overnight line drying PROTOCOL CLAY STAIN MAKING

Fabπc - Muslin cotton ( 197 g / m² )

Soil. Clay ( preferably ex backyard P&G ETC - building )

Soiling procedure Weigh 2 g clay

Add 10 ml mdustπal water

Mix thoroughly via magnetic stirrer

Put template on fabnc ( rubber πng of ± 5 mm thick with inner diameter of 7 cm )

Apply soil with brush [ evenly and consistently using clockwise and counterclockwise strokes to cover the template surface ]

Ageing: Line dry stams overnight before first use

PROTOCOL POLYMER PREPARATION

Weigh polymer ( e.g. 20 g for 1 liter )

Put about 1 / 2 of the required volume as hot demmerahzed water ( above 70 ° C ) m a vessel

Gradually add polymer while stirπng

Keep stirnng until total amount is dispersed

Add remainder of water as cold demmerahzed water while stirnng to lower the temperature of the dispersion

Place vessel m ice water to cool polymer solution down to 0 to 5 °C.

Keep stirnng till transparent solution.

PROTOCOL SPRAYING PROCESS - Fill small vial with polymer solution

- Open mam air valve

- Open air valve of pressure regulator

- Set pressure on 2 bar

- Weigh fabric before spraying

- Spray solution on fabric ( distance vial - fabπc ± 20 cm ) e.g. target 2 g / m²

- Weigh fabnc again

- Line dry fabric for several hours

PROTOCOL WASHING TEST

Stams: Clay and artificial sebum on muslin cotton Internal replicates: 4 / type of stain External replicates: 2

Wash conditions: Mιele W715

40 °C short cycle

30 g Aπel Futur

Brussels city water hardness

After washing and ironing, the stams are graded ( visual grading - see protocol)

PROTOCOL Reference Treatment

Washing of Sebum and Clay stained fabπc without the fabnc care treatment process (Polymer Preparation and Spraying Process steps).

PROTOCOL PSU - grading WO 00/65015 PCT/USOO/l 1056

28

PSU grading is a visual grading versus a reference treatment using the Scheffe scale from 0 to 4 with

Adjunct Materials

The fabric care compositions of the present invention comprise an effective amount of the film-forming polymer, and preferably one or more of the above-described preferred ingredients, and optionally one or more of the following conventional cleaning adjunct materials either to improve the performance of the film-forming polymer, e.g., in the areas of wrinkle control, anti-wear, soil release, tensile strength and the like, or to provide additional benefits, such as odor control, antimicrobial, and the like. The useful optional cleaning adjunct materials are those that are compatible with the film-forming polymer, in that they do not interfere and/or substantially or significantly diminish the benefits provided by the film-forming polymer. The precise nature of these optional cleaning adjunct materials, and levels of incorporation thereof will depend on the physical form of the fabric care compositions, and the nature of the cleaning operation for which it is to be used.

Examples of such cleaning adjunct materials include, but are not limited to, the following.

Preservatives - The fabric care compositions herein may also optionally contain one or more preservatives. The function of the preservatives is to prevent organisms/micro-organisms from breeding and growing on the fabrics treated with the laundry detergent and/or fabric care compositions herein. In the absence of such preservatives, organisms/micro-organisms could grow on the fabrics treated with the laundry detergent and/or fabric care compositions herein because a significant amount of carbohydrates/sugar could remain on the fabrics after treatment. Samtization of fabrics can be achieved by the compositions of the present invention containing antimicrobial mateπals, e g , antibacteπal halogenated compounds, quaternary compounds, and phenolic compounds.

It is preferable to use a broad spectrum preservative, e.g., one that is effective on both bacteπa (both gram positive and gram negative) and fungi. A limited spectrum preservative, e.g., one that is only effective on a single group of microorganisms, e.g., fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity. A mixture of broad spectrum preservatives can also be used. In some cases where a specific group of microbial contaminants is problematic (such as Gram negatives), aminocarboxylate chelators may be used alone or as potentiators in conjunction with other preservatives. These chelators which include, e.g., ethylenediammetetraacetic acid (EDTA), hydroxyethylenediam etnacetic acid, diethylenetnammepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and their salts, and mixtures thereof, can increase preservative effectiveness against Gram-negative bactena, especially Pseudomonas species.

Antimicrobial preservatives useful in the present invention include biocidal compounds, i.e., substances that kill microorganisms, or biostatic compounds, i.e., substances that inhibit and/or regulate the growth of microorganisms.

(1) Organic Sulfur Compounds

Preferred water-soluble preservatives for use in the present invention are organic sulfur compounds. Some non-hmitmg examples of organic sulfur compounds suitable for use in the present invention are:

(a) 3-Isothιazolone Compounds

A preferred preservative is an antimicrobial, organic preservative containing 3- lsothiazolone groups having the formula.

wherein Y is an unsubstituted alkyl, alkenyl, or alkynyl group of from about 1 to about 18 carbon atoms, an unsubstituted or substituted cycloalkyl group having from about a 3 to about a 6 carbon nng and up to 12 carbon atoms, an unsubstituted or substituted aralkyl group of up to about 10 carbon atoms, or an unsubstituted or substituted aryl group of up to about 10 carbon atoms; Ri IS hydrogen, halogen, or a (C1 -C4) alkyl group; and R² is hydrogen, halogen, or a (C1 -C4) alkyl group

Preferably, when Y is methyl or ethyl, Ri and R² should not both be hydrogen. Salts of these compounds formed by reacting the compound with acids such as hydrochloπc, mtnc, sulfunc, etc. are also suitable.

This class of compounds is disclosed in U.S. Pat. No. 4,265,899, Lewis et al., issued May 5, 1981, and incorporated herein by reference. Examples of said compounds are: 5-chloro-2- methyl-4-ιsothιazolm-3-one; 2-n-butyl-3-ιsothιazolone; 2-benzyl-3-ιsothιazolone; 2-phenyl-3- lsothiazolone, 2-methyl-4,5-dιchloroιsothιazolone; ; 5-chloro-2-methyl-3-ιsothιazolone; 2-methyl- 4-ιsothιazolm-3-one; and mixtures thereof. A preferred preservative is a water-soluble mixture of 5-chloro-2-methyl-4-ιsothιazohn-3-one and 2-methyl-4-ιsothιazohn-3-one, more preferably a mixture of about 77% 5-chloro-2-methyl-4-ιsothιazohn-3-one and about 23% 2-methyl-4- ιsothιazohn-3-one, a broad spectrum preservative available as a 1.5% aqueous solution under the trade name Kathon® CG by Rohm and Haas Company

When Kathon® is used as the preservative m the present invention it is present at a level of from about 0.0001% to about 0.01%, preferably from about 0.0002% to about 0.005%, more preferably from about 0.0003% to about 0.003%, most preferably from about 0.0004% to about 0.002%, by weight of the composition.

