WO1991013145A1

WO1991013145A1 - Ionizable polymer cleaning compositions and methods for cleaning stains

Info

Publication number: WO1991013145A1
Application number: PCT/US1991/001178
Authority: WO
Inventors: Dale M. Pickelman; Gene D. Rose; John G. Lenhart; David G. Long; Donald L. Schmidt; John Klier
Original assignee: The Dow Chemical Company
Priority date: 1990-02-28
Filing date: 1991-02-22
Publication date: 1991-09-05
Also published as: JPH05502909A; CA2055432A1; EP0473757A1

Abstract

Disclosed are cleaning compositions useful on oil and grease stains wherein the cleaning compositions generally consist of an ionizable polymer and a nonionic surfactant and/or solvent(s). The cleaning compositions also contemplate the use of a more specific class of such ionizable polymers: the pH independent ionizable polymers and a nonionic surfactant and/or an organic solvent. Further disclosed are methods for cleaning stains from a surface or fabric by contacting the surface or fabric with such various cleaning compositions. Further disclosed are methods of pretreating a stain on a fabric which entails contacting the stain with the composition and washing the fabric in an aqueous solution of a laundry detergent.

Description

IONIZABLE POLYMER CLEANING COMPOSITIONS AND METHODS FOR

CLEANING STAINS

This invention is directed to cleaning compositions and methods useful in removing stains, particularly those of oil and grease or those of oil and grease containing particulates from surfaces or fabric.

Prior art cleaning compositions have not performed as well as desired in removing stains, especially hydrophobia oily ones containing particulates, from surfaces and fabrics. Problems have included insufficient lipophilic compatibility of the cleaning compositions with the stains; lack of wettability sufficient to overcome the work of adhesion at the substrate-stain interface; insufficient stabilization of the stain removed from the surface or fabric; and variability of cleaning efficiency with pH and ionic content of the washing media.

Lipophilic compatibility of prior art cleaning compositions with stains is a problem because such compositions are typically highly aqueous, and, thus, very hydrophilic. Stains which are difficult to clean are either hydrophobic or amphiphilic. Still more difficult to clean are hydrophobic stains containing particulates. Prior art compositions are typically too hydrophilic to clean these stains. Though the inclusion of conventional surfactants and organic solvents may reduce the hydrophilicity of the compositions, the compositions nonetheless are typically still too hydrophilic to remove the stains.

Insufficient wettability to overcome the work of adhesion at the substrate-stain interface is thought to result from the typically highly aqueous nature of such compositions.

Insufficient stabilization of the stain removed from a surface or fabric by prior art cleaning compositions has necessitated the use of chelating, sequestering, and antiredeposition agents. While the agents are efficacious to a certain degree, they are not thought to provide the desired degree of stabilization with hydrophobic stains.

Cleaning efficiency of prior art compositions may vary according to pH or ionic content due to their effect upon the chemical composition of prior art anionic surfactants. Soaps are subject to formation of insoluble lime salts or loss of anionic charge. Such side reactions and ionic variations have necessitated the use of buffering agents, builders and lime soap dispersing aids.

While these effects have been offset somewhat by the use of nonionic surface active agents, the nonionic surfactants alone do not sufficiently address the problems of the aqueous nature of the cleaning media, overcoming the forces of adhesion of stains to the substrate, or stabilization of the soil. Accordingly, there exists a need for: an improved cleaning composition which offers superior cleaning of stains, especially those of oil and grease and those of oil and grease containing particulates; an improved cleaning composition which is more compatible with hydrophobic and nonhydrophilic stains; an improved cleaning composition which offers superior wetting and stabilization of stains and compatibility therewith; and an improved cleaning composition that offers superior cleaning regardless of: composition; pH; or foreign ionic content, of the washing media. Desirably, the cleaning composition would offer superior cleaning without the use of buffering, antiredeposition, chelating, or sequestering agents. Further desirably, such improved cleaning compositions would be available in a concentrated form such as in a solid stick as well as a solution or liquid. The concentrated form not only imparts synergistic cleaning but also imparts greater efficiency for use in a pretreatment function.

Accordingly the present invention includes an improved method of cleaning a stain from a surface or fabric characterized by contacting the stain with a cleaning composition characterized by an ionizable polymer and a nonionic surfactant. Preferably, the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively. More preferably, the ratio of nonionic surfactant to ionizable polymer will be 200:1 to 1:1. Most preferably, the ratio of nonionic surfactant to ionizable polymer will be 100:1 to 1.5:1.

Accordingly the present invention also includes an improved method of cleaning a stain from a surface or fabric characterized by contacting the stain with a cleaning composition characterized by an ionizable polymer and a solvent or mixture of solvents.

Accordingly the present invention also includes an improved method of cleaning a stain from a surface or fabric which is characterized by contacting the stain with a cleaning composition characterized by an ionizable polymer, a nonionic surfactant and a solvent or mixture of solvent(s). Preferably, if the solvent or solvent mixture contains water, the water is present at

10 equal to or less than 60 and more preferably less than 40 weight percent of the cleaning composition, if the solvent or solvent mixture contains organic solvent, the organic solvent can be present up to or equal to 90 -c weight percent of the cleaning composition.

Accordingly the present invention also includes an improved method of pretreating a stain on a surface such as a fabric characterized by contacting the stain

20 with the cleaning composition and washing the surface in water or aqueous solution.

Accordingly the present invention includes an improved method of cleaning a stain from a surface or

,.,-• fabric characterized by contacting the stain with a cleaning composition characterized by a pH independent ionizable polymer and a nonionic surfactant. Preferably, the nonionic surfactant and pH independent ionizable polymer are present in a weight ratio range of

30 1000:1 to 1:4 respectively. More preferably, the ratio of nonionic surfactant to ionizable polymer will be 200:1 to 1:1. Most preferably, the ratio of nonionic surfactant to ionizable polymer will be 100:1 to 1.5:1. Accordingly the present invention also includes an improved method of cleaning a stain from a surface or fabric characterized by contacting the stain with a cleaning composition characterized by a pH independent ionizable polymer and a solvent or mixture of solvents.

Accordingly the present invention also includes an improved method of cleaning a stain from a surface or fabric which is characterized by contacting the stain with a cleaning composition characterized by a pH independent ionizable polymer, a nonionic surfactant and a solvent or mixture of solvent(s). Preferably, if the solvent or solvent mixture contains water, the water is present at equal to or less than 60 more preferably less than 40 weight percent of the cleaning composition, if the solvent or solvent mixture contains organic solvent, the organic solvent can be present up to or equal to 90 weight percent of the cleaning composition.

Accordingly the present invention also includes an improved method of pretreating a stain on a surface such as a fabric characterized by contacting the stain with the cleaning composition and washing the surface in water or aqueous solution.

Accordingly the present invention also includes a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition characterized by a pH independent ionizable polymer containing a nonionic hydrophobic monomer, a nonionic surfactant and a solvent which comprises greater than 10 weight percent of the composition.

Accordingly the present invention also includes a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition which comprises a pH independent ionizable polymer containing more than 60 weight percent of a nonionic hydrophobic monomer and a solvent.

Accordingly the present invention also includes a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition which comprises a pH independent ionizable polymer containing more than 40 weight percent of a nonionic

10 hydrophobic monomer, a nonionic surfactant, 0 to 10 weight percent of an organic solvent, and 0 to 25 weight percent of water. The ionizable polymer is present at 1 to 40 weight percent based upon the total weight of the x r- ionizable polymer and the surfactant, and the weight percents of the solvent are based upon the weight of the composition.

Accordingly the present invention also includes 0 a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition which comprises a pH independent ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer and a nonionic surfactant.

25

Accordingly the present invention also includes a method of pretreating a stain on a fabric comprises contacting the stain with a cleaning composition and washing the fabric in water or aqueous detergent 30 solution. The cleaning composition comprises a pH independent ionizable polymer containing a nonionic hydrophobic monomer and a solvent wherein the organic solvent comprises greater than 10 weight percent of the composition. Alternatively, the cleaning composition may comprise a pH independent ionizable polymer containing a nonionic hydrophobic monomer and a nonionic surfactant.

Accordingly the present invention also includes a cleaning composition comprises a pH independent ionizable polymer containing a nonionic hydrophobic monomer, a nonionic surfactant, and a solvent. The ionizable polymer is present at 1 to 40 weight percent based upon the total weight of the ionizable polymer and the surfactant, and the organic solvent comprises greater than 10 weight percent of the composition.

Accordingly the present invention also includes a cleaning composition characterized by a pH independent ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer and a nonionic surfactant.

