CA2278026A1

CA2278026A1 - Carpet cleaning compositions having increased levels of aminopolycarboxylic acids as anti-resoiling agents

Info

Publication number: CA2278026A1
Application number: CA002278026A
Authority: CA
Inventors: Michael Richard Tyerech
Original assignee: Individual
Current assignee: Reckitt Benckiser LLC
Priority date: 1997-01-16
Filing date: 1997-10-24
Publication date: 1998-07-23
Also published as: BR9714290A; DE69728174T2; GB9700792D0; ZA98318B; EP0960181B1; AU4916797A; ES2213819T3; WO1998031776A1; EP0960181A1; GB2321252A; DE69728174D1

Abstract

Aqueous flowable carpet cleaning composition which comprises the following constituents: A) one or more surfactant compounds selected from anionic, nonionic and amphoteric surfactant compounds; B) an aminopolycarboxylic acid salt as a resoiling inhibiting agent; C) an organic solvent; and, D) optionally, a stain repellency imparting composition especially a fluorine containing compound. These aqueous carpet cleaning compositions may include one or more further optional constituents including but not limited to:
further organic solvents or co-solvents, further resoiling inhibiting agents, fragrances, preservatives, viscosity modifying agents such as thickening agents, preservatives, pH adjusting agents, pH buffers, agents for imparting water repellency to carpets and carpet fibers, and agents for imparting oil repellency to carpets and carpet fibers whose total weight generally comprise not more than about 20 wt%., preferably not more than 10 % by weight of the copositions described.

Description

CARPET CLEANING COMPOSITIONS HAVING INCREASED
LEVELS OF AMINOPOLYCARBOXYLIC ACIDS AS
ANTI-RESOILING AGENTS
The present invention relates to carpet cleaning and treatment compositions.
Carpets provide a pleasant surface covering, especially flooring surfaces, and in some cases wall surfaces, carpets are durable, helps deaden sound transmission, are somewhat thermally insulating, and are readily applied. In order to retain their attractive appearance, such carpet surfaces require maintenance, particularly cleaning.
Frequently, at the time of their production, carpets or carpet fibers are treated with a variety of known compounds to provide the carpet fibers with a degree of repellency, particularly to oil and water. Both oil and water, jointly and severally, are major constituents in a wide variety of staining materials, such as: beverages, food stuffs, as well as other edible and/or imbibable compositions. Further staining compositions include any variety number of other materials which may come into contact with the carpet and which are entrained amongst the carpet fibers and/or upon the carpet fiber surface. Unfortunately, such carpet fiber treatments frequently wear away with time due to the normal wear and tear associated with such an installed carpet surface, and/or may be deleteriously degraded and/or removed by one or more chemicals or other compositions which may be used in the intensive cleaning of a carpet surface.
Exemplary prior art compositions include those described in US 5338475; US
5370919; EP 0648834 and WO 95/14578.
While prior art compositions have met with varying degrees of success, it should be apparent that there exists a real and present need in the art for improved carpet cleaning compositions which are effective in removing stains from soiled carpet surfaces and from soiled carpet fibers. Such a composition desirably provides an efficacious cleaning benefit, and also imparts a recoiling resistance to carpet surfaces cleaned with the composition.
The present invention provides improved liquid carpet cleaning compositions, and improved processes for cleaning and treating carpets.
__ 1 __ AP~1F~ :~D~r ~H~~T
i2~wL~~r~