Other lsothiazolms include l,2-benzιsothιazohn-3-one, available under the trade name Proxel® products; and 2-methyl-4,5-tπmethylene-4-ιsothιazohn-3-one, available under the trade name Promexal®. Both Proxel and Promexal are available from Zeneca. They have stability over a wide pH range (1 e , 4-12) Neither contain active halogen and are not formaldehyde releasing preservatives. Both Proxel and Promexal are effective against typical Gram negative and positive bacteria, fungi and yeasts when used at a level from about 0.001% to about 0.5%, preferably from about 0.005% to about 0.05%, and most preferably from about 0.01% to about 0.02% by weight of the usage composition.

(b) Sodium Pvnthione

Another preferred organic sulfur preservative is sodium pyπthione, with water solubility of about 50%ι. When sodium pyπthione is used as the preservative in the present invention it is typically present at a level of from about 0.0001% to about 0.01%, preferably from about 0.0002% to about 0.005%, more preferably from about 0.0003% to about 0.003%, by weight of the usage composition.

Mixtures of the preferred organic sulfur compounds can also be used as the preservative in the present invention.

(2) Halogenated Compounds

Preferred preservatives for use m the present invention are halogenated compounds. Some non-limiting examples of halogenated compounds suitable for use m the present invention are:

5-bromo-5-nιtro-l,3-dιoxane, available under the trade name Bronidox L® from Henkel. Bromdox L® has a solubility of about 0.46% in water. When Bronidox is used as the preservative in the present invention it is typically present at a level of from about 0.0005% to about 0.02%, preferably from about 0.001% to about 0.01%, by weight of the usage composition;

2-bromo-2-nιtropropane-l,3-dιol, available under the trade name Bronopol® from Inolex can be used as the preservative in the present invention. Bronopol has a solubility of about 25% m water. When Bronopol is used as the preservative m the present invention it is typically present at a level of from about 0.002%o to about 0.1%, preferably from about 0.005% to about 0.05%, by weight of the usage composition; 1 , 1 '-hexamethylene bιs(5-(p-chlorophenyl)bιguamde), commonly known as chlorhexidme, and its salts, e g , with acetic and glucomc acids can be used as a preservative in the present invention The digluconate salt is highly water-soluble, about 70% in water, and the diacetate salt has a solubility of about 1.8% in water When chlorohexidme is used as the preservative in the present invention it is typically present at a level of from about 0.0001% to about 0.04%, preferably from about 0.0005% to about 0.01%, by weight of the usage composition.

l,l,l-Tnchloro-2-methylpropan-2-ol, commonly known as chlorobutanol, with water solubility of about 0.8%; a typical effective level of chlorobutanol is from about 0.1% to about 0.5%, by weight of the usage composition.

4,4'- (Tnmethylenedιoxy)bιs-(3-bromobenzamιdme) dnsethionate, or dibromopropamidme, with water solubility of about 50%; when dibromopropamidine is used as the preservative in the present invention it is typically present at a level of from about 0.0001% to about 0.05%, preferably from about 0.0005% to about 0.01% by weight of the usage composition.

Mixtures of the preferred halogenated compounds can also be used as the preservative the present invention.

(3) Cyclic Organic Nitrogen Compounds

Preferred water-soluble preservatives for use m the present invention are cyclic organic nitrogen compounds. Some non-hmitmg examples of cyclic organic nitrogen compounds suitable for use in the present invention are:

(a) Imidazolidmedione Compounds

Preferred preservatives for use in the present invention are lmidazohdione compounds. Some non-hmitmg examples of imidazolidmedione compounds suitable for use in the present invention are: l,3-bιs(hydroxymethyl)-5,5-dιmethyl-2,4-ιmιdazolιdιnedιone, commonly known as dimethyloldimethylhydantoin, or DMDM hydantom, available as, e g., Glydant® from Lonza. DMDM hydantom has a water solubility of more than 50% in water, and is mamly effective on bacteria When DMDM hydantom is used, it is preferable that it be used in combination with a broad spectrum preservative such as Kathon CG®, or formaldehyde. A preferred mixture is about a 95:5 DMDM hydantom to 3-butyl-2-ιodopropynylcarbamate mixture, available under the trade name Glydant Plus® from Lonza. When Glydant Plus® is used as the preservative in the present invention, it is typically present at a level of from about 0.005%) to about 0.2% by weight of the usage composition;

N-[ 1 ,3-bιs(hydroxymethyl)2,5-dιoxo-4-ιmιdazolιdmyl]-N,N'-bιs(hydroxymethyl) urea, commonly known as diazohdinyl urea, available under the trade name Germall π® from Sutton Laboratones, Inc. (Sutton) can be used as the preservative in the present invention. When

Germall π® is used as the preservative in the present invention, it is typically present at a level of from about 0.01% to about 0.1% by weight of the usage composition;

N,N"-methylenebιs {N'-[ 1 -(hydroxymethyl)-2,5-dιoxo-4-ιmιdazolιdιnyl]urea} , commonly known as lmidazohdmyl urea, available, e.g., under the trade name Abiol® from 3V-Sιgma,

Unicide U-13® from Induchem, Germall 115® from (Sutton) can be used as the preservative in the present invention When lmidazohdmyl urea is used as the preservative, it is typically present at a level of from about 0.05% to about 0.2%, by weight of the usage composition.

Mixtures of the preferred imidazolidmedione compounds can also be used as the preservative in the present invention.

(b) Polvmethoxy Bicvchc Oxazohdme

Another preferred water-soluble cyclic organic nitrogen preservative is polymethoxy bicychc oxazohdme, having the general formula:

where n has a value of from about 0 to about 5, and is available under the trade name Nuosept® C from Hϋls America. When Nuosept® C is used as the preservative, it is typically present at a level of from about 0.005% to about 0.1%, by weight of the usage composition.

Mixtures of the preferred cyclic organic nitrogen compounds can also be used as the preservative in the present invention.

(4) Low Molecular Weight Aldehydes

(a). Formaldehyde

A preferred preservative for use in the present invention is formaldehyde. Formaldehyde is a broad spectrum preservative which is normally available as formalin which is a 37% aqueous solution of formaldehyde. When formaldehyde is used as the preservative in the present invention, typical levels are from about 0.003% to about 0.2%, preferably from about 0.008%> to about 0.1%. more preferably from about 0.01% to about 0.05%, by weight of the usage composition.

(b) Glutaraldehyde

A preferred preservative for use in the present invention is glutaraldehyde. Glutaraldehyde is a water-soluble, broad spectrum preservative commonly available as a 25% or a 50% solution in water. When glutaraldehyde is used as the preservative in the present invention it is typically present at a level of from about 0.005%) to about 0.1%, preferably from about 0.01% to about 0.05%, by weight of the usage composition.