The general class of ionizable polymers useful in the cleaning compositions and methods of the present invention include the class of ionizable polymers represented by Formula I:

A[(B)_b(C)c(D)d(E)_e]F I

In Formula I, A and F are terminal groups and B,C,D, and E represent types of internally covalently bonded groups described herein below that can be covalently bound in any variety of sequences. The subscripts b,c,d, and e are positive numbers that represent the mole fraction of the types of internally covalently bonded groups. Any one kind of internally covalently bonded group type car. occur in a greater number than any other kind of internally covalently bonded group type or not at all for example to impart a homopolymer. More than one kind of each type of any covalently bonded group can occur in any copolymer of this invention. For example, the copolymer may contain (Di), (D2)...(D_π) where n is a positive integer and the sum of the subscripts, b+c+d^*ι+d2 etc. is equal to one.

These internally covalently bonded groups may also occur in any polymer form. For example they may be combined in the form of di-or tri-block or linear polymers, or in the form of branched polymers, or in the form of grafted polymers, or in the form of macromers (such as those taught by Yamashita, et al, J. Polymer Sci: Part A: Polymer Chemistry, Vol 27, 1099-114 (1989)) or in the form of blends of one or more polymers, or in the form of core/shell structures such as those taught in United States Patent No. 4,427,819. The ionizable polymer typically has a number average molecular weight from 1500 to 10,000,000; preferably from 5000 to 4,000,000.

One class of ionizable polymers represented by Formula I is prepared by free radical polymerization of ethylenically unsaturated monomers wherein B, C, D, and E in Formula I, are selected from ethylenically unsaturated monomers described below and A and F represent chain initiator or terminating groups.

Ethylenically unsaturated monomers representative of B in Formula I contain at least one ionizable group that upon ionization is not sensitive to the pH of the medium. Examples of such monomers include, but are not limited to, acrylic or methacrylic esters of alkyl or aryl sulfonates, such as 2- sulfoethylmethacrylate and sulfopropyl methacrylate; acrylamido alkyl or aryl sulfonates. such as acrylamido- 2-methylpropanesulfonic acid; sulfonated aromatic monomers, such as styrene sulfonic acid or vinyl sulfonic acid; and the like. Alternatively, the salts of these monomers may also be useful. The value of b may vary from 0 to 1.0 with the restriction that either monomer B or C must be present in a quantity such that final charge to mass of the ionizable polymer will be at least 0.1 meq/g. If the ionizable polymer is part of a blend of polymers or a core/shell structure, the final charge of the mass of the blend or core/shell structure

1 0 will be at least 0.1 meq/g.

Ethylenically unsaturated monomers representative of C in Formula I contain at least one ionizable group that upon ionization is sensitive to the

,-- pH of the medium. Examples of such monomers include, but are not limited to, monocarboxylate containing monomers, such as acrylic acid and methacrylic acid; dicarboxylate containing monomers, such as itaconic acid, maleic anhydride; and the like. These monomer 0 units can either be added as monomers or can be formed during the polymerization process by the hydrolysis of various esters of these monomers, or their polymers. The value of c may vary from 0 to 1.0 with the restriction that either monomer B or C must be present 5 in a quantity such that final charge to mass of the ionizable polymer will be at least 0.1 meq/g. If the ionizable polymer is part of a blend of polymers or a core/shell structure, the final charge of the mass of 0 the blend or core/shell structure will be at least 0.1 meq/g.

Ethylenically unsaturated monomers representative of D -in Formula I do not contain any ionizable groups and are characterized by having nonionic. hydrophobic units. The term hydrophobic unit or group is taken to mean those monomers, which when in the form of an amorphous homopolymer, would have a solubility in water of less than 0.1 wt% at 20°C. Examples of such monomer include, but are not limited to acrylic and methacrylic acid alkyl and aryl esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, n-butylmethacrylate, t- butylmethacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, phenyl methacrylate, etc; aromatic monomers such as styrene, vinyl toluene, t-butyl styrene, etc; alkyl and aryl esters of dicarboxylate containing monomers, such as itaconic acid, maleic anhydride; α-olefin(s); and the like. The minimum value of d is zero. The maximum value of d will depend on the formula weight of the monomers chosen and will be such that at least 0.1 meq of ionizable charge per gram of final polymer will be present.

Ethylenically unsaturated monomers representative of E in Formula I do not contain any ionizable groups and are characterized by having some water solubility or amphiphilic character. Examples of such monomers include, but are not limited to, acrylic and methacrylic acid alkyl and arylesters of groups that confer water solubility, such as 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, or that are surfactants, such as nonylphenyl polyoxyethylene [10] methacrylate; or acrylamide; and the like. Other examples of such monomers are monomers that are cationic by nature. These can either be sensitive to pH such as the N,N- dimethylaminoethyl methacrylate, or insensitive to pH. such as N,N,N-trimethylaminoethyl methacrylate/dimethyl sulfate (Sipomer^® Q5. Alcoiac): and the like. In the case where cationic or potentially cationic monomers are used the mole fraction of this monomer will be less than that of the anionic or potentially anionic monomers B and C, respectively. In all cases, the minimum value of e is zero. The maximum value of e will depend on the formula weight of the monomers chosen and will be chosen such that at least 0.1 meq of ionizable charge per gram of final polymer will be present.

10 Most preferably, the ionizable polymer is not chosen from polyalkylene glycol monoacrylate, (such as polyethylene glycol monomethacrylate) , polyalkylene glycol alkyl or aryl ether monoacrylate in the molecular

-j- weight range of 2,000 to 200,000 when to be used in combination with an acrylamido sulfonic acid (such as 2- acylamido-2-methyl propane sulfonic acid) at a concentration of greater than 5 preferably 10 weight, more preferably 20 percent based on the total weight of 0 the composition.

The optimal monomers to prepare the ionizable polymer are chosen to effectuate compatibility of the cleaning compositions with the stains and surfaces from 5 which the stain is to be removed. Selection can be made on the basis of a typical formulation scheme employing, e.g., known solubility parameters.

Compositions according to the present invention 0 may employ mixtures of two or more polymers. Such mixtures will contain at least one ionizable polymer and may contain one or more unionizable polymers. The unionizable polymer may be formed from the hydrophilic and hydrophobic monomer combinations described previously, but will be predominantly hydrophobic in character. Vinyl epoxides such as glycidyl methacrylate and allyl glycidyl ether may be copolymerized with the hydrophilic and hydrophobic monomers to form the hydrophobic polymer. Such hydrophobic polymers however, may be formed with or without a vinyl epoxide. The ionizable polymer and nonionic surfactant are selected to compatibilize the nonionic hydrophobic polymer.

Many different methods of forming these mixtures of polymers can be employed. For example, polymers that have been made independently can be combined in a medium that will dissolve both of the polymers or other appropriate conditions that will give a uniform mixture. These mixtures could also be formed by polymerizing monomers in the presence of an already formed ionizable polymer to form what is hereinafter referred to as an interpolymer. These polymerizations could take place in a solvent for both the ionizable polymer and the resulting interpolymer or they could take place in a manner that would lead to the formation of a latex stabilized by the ionizable polymer in water hereinafter referred to as a polymeric colloid. These interpolymers may be chemically bound (grafted) to the original polymer.

Compositions according to the present invention may include a nonionic surfactant. Preferably, the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively. More preferably, the ratio of nonionic surfactant and ionizable polymer will be 200:1 to 1:1. Most preferably, the ratio of nonionic surfactant and ionizable polymer will be 100:1 to 1.5:1. Nonionic surfactants suitable for inclusion in the present cleaning compositions and methods are chosen to impart compatibility between the cleaning composition, the stain and the surface from which the stain is to be removed. Thus, the nonionic surfactant is chosen to impart compatibility of the formulation with the stain and the surface from which the stain is to be removed. The nonionic surfactants and methods include but are not limited to ethylene oxide adducts of alcohols, alkylphenols, fatty acids, fatty acid amides, and fatty acid esters. The surfactant may be monomeric or polymeric. Suitable nonionic surfactants include those taught in The Encyclopedia of Chemical Technology 3rd Ed., Vol. 22, pp. 360-377, which is incorporated herein by reference. Preferred surfactants are ethylene oxide adducts of alcohols and alkyl phenols. Preferred nonionic surfactants selected for inclusion in compositions containing an ionizable polymer will preferably have a hydrophilie-lipophilic balance (HLB) value in the range of from 8 to 15 and more preferably 8 to 13- most preferably 9 to 13. Thus, the preferred nonionic surfactant is water-immiscible, water-insoluble or water-dispersible at room temperature. Nonionic surfactants selected for inclusion in a composition containing an ionizable polymer which has charge density of greater than 2 meq/g may require a nonionic surfactant that is more hydrophobic (ones with a lower HLB).