' WO 98J31776 PCT/US97/19217 Summar;~of the Invention and Detailed Descri ton:
In accordance with one aspect of the present invention there is provided an aqueous flowable carpet cleaning composition which comprises the following constituents:
A) one or more surfactant compounds selected from anionic, nonionic and amphoteric surfactant compounds;
B) an aminopolycarboxylic acid salt as an recoiling inhibiting agent;
C) an organic solvent; and, D) optionally, a stain repellency imparting composition especially a fluorine containing compound.
These aqueous carpet cleaning compositions may include one or more further optional constituents including but not limited to: further organic solvents or co-solvents, further recoiling inhibiting agents, chelating agents, fragrances, preservatives, viscosity modifying agents such as thickening agents, preservatives, pH
1 S adjusting agents, pH buffers, agents for imparting water repellency to carpets and carpet fibers, and agents for imparting oil repellency to carpets and carpet fibers whose total weight generally comprise not more than about 20%wt., preferably not more than 10% by weight of the compositions described.
The present inventor has made the surprising discovery that in the place of, or in addition to, known anti-recoiling agents which are known to be useful in carpet cleaning and treatment compositions, increased amounts of an aminopolycarboxylic acid salts, especially salts of ethylenediaminetetraacetic acid are useful as recoiling inhibiting agents (also sometimes referred to as anti-recoiling agents). Such an effect has surprisingly been observed in compositions which include as well as those which do not include one or more further conventionally known resoiiing inhibiting agents.
This is a significant discovery as it permits the use of low cost and widely available aminopolycarboxylic acid salts to be used in the place of or in conjunction with one or more further conventionally known recoiling inhibiting agents.
The aqueous carpet cleaning and treatment compositions according to the invention include (A) one or more surfactant compounds selected from anionic, nonionic and zwitterionic surfactant compounds.
__ 2 __ ~. t.
., ,.. . . , WO 98/31'796 PCT1US97/19217 - --Exemplary useful anionic surfactants include known art compounds, including organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. Included in the term "alkyl" is the alkyl portion of aryl groups.
These include but are not limited to: alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkylpolyglycosides, diphenyl sulfonate derivatives, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates.
Generally, the alkyl or acyl radical in these various compounds comprises a carbon chain containing 8 to 20 carbon atoms, and preferably comprises a carbon chain 1 S containing 12 to 20 carbon atoms, The alkyl or acyl radical may be linear or branched.
Mixtures of two or more anionic surfactants may be used as well. Further exemplary anionic surfactants which may be used include fatty acid salts, including salts of oleic, ricinoleic, palmitic, and stearic acids; copra oils or hydrogenated copra oil acid, and acyl lactylates whose acyl radical contains 8 to 20 carbon atoms. Other anionic surfactants not particularly enumerated here may also find use in conjunction with the' compounds of the present invention.
Preferred as the anionic surfactant constituent are alkyl sulfates, alkyl benzene sulfates, and alkane sulfonates, particularly water soluble salts thereof and especially preferred are those containing from 11 to 17 carbon atoms in their alkyl radical, which may be straight chained or branched. Useful water soluble salts which are effective in producing salt forms of the surfactant include, but are not limited to:
sodium, potassium, ammonium, magnesium, chloride and mono-, di- and tri- C,-C, alcohol ammoniums, amine and aminoalcohol salts forms. Desirably, the anionic surfactants are ones which may be characterized as having a low chloride content.
Exemplary preferred alkyl sulfates include sodium lauryl sulfate, alkyl benzene sulfates, and alkane sulfonates particularly ones characterized as having a low __ 3 __ WO 98/31776 PCT/US97/19Z17 _ -chloride content. Desirably the anionic surfactant is also selected to be of a type which dries to a friable powder. Such a characteristic facilitates the subsequent removal of such anionic surfactants from a fibrous substrate, especially carpets and.
carpet fibers, such as by bnishing or vacuuming.
The anionic surfactant according to constituent (A) may be included in the present inventive compositions in an amount of from 0 - 5 %wt., but is desirably included in amounts of from 0.1 - 2% wt., and most desirably is included in amounts of 0.5 - 1.5% wt. which provides advantageous cleaning properties to the inventive compositions. Such recited weights are based on the weight of anionic compounds or "actives" in an anionic surfactant containing preparation. Also, as noted previously, a plurality of anionic surfactants may be used.
The compositions according to the invention also include minor amounts of one or more nonionic surfactants particularly alkoxylated aliphatic primary alcohols and alkoxylated aliphatic secondary alcohols. Such include for example C$
C,°
primary or secondary aliphatic alcohols condensed with from 2 - 10 moles of one or more alkylene oxides. Such alkoxylated compounds specifically include ethylene oxide, propylene oxide and butylene oxides, of which ethylene oxide, propylene oxide, or mixtures thereof are preferred, and further of which condensates containing only ethylene oxide as the alkoxyl moiety is most preferred.
Desirably the nonionic surfactant constituent, when present, is selected from alkoxylated Cx - C,; primary aliphatic alcohols, and an alkoxylated C,o C,5 secondary aliphatic alcohol in which ethylene oxide and/or propylene oxide represents the alkoxylate moiety of such surfactants.
Illustrative examples of these preferred water soluble nonionic ethoxylated phenols and/or ethoxylated alcohols surfactants C,, - C" linear primary alcohols which include an average of 6 ethoxy groups per molecule, C" - C,; secondary alcohol which includes an average of 9 ethoxy groups per molecule, alkoxylated linear aliphatic C~- C") alcohol having a number of both ethoxy and propoxy groups per molecule, and C,° - C,, alkoxylated fatty alcohols.
Other known nonionic surfactant compounds are contemplated as being useful in the compositions according to the present invention and these include alkoxylated __ 4 __ ' WO 98/31776 PGT/US97/19Z17 - --alkyl aromatic compounds. Such compounds contain at least one aromatic moiety, such as a phenol, as well as an alkyl chain, which may be straight chained or branched. Desirably the aromatic moiety is CS C" and particularly C6 aromatic moieties are preferred, and wherein the alkyl chain is a CR-C2° alkyl group. The alkoxyl groups in such may be ethylene oxide, propylene oxide and butylene oxides, of which ethylene oxide, propylene oxide, or mixtures thereof are preferred, and further of which ethylene oxide is most preferred.
Such alkoxylated alkyl aromatic compounds include nonyl phenol ethoxylates, isooctyl phenol ethoxylates and particularly a C,~ C,, ethoxylated octyl phenol with an average of 1.5 ethoxy groups per molecule.
Nonionic surfactants according to constituent (A) may be included in the present inventive compositions in an amount of from 0 - 5% wt., desirably from 0.001 -1 % wt., more desirably are included in amounts of from 0.05 - 0.5%wt., and most desirably are included in amounts of from 0.1 - 0.3 %wt. which amounts provide advantageous cleaning properties to the inventive compositions. Such recited weights are based on the weight of nonionic compounds or "actives" in a nonionic surfactant containing preparation. It is also to be understood that a plurality of nonionic surfactants may be used.
The amphoteric surfactant according to constituent (A) may be any of a number of compounds known to the art, including amphoteric imidazolinium derivatives, and especially betaines such as alkylbetaines and amidoalkylbetaines.
The amphoteric surfactants of constituent (A), when present, may be included in the present inventive compositions in an amount of from 0 - 5% wt., but is desirably included in amounts of from 0 - 2% wt., and most desirably is included in amounts of from 0 - 1 % wt. which provides advantageous cleaning properties to the inventive compositions. Such recited weights being based on the weight of amphoteric compounds or "actives" in an amphoteric surfactant containing preparation.
Such recited weights being based on the weight of amphoteric compounds or "actives"
in a amphoteric surfactant containing preparation. Also, it is contemplated that a plurality of amphoteric surfactants may be used.
__ 5 __ ' WO 98131776 PCT/US97119217 - --It is to be understood that the total of the combined weights of the anionic, nonionic and amphoteric surfactants denoted are present in the inventive compositions in an amount of from 0.1 - 1 I %wt., but are desirably present in amounts of from 0.15 - 4.5%wt., and most desirably are present in amounts of from O.G - 2.8%wt.
The compositions of the invention include (B} an aminopolycarboxylic acid salt as an resoiling inhibiting agent. The aminopolycarboxylic acids are compounds in which the amino nitrogen is attached to two or more substituent groups.
Many such aminopolycarboxylic acids and their salts are known to the art. Preferred for use as the aminopolycarboxylic acid salt constituent in the present inventive compositions are the salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and N-hydroxyethytethylenediaminetriacetic acid, as well as mixtures thereof.
The preferred salts of these acids are the potassium and the sodium salts, of which two the sodium salt is generally to be preferred. The aminopolycarboxylic acid salt (B) is desirably present in amounts of from 0.1 - 50 %wt., more desirably from about 0.5 6.0 %wt., and most desirably from 1.0 to 3.0 %wt.
It has been surprisingly been discovered by the inventor that carpet cleaning compositions may be provided with a significant amount of soil redeposition inhibition by the incorporation into their formulations of amounts of salts of aminopolycarboxylic acid, especially ethylenediaminetetraacetic acid. What is further surprising is that such an inclusion may be in conjunction to the use of one or more fluorochemicals which are known to the art to inhibit soil redeposition, or that the such fluorochemicals may be wholly absent from such formulations and due to the inclusion the treated carpet still exhibits an excellent soil redeposition inhibition effect.
The aqueous carpet cleaning compositions include as constituent (C) an organic solvent constituent which may be a single solvent or which may be a mixture of two or more organic solvents. A wide range of known materials may be used and without limitation these include water soluble or miscible alcohols, glycols, acetates, ether acetates and glycol ethers. Exemplary such aicohols useful in the compositions of the invention include C,-CK alcohols which may be straight chained or branched, and which are specifically intended to include both primary, secondary and tertiary __ G __ alcohols. Exemplary glycol ethers include those glycol ethers having the general structure R~ O-Re-OH, wherein Ra is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and R,, is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units. Preferred are glycol ethers having one to five glycol monomer units. These are C,-C,° glycol ethers.
By way of further non-limiting example specific organic solvents include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol) ethanol, methanol, diethylene glycol monoethyl ether acetate and particularly advantageously ethylene glycol hexyl ether, diethyiene glycol hexyl ether, as well as the C,-Cg primary and secondary alcohols. Many such organic solvents are presently commercially available. The organic solvent (C) constituent is desirably present in amounts of to about 20 %wt., more desirably from about 0.1 - 5 %wt., and most desirably from 0.1 to 3.0 %wt.
Desirably the one or more organic solvents which make up the organic solvent constituent (C) exhibit a low vapor pressure, particularly less than 0.05 mm Hg at a temperature of 25°C. Such preferred organic solvents ensure quick evaporation from treated carpets or other fibrous surfaces, and also minimize the residence time of any films formed by the inventive compositions on such treated surfaces, which in turn improves the anti-recoiling characteristics of the inventive compositions.
As is noted above, the compositions according to the invention are aqueous in nature. Water is added to order to provide to 100% by weight of the compositions of the invention, and is preferably substantially free of any undesirable impurities such as organics or inorganics, especially mineral salts.
As has been previously noted, the compositions of the invention may include one or more optional constituents many of which are recognized as conventional additives to aqueous carpet cleaning or treatment compositions.
One optional constituent which is desirably included is one or more chelating agents. Useful as chelating agents include those known to the art, inter alias gluconic acid, tartartic acid, citric acid, oxalic acid) lactic acid, nitrilotriacetic acid, polyacrylic __ 7 __ acid salts, diethylene triamine pentaacetic acid, and their water soluble salts, especially the alkali metal salts and particularly the sodium salts thereof, as well as aminopolycarboxylic acids and salts thereof wherein the amino nitrogen has attached thereto two or more substituent groups, including the sodium and potassium salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid which have been described above with reference to constituent (B). In the case that a chelating agent is added other than a aminopolycarboxylic acids and salts, it is generally added in only minor amounts, i.e., less than about 0.5%wt. but due to the amount of the aminopolycarboxylic acids and salts present as constituent (B), the use of a further chelating agent is generally not necessary.
As a further optional constituent there may be advantageously included is a preservative constituent. As a significant portion of the formulation comprises water, it is preferably that the preservative be water soluble. Such water soluble preservatives include compositions which include parabens, including methyl parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-nitropropane-I,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, and mixtures thereof.
The compositions according to the invention optionally but desirably include an amount of a pH adjusting agent or pH buffer composition. Such compositions include many which are known to the art and which are conventionally used. By way of non-limiting example pH adjusting agents include phosphor containing compounds, monovalent and polyvalent salts such as of silicates, carbonates, and borates, certain acids and bases, tartarates and certain acetates. By way of further non-limiting example pH buffering compositions include the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same. Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers. It may also be suitable to use as buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, and their alkali metal salts. Desirably the compositions -_ g __ ' wo ~3m~s rc~rrtrs9~nni~ ~ --according to the invention include an effective amount of an organic acid and/or an inorganic salt form thereof, which may be used to adjust and maintain the pH
of the compositions of the invention is the desired pH range. Particularly useful is citric acid and sodium citrate which are both widely available and which are effective in providing these pH adjustments and buffering effects.
Further useful optional constituents include optical brighteners, including those based on stilbene derivatives and distyrylbiphenyl derivatives.
Oxidizing agents known to the art, including hydrogen peroxide, may be used in the inventive compositions however as these are frequently unstable and their efficacy is known to quickly degrade over time making their use to be desirably avoided.
The compositions of the invention may optionally include one or more constituents which are intended to modify the visual appearance thereof, such as one or more coloring agents, such as dyes and/or pigments, as well as compositions which act as opacifiers. These are generally included in only minor amounts, but are desirably omitted.
The compositions of the invention may also optionally include fragrance compositions or other composition for modifying the scent characteristics of the inventive compositions. Such may be any of a number of known materials, including those known to be effective in absorbing odors, those luiown useful in masking odors, as well as those which are known to impart or provide a specific scent.
Fragrances, whether naturally or synthetically produced may be used in the inventive compositions.
Although the inventive compositions provide excellent anti-resoiling characteristics when they include only an aminopolycarboxylic acid salt as a recoiling inhibiting agent, the use of one or more further anti-resoiling agents is contemplated.
Such compositions include compounds exhibiting an anti-recoiling effect for example, colloidal silica, aluminum oxides, styrene-malefic anhydride copolymer resins, polyvinylpyrrolidone, polyacrylates, polycarboxylates, modified cellulose polymers, vinyl acetate/maleic anhydride copolymer resins, cationic amines, aliphatic quaternary ammonium salts known to have anti-static properties, imidazoline salts as well as others known to the art. Such compounds which inhibit resoiling may be added in __ g __ amounts of from 0 - 2%wt., but when present are desirably included in amounts of from 0.001 %wt - 1 %wt.
Particularly preferred anti-recoiling compounds useful in the present inventive compositions are fluorinated acrylic polymers; the inclusion of such fluorinated acrylic polymers and salts in the compositions of the invention improves the recoiling resistance of fibrous substrates treated with said compositions. A specific and preferred fluorinated acrylate copolymer is one which confonms to the formula (C):
CF3(CF2)~CH20COC(CH3)=CHZ (C) wherein n represents a value of from 6 - 8.
This fluorinated acrylate copolymer may be generally characterized by a total fluorine content based on polymer solids of approximately O.G percent. This fluorinated acrylate copolymer may also contain a zinc complex to act as a crosslinker. The number average (Mn) and weight average (Mw) molecular weights are generally in the range of approximately 9,000 and approximately 10,500 respectively. Such a fluorinated acrylate copolymer may be obtained commercially as a water based dispersion of approximately 76-77 weight % water; 18-19 weight acrylate copolymer; 1 weight % nonylphenoxypolyethoxyethanol; 1 weight %
sodium lauryl sulfate; and 1 weight % zinc oxide complex (with said weight % of the ingredients based on the total weight of the water dispersion), as SYNTRAN~