(5) Quaternary Compounds Preferred preservatives for use m the present invention are catiomc and/or quaternary compounds. Such compounds include polyammopropyl biguamde, also known as polyhexamethylene biguamde having the general formula:

HCl«NH₂-(CH2)3-[-(CH2)3-NH-C(=NH)-NH-C(=NH»HCl)-NH-(CH2)3-]_x-(CH₂)3-NH-

C(=NH)-NH»CN

Polyammopropyl biguamde is a water-soluble, broad spectrum preservative which is available as a 20%> aqueous solution available under the trade name Cosmocil CQ® from ICI Ameπcas, Inc., or under the trade name Mikrokill® from Brooks, Inc.

l-(3-Chlorallyl) -3,5,7-tπaza-l-azonιaadamantane chlonde, available, e.g., under the trade name Dowicil 200 from Dow Chemical, is an effective quaternary ammonium preservative; it is freely soluble in water; however, it has the tendency to discolor (yellow), therefore it is not highly preferred.

Mixtures of the preferred quaternary ammonium compounds can also be used as the preservative the present invention.

When quaternary ammonium compounds are used as the preservative m the present invention, they are typically present at a level of from about 0.005% to about 0.2%>, preferably from about 0.01% to about 0.1%, by weight of the usage composition.

(6) Dehvdroacetic Acid

A preferred preservative for use the present invention is dehydroacetic acid. Dehydroacetic acid is a broad spectrum preservative preferably m the form of a sodium or a potassium salt so that it is water-soluble. This preservative acts more as a biostatic preservative than a biocidal preservative. When dehydroacetic acid is used as the preservative it is typically used at a level of from about 0.005% to about 0.2%, preferably from about 0.008%> to about 0.1%, more preferably from about 0.01% to about 0.05%, by weight of the usage composition. (7) Phenyl and Phenolic Compounds

Some non-hmitmg examples of phenyl and phenolic compounds suitable for use in the present invention are:

4,4'-dιamιdιno-α,ω-dιphenoxypropane dnsethionate, commonly known as propamidine isethionate, with water solubility of about 16%; and 4,4'-dιamιdιno-α,ω-drphenoxyhexane dnsethionate, commonly known as hexamidine isethionate. Typical effective level of these salts is about 0.0002% to about 0.05% by weight of the usage composition.

Other examples are benzyl alcohol, with a water solubility of about 4%; 2-phenylethanol, with a water solubility of about 2%; and 2-phenoxyethanol, with a water solubility of about 2.67%; typical effective level of these phenyl and phenoxy alcohol is from about 0.1% to about 0.5%), by weight of the usage composition.

(8) Mixtures thereof

It is preferred that no, or essentially no, volatile low molecular weight monohydπc alcohols such as ethanol and/or isopropanol are intentionally added to the composition of the present invention since these volatile organic compounds will contribute both to flammabihty problems and environmental pollution problems. If small amounts of low molecular weight monohydnc alcohols are present m the composition of the present invention due to the addition of these alcohols to such things as perfumes and as stabilizers for some preservatives, it is preferable that the level of monohydπc alcohol be less than about 5%, preferably less than about 3%, more preferably less than about 1%.

(9) Mixtures thereof

The preservatives of the present invention can be used in mixtures in order to control a broad range of microorganisms.

Bactenostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, e.g., less than about pH 4, preferably less than about pH 3, or a basic pH, e g., greater than about 10, preferably greater than about 11. (10) Highly preferred preservatives

Highly preferred preservatives for use in the compositions of the present invention are selected from the group consisting of: isothiazolones; bronopol; hydantoms; oxazohdmes, glutaraldehyde; lsethionates; quats (benzalkomums); and mixtures thereof.

Perfumes - The fabπc care compositions of the present invention can further compπse a perfume component.

Fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic ongm. The range of the natural raw substances can embrace not only readily- volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation. In this list of perfume ingredients, some are commercial names conventionally known to one skilled m the art, and also includes isomers. Such isomers are also suitable for use m the present invention. A typical disclosure of suitable ketone and/or aldehydes, traditionally used m perfumery, can be found m "perfume and Flavor Chemicals", Vol. I and π, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5. Preferred for the purpose of the present invention are the aldehydes or ketones based products.

- Natural products such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandann oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgra oil Paraguay, wormwood oil;

- Alcohols such as famesol, geraniol, lmalool, nerol, phenylethyl alcohol, rhodmol, cinnamic alcohol;

- Aldehydes such as citral, He onal™, alpha-hexyl-cmnamaldehyde, hydroxycitronellal, Lihal ™ (p-tert.butyl-alpha -methyldihydrocinnamaldehyde), methylnonylacetaldehyde, 1 -decanal, benzaldehyde, florhydral, 2,4-dιmethyl-3-cyclohexen-l-carboxaldehyde; cιs/trans-3,7-dιmethyl- 2,6-octadιen-l-al; hehotropm, 2,4,6-tπmethyl-3-cyclohexene-l-carboxaldehyde; 2,6-nonadιenal; alpha-n-amyl cinnamic aldehyde, P T. Buc al, lyral, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenal, and mixture thereof;

- Ketones such as allyhonone, alpha-ionone, beta -lonone, lsoraldem (isomethyl- alpha -lonone), methy onone, Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl- lonone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone. Damascenone. methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof;

- Esters such as allyl phenoxyacetate, benzyl sa cylate, cmnamyl propionate, citronellyl acetate, citronellyl ethoxolate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc.;

- Lactones such as gamma-undecalactone, various components often used m perfumery, such as musk ketone, indole, p-menthane-8-thιol-3-one, and methyl-eugenol;

- Acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those compnsmg phenylethyl moieties, or more recently developed specialties such as those descπbed m a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S. Pat. No.

5 ,084,440, issued January 28, 1992, assigned to Givaudan Corp. ;

- Recent synthetic specialties include the enol ethers of alkyl-substituted oxo-tetrahns and oxo- mdanes as descπbed in U.S. Pat. 5,332,725, July 26, 1994, assigned to Givaudan; or Schiff Bases as descnbed in U.S. Pat. 5,264,615, December 9, 1991, assigned to Givaudan;

- Perfume aldehyd and ketone amine addition products as descnbed in pending patent application EP 98870227.0 and co-pendmg patent application EP 99870026.4, both m the name of Procter & Gamble Company.

Generally, when incorporated in the fabπc post-treatment compositions of the present invention, the perfume will be compnsed at a level of 0% to 10%, preferably 0% to 3%, more preferably 0% to 1% by weight of the total composition.

Polysacchandes - "Polysacchandes" herein is meant natural polysacchaπdes, and does not include polysacchande deπvatives or modified polysacchandes. Suitable polysacchandes for use in the treating compositions of the present invention include, but are not limited to, gums, arabmans, galactans, seeds and mixtures thereof.