Compositions and methods according to the present invention may further include a conventional anionic or amphoteric surfactant, including hydrotropes, with or without the above-described nonionic surfactant(s) . Suitable anionic surfactants include. but are not limited to linear alkylbenzene sulfonates, alpha olefin sulfonates, alkyl sulfonates, alkyl ether sulfates, alkyl sulfosuccinates, and sulfonate derivatives of nonionic surfactants. Suitable anionic surfactants include those taught in The Encyclopedia of Chemical Technology 3rd Ed., Vol. 22, pp. 347-360, which is incorporated herein by reference. Preferred anionic surfactants are alkylbenzene sulfonates, and a most preferred one is dodecyl benzene sulfonic acid and para- toluene sulfonic acid and the like.

Compositions according to the present invention may take the form of a liquid, emulsion, dispersion or solution, semi-solid, or a soft solid or stick. Solid stick compositions may be formed by dispersing the various disclosed compositions into a semi-hard carrier medium. Solid stick prespotting and stain removing compositions and methods for making and using are seen in United States 4,842,762, United States 4,396,521, and United States 3,664,962, all of which are incorporated herein by reference. An example of a semi-hard carrier medium is stearic acid.

Cleaning compositions of the present invention may contain one or more solvents. For reasons of economy, water is a desirable solvent. If the solvent or solvent mixture contains water, the water is present at equal to or less than 60 preferably less than 40 weight percent of the cleaning composition, if the solvent or solvent mixture contains organic solvent(s). the organic solvent(s) can be present up to or equal to 90 weight percent of the cleaning composition. The compositions will preferably incorporate an organic solvent such as d-limonene to provide greater hydrophobicity. The composition may comprise greater than 10 weight percent organic solvent based upon the weight of the composition. The use of two or more different organic solvents may be efficacious in providing enhanced cleaning over that of the use of one organic solvent. Preferred organic solvents include terpenes such as d-limonene, nonodorous petroleum distillates, diols, and etherated diols such as dipropylene glycol monomethyl ether as well as methyl laurate, cotton seed oil, dodecyl benzene, dibasic

10 esters and mixtures thereof. For purposes of this specification, the nonionic surfactant is not considered an organic solvent because of its surface activity.

Compositions according to the present invention x c as variously taught herein may be formed with a nonionic surfactant in lieu of or in combination with an organic solvent. In compositions containing a nonionic surfactant and not an organic solvent, the composition will preferably comprise greater than 10 weight percent 0 nonionic surfactant.

A specific class of ionizable polymers of the present invention include pH independent ionizable polymers. 5

Such pH independent ionizable polymers useful in the cleaning compositions and methods of the present invention can include some of the cationic ionizable backbone polymers described in United States Patents 0 4,337,185 and the anionic ionizable backbone polymers described in 4,427,819. both of which are incorporated herein by reference. The pH independent ionizable polymers may contain both pH dependent and independent groups, but are preferably pH independent in overall character. That is, the mole fraction of all B monomers of Formula I minus the mole fractions of all cationic E monomers must be greater than the mole fraction of all the C monomers. Such pH independent ionizable polymers preferably have monomeric hydrophobic units and/or side- chain forming hydrophobic units, thus, forming a polymer with surface activity.

The pH independent ionizable polymer preferably has a net anionic charge upon ionization, and is selected to optimize stabilization of nonionic hydrophobic mixtures of monomerics, polymerics and particulates in water. Such ionizable polymer comprises a combination of pH independent anionic monomers and nonionic monomers, for example groups B and D in Formula I herein above. Preferred anionic monomers include sulfonated monomers such as 2-sulfoethyl methacrylate (2-SEM), styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS^®) , and ethylene sulfonic acid. Preferably, such ionizable polymer comprises combinations of anionic monomers and nonionic hydrophobic and hydrophilic monomers. Such ionizable polymers may include pH dependent ionizable monomers such as carboxylated monomers, for example from group C in Formula I, but will contain a greater proportion of pH independent ionizable monomers such that the pH independent character of the polymer is maintained. That is, the mole fraction of all B monomers of Formula I minus the mole fractions of all cationic E monomers must be greater than the mole fraction of all the C monomers. Preferably, such ionizable polymer is further formed by the copolymerization of ethylenically unsaturated monomers. Preferably, such ionizable polymers comprise greater than 40, more preferably greater than 60, and most preferably greater than 70 weight percent hydrophobic monomer.

The pH independent ionizable polymer may have a charge density up to 10. The pH independent ionizable 5 polymer preferably has a charge density of between 0.1 to 5.0 and more preferably 0.15 to 2.0 milliequivalents per gram.

The pH independent ionizable polymer may have a

10 molecular weight up to 10,000,000 weight average molecular weight. The pH independent ionizable polymer is preferably between 2000 to 400,000 weight average molecular weight, more preferably from 5000 to 50,000 weight average molecular weight. 15

Nonionic, hydrophobic units suitable for incorporation and copolymerization into the pH independent ionizable polymer include those derived from any copolymerizable ethylenically unsaturated monomer

20 which, when in the form of an amorphous homopolymer, would have a solubility in water of less than 0.1 percent at 20°C. Nonionic hydrophobic units include, but are not limited to styrene, t-butyi styrene, vinyl _pr- toluene, methyl methacrylate, n-butyl methacrylate. lauryl methacrylate and 2-ethylhexyl acrylate.

Other monomers such as nonionic, amphiphilic monomers suitable for incorporation and copolymerization

30 into the pH independent ionizable polymer backbone include those derived from ethylenically unsaturated monomers that contain various hydrophobe containing side chains and are represented by group E in Formula I. These monomers can be described by the formula:

R R

I

H₂C=C-ZWR ' where R is either H or -CH ; Z is a suitable linking

0 group, such as |! ; W is a

-C-0- hydrophilic extending group, such as a - CH2CH2-0-}^* _n, with n typically less than 100 and preferably no more than 40; and R' is the hydrophobic group, such as

•> -C₁₂H₂₅

or . Specific examples

of monomers of this type are behenyl poly (oxyethylene)[25] methacrylate and nonylphenoxy poly(oxyethylene)[10]methacrylate.

Nonionic, hydrophobic monomers useful in the copolymerization of pH independent ionizable polymers include but are not limited to styrenics, acrylates, methacrylates, isoprene, butadiene, ethylene, vinyl chloride, and vinylidene chloride. By copolymerization with a suitable monomer(s) and in suitable proportion(s) , ionizable polymers having desired properties are obtained. Copolymer selections are made from known techniques for matching compatibility and solubility.

In some cases, it is advantageous to employ small amounts (e.g., usually less than 50 weight percent and preferably less than 10 and more preferably less than 5 weight percent based upon the weight of the ionizable polymer) of very hydrophilic but nonionic co onomers represented by Group E in Formula I, for control of the surface activity and water compatibility of the ionizable polymer without having to use more of the ionic comonomers. Acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethylmethacrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, dihydroxy propylmethacrylate, and polyoxyethylene glycol monoacrylates and methacrylates are particularly useful for this purpose. Preferred nonionic hydrophilic monomers are those which form water-swellable or water compatible homopolymers. 0 Low concentrations of monomers with weak acid (Group C in Formula I) or weak base groups (Group E in Formula I) and salts thereof may also be used provided that the pH independence of the ionizable polymer 5 backbone is maintained, e.g., a minor amount of a vinyl monomer such as acrylic acid or aminoethyl methacrylate (or the hydrochloride salt thereof) could be included to promote adhesion, serve as reactive sites and the like.

_Q Compositions according to the pH independent ionizable polymer may employ mixtures of two or more polymers as similarly described herein above for ionizable polymers.

r Compositions according to the present invention utilizing a pH independent ionizable polymer may include a nonionic surfactant as described herein above for ionizable polymers. The nonionic surfactant is present in such an amount that the ionizable polymer is preferably from about 1 to about 40, more preferably from about 20 to about 30, and most preferably about 25 weight percent based upon the total weight of the ionizable polymer and the nonionic cosurfactant. Compositions and methods according to the present invention utilizing a pH independent ionizable polymer may further include a conventional anionic or amphoteric surfactant as discussed herein above.

Compositions according to the present invention utilizing a pH independent ionizable polymer may take the form of a liquid, emulsion, dispersion or solution, semi-solid, or a soft solid or stick as discussed herein above.