(Interpolymer Corporation, Canton, MA). When this SYNTRAN~ 1575 composition is employed as constituent (b), it may be included in the present inventive compositions in amounts such that the fluorinated acrylate copolymer is present from 0.001 - 2%wt., desirably in amounts of from 0.001 %wt - 0.75%wt., and most desirably in amounts of from 0.05%wt. - 0.5%wt. with such recited weights being based on the weight of the fluorinated acrylic polymers and/or salts thereof present.
One further particularly anti-resoiling compound particularly useful in the present inventive compositions is a non-halogenated, especially a non-fluorinated, acrylic polymer compound which may be represented by the formula (D):
(-CH2 CH(COOR)-)" (D) wherein n is a value greater than 50.
Such a non-fluorinated acrylic polymer is presently commercially available and may be obtained as an aqueous dispersion which includes 78-79%wt. water, 18-19%wt.
of the non-fluorinated acrylic polymer, 1 %wt. of sodium lauryl sulfate, 1 %wt.
sodium nonylpehnoxypolyethoxyethanol sulfate, and 1 %wt. zinc oxide complex as SYNTRAN~ 1580, as well as an aqueous dispersion which includes 74-75%wt.
water, 23-24%wt. of the non-fluorinated acrylic polymer, 1 %wt. of sodium mono-alkylarylpolyethoxy sulfosuccinate, and 1 %wt. sodium lauryl sulfate sulfate as SYNTRAN~1588. These materials are considered to be infinitely miscible in water by the manufacturer, and the former is provided as an aqueous dispersion having a pH
of 8.3 to 9.3, and the latter is provided as an aqueous dispersion having a pH
of 7.7 to 8.7. Both of these materials may be obtained from Interpolymer Corporation (Canton, MA).
As noted previously, the inventive compositions may include one or more further optional constituents which impart a degree of water repellency, oil repellency or both water and oil repellency to carpet fibers and carpet surfaces. These include for example, compositions recited in U.S. Patent No. 4,145,303 and U.S. Patent No.
3,901,727 both to Loudas, U.S. Patent No. 5,370,919 to Fieuws as well as those described in commonly assigned, U.S. Patent No. 5,712,240 and U.S. Patent No. 5,861,365.
An advantageously used material for imparting water and/or oil repellency to the compositions of the invention includes a fluoroaliphatic oligomer or polymer (the term oligomer hereinafter includes polymer unless otherwise indicated) represented by the general formulae ( 1 ) and (2):
(R~)SZI(R3),,~'B1t (1) ((Rr)sZI(R3)y.Z'B'l~w (2) where R, is a fluoroaliphatic radical, Z is a linkage through which R, and (R3)y moieties are covalently bonded together, ..:.. . , _. v ; .v--a . ~;= _. _ .

' WO 98/31776 PCT/US97J19217 - --(R3)y is a poly(oxyalkylene) moiety, R3 being an oxyalkylene group with 2 to 4 carbon atoms and y is an integer (where the above formulas are those of individual compounds) or a number (where the above formulas are those of mixtures) at least 1, preferably 1 to 125 and can be as high as 180 or higher, B is a hydrogen atom or a monovalent terminal organic radical, B' is B or a valence bond, with the proviso that at least one B' is a valence bond interconnecting a Z-bonded R3 radical to another Z, Z' is a linkage through which B, or B', and R3 are covalently bonded together, s is an integer or number of at least 1 and can be as high as 25 or higher, t is an integer or number of at least i, and can be as high as 60 or higher, and w is an integer or number greater than 1, and can be as high as 30 or higher.
In formulas ( 1 ) and (2), where there were a plurality of R, radicals, these may be either the same or different. This also applies to a plurality of Z, Z', R3, B, B', and, in formula (2), a plurality of s, y and t.
R, is a stable, inert, nonpolar, preferably saturated monovalent moiety which is both oieophobic and hydrophobic. A fluorinated oligomer preferably comprises from 1 to about 25 R, groups and preferably comprises about 5 percent to about 30 percent, and more preferably about 8 percent to about 20 percent fluorine by weight based on the total weight of the oligomer, the loci of the fluorine being essentially in the R, groups. R, preferably contains at least about 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about G to about 12 carbon atoms.
R, can contain straight chain, branched chain, or cyclic alkyl groups. R~ is preferably free of polymerizable olefinic unsaturation and can optionally contain caternary heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that each R~
contain about 40%.to about 78% fluorine by weight, more preferably about 50%
to about 78% fluorine by weight. The terminal portion of the R, group contains a fully fluorinated terminal group. This terminal group preferably contains at least 7 fluorine atoms, e.g., CF3CF2CF2; (CF3)zCF; CFZSFS, or the like.
Perfluorinated aliphatic groups, i.e., those of the formula C"F2"+~, are the most preferred embodiments of R~