Suitable polysacchaπdes that are useful m the present invention include polysacchaπdes with a degree of polymeπzation (DP) over 40, preferably from about 50 to about 100,000, more preferably from about 500 to about 50,000, constituting sacchandes preferably include, but are not limited to, one or more of the following sacchandes: isomaltose, isomaltotnose, isomaltotetraose, lsomaltoo gosacchaπde, fructoohgosacchaπde, levoohgosacchandes. galactoohgosacchaπde, xyloohgosacchaπde, gentioohgosacchandes, disacchaπdes, glucose, fructose, galactose, xylose, mannose, arabmose, rhamnose, maltose, sucrose, lactose, maltulose, ribose, lyxose, allose, altrose, gulose, idose, talose, trehalose, nigerose, kojibiose, lactulose, oligosacchaπdes, maltoo gosacchandes, tπsacchaπdes, tetrasacchandes, pentasacchandes, hexasacchandes, ohgosacchaπdes from partial hydrolysates of natural polysacchande sources and mixtures thereof.

The polysacchaπdes can be extracted from plants, produced by organisms, such as bacteπa, fungi, prokaryotes, eukaryotes, extracted from animals and/or humans. For example, xanthan gum can be produced by Xanthomonas campestris, gellan by Sphingomonas paucimobihs, xyloglucan can be extracted from tamannd seed

The polysacchandes can be linear, or branched in a vaπety of ways, such as 1-2, 1-3, 104, 1-6, 2- 3 and mixtures thereof.

It is desirable that the polysacchandes of the present invention have a molecular weight in the range of from about 10,000 to about 10,000,000, more preferably from about 50,000 to about 1,000,000, most preferably from about 50,000 to about 500,000.

Preferably, the polysacchande is selected from the group consisting of: tamannd gum (preferably consisting of xyloglucan polymers), guar gum, locust bean gum (preferably consisting of galactomannan polymers), and other industnal gums and polymers, which include, but are not limited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psylhum seed, quince seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, chitin, hydroxyalkyl cellulose, arabinan (preferably from sugar beets), de-branched arabinan (preferably from sugar beets), arabmoxylan (preferably from rye and wheat flour), galactan (preferably from lupm and potatoes), pectic galactan (preferably from potatoes), galactomannan (preferably from carob, and including both low and high viscosities), glucomannan, hchenan (preferably from Icelandic moss), mannan (preferably from ivory nuts), pachyman, rhamnogalacturonan, acacia gum, agar, algmates, chitosan, clavan, hyaluronic acid, hepaπn, lnu n, cellodextnns, and mixtures thereof. These polysacchaπdes can also be treated (preferably enzymatically) so that the best fractions of the polysacchaπdes are isolated More preferred polysacchandes have a β-hnked backbone.

Xyloglucan polymer is a highly preferred polysacchande for use in the laundry and/or fabπc care compositions of the present invention. Xyloglucan polymer is preferably obtained from tamannd seed polysacchandes. The preferred range of molecular weights for the xyloglucan polymer is from about 10,000 to about 1,000,000, more preferably from about 50,000 to about 200,000.

Polysacchandes, when present, are normally incorporated in the treating composition of the present invention at levels from about 0.1% to about 25%, preferably from about 0.2% to about 10%) by weight of the treating composition.

Polysacchaπdes have a high affinity for binding with cellulose. Without wishing to be bound by theory, it is believed that the binding efficacy of the polysacchandes to cellulose depends on the type of linkage, extent of branching and molecular weight. The extent of binding also depends on the nature of the cellulose (i.e., the ratio of crystalline to amorphous regions in cotton, rayon, lmen, etc.).

The natural polysacchandes can be modified with amines (pnmary, secondary, tertiary), amides, esters, ethers, alcohols, carboxyhc acids, tosylates, sulfonates, nitrates, phosphates and mixtures thereof. Such a modification can take place in position 2, 3 and/or 6 of the glucose unit. Such modified or deπvatized polysacchandes can be included in the compositions of the present invention in addition to the natural polysacchandes.

Nonhmiting examples of such modified polysacchandes include: carboxyl and hydroxymethyl substitutions (e.g., glucuronic acid instead of glucose); ammo polysacchaπdes (amme substitution, e.g., glucosamme instead of glucose); C C₆ alkylated polysacchandes; acetylated polysacchande ethers; polysacchandes having ammo acid residues attached (small fragments of glycoprotem); polysacchandes containing sihcone moieties. Suitable examples of such modified polysacchandes are commercially available from Carbomer and include, but are not limited to, ammo algmates, such as hexanediamme alginate, amme functionahzed cellulose-like O-methyl- (N-l,12-dodecanedιamme) cellulose, biotin hepaπn, carboxymethylated dextran, guar polycarboxyhc acid, carboxymethylated locust bean gum, caroxymethylated xanthan, chitosan phosphate, chitosan phosphate sulfate, diethylaminoethyl dextran, dodecylamide alginate and mixtures thereof. Ohgosacchaπdes - The compositions of the present invention may include ohgosacchaπdes Suitable o gosacchaπdes that are useful in the present invention include oligosacchaπdes with a degree of polymeπzation (DP) of less than 20, preferably from about 1 to about 15, more preferably from about 2 to about 10, constituting monosacchandes preferably include, but are not limited to, one or more of the following monosacchandes: glucose, fructose, galactose, xylose, mannose, arabmose, rhamnose, nbose, lyxose, allose, altrose, gulose, idose, talose, and/or their denvatives. Preferred ohgosacchaπdes have a molecular weight in the range of from about 300 to about 8000. Branched ohgosacchandes are preferred over linear oligosacchaπdes.

Nonhmiting examples of suitable oligosacchaπdes can be obtained commercially from any of the suppliers - Carbomer (fructo-ohgosacchaπdes, levo-o gosacchandes, muhn, dextra 5000, cellosacchaπdes, etc.,), Grain Processing Corporation (maltodextπn), Pharmacica Biotech (Dextran senes), Palatmit (isomalt) and Showa Sangyo (Isomalto-500).

Ohgosacchandes, when present, are normally incorporated in the cleaning composition at levels from about 1% to about 25%>, preferably from about 2% to about 10% by weight of the laundry and/or fabπc care composition.

Surfactant System - Detersive surfactants can be, and preferably are included in the fabπc care compositions of the present invention. When present, surfactants compnse at least 0.01%, preferably at least about 0.1%, more preferably at least about 0.5%, most preferably at least about 0.5% to about 5% by weight of the fabnc care composition.

The detersive surfactant can be noniomc, amonic, ampholytic, zwittenomc, catiomc, semi-polar noniomc, and mixtures thereof, nonhmiting examples of which are disclosed in U.S. Patent Nos. 5,707,950 and 5,576,282. Preferred fabπc care compositions compnse aniomc detersive surfactants or mixtures of amonic surfactants with other surfactants, especially noniomc surfactants.

Amonic surfactants are highly preferred for use with the fabπc care compositions of the present invention.

Nonhmiting examples of surfactants useful herein include the conventional Ci i-Cjg alkyl benzene sulfonates and pπmary, secondary and random alkyl sulfates, the Ci Q-Ci g alkyl alkoxy sulfates, the C J Q-CI S alkyl polyglycosides and their corresponding sulfated polyglyco- sides, Cj2-Ci8 alpha-sulfonated fatty acid esters, C12-C18 alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetames ("sul- taines"), Cjo- i8 amme oxides, and the like. Other conventional useful surfactants are listed in standard texts

The surfactant is preferably formulated to be compatible with enzyme and bleaching components, if any, present m the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.