Cleaning compositions of the present invention utilizing pH independent polymers may contain one or more solvents as discussed herein above. The compositions will preferably comprise up to about 40, more preferably about 25 or less, and most preferably about 15 or less weight percent water based upon the weight of the composition.

Compositions according to the present invention utilizing pH independent polymers as variously taught herein may be formed with a nonionic surfactant in lieu of or in combination with an organic solvent as herein described above.

Methods for cleaning a stain on a surface or fabric are characterized by contacting the stain with any of the cleaning compositions of the present invention described herein above. Contacting the stain with the cleaning composition may mean contacting the area of the surface or fabric where the stain resides in addition to directly upon the stain itself. The term stain includes any substance which is embedded or not embedded, solid or liquid, wet or dry, and at or beneath the surface or fabric, and is not to be construed as limiting.

After any of the cleaning compositions of the present invention have been applied to or contacted with the stain, the stain may be removed by wiping with a substrate such as a wet cloth or sponge, or by contacting the stain with water such as by washing with a substantially aqueous media. In the case of fabric, the composition-treated stain is preferably laundered with water and more preferably with an aqueous solution of mostly water and a conventional laundry detergent.

Thus, it is possible to formulate a cleaning composition offering superior cleaning in accordance with the present invention without the inclusion of prior art sequestering or chelating agents such as EDTA, phosphates, nitriloacetates, and aminopolycarboxylic acids. Inclusion of such prior art agents may however, be appropriate in use as a cosequestrant, as a sequestrant for substances not efficiently sequestrable by the present compositions, or as an agent for some other purpose.

It is possible to formulate a cleaning composition offering superior cleaning in accordance with the present invention without the inclusion of prior art antiredeposition agents, builders, and the like. It is understood however, that such agents may be included as coagents for the same purposes or as an agent for some other purpose.

The compositions and methods according to the present invention may be utilized effectively to clean soils and oily stains such as motor oil. cooking oil. bacon grease and mayonnaise and oily particulate stains such as lipstick and liquid makeup. Such compositions and methods may also be effectively utilized on oily stains having particulates of carbon or dirt such as dirty motor or diesel oil. Such compositions and methods may also be utilized effectively to clean stains of lesser hydrophobicity than oil and grease such as grass, blood, and carbohydrates such as starch on surfaces and fabrics. 0 Compositions and methods according to the present invention may be effectively utilized in laundry pretreating, stain removing, industrial and household degreasing, metal cleaning, paint stripping, and general -- purpose industrial and household cleaning.

The invention is further illustrated but not limited by the following examples wherein all parts are by weight unless otherwise specified. 0 ExamDles:

The following examples test the cleaning effectiveness of various test compositions comprising an ionizable polymer with and without hydrophobic polymer, - and/or nonionic surfactants as a pretreat stain remover on fabric using varying conditions in a subsequent laundry cycle. Various types of ionizable polymers, hydrophobic polymers, and nonionic surfactants are utilized. 0

Fabrics utilized in the following examples include 100 percent polyester, a 65/35 percent polyester-cotton (polycotton) blend, and 100 percent cotton. Prior to staining, the fabrics are laundered three times with a commercial laundry detergent to remove any finish applied to the fabric at the manufacturer. The fabrics are cut into^' 3X4 inch swatches, and stained with 7 drops (about 0.2 grams) of dirty motor oil. The oil is obtained from a diesel engine crankcase. The oil contains particulate carbon and dirt. The stain is allowed to sit overnight.

About 1.5 grams of each of the test compositions is placed in the form of a thin layer on the stain. After the test compositions have contacted the stains for about 5 minutes, the swatches are placed in a Terg-0-Tometer™ United States Testing Company Model 7243S for about 15 minutes (unless otherwise specified) at 100 rpm. The swatches are laundered with an aqueous solution of a heavy duty commercial laundry detergent (hereinafter referred to in the Examples as "detergent") or with water only. The temperature of laundering is around 50°C unless otherwise indicated. The water is tap water from the City of Midland, Michigan or deionized water unless otherwise indicated. Where detergent solution is utilized, the detergent concentration is about 1.0 gm/liter of water. After laundering, the swatches are rinsed for 5 minutes, and allowed to air-dry overnight.

The swatches were analyzed along with unstained swatches on a Hunter Labscan 45°/0° D25-PC2 Colorimeter of Hunter Associates Laboratory, Inc. using the CIE 1931 standard source illuminant C. Alternatively on a MiniScan™ Spectrocolorimeter version MS450CL with a 45°/0° geometry and large viewing area option using the CIE XYZ Scale, CIE 1931 2° standard observer and CIE 1931 standard source illuminant C.

The Labscan is first calibrated using a black tile and then a white tile. The swatches are read with an oval template which has axes of lengths of 35 mm and 45 mm to reduce the area analyzed to a uniform shape. The MiniScan is first calibrated using a factory issued white tile; the black standard is internal. The swatches are read by setting the one inch diameter

10 sample port of the MiniScan onto the sample surface and flashing a known light source at the sample surface and taking a reading of the light reflected. Unstained fabric (100 percent clean) and stained, unwashed fabric -,- (100 percent dirty) were analyzed to determine the range of cleaning. Percent cleaning is determined on basis of hue and brightness.

Set I. Ionizable Polymers: 0 Example 1A: Preparation of an Ionizable Polymer

An ionizable copolymer comprising 97.6 percent MMA, 2.4 percent 2-SEM (2-sulfoethyl methacrylate) by weight is prepared according to the following procedure.

25 The 2-SEM will provide a charge of 0.125 meq/g of this polymer.

The polymerization is achieved by adding 133•33 parts of methyl ethyl ketone (MEK) to a stirred

30 reactor provided with a nitrogen atmosphere, a condenser, and inlets for monomer and initiator addition. The reactor is purged with nitrogen and heated to 80°C by a constant temperature water bath. Two solutions are prepared for addition to this reaction flask: a) the solution of monomers prepared in MEK and b) an initiator solution is prepared by adding 2.5 parts of VAZO^® 64 initiator (marketed by E. I. duPont deNemours & Co.) to 133.33 parts of MEK. These two solutions are added by syringe to the heated MEK in the reaction flask in 18 equal volumes once every 10 minutes over a total time of about 3 hours. After all of the monomer and initiator solutions are added, the mixture is heated to achieve greater than 90 percent conversion which typically requires 3 additional hours ^'to complete

10 the polymerization. The final product is a clear amber solution.

A test composition is prepared by adding 3 parts of NIS-5 (nonionic surfactant with an average of 5 ethylene

,-- oxide adducts) to a copolymer solution containing 1 part of the copolymer as described above. The MEK solvent is removed from this solution by rotoevaporation under vacuum at 50°C to obtain a mixture that consists of 98 percent solids. Stained fabrics utilizing the test 0 composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 62.2, and percent cleaning on polycotton is 48.8.

5 An ionizable copolymer comprising 90.5 percent MMA, 9.5 percent 2-SEM by weight is prepared according to the procedure above. The 2-SEM will provide a charge of 0.488 meq/g of this polymer. A test composition is formed from the same charged polymer and NIS-5 according 0 to the procedure above. Solids content is determined to be 98.0 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 85.0, and percent cleaning on polycotton is 66.2.

Example 1B:

An ionizable copolymer is prepared by free radical polymerization of 82.4 percent MMA, and 17.6 acrylamido-2-methylpropanesulfonic acid (AMPS^®) by weight similarly to Example 1A except 33 grams of water is added to each of the MEK or MEK solutions. The AMPS^® will provide a charge of 0.851 meq/g of this polymer. A test composition if formed from the same charged polymer and NIS-5 according to the procedure of Example 1A. Solids content is determined to be 99 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 53.0, and percent cleaning on polycotton is 36.0.

Comparative Example I (control fabric):

Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 23, and percent cleaning on polycotton is 14. Methodology is the same as in previous examples These fabrics were also utilized in Examples 1A and 1B.

Pretreatment Comparative Example

Stained fabrics utilizing a commercial soil and stain remover composition (Spray'n Wash^®Stain Stick Tough Stain Remover for Laundry, DowBrands Inc.) as a control are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 27. and percent cleaning on polycotton is 27.