' WO 98/31T16 PCT/US97/19217 _ Generally, the oligomers will contain about S to 40 weight percent, preferably about 10 to 30 weight percent, of carbon-bonded fluorine.
In the poly(oxyalkylene) radical, (R3)y, R3 is an oxyalkylene group having 2 to 4 carbon atoms, such as -OCHZCHZ , -OCHZCHZCHZ , -OCHZCH2CH2CH2 , -OCH(CH3)CHz , and -OCH(CH3)CH(CH3)-, the oxyalkylene units in said poly(oxyalkylene) being the same, as in poly(oxypropylene), or present as a mixture, as in a heteric straight or branched chain or randomly distributed oxyethylene, oxypropylene and oxybutylene units or as in a straight or branched chain of blocks of oxyethylene units and/or blocks of oxypropylene units and/or blocks of oxybutylene units. The poly(oxyalkylene) chain can be interrupted by or include one or more catenary linkages. Where said catenary linkages have three or more valences, they provide a means for obtaining a branched chain of blocks of oxyalkylene units.
The poly(oxyalkylene) radicals in the oligomers can be the same or different, and they can be pendent. The molecular weight of the poly(oxyalkylene) radical can be about to 2,500 and higher, e.g., 100,000 to 200,000 or higher.
The function of the linkages Z and Z' is to covalently bond the fluoroaliphatic radicals, R,, the poly(oxyalkylene moieties, (R3)y and radicals B and B' together in the oligomer. Z and Z' can be a valence bond, for example, where a carbon atom of a fluoroaliphatic radical is bonded or linked directly to a carbon atom of the poly(oxyalkylene) moiety. Z and Z' each can also comprise one or more linking groups such as polyvalent aliphatic and polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, phosphoxy, amine, and combinations thereof, such as oxyalkylene, iminoalkylene, iminoarylene, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane, urea, and ester. The linkages Z and Z' for a specific oligomer will be dictated by the ease of preparation of such an oligomer and the availability of necessary precursors thereof.
Illustrative linking groups Z are alkylene groups, such as ethylene, isobutylene, hexylene, and methylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as ' WO 98/31776 PG"T/US97119217 -CHy~CHZ ~CH2~
and ~ ~/ having up to 20 carbon atoms, aryiene groups, such as tolylene, -CBH3(CH3) -, poly(oxyalkylene) groups, such as -(CZH40)yCZH4 where y is 1 to about 5, and various combinations of these groups.
Such groups can also include other hetero moieties (besides -O-), including -S
and -N-. However, Z is preferably free of groups with active hydrogen atoms.
From the above description of Z and Z' it is apparent that these linkages can have a wide variety of structures, and in fact where either is a valence bond, it does not even exist as a structure. However large Z or Z' is, the fluorine content (the locus of which is R,) is in the aforementioned limits set forth in the above description, and in general the total Z and Z' content of the oligomer is preferably less than 10 weight percent of the oligomer.
The monovalent terminal organic radical, B, is one which is covalently bonded through Z', to the poly(oxyalkylene) radical.
Though the nature of B can vary, it preferably is such that it complements the poly(oxyalkylene) moiety in maintaining or establishing the desired solubility of the oxyalkylene. The radical B can be a hydrogen atom, an acyl radical such as CsHSC(O~, an alkyl radical, preferably lower alkyl, such as methyl, hydroxyethyl, hydroxypropyl, mercaptoethyl and aminoethyl, or an aryl radical, such as phenyl, chlorophenyl, methoxyphenyl, nonylphenyl, hydroxphenyl, and aminophenyl.
Generally, Z'B will be less than 50 weight percent of the (R3)~'B moiety.
The fluoroaliphatic radical-containing poly(oxyalkylene) compounds used in the compositions according to the present invention can be prepared by a variety of known methods, such as by condensation, free radical, or ionic homopolymerization or copolymerization using solution, suspension, or bulk polymerization techniques, e.g., see "Preparative Methods of Polymer Chemistry", Sorenson and Campbell, 2nd ed., Interscience Publishers.
Many of such fluoroaliphatic radical-containing poly(oxyalkylene) compounds are presently commercially available.

WO 9$131776 PCTIUS97/19217 In one preferred embodiment of the invention the fluoroaliphatic radical-containing poly(oxyalkylene) compound contains a fluoroalkyl radical having 3 to 20 carbon atoms, wherein perfluoroalkyl radicals are particularly preferred.
In a further preferred embodiment the fluoroaiiphatic radical-containing poly(oxyalkylene) compound can contain 1 to 15, but more preferably 1-2, and most preferably an average of about 1.5 ethylene and/or propylene radicals per molecule of the fluoroaliphatic radical-containing poly(oxyalkylene) compound.
Particularly preferred is the fluoroaliphatic radical-containing poiy(oxyalkylene) compound include those which may be represented by the following general structural formula (3):
CaF28+,N(CHs)(W)a(A)~B X' ( in which:
B represents a water soluble group selected from sulfate, sulfonate, carboxylate, phosphate, phosphonate or halogen group;
W represents a lower alkyl group especially a -CH2-, -CHZCHZ- and/or -CH2CH2CH2 ;
A represents an ethoxy (OCZH4), propoxy (OC3Hs), and/or butoxy (OC4H8) or a mixture of two or mere such groups;
X+ is a salt forming counterion such as an organic counterion, or an inorganic counterion such as an alkali or alkaline earth metal counterion.
n represents a value of between I and 8, preferably is a value of from 1 to 5 inclusive, and most preferably is a value of from about 1 to about 3;
a represents a value of between 1 and 12) preferably is a value of from 5 to inclusive, and most preferably is a value of from about 6 to about 9;
A particularly advantageous fluoroaliphatic radical-containing poly(oxyalkylene) compound which may be used as constituent (a) of the present invention is one which is presently commercially available as Fluorad~ FC-138 from the Minnesota Mining and Manufacturing Co. (St. Paul, MN) which is described as being a composition consisting essentially of: 37% wt. water, 27% wt. of the ' wo 9smr~6 rc~r~s97n9zm - --fluorochemica! salt, 18%wt. of isopropyl alcohol, and 18%wt. of 2-butoxyethanol.
While not wishing to be bound to the following representation, it is believed that this advantageous fluoroaliphatic radical-containing poly(oxyalkylene) compound is a fluorochemical salt is extremely similar to or which may be represented by the following general structural formula (4):
C8F"N(CH3)(CHZ)3(A)~OS02 X+ (4) in which:
n represents a value of between 1 and 3, preferably is a value of from 1 to 2 inclusive, and most preferably is a value of about 1.5;
A represents an ethoxy (OCZH4) group, propoxy (OC3H6) group, or a mixture of such groups, but preferably represents ethoxy;
X+ is a salt forming counterion such as an alkali or alkaline earth metal counterion.
The fluoroaliphatic radical-containing poly(oxyalkylene) compound according to constituent (a) is included in the compositions of the invention in amounts of from between about 0.001 %wt. to about 3%wt.; more desirably the fluoroaliphatic radical-containing poly(oxyalkylene) compound is present in an amount of from 0.1 %wt.
and 0.5%wt. based on the total weight of the composition. It is understood that such fluoroaliphatic radical-containing poly(oxyalkylene) compound may be provided with further constituents, such as water, one or more surfactants in commercial preparations.
These are described in further detail in U.S. Patent No. 5,370,919 to Fieuws, as noted above.
Particularly advantageously used materials which may impart water and/or oil repellency to treated substrates include certain fluorosurfactant compositions which may be added in amounts which facilitate the oil repellent, viz., the oleophobic characteristics of substrates treated with the compositions being taught herein. One such exemplary further fluorosurfactant composition which is desirably included in the compositions of the invention is a perfluoropropionate according to the formula:
-- i G --F(CFZ)~ CHZCH2-S-CHZCH2-COO'X' (A) where:
n is an integer having a value of 6 to 12; and, X' is a salt forming counterion, preferably lithium.
Another such exemplary further fluorosurfactant composition includes a perfluoroalkyl phosphate or salt thereof according to the formula (B):
O
CF3-CF2(CF2CF2)n-CH2CH2-O- ~ =O (B
O
where:
n is an integer having a value of from 6 to 12.
These fluorosurfactant compositions according to formulae (A) and (B) may be used singly, or may be used in a mixture. When used as a mixture, desirably the weight ratio of the perfluoropropionate to the perfluoroalkyl phosphate is in the range of firom about 1:1 to 1:2. Such a mixture is presently commercially available as ZONYL~ 7950.
Such fluorsurfactant compositions include those which are described in US
5,439,610 to Ryan, et al., the contents of which patent are herein incorporated by reference.
Additional exemplary further fluorosurfactant compositions which are desirably included in the compositions of the invention include materials are presently commercially available under the tradena~ne ZONYLO from E.I. DuPont de Nemours Co. Exemplary materials include ZONYL~ FSA which is described as being F(CF2CF2)~8CH2CH2SCH2CHZCOZLi; ZONYLm FSP which is described as being (F(CFZCF2)3$CH2CH20)P(O)(ONH,)2; ZONYL~ FSE which is described as being (F(CF2CFz)3~CHZCH20)ZP(O)(ONH,)2; ZONYL~ UR which is described as being (F(CFZCF2)s.8CH2CH20)P(O)(OH)Z as well as (F(CFZCF2)~CHZCH20)ZP(O)(OH);
ZONYL~ FSJ which is described as being (F(CF2CF2)3$CH2CH~0)P(O)(ONH4)2 in conjunction with a nonfluorinated surfactant; ZONYL~ TBS which is described as being F(CFZCF2)~CHZCH2S03H as well as F(CFzCF2)3$CH2CHZS03NH4. Each of these materials may be used jointly such as in a mixture of two or more __ 17 __ flurorosurfactants, or singly. Of these materials, those available as ZONYL~
7950 are particularly preferred.
A yet further material which improves the resoiling resistance of fibrous substrates treated of the inventive compositions are certain fluorinated acrylic polymers,_including those which conform to the formula (C):
CF3(CF2)~CH20COC(CH3)=CH2 (C) wherein n represents a value of from 6 - 8.
This fluorinated acrylate copolymer may be generally characterized by a total fluorine content based on polymer solids of approximately 0.6 percent. This fluorinated acrylate copolymer may also contain a zinc complex to act as a crosslinker. The number average (Mn) and weight average (Mw) molecular weights are generally in the range of approximately 9,000 and approximately 10,500 respectively. Such a fluorinated acrylate copolymer may be obtained commercially as I S a water based dispersion of approximately 76-77 weight % water; 18-19 weight acrylate copolymer; I weight % nonylphenoxypolyethoxyethanol; I weight %
sodium lauryl sulfate; and 1 weight % zinc oxide complex (with said weight % of the ingredients based on the total weight of the water dispersion), as SYNTRAN~