Noniomc Surfactants - Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the noniomc surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. Commercially available noniomc surfactants of this type include Igepal^M CO-630, marketed by the GAF Corporation; and Tnton™ X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The condensation products of pnmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the noniomc surfactant of the noniomc surfactant systems of the present invention. Examples of commercially available noniomc surfactants of this type include TergitolT 15-S-.9 (the condensation product of C\ \- C _ζ linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight distnbution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol^M 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), Neodol^M 45-7 (the condensation product of CJ4-C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45.5 ^_e condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro *M EOB (the condensation product of C^- C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

Also useful as the noniomc surfactant of the surfactant systems of the present invention are the alkylPolysacchaπdes disclosed in U S. Patent No. 4,565,647.

Preferred alkylpolyglycosides have the formula- R²0(C_nH2_nO)t(glycosyl)_x wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.1.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional noniomc surfactant systems of the present invention. Examples of compounds of this type include certain of the commercially-available PlurafacTM F404 and PluromcTM surfactants, marketed by BASF.

Also suitable for use as the noniomc surfactant of the noniomc surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme. Examples of this type of noniomc surfactant include certain of the commercially available TetromcTM compounds, marketed by BASF.

Preferred for use as the noniomc surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of pnmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylPolysacchandes, and mixtures thereof. Most preferred are Cg-Ci4 alkyl phenol ethoxylates havmg from 3 to 15 ethoxy groups and Cg-Ci 8 alcohol ethoxylates (preferably C\§ avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.

Highly preferred noniomc surfactants are polyhydroxy fatty acid amide surfactants of the formula: R² - C(O) - NCR¹) - Z wherein R¹ is H, or R¹ is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl or a mixture thereof, R² is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated denvative thereof. Preferably, R is methyl, R² is a straight Ci _\$ alkyl or Ci g-ig ^allcyl ^or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is denved from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction.

Amonic Surfactants - Suitable amonic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C -C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the Amencan Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting mateπals would include natural fatty substances as deπved from tallow, palm oil, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, compπse alkyl ester sulfonate surfactants of the structural formula

O

II

R³ - CH - C - OR⁴

I so₃M wherein R³ is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a Ci -Cg hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamme, and tπethanolamme. Preferably, R³ is Cio-C_jg alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ IS C₁₀-C₁₆ alkyl.

Other suitable amonic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl havmg a C10-C20 ^alkyl component, more preferably a C\₂- C1 alkyl or hydroxyalkyl, and M is H or a cation. Typically, alkyl chains of Ci2-Cι g are preferred for lower wash temperatures (e.g. below about 50°C) and Cι g.1 alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).

Other amonic surfactants useful for detersive purposes include salts of soap, C -C22 pnmary of secondary alkanesulfonates, C -C24 olefmsulfonates, sulfonated polycarboxyhc acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as descnbed in Bntish patent specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfa.es (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, lsethionates such as the acyl lsethionates, N-acyl taurates, alkyl succmamates and sulfosuccmates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccmates (especially saturated and unsaturated Cg-C_j2 diesters), acyl sarcosmates, sulfates of alkylPolysacchaπdes such as the sulfates of alkylpolyglucoside (the noniomc nonsulfated compounds being descnbed below), branched pnmary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2θ)ι_c-CH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resm acids and hydrogenated res acids are also suitable, such as rosm, hydrogenated rosin, and resm acids and hydrogenated resin acids present in or denved

Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A vaπety of such surfactants are also generally disclosed m U.S. Patent 3,929,678, issued December 30, 1975 to Laughlm, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).

Highly preferred amonic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mS03M wherein R is an unsubstituted CJQ- C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C1 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, tnmethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdimum cations and those deπved from alkylammes such as ethylamine, diethylamine, tnethylamme, mixtures thereof, and the like. Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (Ci2-CιgE(1.0)M), C12-C1 alkyl polyethoxylate (2.25) sulfate (C₁ -C₁₈E(2.25)M), C^-C^ alkyl polyethoxylate (3.0) sulfate (Ci2-Ci8-i(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (Cj2-Ci8E( .0)M), wherein M is conveniently selected from sodium and potassium.

When included therein, the fabnc care compositions of the present invention typically compnse from about 1%, preferably from about 3% to about 40%, preferably about 20% by weight of such amonic surfactants.

Ampholvtic Surfactants - Ampholytic surfactants, examples of which are descnbed in U.S. Patent No. 3,929,678, are also suitable for use m the fabπc care compositions of the present invention.

When included therein, the fabπc care compositions of the present invention typically comprise from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such ampholytic surfactants.

Zwittenonic Surfactants - Zwitteπomc surfactants, examples of which are descnbed m U.S. Patent No. 3,929,678, are also suitable for use in the fabπc care compositions of the present invention. When included therein, the fabπc care compositions of the present invention typically compπse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such zwitteπonic surfactants.

Semi-polar Noniomc Surfactants - Semi-polar noniomc surfactants are a special category of noniomc surfactants which include water-soluble amme oxides having the formula:

O

R3(OR⁴)_xN(R5)₂ wherein R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups (the R^ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a nng structure); water- soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

The amine oxide surfactants in particular include C_jQ-Ci g alkyl dimethyl amme oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amme oxides.

When included therein, the fabnc care compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such semi-polar noniomc surfactants.

Cosurfactants - The fabπc care compositions of the present invention may further compπse a cosurfactant selected from the group of pnmary or tertiary amines. Suitable pnmary amines for use herein include amines according to the formula R1NH2 wherein R^ is a Cg-Ci 2_; preferably Cg-C^ alkyl chain or R4X(CH₂)_n. is -0-,-C(0)NH- or -NH^ R4 is a C₆-C₁ alkyl chain n is between 1 to 5, preferably 3. R\ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.

Preferred amines according to the formula herein above are n-alkyl ammes. Suitable amines for use herein may be selected from 1 -hexylamine, 1-octylamme, 1-decylamme and laurylamine. Other preferred pnmary ammes include C8-C10 oxypropylam e, octyloxypropylamme, 2-ethylhexyl-oxypropylamme, lauryl amido propylamme and amido propylamme. The most preferred ammes for use in the compositions herein are 1-hexylamιne, 1- octylamme, 1 -decylamine, 1-dodecylamme. Especially desirable are n-dodecyldimethylamme and bishydroxyethylcoconutalkylamme and oleylamme 7 times ethoxylated, lauryl amido propylamme and cocoamido propylamme.