Example 1C;

r- SPS: Partially sulfonate poly(styrene) is prepared by reacting poly(styrene) MW = 50,000, Polysciences) with chlorosulfonic acid in chloroform. A solution of poly(styrene) in chloroform (20wt%) is cooled to 0°C. The chlorosulfonic acid in chloroform is slowly added

10 with mixing for approximately one hour. After addition, the mixture is allowed to warm to room temperature overnight. The resulting extent of sulfonation is determined to be 0.985 meq/q by potentiometric titration. 5

Stained fabrics utilizing the test compositions indicated in the following Tables are laundered at 50°C for 15 minutes as indicated with the water and/or detergent solution. These test compositions are 0 prepared by combining the indicated ionizable copolymers and NIS-5 in an amount required to give the weight percent solids of the ionizable polymer based on the ionizable copolymer plus NIS-5 shown in the Tables. In _J- some cases the ionizable copolymers are added to the

NIS-5 in the form of a solution in some solvent, such as chloroform, or methyl ethyl ketone, or water. In these cases, these solvents are removed by rotoevaporation at 50°C under at least 29 inches of vacuum for two hours. 0 When water is initially present in the formulations they are additionally heated at 8θ°C for one hour to assure removal of the water. The resulting percent cleaning on cotton and on polycotton are given in the Tables indicated that a wide variety of ionizable homopolymers and copolymers are capable of providing improved cleaning of fabrics. These include:

1. Poly(Acrylic Acid) with weight average molecular weight between 1800 and 4,000,000 and concentrations between 0.5 and 50 wt%.

2. Poly(Acrylic Acid) mixture with sulfonic acid (either dodecylbenzene sulfonic acid or toluene sulfonic acid monohydrate) with a polymer weight average molecular weight between 1800 and 450,000 and concentrations between 0.5 wt% and 17 wt% and sulfonic acid concentrations between 1.5 and 50 wt*.

3. Sulfonated poly(styrene) with weight average molecular weight between 6500 and 70,000, degrees of sulfonation between 10 mole_/ζ and 100 mole% and concentrations between 4 vιt% and 29.5 wt%, also including blends of sulfonated poly(styrene) with poly(methyl methacrylate).

4. Miscellaneous polymers with concentrations from 4.4 to 24.3 tjt including methyl cellulose (M0C), chondroitin sulfate, dextran sulfate, sulfoethyl cellulose, and polymethacrylic acid).

TABLE I (1) Poly(Acrylic Acid) in NIS-5 - weight percents are based on total formulation weights

TABLE II

(2) Poly(Acrylic Acid) and Dodecyl Benzene Sulfonic Acid in NIS-5

TABLE II Continued Poly(Acrylic Acid) and Toluene Sulfonic Acid in NIS-5

0

TABLE III

Toluenesulfonic Acid

5 (3) Sulfonated Poly(Styrene) in NIS-5

TABLE IV

(4) Miscellaneous

C = Cotton

AD = Aqueous Detergent

PC = Poly/Cotton

= Water P(MAA) = Poly(methacrylic acid).

Versa^® TL4 = Sulfonated styrene maleic anhydride copolymer by National Starch and Chemical, weight average molecular weight=20,000.

5

Narlex™ D82 = Sulfonated vinyl toluene maleic anhydride copolymer by National Starch and Chemical, weight average molecular weight=25,000.

_ιn DBS = dodecylbenzene sulfonic acid.

MOC = methyl cellulose

MOC 15 = methyl cellulose with 2% aqueous solution having a viscosity of 15 centipoise. 5

MOC 25 = methyl cellulose with 2% aqueous solution having a viscosity of 25 centipoise.

MOC 400 = methyl cellulose with 2% aqueous solution 0 having a viscosity of 400 centipoise.

Sample Description:

A. Sulfonated poly(styrene) 6500 was _c converted from the sodium to hydrogen ion form by passing an aqueous solution through DOWEX 50W strong acid ion exchange resin.

B. The following polymers were obtained as 0 aqueous solution from Polyscience (Warrington PA) . Poly(acrylic acid) P(AA) in hydrogen ion form

MW= 5,000 50% solids in water

MW= 1,800 65% solids in water

MW= 50,000 25% solids in water

MW= 90,000 25% solids in water

MW= 150,000 25% solids in water

450,000 powder 4,000,000 powder

Sources for Other Polymers

Polymer Source Form

-Sulfoethyl Cellulose American Tokyo Kasei Powder (0.15 meq/g)

-Methyl Cellulose (MOC) 2% Aqueous Solution 15 cp Aldrich Powder 25 cp 400 cp

-*Versa^<s> TL4 National Starch 25% Solids and Chemical in water

-*Narlex D-82 National Starch Powder and Chemical

*These samples were converted to the hydrogen ion form by stirring for hr. with a 4=1 (wt.-wt.) excess of Dowex 50W Ion exchange Resin in an aqueous slurry. The "Dowex" was removed by filtration and the process was repeated.

Example 1D:

A charged polymer comprising 82.0 percent MMA and 18.0 percent 2-SEM by weight is prepared according to the procedure of Example 1A. The 2-SEM will provide a charge of 0.925 meq/g of the copolymer. A test composition is formed from the same charged polymer and a variety of nonylphenol ethoxylate (Igepal'^E nonionic surfactants from GAF Chemicals and Tergitol'¹ surfactants from Union Carbide) and alcohol ethoxylate nonionic surfactants (Neodol^® nonionic surfactants from Shell) according to the procedure of Example 1A. Stained fabrics utilizing the test compositions are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton and percent cleaning on polycotton are given in Table V. These data show that good cleaning can be obtained with both the nonylphenol ethoxylates (e.g., Igepal^® C0-520) and the linear alcohol ethoxylates (e.g., Neodol^® 23.5). These data also show that the cleaning for a given formulation will depend on the HLB of the nonionic surfactant used in the formulation. The nonionic surfactant blends in Table V were prepared by combining various ratios of other Neodol^® surfactants. Blend 1 contains 77 percent of Neodol^® 25-3 and 23 percent of Neodol^® 25-9, blend 2 contains 50 percent of Neodol^® 23-3 and 50 percent of Neodol^® 23-6.5, blend 3 contains 32 percent of Neodol^® 25-3 and 68 percent of Neodol^® 25-9.

Table V The Effect of Nonionic on Cleaning

Example IE: Preparation of Ionizable Polymer

An ionizable polymer is prepared by adding 920 parts of deionized water and 1167 parts of isopropanol to a stirred reactor provided with a nitrogen atmosphere and maintained at 50°C while continuously adding reactants from five separate sources with proportionate feeds over 120 minutes and the resulting polymerization is allowed to continue for an additional 2 hours. Feed compositions are as follows:

After polymerization, 3,333 parts of deionized water are added and 1,715 parts of volatile IPA and Feed

0

hydroperoxide 5

80 Deionized water

water are removed by vacuum distillation at about 50°C. The devolatilized polymers solution measures 17.8 0 percent solids and 2.4 meq of strong and weak acid per gram of polymer solids.

Example IF: Preparation of Polymeric Colloid

_c The solution of Example 1E is used as the water based stabilizer for the emulsion polymerization of hydrophobic monomers styrene and 2-ethylhexyl acrylate. 225 parts of each of the monomers were added to 2,528 parts of the water based stabilizer (450 parts ionizable 0 copolymer) and diluted with 526 parts deionized water. This mixture is heated to and maintained at about 50°C under a nitrogen atmosphere while adding proportionately from separate feed systems of 0.90 parts t-butyl hydroperoxide in 48 parts of water and 0.68 parts sodium formaldehyde sulfoxylate in 48 parts water over about 30 minutes. After completing the additions, heating is continued for another 2 hours. An aliquot reveals (a)

24.8 percent solids indicating essentially complete reaction, (b) approximately 1.2 meq strong and weak acid per gram of solids, and (c) an average particle size of about 0.1 micron.

Example 1G: Preparation of a Composition of an Ionizable Polymer Colloid and Nonionic Surfactants

The final liquid-solid mixture of Example 1F is blended with nonionic surfactants in a quantity to produce test compositions comprising 75 parts by weight nonionic surfactant to 25 parts of the polymeric colloid. The water content is reduced to about 5 percent by vacuum distillation at 80°C. The nonionic surfactants used are either nonyl phenol with 5 moles of ethylene oxide adduct (NIS-5) or a 14 to 15 carbon alcohol with 7 moles of ethylene oxide adduct (45-7).

Comparative Example:

Standard fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 29, and percent cleaning of polycotton is 7. Fabrics of the same manufacture were used in Example 1H.

Pretreatment Comparative Example

Stained fabrics utilizing a commercial soil and stain remover composition (Spray'n Wash^®Stain Stick Tough Stain Remover for Laundry, DowBrands Inc.) as a control are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 26 and percent cleaning on polycotton is 26.