(Interpolymer Corporation, Canton, MA). When this SYNTRAN~ 1575 composition is employed as constituent (b), it may be included in the present inventive compositions in amounts such that the fluorinated acrylate copolymer is present from 0.001 - 2%wt., desirably in amounts of from 0.001 %wt - 0.75%wt., and most desirably in amounts of from 0.05%wt. - 0.5%wt. with such recited weights being based on the weight of the fluorinated acrylic polymers and/or salts thereof present.
One further particularly useful anti-resoiling compound present inventive compositions is a non-halogenated, especially a non-fluorinated, acrylic polymer compound which may be represented by the formula (D):
(-CHZ CH(COOR)-)~ (D) wherein n is a value greater than 50.
__ I g __ Such a non-fluorinated acrylic polymer is presently commercially available and may be obtained as an aqueous dispersion which includes 78-79%wt. water, 18-19%wt.
of the non-fluorinated acrylic polymer, 1 %wt. of sodium lauryl sulfate, 1 %wt.
sodium nonylpehnoxypolyethoxyethanol sulfate, and 1 %wt. zinc oxide complex as SYNTRAN~ 1580, as well as an aqueous dispersion which includes 74-75%wt.
water, 23-24%wt. of the non-fluorinated acrylic polymer, 1 %wt. of sodium mono-alkylarylpolyethoxy sulfosuccinate, and 1 %wt. sodium lauryl sulfate sulfate as SYNTRAN~1588. These materials are considered to be infinitely miscible in water by the manufacturer, and the former is provided as an aqueous dispersion having a pH
of 8.3 to 9.3, and the latter is provided as an aqueous dispersion having a pH
of 7.7 to 8.7. Both of these materials may be obtained from Interpolymer Corporation (Canton, MA).
In the compositions according to the invention the total weight of such optional constituents should not exceed about 20% by weight of the total weight of the composition, more preferably should not exceed about 10% by weight and is most preferably comprise less than about 7% by weight based on the total weight of the composition according to the invention.
It is to be understood that although the aqueous compositions taught herein have been generally discussed in conjunction with the cleaning of carpets and carpet fibers, they may be used to treat fibers, textiles and fabrics. These include those made with or of one or more naturally occurnng fibers, such as cotton and wool, regenerated natural fibers including regenerated cellulose, and those made with or of synthetically produced fibers, such as polyamides, polyolefins, polyvinylidene chlorides, acetate, nylons, polyacrylics, rayon, and polyester fibers. Blends of two or more such fibrous materials are also expressly contemplated. Such textiles and fabrics may be woven, non-woven or knitted materials.
The compositions of the invention can be prepared in a conventional manner such as by simply mixing the constituents in order to form the ultimate aqueous cleaning composition. The order of addition is not critical. Advantageously ail of the constituents other than water are added to a portion of the total amount of water, and then well mixed. Desirably the surfactants are first added to a volume of water, -- 19 __ WO 98/31776 PCTlUS97/19217 - "
followed by any remaining ingredients especially the optional constituents and then any remaining amount of water. In some cases, where certain of the desired constituents (such as certain nonionic surfactants) are not liquids at room temperature, such may need to be melted, and/or dispersed in an aliquot of the volume of water, usually aided by a dispersing or solubilizing aid. Subsequently any remaining balance of water, if any should be required, is then added. Any pH adjusting agents and/or pH buffering compositions are desirably added last to be in a sufficient amount in order to bring the formed composition within the pH range desired.
The compositions according to the invention may be conveniently applied to a substrate in any of a variety of conventional fashions, such as by spraying;
dipping, coating, padding, foam or roller application, or by a combination of one or more of these, or with other methods not noted here but known to the art. The compositions according to the invention are used in a conventional manner in the cleaning of carpet surfaces. Generally, carpets are effectively cleaned by spraying about 5 grams per square foot of the carpeted surface with the aqueous cleaning composition and subsequently allowing said composition to penetrate among the carpet surface and the fibers. Desirably, this is further facilitated by the use of a manual agitation action, such as by rubbing an area of the carpet to be treated with a device such as a brush, sponge, mop, cloth, non-woven cloth, and the like until the aqueous composition is well intermixed amongst the carpet fibers. Subsequently, the treated area is permitted to dry, which usually requires from as little as 5-10 minutes in areas of high heat and low humidity to as much as an hour or more in poorly heated and high humid locations. Generally, however, the drying period under typical conditions is between about 15 minutes to about 30 minutes. Optionally, but desirably, any remaining composition may be removed from the carpet such as by vacuuming in a conventional manner. In a further optional technique, the carpet may be brushed so to remove any residue of the aqueous composition from amongst the carpet fibers, and then vacuumed or brushed out from the carpeted area.
In contrast to many of the compositions known in the prior art, the aqueous compositions according to the present invention provide surprisingly good cleaning efficacy, and simultaneously a surprisingly effective anti-recoiling characteristic to the treated carpet surface. Thus, the compositions of the present invention provide surprisingly provide these desirable benefits using low cost and widely available materials, frequently without the necessary inclusion of costlier known-art anti-resoiling agents or with such costlier materials in smaller amounts.
The following examples illustrate the superior properties of the formulations of the invention and particular preferred embodiments of the inventive compositions.
The terms "parts by weight" or "percentage weight" are used interchangeably in the specification and in the following Examples wherein the weight percentages of each of the individual constituents are indicated in weight percent based on the total weight of the composition, unless indicated otherwise.
The following examples illustrate the superior properties of the formulations of the invention and particular preferred embodiments of the inventive compositions.
Exemplary formulations illustrated on Table 1 indicate the weight percentages of each of the individual constituents based on the total weight of the composition of which it forms a part.
The example formulations described in more particular detail on Table 1 below were prepared in accordance with the following general protocol. To a mixing vessel (glass beaker equipped with a magnetic stirrer) was first provided a part of the total amount of water, the agitator was then energized, and to the water was then added the remaining constituents. The order of the addition of the remaining constituents varied from formulation to formulation as the order of addition is not critical, but the addition of surface active agents first to the water was generally done as aiding in the dissolution/dispersion of the remaining constituents. The contents of the mixing vessel were well mixed, and ultimately the remaining balance of water, if any was required, was then added. These example formulations were used "as prepared", that is to say without further dilution in the subsequent testing protocols.
Examples which fall within the scope of the invention are denoted as "Ex.", while "comparative" examples are prefixed with "C".

wo ~m~6 rcz'ms9~n~m TABLE 1 _ _ ~~

Formulation: C1 C2 C3 Ex.1 Ex.2 Ex.3 Ex.4 tetrasodium EDTA -- -- -- 2.5 2.5 5.0 6.0 (38%) fluorochemical salt-- -- 0.4 0.4 -- -- --(30%) sodium lauryl sulfate4.0 4.0 4.0 4.0 4.0 4.0 4.0 (30%) ethylene glycol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 monohexyl ether alkoxyiated alcohol-- 0.25 0.25 0.25 0.25 0.25 0.25 isopropanol 2.0 2.0 2.0 2.0 2.0 2.0 2.0 fragrance 0.2 0.2 0.2 0.2 0.2 0.2 0.2 preservative (1.5%)0.05 0.05 0.05 0.05 0.05 0.05 0.05 citric acid 0.01 0.01 0.01 0.01 0.25 0.57 --sulfuric acid (20%)-- -- -- -- -- -- 2.43 DI water 92.7492.49 92.09 89.5989.75 86.9584.07 The identity of the individual constituents used to produce the formulations of Table I
are indicated on Table 2, below. The amounts in Table 1 are on an "as is"
basis as supplied by the respective supplier. The weight percentages of "actives" in a respective constituent are indicated on Table 2, below.

tetrasodium EDTA Hampene~ 100 (Hampshire Chemical (38%) actives_.................._._.~...
__._...~~--_.. _ ~
~
3g/
!!~_ C
:

_...~._ ..
fluorochemical .
salt ._ _ ._ __ .
ZONYL~ 7950 (EI DuPont de Nemours)) 30% 30%wt..,.actives ( ) ' .__......_._._..___.~_...._-.__-___-___..____....