LFNIs - Low foaming noniomc surfactants (LFNT) which are descπbed in U.S. Patent Nos. 5,705,464 and 5,710,115 can be included in the fabπc care compositions of the present invention. LFNI may be present in amounts from 0.01% to about 10% by weight, preferably from about 0.1% to about 10%, and most preferably from about 0.25% to about 4%. LFNIs are most typically used in automatic dishwashing detergent compositions (ADDs) on account of the improved water-sheetmg action (especially from glass) which they confer to the ADD product. They also encompass non-silicone, nonphosphate polymeπc mateπals further illustrated hereinafter which are known to defoam food soils encountered m automatic dishwashing.

Preferred LFNIs include noniomc alkoxylated surfactants, especially ethoxylates denved from pnmary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers as descnbed m U.S. Patent Nos. 5,705,464 and 5,710,115.

LFNIs which may also be used include those POLY-TERGENT® SLF-18 noniomc surfactants from Olm Corp., and any biodegradable LFNI having the melting point properties discussed heremabove.

These and other noniomc surfactants are well known in the art, being descnbed in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.

Dispersants - One or more suitable polyalkyleneimme dispersants may be incorporated into the fabnc care compositions of the present invention. Examples of such suitable dispersants can be found in European Patent Application Nos. 111,965, 111,984, and 112,592; U.S. Patent Nos. 4,597,898, 4,548,744, and 5,565,145. However, any suitable clay/soil dispersent or anti- redepostion agent can be used in the fabnc care compositions of the present invention.

In addition, polymenc dispersing agents which include polymeric polycarboxylates and polyethylene glycols, are suitable for use m the present invention. Unsaturated monomenc acids that can be polymeπzed to form suitable polymeπc polycarboxylates include acrylic acid, maleic acid (or maleic anhydnde), fumanc acid, ltacomc acid, acomtic acid, mesaconic acid, citraco c acid and methylenemalonic acid. Particularly suitable polymenc polycarboxylates can be deπved 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 preferably 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 example, the alkali metal, ammonium and substituted ammonium salts Soluble polymers of this type are known materials. Use of polyacrylates of this type m detergent compositions has been disclosed, for example, m U.S. 3,308,067.

Acryhc/maleic-based copolymers may also be used as a preferred component of the dispersmg/anti-redeposition agent. Such matenals include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers m the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments m such copolymers will generally range from about 30: 1 to about 1 :1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known matenals which are descπbed in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descπbes such polymers compnsmg hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acryhc/vinyl alcohol terpolymers. Such mateπals are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/v yl alcohol

Another polymeπc matenal which can be included is polyethylene glycol (PEG). PEG can exhibit 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.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.

Soil Release Agents - The fabπc care compositions according to the present invention, to the extent that such soil release agents have not been previously discussed above as film-forming agents, may optionally compπse one or more soil release agents. If utilized, soil release agents will generally comprise from about 0 01%, preferably from about 0.1%, more preferably from about 0.2% to about 5%, preferably to about 2% by weight, of the composition. Nonhmiting examples of suitable soil release polymers are disclosed m: U.S. Patent Nos. 5,728,671, 5,691,298; 5,599,782, 5,415,807; 5,182,043; 4,956,447; 4,976,879; 4,968,451; 4,925,577; 4,861,512; 4,877,896; 4,771,730; 4,711,730; 4,721,580; 4,000,093; 3,959,230; and 3,893,929; and European Patent Application 0 219 048.

Further suitable soil release agents are descπbed in U.S. Patent Nos. 4,201,824; 4,240,918; 4,525,524; 4,579,681; 4,220,918; and 4,787,989; EP 279,134 A; EP 457,205 A; and DE 2,335,044.

Chelatmg Agents - The fabπc care compositions of the present invention herein may also optionally contain a chelatmg agent which serves to chelate metal ions and metal impunties which would otherwise tend to deactivate the bleaching agent(s). Useful chelatmg agents can include ammo carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelatmg agents and mixtures thereof. Further examples of suitable chelatmg agents and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.

The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelatmg agents will generally compπse from about 0.01% to about 2%, more preferably from about 0.1% to about 1% by weight of the fabnc care compositions herein.

Hydrogen Bond Breaking Agents - Suitable hydrogen bond breaking agents including, but not limited to, plant expansin and urea can optionally be incorporated into the fabπc care compositions of the present invention.

pH and Buffeπng Nanation - Many of the fabπc care compositions descnbed herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffenng capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc , and are well known to those skilled in the art.

Other Matenals - Other cleaning adjunct mateπals optionally included in the treating compositions of the present invention can include one or more mateπals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct matenals comprise, m total, from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as clay soil removal/anti- redeposition agents, bnghteners, dyes, perfumes, structure elasticizing agents, earners, hydrotropes, processing aids, fillers, germicides, alkalinity sources, solubilizing agents and/or pigments. Suitable examples of such other cleaning adjunct matenals and levels of use are found in U.S. Patent Nos. 5,576,282, 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101.

Methods of Treating

Fabncs can be treated with the film-forming polymer-containmg fabnc care compositions by any method known m the art that accomplishes contacting the fabnc with the film-forming polymer- containmg fabnc care composition.

A preferred embodiment of the present invention is a method for treating a fabnc m need of treatment, wherein the method compnses contacting the fabπc with an effective amount of film- formmg polymer-containing fabπc care composition such that the fabπc care composition treats the fabnc.

Other suitable methods include, but are not limited to, soaking the fabnc in a solution containing the film-formmg polymer-containmg fabnc care composition; spraying the fabnc with a solution containing the film-formmg polymer-containmg fabπc care composition; rubbing the fabnc with a solid containing the film-forming polymer-containmg fabπc care composition; dipping the fabπc m a solution containing the film-forming polymer-containmg fabnc care composition; rolling the film-formmg polymer-contammg fabπc care composition onto the fabπc, spreading the film-formmg polymer-contammg fabπc care composition onto the fabric and brushing the film-formmg polymer-containmg fabπc care composition onto the fabric Such methods can be used in industrial applications, such as in the textile industry, or in residential (domestic) applications, preferably, the methods are used in the residential (domestic) applications.

Further, these methods can be used independently of one another, or can be combined, concurrently or sequentially.

The use of the fabπc care compositions of the present invention m accordance with these methods maintains the color appearance and/or pill prevention and/or abrasion resistance of a fabnc in need of treatment through multiple wash cycles.

Product/Instructions

The present invention also encompasses the inclusion of instructions on the use of the film- formmg polymer-containing fabπc care compositions with the packages containing the fabπc care compositions herein or with other forms of advertising associated with the sale or use of the fabnc care compositions. The instructions may be included m any manner typically used by consumer product manufacturing or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and/or other wπtten or oral instructions which may be connected to the purchase of the fabnc care compositions.

The instructions, for instance, may include information relating to the temperature of the wash water; washing time; recommended settings on the washing machine; recommended amount of the fabπc care composition to use; pre-soakmg procedures; and spray-treatment procedures.

A product compnsmg a film-formmg polymer-contaming fabnc care composition, the product further including instructions for using the fabπc care composition to treat a fabnc m need of treatment, the instructions including the step of: contacting said fabπc with an effective amount of said fabπc care composition for an effective amount of time such that said composition treats said fabπc.