Example 1H:

r- Stained fabrics utilizing test compositions of

Example 1G are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5 and 45-7 is 82 and 70 respectively. Percent cleaning on polycotton with the

10 same order of nonionic combinations is 44 and 38.

Example 1Ha: Preparation of Compositions of an Ionizable Detergent Polymer and Nonionic Surfactants

,r QR-1265, a carboxylated detergent polymer from

Rohm & Haas, United States Patent 4,797,223, having an ionizable content of 3.75 meq of charge per gram of polymer, is blended individually with different nonionic surfactants in a quantity for testing comprising 75

20 parts by weight of nonionic surfactant and 25 parts polymer solids. The water content is reduced to about 5 percent by vacuum distillation at 80°C. The nonionic surfactants are nonyl phenol with 4 or 5 or 6 ethylene oxide adducts or Neodol^® 45-7 (product by Shell Chemical

25 Company) depending on the example. The nonyl phenol surfactants are designated NIS-4, NIS-5 or NIS-6 based on the respective levels of ethylene oxide, and the 14 to 15 carbon alcohol with 7 moles ethylene oxide adduct

₃₀ as 45-7. Comparative Example:

Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on

cotton is 29, and percent cleaning on polycotton is 11. Fabrics of the same manufacture were used in Examples 1Hb and the following comparative nonionic examples and 1He.

Pretreatment Comparative Example:

Example 1Hb:

Stained fabrics utilizing test composition of Examples 1Ha are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combination with NIS-4, NIS-5, NIS-6, and 45-7 is 49, 29, 23, and 47 respectively. Percent cleaning on polycotton with same order of nonionic combination is 15, 20, 19, and 29.

Comparative Example:

Stained fabrics utilizing nonionic surfactants without charged polymers are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton with NIS-4, NIS-5, NIS-6 and 45-7 is 19, 25, 18, and 30 respectively. Percent cleaning on polycotton with the same order of nonionic combinations is 7, 9, 12, and 23- Example IHc: Preparation of Colloid with Ionizable Polymer and Hydrophobic Monomers

A solution of QR-1265 (water soluble carboxylated polymer from Rohm & Haas, United States Patent 4,797,223) mixed with hydrophobic monomers styrene and 2-ethylhexyl acrylate and emulsion polymerized using the procedure of Example 1F. An aliquot reveals (a) 24.2 percent solids indicating the reaction to be essentially complete, (b) approximately

10 1.9 meq weak acid per gram solids, and (c) the colloid average particle diameter is about 0.1 micron. The resulting polymeric solids are about 50 percent QR-1265 charged polymer and about 25 percent styrene and 25 x r- percent 2-ethylhexyl acrylate.

Example IHd: Preparation of a Ionizable .Colloid and Nonionic Surfactants

The liquid-solid colloid of Example 1Hc 0 (hydrophobic modification of water soluble detergent polymer) blended with different nonionic surfactants in a quantity for testing 75 parts by weight of nonionic surfactant and 25 parts polymer solids. The water r content is reduced to about 5 percent by vacuum distillation at 80°C. The nonionic surfactants are nonyl phenol with 5 ethylene oxide adducts or Neodol^® 45-7 (product from Shell Chemical Company) depending on example. The nonyl phenol 5 moles ethylene oxide 0 surfactant is designated as NIS-5 and the 14 to 15 carbon alcohol with 7 moles ethylene oxide as 45-7. Example 1He :

Stained fabrics utilizing test compositions of Example d are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5 and 45-7 is 62 and 75. Percent cleaning on polycotton with the same order of nonionic combinations is 39 and 38.

Set II. pH Independent Ionizable Polymer (The following examples are additional examples of pH independent ionizable polymers; some of the examples of Set I also include pH independent ionizable polymers)

Example 2A: Preparation of a pH Independent Ionizable Polymer

An ionizable polymer is prepared by adding 1000 parts of isopropanol and 650 parts of deionized water to a stirred reactor provided with a nitrogen atmosphere and maintained at 50°C while continuously adding reactants from five separate sources with proportionate feeds over 120 minutes and the resulting polymerization is allowed to continue for an additional 2 hours. Feed compositions are as follows:

Feed Parts Component

Deionized Water

2-Sulfoethyl Methacrylate (2-SEM)

Dimethylaminoethy1 methacrylate (DMAEMA)

Methyl methacrylate (MMA)

2-Mercaptoethanol

Deionized Water 0 Tertiary(t)-butyl

Hydroperoxide

Deionized Water

Sodium Formaldehyde Sulfoxylate 5 118.5 Deionized Water

Example 2B: Preparation of a Solution of an Ionizable Polymer and Glycidyl Methacrylate

0 The solution formed in Example 2B is added to 2500 parts deionized water followed by devolatilization of 1700 parts. The devolatized solution of ionizable polymer is mixed with 56.3 parts of glycidyl j- methacrylate (GMA) while heating for two hours at 50°C. The solution of ionizable polymer and glycidyl methacrylate has a solids content of 22.1 percent, a specific gravity of 1.05 g/cc at 25°C, pH of about 2, and a viscosity of 15 cp at 25°C. The ionizable polymer 0 has a total acid content of about 1.9 meq/g and an average molecular weight of less than 40,000. Example 3B: Preparation of Hydrophobic Copolymers

The solution of Example 2B is used as the water based stabilizer for the emulsion polymerization of hydrophobic copolymers.

Hydrophobic styrene/2-ethyl hexyl acrylate copolymers are prepared by copolymerization in the presence a portion of the ionizable polymer-glycidyl methacrylate solution. 100 parts each of styrene (S) and of 2-ethyl hexyl acrylate (2-EHA) are stirred together in an aqueous solution of 1448 parts of deionized water, 10 parts of isopropanol and 909 parts of the ionizable polymer-glycidyl methacrylate solution of Example 2B (22 percent solids by material balance). This mixture is heated to and maintained at 50°C under a nitrogen atmosphere while adding proportionately from separate feed systems of 0.40 part t-butyl hydroperoxide in 50 parts of water and 0.30 parts sodium formaldehyde sulfoxylate in 50 parts water over about 30 minutes. After completing the additions, heating is continued for another 3 hours. An aliquot reveals (a) a 15 percent solids content indicating the reaction to be complete, (b) approximately a 0.9 milliequivalent total acid content per gram solids and (c) a very small particle size, about 450 Angstroms as indicated by its translucent, bluish appearance. The resulting polymeric solids are about 50 weight percent of MMA/2-SEM/DMAEMA ionizable polymer and about 50 weight percent of GMA/S/2-EHA hydrophobic polymer.

A portion of the final liquid-solids mixture is concentrated to 40 percent solids, and still has a pourable viscosity at room temperature. Example 4B: Preparation of a Composition of an Ionizable Polymer and Nonionic Surfactant

The final liquid-solids mixture of Example 3B is blended with a nonionic surfactant in a quantity sufficient to produce test compositions comprising 75 parts by weight of a nonionic surfactant to 25 parts of the ionizable polymer system. The water content is lowered by vacuum distillation at 80°C to about 5 percent. The nonionic surfactant is a nonyl phenol with 5 or 9 ethylene oxide adducts depending upon the example. The nonionic surfactant with an average of 5 ethylene oxide adducts is designated as NIS-5, and the one with 9 as NIS-9.

The following examples test the cleaning effectiveness of various test compositions of the ionizable polymer with and without hydrophobic polymer, and/or nonionic surfactants as a pretreat stain remover on fabric using varying conditions in a subsequent laundry cycle. Various types of ionizable polymers, hydrophobic polymers, and nonionic surfactants are utilized.

Comparative Example 1B:

Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 32, and percent cleaning on polycotton is 12, Fabrics of the same manufacture were used in Examples 5B-9B. Example 5B :

Stained fabrics utilizing the test composition of Example 4B having NIS-5 are laundered as indicated with the detergent solution. Percent cleaning on polyester is 86.8 at 8 minutes of laundering and 89.5 at 15 minutes of laundering. Percent cleaning on polycotton is 29.0 at 8 minutes and 33• 1 at 15 minutes. Percent cleaning of cotton is 47.9 at 8 minutes and 47.0 at 15 minutes.

Example 6B:

Stained fabrics utilizing the test compositi .o.n of Example 4B having NIS-9 are laundered as indicated with water only. Percent cleaning efficiency on polyester is 60.8 at 8 minutes of laundering and 67.6 at 15 minutes of laundering. Percent cleaning on polycotton is 17.4 at 8 minutes and 20.5 at 15 minutes. Percent cleaning on cotton is 30.0 at 8 minutes and 31.8 at 15 minutes.