-~._ ....
sodium lauryl Rhodapon~ LCP (Rhone-Poulenc Co., sulfate (30%) Princeton NJ). 30%wt. actives_ ~

~!. ,_, _ _ (lJnion Carbide ethylene glycol r ~Hexyl CELLOSOLVE~

monohexyl ether -. _ Corp., Danbu_ ry CT) _ _ __._Y _..-__ _,~-~

alkoxylated alcoholPolyTergent SL-55~ (Olin Chemical Co.) ~

_-._ Stamford CT) _ __._...__.._~......
___ ...
;_.
-__ .. ~
_Isopropanol _,._,-_~
'sopropanol_-_ ~~__._._.__ ~.~_- ~._. .

g ,~,._.. - pro ...rietar , com osition Fra ra nce _....__._..._._p .._..........Y.._...
..__.....p ..._._._ ___ _.__._...._..-_~._ _._.__._....____~.

preservative (1.5%)Kathon~ CGIICP (Rohm & Haas Co., _ Philadelphia P_A), 1.5_/ activesT.,~~_._-__T

citric acid ~ anhydrous citric acid _ __ _.__ _..__.u...
~.~
~-T
~~~

_. _ } _.~_ ___._._......._._....__........_._.....
sulfuric acid _.__._.__._.____..._.._ (20% _,_. .
es _ __ _.aqueous.,sulfuric-acid,,.20%wt.
activ DI water deionized water The formulations denoted on Table 1 above were tested for their general cleaning and anti-resoiling behaviour on standardized carpet substrates in accordance with two tests, "Jar Mill" and "Hallway" tests. In both of these tests carpet swatches made of a medium pile density light beige colored level loop nylon carpeting were used as a standard testing substrate. Such carpet swatches are similar to those presently commercially available as DuPont Stainmaster~ carpets from a variety of commercial sources. Such carpet swatches were used as standard testing substrates in the following evaluations of cleaning and anti-resoiling as further described below.
From the tested carpet swatches, reflectance was evaluated utilizing a Gardner Colorimeter, using an "LAB color scale". These results were used to provide a quantitative means for light reflectance, which was a useful measure of anti-recoiling behaviour of a tested formulation. These results were also evaluated against a carpet surface which was untreated by any composition, and is indicated as a "control(untreated)" in the following tables.
The Jar Mill test was generally in accordance with the AATCC Test Method 123-1989 for "Carpet Soiling: Accelerated Soiling Method" as published in the AATCC
Technical Manual, published 1992.
The Jar Mill test was performed three times using different formulations; the identity of these particular formulations is denoted on Table 3, following.
In each one of the tests there was used a different test carpet swatch as described above having a length of approximately 23 inches (58.5 cm) and a width of approximately 6 inches ( 15.25 cm). These test carpet swatches were divided into successive zones, each zone having a width of 6 inches ( 15.25cm) and occupying portions along the length of the carpet swatch. The zones, were ordered in numerical succession beginning at one end of the carpet swatch and continuing in contiguous zones to the opposite end of the carpet swatch. Specifically, zone 1 which was contiguous with one end of the carpet swatch, had a width of 6 inches ( 15.25 cm) and a length of 4 inches ( 10.5 cm), thus providing a test carpet surface area of 24 square inches ( 160 square cm).
The next contiguous zone was zone 2 being 6 inches ( 15.25 cm) in width and 3 inches (7.6 cm) in length, providing a test carpet surface area of 18 square inches (116 square cm). The third zone, contiguous with the end of the second zone was 6 inches (15.25 cm) in width and 3 inches (7.6 cm) in length, thus again providing a test carpet surface area of 18 square inches ( 116 square cm) . The next, zone 4 was contiguous to zone 3 and had a width of 6 ,0.r'~IEND~ED SHEET
I~EA/c?

inches ( 15.25 cm) and a length of 3 inches (7.6 cm), again providing a test carpet surface area of 18 square inches ( 1 I 6 square cm). The next zone, zone 5, was contiguous to the prior zone 4, was 6 inches ( 15.25 cm) in width and also 3 inches ( 15.25 cm) in length and this provided a test carpet surface area of 18 square inches ( I 16 square cm). The next succeeding zone, zone 6, had a width of 6 inches ( I 5.25 cm) and a length of 3 inches (7.6 cm), providing a test carpet surface area of 18 square inches ( 116 square cm). The final zone, which occupied the remaining portion of the carpet test swatch, and was contiguous to zone 6, was 6 inches in width ( 15.25 cm), and occupied the remaining 4 inches ( 10.5 cm) in length of the carpet test swatch and is designated as zone 7. This zone 7 provided a carpet test area of 24 square inches ( 160 square cm).
In accordance with Test 1, to zone 2, as described above, was applied approximately 3.65 grams of Formulation C2. Similarly to zone 4 was applied approximately3.65 grams of formulation according to C3, and in a like manner approximately 3.65 grams of the formulation according to Example 1 was applied to zone 6. Thereafter, each of these zones of the carpet test swatch were rubbed into the carpet utilizing 20 transverse strokes and 20 longitudinal strokes which were manually applied in a uniform manner utilizing a clean folded laboratory non-woven wipe (KIMWIPE~ Kimberly Clark Corporation). The carpet test swatch was then permitted to dry overnight.
The next day, the treated test carpet swatch was then subj ected to the AATCC
Test Method 123-1989 wherein the carpet swatch was tumbled with a prepared synthetic soil for an established period of time. This synthetic soil comprised the following: 28% by weight peat moss; 17% by weight Portland cement; 17% by weight Kaolin clay; 17% by weight silica (200 mesh); 1.75% by weight carbon black (lamp or furnace black); 0.50% by weight red iron oxide; and 8.75% by weight of medicinal grade mineral oil. This synthetic soil was prepared in accordance with the recited AATCC Test Method.
The carpet swatches were then placed into porcelain ball mill jars and tumbled with specimens of the synthetic prepared soil as well as flint pebbles for a time.
interval of 5 minutes, after which the test carpet swatch was removed.
Subsequently, the test carpet swatch was cleaned by light vacuuming with a tank type vacuum cleaner in accordance with the AATCC test protocols.

/-~,i~l~~.~r-~,,~~ ~~-"CT
ir;'~;-.~~

Subsequently, the test carpet swatch was evaluated for light reflectance utilizing a BYK Gardener Spectrophotometer/Colorimeter set on "D65"
illumination.
Nine readings were taken of each zone of the test carpet swatch, and the mean value for "L" as reported by the BYK device. This reading indicates the "lightness"
or S "darkness". of an evaluated sample, which provided the most relevant data with respect to the level of the anti-resoiling properties of a test formulation.
These readings are reported in Table 3.
Similarly, the protocol outlined above was repeated for test 2, except that in zone 2 was applied approximately 3.65 grams of the Formulation of C2, to zone 4 was applied approximately 3.G5 grams of the formulation of Example 2, and to zone 6 was applied approximately 3.G5 grams of formulation according to Example 3. All other portions of the tests were performed in substantially the same manner as described above with reference to Test 1. The percent reflectance, as obtained from the BYK
1 Gardener Spectrophotometer/Colorimeter, is similarly reported on Table 3.
Similarly, the same general protocol as performed for test 1 was also utilized in performing Test 3. However, in test 3, approximately 3.G5 grams of the formulation according to C 1 was applied to zone 2, approximately 3.65 grams according to C2 were applied to zone 4, and approximately 3.65 grams of the formulation according to Example 4 were applied to zone 6 of the standard carpet swatch. Again, the results as obtained from the measurements utilizing the BYK
Gardener Spectrophotometer/ Colorimeter are reported on Table 3.
As may be seen from the results reported for Test 1, the formulation according to C2 contained no fluorochemical and no EDTA constituent, and also demonstrated the poorest anti-resoiling properties. The formulation according to C3 including a fluorochemical constituent, and showed a slight increase in the anti-resoiling properties. Surprisingly, however, the addition of the amounts of EDTA salt, further in conjunction with the fluorochemical as illustrated in Example l, provided a substantial increase in the anti-resoiling properties which is both better than the formulation according to C3 as well as better than the control (untreated) test carpet swatch.