The product may be contained in a spray dispenser An article of commerce compnsmg a container containing a sihcone- and starch-free fabπc care composition comprising a film-forming polymer, which forms a temporary film on fabπcs such that stams that come into contact with said temporary film can be removed from said fabric upon washing; wherein said container includes instructions for protecting fabrics from stains compnsmg the instruction to apply said fabπc care composition to the surface of a fabnc m need of treatment. Preferably, the fabnc care composition of the present invention is applied to a fabπc in need of treatment m a post-cleaning treatment process.

Examples

The following examples are meant to exemplify compositions of the present invention, but are not necessanly meant to limit or otherwise define the scope of the invention. In the fabπc care compositions, any enzyme levels are expressed by percent of pure enzyme by weight of the total composition and unless otherwise specified, the adjunct matenals are expressed as percent of cleaning adjunct matenals by weight of the total compositions.

Further, in the following examples some abbreviations known to those of ordinary skill m the art are used, consistent with the disclosure set forth herein, and/or as defined herein below.

DEQA Dι-(tallowyl-oxy-ethyl) dimethyl ammonium chlonde

DOEQA Dι-(oleyloxyethyl) dimethyl ammonium methylsulfate

DTDMAC Ditallow dimethylammonium chlonde

CTMAC coconut tnmethyl ammonium chlonde

DMHELAC dimethyl hydroxyethyl lauryl ammonium chlonde pKa of hydroxyl proton = 12.7

DAHEAMS NN-dι(alkoyl -oxy-ethyl)-N-methyl, N-(2-hydroxyethyl), ammonium methyl sulfate with Ci g-C^g chain length

QAS R2.N+(CH3)2(C₂H₄OH) with R₂ = C₁₂-C₁₄.

QAS 1 R2.N+(CH3)2(C₂H₄OH) with R₂ = Cg-Ci i .

CXYEZ ^• A C\χ - Cι γ predominantly linear pnmary alcoh condensed with an average of Z moles of ethylene oxide Neodol 45-13 C14-C15 linear primary alcohol ethoxy late, sold by Shell

Chemical CO.

Photoactivated Bleach Sulfonated zinc phtalocyanine encapsulated in dextrin soluble polymer.

Photoactivated Bleach 1 Sulfonated alumino phtalocyanine encapsulated in dextrin soluble polymer.

CMC Sodium carboxymethyl cellulose.

HEC Hydroxyethylcellulose

HPC Hydroxypropylcellulose

HBMC Hydroxybutylmethylcellulose

MHPC Methylhydroxypropylcellulose

MHEC Methylhydroxyethylcellulose

MC Methylcellulose

Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl.

Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5-triazin-2-yl) stilbene-2:2'-disulfonate.

PEG Polyethylene glycol, of a molecular weight of 400-30.000. Alcohol Ethanol, methanol, propanol,...

Having described the invention in detail with reference to preferred embodiments and the examples, it will be clear to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

EPO STYLE CLAIMS FOR 7535

1. A fabric care composition comprising: a) a film-forming polymer; provided that said composition is free of:

I) resms; n) sihcone; in) compounds having a molecular weight of from 4,500 to 12,000 and selected from the group consisting of the ethylene oxide adducts of C12 - Ci 8 fatty alcohols, C\ - Cj saturated fatty alcohols, and C 14 - C 1 alkyl phenols; IV) quaternary ammonium compounds of the formula:

R²

1 I © — τ 4

R— — N N— R- R #

wherein one or two of R^ - R^ are C - C25 alkyl groups or alkenyl groups and the others are C\ - C3 alkyl groups or hydroxyalkyl groups; and X" is an amon group; v) noniomc surfactants having an HLB of 2-16; vi) ionic surfactants having a cntical micelle concentration of less than 1.0 mmol; vn) water-soluble inorganic salts; vni) quaternary ammonium compounds of the formula:

wherein R* and R^ are C\ - C22 alkyl groups or alkenyl groups, R⁸CONHC_mH_2m, R⁹NHCOC_mH_2m, or R⁹OCm_m ^Hn2₂m_m w whneerreeimn R⁸ IS C\ \ - C21 alkyl or alkenyl groups, R⁹ is C\₂ - C₂₂ alkyl or alkenyl groups and m is 1-5; R^ and R⁴ are H, C - C4 alkyl groups or (CHY- CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X^" is H, CH3SO4, C₂H₅S0₄, V₂ S0₄, HC0₂, CH₃C0₂ or HOCH₂COO and p ιs l-5; IX) compounds of the formula:

wherein R^ and R° are C\ \ - C₂\ alkyl groups or alkenyl groups, R⁸COOC_mH_2m, R⁹OCOC_mH_2m, R⁸CONHC_mH_2m, R⁹NHCOC_mH_2m or R⁹OC_mH2_m wherein R⁸ is Ci 1 - C₂ alkyl or alkenyl groups, R⁹ is C\ - C₂ alkyl or alkenyl groups and m is 1-5; R^ is H, C 1 - C4 alkyl groups or (CHY-CHZp)OH where Y and Z are H or

CH3 provided that at least one of Y or Z is H; and X" is H, CH3SO4, C2H5SO4, Vi SO4, HC0₂, CH3CO2 or HOCH₂COO and p is 1-5; Q is

O or NH; and n is 1-3; x) compounds of the formula:

wherein R³, R⁴and R⁷ are H, C\ - C₄ alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X' is H, CH3SO4, C2H5SO4, ^lA S0₄, HC0₂, CH₃CO₂ or

HOCH2COO and p is 1-5; R⁵ and R⁶ are Ci 1 - C21 alkyl groups or alkenyl groups, R⁸COOC_mH_2m, R⁹OCOC_mH_2m, R⁸CONHC_mH_2m, R⁹NHCOC_mH_2m or R⁹OC_mH_2m wherein R⁸ is C - C₂ι alkyl or alkenyl groups, R⁹ is Ci 2 - C22 alkyl or alkenyl groups and m is 1-5: R³ is H, Cj - C₄ alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X" is H, CH3SO4, C₂H₅S0₄, Vi SO4, HC0₂, CH3CO2 or HOCH₂COO and p is 1-5; xi) compounds of the formula:

wherein R^ and R^ are C\ - C₂ alkyl groups or alkenyl groups, R⁸CONHC_mH_2m, R⁹NHCOC_mH_2m, or R⁹OC_mH_2m wherein R° is Cj 1 - C \ alkyl or alkenyl groups, R⁹ is C_j2 - C22 alkyl or alkenyl groups and m is 1-5; R³ and Rr are H, Ci - C4 alkyl groups or (CHY- CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X' is H, CH3SO4, C₂H₅S0₄, V₂ SO4, HCO2, CH₃C0 or

xii) compounds of the formula:

wherein R^ and R^ are C[ j - C21 alkyl groups or alkenyl groups, R⁸COOC_mH_2m, R⁹OCOC_mH2_m, R⁸CONHC_mH_2m,