Example 7B

Stained fabrics utilizing the test composition of Example 4B having NIS-5 are laundered for 15 minutes as indicated with the detergent solution at various temperatures. Percent cleaning on cotton is 47.0, 39.6, and 36.9 at laundering temperatures of 50, 26.7, and 12.8°C respectively. Percent cleaning on polycotton is 20.5, 18.0, and 10.9 at laundering temperatures of 50, 26.7, and 12.8°C respectively. Example 8B

Stained fabrics utilizing the test composition of Example 4B having NIS-9, and laundered for 15 minutes as indicated with water only at various temperatures:

5

Percent cleaning on cotton is 31.8, 23.0, and

20.3 at laundering temperatures of 50, 26.7, and 12.8°C respectively.

₁₀ Example 9B

Stained fabrics utilizing the test composition of Example 4 having NIS-5 are laundered at 50°C for 15 minutes as indicated with hard water prepared by adding ₁₅ 300 ppm of a CaCO^/MgCO-^ mixture (2/1 weight ratio) to tap water. Percent cleaning on cotton is 36.9, and percent cleaning on polycotton is 29.4.

Example 10B

20 An ionizable polymer comprising MMA/2- SEM/DMAEMA in weight proportions of 55.3/38.2/6.5 is prepared in accordance with Example 2B. A hydrophobic copolymer comprising GMA/S/2-EHA in weight proportions _pc- of 5.3/83.0/11.7 is polymerized in the presence of the ionizable polymer as in Example 3B. The polymer mixture contains equal proportions by weight of the ionizable polymer and the hydrophobic copolymer. The polymer mixture is blended with a nonionic surfactant, and

30 subsequently devolatilized to contain about 5 weight percent water.

The test composition is prepared by adding to the polymer mixture a nonionic surfactant, Neodol^® 45-7 (marketed by The Shell Chemical Company), in a 3:1 ratio by weight based on the weight of the surfactant to the solid components of the polymer mixture to form a surfactant-polymer mixture. D-limonene and Isopar^® M (marketed by Exxon Corp.) are further added to the surfactant-polymer mixture as organic solvents. The test composition comprises (surfactant-polymer)/d- limonene/Isopar^® M in weight proportions of 40/20/40.

Comparative Example:

Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 23, and percent cleaning on polycotton is 14. Methodology is the same as in previous examples except that fabrics utilized are of the same blends but of different manufacture. These fabrics were also utilized in Example 11B-18B.

Example 11B;

Stained fabrics utilizing the test composition of Example 10B are laundered at 50°C for 15 minutes with a commercial laundry detergent. Percent cleaning on cotton is 100, and percent cleaning on polycotton is 92. When laundered at 50°C for 15 minutes with water, percent cleaning on cotton is 99.8, and percent cleaning on polycotton is 92.4.

Example 12B: Preparation of an Ionizable Polymer and a Composition of Said Ionizable Polymer and a Nonionic Surfactant

An ionizable polymer with a weight average molecular weight of about 10,000 is prepared by free radical polymerization of methyl methacrylate (MMA) and 2- sulfoethyl methacrylate (2-SEM). It is polymerized by adding 133.33 parts of methyl ethyl ketone (MEK) to a stirred reactor provided with a nitrogen atmosphere, a condenser, and inlets for monomer and initiator addition. The reactor is purged with nitrogen and heated to 80°C by a constant temperature water bath. Two solutions are prepared for addition to this reaction flask: A solution of monomers is prepared by adding 23.26 parts of 2-SEM and 102.08 parts of MMA to 133-33

10 parts of MEK. An initiator solution is prepared by adding 2.5 parts of VAZO^® 64 initiator (marketed by E. I. duPont deNemours & Co.) to 133-33 parts of MEK. These two solutions are added by syringe to the heated MEK in the reaction flask in 18 equal volumes once every

15 10 minutes over a total time of about 3 hours. After all of the monomer and initiator solutions are added, the mixture is heated for 3 additional hours to complete the polymerization. The final product is a clear amber solution. The weight percent solids of this solution is

20 determined to be 24.8. Thus, the conversion of the monomer to copolymer is essentially 100 percent. The composition of this copolymer is 89.5 mole percent MMA and 10.5 mole percent 2-SEM. The 2-SEM will provide a p_c- charge of 0.956 meg/gram of this copolymer.

A test composition is prepared by adding 3 parts of NIS-5 to a copolymer solution containing 1 part of the copolymer. The MEK solvent is removed from this

30 solution by rotoevaporation under vacuum at 50°C to obtain a mixture that consists of 97.4 percent solids. These solids consist of the nonionic surfactant and the copolymer in a 3 to 1 weight ratio, respectively. Example 1 3B

Stained fabrics utilizing the test composition of Example 12B are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 75.2, and percent cleaning on polycotton is 45.8.

Example 14B

An ionizable polymer comprising 77.5 percent

MMA, 12 percent 2-SEM, and 10.5 percent lauryl methacrylate (LMA) by weight is prepared according to the procedure of Example 12B. The 2-SEM will provide a charge of 0.948 meg/gram of this copolymer. A test composition is formed from the same ionizable polymer and NIS-5 according to the procedure of Example 12B. Solids content is determined to be 98.1 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 67.8, and percent cleaning on polycotton is 48.1.

Example 15B

An ionizable polymer comprising 73-8 percent

MMA, 16.5 percent 2-SEM, and 9.7 percent nonylphenoxypoly([10] oxyethylene) methacrylate (NP10MA) by weight is prepared according to the procedure of Example 12B. The 2-SEM will provide a charge of 0.933 meg/gram of this copolymer. A test composition is formed from the same ionizable polymer and NIS-5 according to the procedure of Example 12B. Solids content is determined to be 99.6 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 70, and percent cleaning on polycotton is 44.5.

Example 16B

An ionizable polymer comprising 91.0 percent styrene, 9.0 percent 2-SEM by weight is prepared according to the procedure of Example 12B. The 2-SEM will provide a charge of 0.804 meg/gram of this copolymer. A test composition is formed from the same ionizable polymer and NIS-5 according to the procedure of Example 12B. Solids content is determined to be 97.7 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 58.7, and percent cleaning on polycotton is 47.6.

Example 17B

An ionizable polymer comprising 89.5 percent methylmethacrylate, 10.5 percent 2-SEM by weight is prepared according to the procedure of Example 12B. The 2-SEM will provide a charge of 0.956 meg/gram of this copolymer. For purposes of this example, the test composition is formed by substituting the nonionic surfactant with Dowanol^® DPM (marketed by The Dow Chemical Company) brand dipropylene glycol monomethyl ether. The Dowanol^® DPM comprises 75.1 percent by weight of the test composition. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 34.5, and percent cleaning on polycotton is 37.9. Example 18B

The test composition of Example 17B is again utilized except that the fabrics are laundered with water only. Percent cleaning on cotton is 25.0, and percent cleaning on polycotton is 28.0.

Comparative Example

Stained fabrics utilizing a test composition consisting only of Dowanol^® DPM (The Dow Chemical

Company) brand dipropylene glycol monomethyl ether are laundered at 50°C for 15 minutes as indicated with detergent solution or with water. Percent cleaning on cotton is 25, and percent cleaning on polycotton is 11 when laundered in the detergent solution. Percent cleaning on cotton is 17, and percent cleaning on polycotton is 4 when laundered in water.

Example 1 9B

A solid stick composition utilizing a test composition of the ionizable polymer composition of Example 3B and NIS-5, as made in Example 4B in the same 5 proportions, is formulated in a stick form in the following manner:

Components and Concentration Grams

First Mixture

10 d-Limonene

PEG-900

Water

Sodium Borate Decahydrate

15

50 percent NaOH in water

Stearic Acid

Dodecyl Benzene Sulfonic Acid

(LAS)

20 The ionizable polymer MMA/2-SEM/DMAEMA and hydrophobic copolymer GMA/S/2-EHA of Example 3B is mixed with NIS-5 according to the method of Example 4B to form a first mixture. The first mixture and d-Limonene were mixed together and heated to 60°C to form a second

^-> mixture. Polyethylene glycol of about 900 average molecular weight is added and heated to 65°C . Water, borate and NaOH are mixed together and heated until the solution is clear to form a third mixture. The third mixture is mixed together with the second mixture and

30 heated to 77°C to form a fourth mixture. Stearic acid ((70 percent C-_jg) is then mixed together with the fourth mixture and heated to 77°C to form a fifth mixture. The fifth mixture is allowed to drop in temperature to 70°C under constant agitation. When the 70°C temperature level is reached, the LAS is mixed therein to form a sixth mixture. The sixth mixture is allowed to cool to 60°C under constant agitation, and then poured into a mold wherein the solid stick test composition forms.