WO 98131'Tl6 PCT/US97/19Z17 Turning now to the results reported in conjunction with Test 2, each of the formulations in Test 2 contained no fluorochemical constituent. As may be seen from the results, the formulation according to C2 contained no fluorochemical and no EDTA salt and showed poor anti-resoiling properties. The next formulation according to Example 2 contained a small amount of EDTA salts, and demonstrates similar anti-resoiling properties to that of C2. Again, surprisingly the addition of higher amounts of EDTA salts to the formulation, as is demonstrated by Example 3 of Test 2, shows a significant and surprising improvement in the anti-resoiling properties. It was also observed that the controlled (untreated) test carpet swatch demonstrated excellent anti-resoiling characteristics. This can in part be attributed to the fact that the controlled (untreated) test carpet swatches were not provided with any liquid chemical compositions, such as formulations of Table 1, and thus would have a minimal or negligible effect on attracting soil to their untreated surfaces.
With respect now to the results reported for Test 3, the first formulation I 5 according to C 1 included no nonionic surfactant constituent, no fluorochemical constituents, and no EDTA salts and yet provided a good amount of anti-recoiling characteristics to the carpet surface. The absence of certain constituents, especially the nonionic surfactants which are known to the art to be sticky and tacky good attractors and retainers of soil particles, are absent from the formulation according to C 1. Turning now to the formulation according to C2, this formulation included nonionic surfactants, and a concomitant decrease in the anti-resoiling properties of the test carpet swatch are observed. Turning now to the remaining formulation according to Example 4 which included a significant amount of EDTA salts as well as the same amount of the nonionic surfactant according to.C2. Surprisingly, a striking improvement in the anti-resoiling properties, notwithstanding the relatively high amounts of the nonionic surfactant constituent, were achieved. Further, the results obtained with use of formulation of Example 4, were favorably comparable to that of the control (untreated) portion of the test carpet swatch. It was also noted that in Example 4, the increased amount of citric acid was provided as a pH adjusting agent.

Test Formulation % Reflectance 1 C2 51.67 C3 54.38 Ex.1 60.44 Control (untreated) 59.66 2 C2 54.56 Ex.2 54.11 Ex.3 57.94 Control (untreated) 61.82 3 C1 60.49 C2 57.28 Ex.4 60.38 Control (untreated) 61.81 Hallwa"LTest:
A test designed to be more representative of the results, of a more characteristic setting for a carpet was performed. In this test, a test carpet swatch, treated with several of the formulations noted in Table 1 was installed in a busy hallway for a period of time.
The carpet swatch was of the DuPont Stainmaster~ carpet type described above, and measured 3 feet in width and 7 feet in length. This carpet swatch was divided into five zones, the first Zone 1 beginning at one end and being 3 feet in width and 2 feet in length. Zone 2 being contiguous to the prior zone 1 and being 3 feet (0.9 metres) in width and extended for 1 foot (0.3 m) in length. The next contiguous zone, Zone 3, 3 feet (0.9 m) in width and extending 1 (0.3 m) foot in length. Zone 4, contiguous to the prior Zone 3, 3 feet (0.9 m) in width and 1 foot (0.3 m) in length. The final Zone 5, being the remaining 2 feet (0.6 m) in length of the test carpet swatch and 3 feet (0.9 m) in width.
This test carpet swatch was treated in accordance with the following protocol:
Zone 1 and Zone 5 were left untreated and are designated "control (untreated)", and were used as a comparative example. To Zone 2 was applied approximately 50 grams of the formulation according to C 1, as described in detail in Table 1 above. To Zone 3 was applied 50 grams of Formulation C2 of Table 1, and to Zone 4 was applied 50 grams of the formulation according to Example 4, each of which are described in Table 1 above.
Thereafter, each of these formulations were rubbed into their respective zones of the carpet utilizing 20 transverse strokes and 20 longitudinal strokes. Rubbing was manually applied in a uniform manner utilizing a clean folded laboratory non-woven wipe (KIMWIPE~, Kimberly Clark Corporation). The carpet test swatch was then permitted to dry overnight.
__ 2~ __ n ., ,, -.. . .- - -.,~ . ~ T
!'\i'n1w~.~~ . . .. .,y 1 I 1 .. .

WO 98/31'176 PCT/U897/19217 The thus treated test carpet swatch was installed in the hallway, and taped down using a strong adhesive tape at its edges. The carpet was retained in this location for four weeks, and the normal passerbys of the hallway were permitted to pass over the total surface of the thus installed test carpet swatch. It was estimated that approximately 16,000 individuals passed across the surface of the test carpet swatch during this four-week interval. Subsequently, the test carpet swatch was removed from the floor, and each of the zones was evaluated utilizing the BYK
Gardener Spectrophotometer/Colorimeter set for D65 illumination as described above with reference to the Jar Mill testing. As therein, nine readings were taken on each of the zones, and the mean value of these are reported on Table 4, below.

Test Formulation % Reflectance 4 ~ C1 79.84 C2 79.14 Ex.4 79.95 As can be seen by the results reported on Table 4, the formulation according to C 1 included no nonionic constituent, no fluorochemical constituent and no EDTA
salts. The formulation according to C2 included a nonionic surfactant constituent, no fluorocarbon constituent and no EDTA salt in its make up. As can be seen, its 1 S reported percentage light reflectance was somewhat inferior to that of the prior sample.
Surprisingly; the formulation according to Example 4 which included no fluorochemicai, but did include a higher amount of EDTA salts provided significantly improved results, with the highest reflectance of reading of any of the tested areas of the test carpet substrate in this test, text No. 4. Thus, it can be seen that notwithstanding the increased amounts of the nonionic surfactant, the addition of the greater amounts of the tetra sodium EDTA salts to the compositions of Example provided a significant improvement to the overall anti-resoiling properties of the formulation, which were better than the formulation according to C l, as well as the _ nonionic surfactant containing formulation of C2.
F:\US ERS\ANP\FR\0829112490D I \249p°two.doc ~, , .3 , , ~. ( , . a _- 2g __ ... ! ~ r

Claims

Claims:

1. An aqueous carpet cleaning composition which comprises the following constituents:
A) 0.1 - 11 %wt. of one or more surfactant compounds selected from anionic, nonionic and amphoteric surfactant compounds;
B) 0.5 - 50%wt. of an aminopolycarboxylic acid salt;
C) 0.1 - 5.0%wt. of an organic solvent; and, D) 0 - 20%wt. of one or more optional constituents including but not limited to:
further organic solvents or co-solvents, further recoiling inhibiting agents, chelating agents, fragrances, preservatives, viscosity modifying agents such as thickening agents, preservatives, pH adjusting agents, pH buffers, agents for imparting water repellency to carpets and carpet fibers, and agents for imparting oil repellency to carpets and carpet fibers, a stain repellency imparting composition based on a fluorine containing compound.
2. An aqueous carpet cleaning composition according to claim 1 which comprises:
0.5 - 1.5% wt. of an anionic surfactant based on one or more sulfate or sulfonate compounds;
0.05 - 0.5%wt. of a nonionic surfactant based on one or more alkoxylated aliphatic alcohols;
0.1 - 6.0%wt. a salt of an aminopolycarboxylic acid;
0:1- 5.0%wt. of at least one organic solvent constituent;
0 - 10%wt. of one or more constituents selected from organic solvents or co-solvents, chelating agents, fiuther resoiling inhibiting agents, fragrances, preservatives, viscosity modifying agents; pH adjusting agents, pH buffers, agents for imparting water repellency to carpets and carpet fibers, and agents for imparting oil repellency to carpets and carpet fibers, stain repellency imparting compositions based on a fluorine containing compound.

3. An aqueous carpet cleaning composition according to claim 3 which comprises:
0.1 - 5.0%wt. of at least one organic solvent wherein said organic solvent exhibits a vapor pressure of less than 0.05mm Hg at a temperature of 25°C.
4, An aqueous carpet cleaning composition according to claim 1 which comprises at least 1% wt. of an aminopolycarboxylic acid;
5. An aqueous carpet cleaning composition according to claim 1 which comprises a fluorinated acrylate copolymer is one which conforms to the formula (C):

CF3(CF2)n CH2OCOC(CH3)=CH2 (C) wherein n represents a value of from 6 - 8.
6. An aqueous carpet cleaning composition according to claim 1 which comprises a non-fluorinated, acrylic polymer compounds which may be represented by the formula (D):

(-CH2-CH(COOR)-)n (D) wherein n is a value greater than 50.
7. An aqueous carpet cleaning composition according to claim 1 which comprises a fluoroaliphatic oligomer or polymer represented by the formula (1) and (2):