R⁹NHCOC_mH_2m or R⁹OC_mH_2m wherein R⁸ is Cπ - C₂ι alkyl or alkenyl groups, R⁹ is C\ - C₂₂ alkyl or alkenyl groups and m is 1-5; R³ IS H, C 1 - C₄ alkyl groups or (CHY-CHZp)OH where Y and Z are H or CH3 provided that at least one of Y or Z is H; and X^" is H, CH3SO4, C2H5SO4, V2 SO4, HC0₂, CH3CO2 or HOCH₂COO and p is 1-5; Q is

xni) water repellents; xiv) at least one of: a) hpophihc surfactants having a HLB of 6 or less; and b) propellants; xv) at least one of: a) polymers or their salts prepared by polymeπzation of a monomer having at least a vmyl group and/or an aromatic ring, a sulfonic group and an average molecular weight of 10,000 to 500,000; and b) carboxyhc acid-contammg polymers or salts thereof having recurπng units of the formula [I]:

X Z

[I]

wherein X, Y and Z are each H, CH₃, COOH or CH₂COOH; and n is 10 to 2000; or of the formula [II]:

H

I

(— C-O— )_m COOH

[π]

wherein m is 10-200; xv) swelling clay matenals; xvi) alkalis; xvn) gelatinous matenals; xvin) at least one of: a) benzoic acid; b) fluroescent bπghtenmg agents; and c) perfumes; xix) starch and starch denvatives.

2. The composition according to Claim 1 wherein said film-formmg polymer is a water- soluble cellulose deπvative or one or more substituted β-l,4-glucans, preferably selected from the group consisting of: carboxymethylcellulose, ethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxybutylcellulose, methylcellulose, methoxypropyl methyl cellulose, carboxymethylhydroxyethylcellulose, hexylcarboxymethyl cellulose, C\₂ - C20 alkyl carboxymethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose and mixtures thereof, more preferably selected from the group consisting of: hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hexylcarboxymethyl cellulose, Ci 2 - C20 alkyl carboxymethylcellulose and mixtures thereof.

3. The composition according to Claim 1 wherein said fabπc care composition provides stain and or soil removal benefits to fabncs without inhibiting the clay stam removal properties of the fabnc in a subsequent cleaning process.

4. The composition according to Claim 1 wherein said film-formmg polymer exhibits a viscosity of at least 5 Cp, preferably at least 10 Cp m a 2% by weight aqueous solution.

5. The composition according to Claim 1 wherein said composition further compnses one or more quaternary ammonium compounds, preferably one or more biodegradable quaternary ammonium compounds, more preferably said one or more biodegradable quaternary ammonium compounds, when present, are present m said composition at a level of from 0.01% to 5% by weight of the composition.

6. The composition according to Claim 1 wherein said film-formmg polymer is present in said fabnc care composition at a level of from 0.001% to 20%, preferably from 0.02% to 5%, more preferably from 0.05% to 2% by weight of the composition.

7. A method for treating a fabnc, preferably a garment, m need of treatment, said method compnsmg the step of contacting said fabnc with a sihcone- and starch-free fabnc care composition comprising a film-formmg polymer that forms a temporary film on said fabπc such that stams that come into contact with said temporary film can be removed from said fabπc upon washing.

8. The method according to Claim 7 wherein said fabπc care composition is applied to a fabπc duπng a post-cleaning treatment process or to a new or clean fabnc pnor to weaπng by a consumer.

The method according to Claim 7 wherein said film-forming polymer is a water- soluble cellulose derivative or one or more substituted β-l,4-glucans, preferably selected from the group consisting of: carboxymethylcellulose, ethylhydroxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxybutylcellulose, methylcellulose, methoxypropyl methyl cellulose, carboxymethylhydroxyethylcellulose, hexylcarboxymethyl cellulose, C - C20 alkyl carboxymethylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose and mixtures thereof, more preferably selected from the group consisting of: hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hexylcarboxymethyl cellulose, C12 - C20 alkyl carboxymethylcellulose and mixtures thereof.

10 The method according to Claim 7 wherein said fabπc care composition further compnses one or more quaternary ammonium compounds, preferably one or more biodegradable quaternary ammonium compounds, more preferably said one or more biodegradable quaternary ammonium compounds, when present, are present in said composition at a level of from 0.01% to 5% by weight of the composition.

11. The method according to Claim 7 wherein said film-formmg polymer is present on the surface of said treated fabnc at a level of at least 0.01 g/m² , preferably from 0.05 g/m² to 10 g/m².

12. The method according to Claim 7 wherein said film-formmg polymer is present in said fabnc care composition at a level of from 0.001% to 20%, preferably from 0.02% to 5%, more preferably from 0.05% to 2% by weight of the composition.

13. The method according to Claim 7 wherein said film-formmg polymer exhibits a viscosity of at least 5 Cp, preferably at least 10 Cp m a 2% by weight aqueous solution.

14. The method according to Claim 7 wherein said fabπc care composition is applied to said fabnc by a spray application, preferably by a non-aerosol spray application.

15 A sihcone- and starch-free fabnc care composition compnsmg: a) from 0.02% to 5% of a film-formmg polymer; b) from 0.01% to 5% of a quaternary ammonium compound; c) optionally, from 0.01% to 80% adjunct mateπals; and d) balance solvent wherein said solvent is selected from the group consisting of water, alcohol, polyethylene glycol and mixtures thereof; wherein said weight ratio of said film-formmg polymer to quaternary ammonium compound is from 50^* 1 to 1 :5

16. An article of commerce compnsmg a container containing a sihcone- and starch-free fabric care composition compnsmg a film-formmg polymer, which forms a temporary film on fabncs such that stams that come into contact with said temporary film can be removed from said fabnc upon washing; wherein said container includes instructions for protecting fabπcs from stams compnsmg the instruction to apply said fabnc care composition to the surface of a fabπc in need of treatment.

17. The article according to Claim 16 wherein said instructions further compπse applying said fabπc care composition to the surface of a fabnc m need of treatment dunng a post-cleaning treatment process.

18. A fabπc care composition compnsmg: a) a film-forming polymer; and b) a biodegradable quaternary ammonium compound, and c) optionally, but preferably a noniomc surfactant havmg an HLB value of

8-14, and d) optionally, but preferably a perfume.

19. A fabnc care composition compnsmg: a) a film-formmg polymer; and b) a noniomc surfactant having an HLB value of 8-14.

20 A fabnc care composition compnsmg: a) a film-formmg polymer; and b) a perfume.

21 A method for protecting a surface against soiling, said method compnsmg the step of contacting said surface with a surface care composition compnsmg a film-forming polymer that forms a temporary film on said surface such that stams that come into contact with said temporary film can be removed from said surface upon washing

22. A method for treating a surface m need of treatment, said method compnsmg the step of contacting said surface with a surface care composition comprising a film-formmg polymer that forms a temporary film on said surface such that stams that come into contact with said temporary film can be removed from said surface upon washing.