(R f)S Z[(R3)y Z'B]t (1) (R f)s Z[(R3)Y Z'B']t]W (2) where R f is a fluoroaliphatic radical, Z is a linkage through which R f and (R3)y moieties are covalently bonded together, (R3)y is a poly(oxyalkylene) moiety, R3 being an oxyalkylene group with 2 to 4 carbon atoms and y is an integer (where the above formulas are those of individual compounds) or a number (where the above formulas are those of mixtures) at least 1, preferably 1 to 125 and can be as high as 180 or higher, B is a hydrogen atom or a monovalent terminal organic radical, B' is B or a valence bond, with the proviso that at least one B' is a valence bond interconnecting a Z-bonded R3 radical to another Z, Z' is a linkage through which B, or B', and R3 are covalently bonded together, s is an integer or number of at least 1 and can be as high as 25 or higher, t is an integer or number of at least 1, and can be as high as 60 or higher, and w is an integer or number greater than 1, and can be as high as 30 or higher.
8. An aqueous carpet cleaning composition according to claim 1 which comprises fluoroaliphatic radical-containing poly(oxyalkylene) compound include those which may be represented by the following general structural formula (3):

C a F2a+1N(CH3)(W)3(A)n B- X+ (3) in which:
B represents a water soluble group selected from sulfate, sulfonate, carboxylate, phosphate, phosphonate or halogen group;
W represents a lower alkyl group especially a -CH2-, -CH2CH2- and/or -CH2CH2CH2-;
A represents an ethoxy (OC2H4), propoxy (OC3H6), and/or butoxy (OC4H8) or a mixture of two or more such groups;

X+ is a salt forming organic or inorganic counterion;
n represents a value of between 1 and 8;
represents a value of between 1 and 12.
9, An aqueous carpet cleaning composition according to claim 1 which comprises a fluorochemical salt which may be represented by the following general structural formula (4):

C8F17N(CH3)(CH2)3(A)n OSO2- X+ (4) in which:
n represents a value of between 1 and 3;
A represents an ethoxy (OC2H4), propoxy (OC3H6), or a mixture of such groups; and, X+ is a salt forming counterion.
10. An aqueous carpet cleaning composition according to claim 1 which comprises a perfluoropropionate according to the formula:

F(CF2)n-CH2CH2S-CH2CH2COO-X+ (A) where:
n is an integer having a value of 6 to 12; and, X+ is a salt forming counterion, 11. An aqueous carpet cleaning composition according to claim 1 which comprises perfluoroalkcyl phosphate or salt thereof according to the formula (B):

where:
n is an integer having a value of from 6 to 12.
12. An aqueous carpet cleaning composition according to claim 1 which comprises a fluorinated acrylic polymer according to formula (C):

CF3(CF2)n CH2OCOC(CH3)=CH2 (C) wherein n represents a value of from 6 - 8.
13. An aqueous carpet cleaning composition according to claim 1 which comprises a non-fluorinated acrylic polymer compound according to formula (D):
(-CH2CH(COOR)-)n (D) wherein n is a value greater than 50.
14. A process for cleaning and providing an anti-resoiling benefit to a carpet, textile or fabric which comprises the process step of applying an effective amount of the composition according to claim 1 to the a carpet, textile or fabric.

1. An aqueous carpet cleaning composition which comprises the following constituents:
A) 0.1 - 11 %wt. of one or more surfactant compounds selected from anionic, nonionic and amphoteric surfactant compounds;
B) 0.5 - 50%wt. of an aminopolycarboxylic acid salt;
C) 0.1 - 5.0%wt. of an organic solvent; and, D) 0 - 20%wt. of one or more optional constituents including but not limited to:
further organic solvents or co-solvents, further recoiling inhibiting agents, chelating agents, fragrances, preservatives, viscosity modifying agents such as thickening agents, preservatives, pH adjusting agents, pH buffers, agents for imparting water repellency to carpets and carpet fibers, and agents for imparting oil repellency to carpets and carpet fibers, a stain repellency imparting composition based on a fluorine containing compound.

2. An aqueous carpet cleaning composition according to claim 1 which comprises:
0.5 - 1.5% wt. of an anionic surfactant based on one or more sulfate or sulfonate compounds;
0.05 - 0.5%wt. of a nonionic surfactant based on one or more alkoxylated aliphatic alcohols;
0.1 - 6.0%wt. a salt of an aminopolycarboxylic acid;
0.1 - 5.0%wt. of at least one organic solvent constituent;
0 - 10%wt. of one or more constituents selected from organic solvents or co-solvents, chelating agents, further recoiling inhibiting agents, fragrances, preservatives, viscosity modifying agents; pH adjusting agents, pH buffers, agents for imparting water repellency to carpets and carpet fibers, and agents for imparting oil repellency to carpets and carpet fibers, stain repellency imparting compositions based on a fluorine containing compound.

3. An aqueous carpet cleaning composition according to claim 3 which comprises:
0.1 - 5.0%wt. of at least one organic solvent wherein said organic solvent exhibits a vapor pressure of less than 0.05mm Hg at a temperature of 25°C.

4. An aqueous carpet cleaning composition according to claim 1 which comprises at least 1% wt. of an aminopolycarboxylic acid salt.

5. An aqueous carpet cleaning composition according to claim 1 which comprises a fluorinated acrylate copolymer is one which conforms to the formula (C):
CF3(CF2)n CH2OCOC(CH3)=CH2 (C) wherein n represents a value of from 6 - 8.

6. An aqueous carpet cleaning composition according to claim 1 which comprises a non-fluorinated, acrylic polymer compounds which may be represented by the formula (D):
(-CH2-CH(COOR)-)n (D) wherein n is a value greater than 50.

7. An aqueous carpet cleaning composition according to claim 1 which comprises a fluoroaliphatic oligomer or polymer represented by the formula (1) and (2):
(R f)s Z[(R3)y Z'B]t (1) [(R f)s Z[(R3)y Z'B']t]w (2) where R f is a fluoroaliphatic radical, Z is a linkage through which R f and (R3)y moieties are covalently bonded together, (R3)y is a poly(oxyalkylene) moiety, R3 being an oxyalkylene group with 2 to 4 carbon atoms and y is an integer (where the above formulas are those of individual compounds) or a number (where the above formulas are those of mixtures) at least 1, preferably 1 to 125 and can be as high as 180 or higher, B is a hydrogen atom or a monovalent terminal organic radical, B' is B or a valence bond, with the proviso that at least one B' is a valence bond interconnecting a Z-bonded R3 radical to another Z, Z' is a linkage through which B, or B', and R3 are covalently bonded together, s is an integer or number of at least 1 and can be as high as 25 or higher, t is an integer or number of at least 1, and can be as high as 60 or higher, and w is an integer or number greater than 1, and can be as high as 30 or higher.

8. An aqueous carpet cleaning composition according to claim 1 which comprises fluoroaliphatic radical-containing poly(oxyalkylene) compound include those which may be represented by the following general structural formula (3):
C a F2a+1N(CH3)(W)3(A)n B- X+ (3) in which:
B represents a water soluble group selected from sulfate, sulfonate, carboxylate, phosphate, phosphonate or halogen group;
W represents a lower alkyl group especially a -CH2-, -CH2CH2- and/or -CH2CH2CH2-;
A represents an ethoxy (OC2H4), propoxy (OC3H6), and/or butoxy (OC4H8) or a mixture of two or more such groups;

X+ is a salt forming organic or inorganic counterion;
n represents a value of between 1 and 8;
a represents a value of between 1 and 12.

9. An aqueous carpet cleaning composition according to claim 1 which comprises a fluorochemical salt which may be represented by the following general structural formula (4):
C8F17N(CH3)(CH2)3(A)n OSO2- X+ (4) in which:
n represents a value of between 1 and 3;
A represents an ethoxy (OC2H4), propoxy (OC3H6), or a mixture of such groups; and, X+ is a salt forming counterion.

10. An aqueous carpet cleaning composition according to claim 1 which comprises a perfluoropropionate according to the formula:
F(CF2)n-CH2CH2-S-CH2CH2-COO-X+ (A) where:
n is an integer having a value of 6 to 12; and, X+ is a salt forming counterion,

11. An aqueous carpet cleaning composition according to claim 1 which comprises perfluoroalkyl phosphate or salt thereof according to the formula (B):

where:
n is an integer having a value of from 6 to 12.

12. An aqueous carpet cleaning composition according to claim 2 which comprises a fluorinated acrylic polymer according to formula (C):
CF3(CF2)n CH2OCOC(CH3)=CH2 (C) wherein n represents a value of from 6 - 8.

13. An aqueous carpet cleaning composition according to claim 2 which comprises a non-fluorinated acrylic polymer compound according to formula (D):
(-CH2-CH(COOR)-)n (D) wherein n is a value greater than 50.

14. A process for cleaning and providing an anti-resoiling benefit to a carpet, textile or fabric which comprises the process step of applying an effective amount of the composition according to claim 1 to the a carpet, textile or fabric.