Examples 20B-22B utilized the same fabrics as in Comparative Example 1B. Methodology is consistent with previous examples.

Example 20B

Stained fabrics utilizing the test composition of Example 19B are laundered for 15 minutes at 50°C in water only. Percent cleaning on cotton is 67, and percent cleaning on polycotton is 53.

Example 21B

Stained fabrics utilizing the test composition of Example 19B are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 76 and percent cleaning on polycotton is 72.

Example 22B

Stained fabrics utilizing the test composition of Example 19B are laundered in hard water for 15 minutes at 50°C. The hard water prepared by adding 300 ppm of a CaCO*3/MgCθ3 mixture (2/1 weight ratio) to tap water. Percent cleaning on cotton is 77.8, and percent cleaning on polycotton is 65.0. REMOVING DMO (DIESEL) FROM COTTON Nl, QR-1265, & QR 1265//S/2-EHA BLENDS

80

• 45-7/1265//S/2-EHA COLLOID

70

• CO-520/1265//S/2-EHA

60 COLLOID

50

O • NP-4/1265

DETERGENT POLYMER • 45-7/1265

DE TERGENT POLYMER

U-l _] 40

30 • CO-520/1265 • 45-7

Aqueou s Detergent DETERGENT POLYMER

• CO 520

• NP-6/1265

20 DETERGENT POLYMER

• NP a,

• NP 6

10

0

10 HLB 11 12

REMOVING DMO (DIESEL) FROM POLYCOTTON

10 HLB 1 1 12

Example 23B: Hydrophilic Surface Modification of Hydrophobic Core Rubber Latex

The solution of Example 2B is used as the water based ionic copolymer for surface modification of a hydrophobic rubber latex.

Preparation of the core-shell latex involves grafting the ionic copolymer of Example 2B with shell monomers of styrene plus methyl methacrylate onto a monodispersed sub-micron crosslinked rubber latex having an average particle diameter of 119 nm as measured by a Brice-Phoenix Universal Light Scattering Photometer. The extent of crosslinking of the core rubber can be estimated from a determination of percent gel (90 percent non-extractable polymer) and swell index (15 s.i., measure of imbibition of solvent by test polymer). A method for determining the present gel and swelling index is disclosed in United States Patent 4,146,589. The rubber latex particles are styrene-butadiene copolymer (7 percent styrene, 93 percent butadiene) and stabilized by 3 percent sodium dodecylbenzene sulfonate soap (based on polymer). The grafting procedure includes a two stage addition and temperature change.

1,875 grams of the previously described rubber latex containing 600 grams rubber solids are charged to a 5 liter reactor equipped with a mechanical stirrer, temperature control, cold water jacketed reflux condenser, and an inert atmosphere of nitrogen. 4.00 grams of VAZO^® 64 (2,2'-Azobis (2-Methylpropanenitrile) ) from DuPont is added to the stirred (150 rpm) reactor. The head space in the reactor is continuously flushed with nitrogen and the contents heated to 70°C. 905 grams of the soluble ionic polymer solution from Example 2B (200 grams solids) along with 100 grams each of shell monomers styrene and methyl methacrylate were added to the reactor at an initial rate of 20 percent of their respective totals over 150 minutes. During the remaining 80 percent feed additions over 90 minutes, the reactor temperature is increased to 8θ°C and maintained for another 120 minutes. An aliquot reveals 32.9 percent solids and 0.38 milliequivalents total anionic charge per gram of polymer solids. The resulting polymeric solids are about 60 weight percent crosslinked rubber, 20 weight percent ionic copolymer, 10 weight percent each of styrene and methyl methacrylate.

Example 24B: Preparation of Compositions of an Ionizable Polymer and Nonionic Surfactants

The final liquid-solids colloid of Example 23A is blended individually with different nonionic surfactants in a quantity for testing comprising 75 parts by weight of nonionic surfactant and 25 parts polymer solids. The water content is reduced to about 5 percent by vacuum distillation at 80°C. The nonionic surfactants are nonyl phenol with 5 or 6 ethylene oxide adducts or Neodol^® 45-7 (product by Shell Chemical Company) depending on the example. The nonionic surfactant with an average of 5 ethylene oxide adducts is designated as NIS-5, similarly NIS-6, and the 14 to 15 carbon alcohol with 7 moles ethylene oxide adduct as 45-7. Comparative Example:

Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 23, and percent cleaning on polycotton is 13. Fabrics of the same manufacture were used in Example 25B and 26B.

Example 25B:

Stained fabrics utilizing test compositions of Example 24B are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5, NIS-6, and 45-7 is 47, 53, and 63 respectively. Percent cleaning on polycotton with the same order of nonionic combinations is 36, 49, and 54.

Example 26B:

Stained fabrics utilizing test compositions of Example 24B are laundered in water only for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5, NIS-6, and 45-7 is 29, 39, and 54 respectively. Percent cleaning on polycotton with the same order of nonionic combinations is 16, 36, and 54.

Example 27B

A copolymer comprising 33-6 percent by weight styrene (S), 61.0 percent by weight 2-ethylhexyl acrylate (EHA) and 5.4 per-cent by weight 2,3- dihydroxypropyl methacrylate (HPMA) is prepared according to the procedure of Example 12B. A test composition if formed by combining 1 part of the copolymer prepared in this example with 3 parts of NIS-5. The MEK solvent is removed from this solution by rotoevaporation at 80 °C to obtain a mixture that has 98.3 percent solids. These solids consist of the nonionic surfactant and the hydrophobic, non- ionizable copolymer in a 3 to 1 weight ratio, respectively. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 38.7, and percent cleaning on polycotton is 25.5

A test composition is formed by combining 0.5 parts of the hydrophobic, non-ionizable copolymer prepared in this example plus 0.5 parts of the polymer prepared in Example 12B and 3 parts of NIS-5. The MEK solvent is removed from this solution by rotoevaporation at 80 °C to obtain a mixture that has 100 percent solids. These solids consist of the nonionic surfactant and the copolymer in a 3 to 1 weight ratio, respectively. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 69.5, and percent cleaning on polycotton is 68.4.

A test composition is formed by combining 1 part of the copolymer prepared in Example 12B and 3 parts of NIS-5. The MEK solvent is removed from this solution by rotoevaporation at 80 °C to obtain a mixture that has 100 percent solids. These solids consist of the nonionic surfactant and the copolymer in a 3 to 1 weight ratio, respectively. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 63.1, and percent cleaning on polycotton is 52.2.

This example illustrates that a hydrophobic, non-ionizable copolymer, such as that prepared in this example, will improve the cleaning performance of nonionic surfactants. It further illustrates that a blend of this hydrophobic non-ionizable copolymer with an ionizable copolymer improves the better cleaning performance of nonionic surfactants to an even greater extent than the hydrophobic, non-ionizable hydrophobic copolymer in combination with the nonionic surfactant.

The following illustration demonstrates the synergy of the nonionic surfactant and polymer interaction as a function of diluent concentration. The graph shows the improved cleaning efficacy to occur when the water concentration is less than 80 weight percent of the total cleaning composition. Greater improvement in cleaning occurs at less than 60 percent water and continues to increase as the water concentration decreases to about 20 percent.

Cleaning Versus Water Content

Pretreatment cleaning with just poly(acrylic acid). (Mw = 450,000)/water formulation renders the following results.

TableVI

Cleaning Versus Water Content

Influence of water content of pretreatment composition formulation on percent cleaning of soil on swatches laundered in aqueous detergent solutions

0 10 20 30 40 50 60 70 80 90 100 Water Content (Weight Percent)

Samples: 1.5 wt percent poly(acrylic acid) weight average molecuar weight = 450,000 5 wt. percent Dodecylbenzenesulfonic Acid Remainder Igepal^® CO-520

Curve represents mixtures of "A" with deionized water, plotting cleaning versus water content

Igepal CO-520 Nonionic Surfactant 'B'

Curve represents mixtures of "B" with deionized water, plotting cleaning versus water content

Samples prepared by mixing "A" or "B" with deionized water in the desired ratios.

Claims

1. A method of cleaning a stain from a surface or fabric by contacting the stain with a composition characterized by a) an ionizable polymer and b) solvent(s) .

2. The method according to Claim 1 wherein if the solvent(s) contains water, the water is present at equal to or less than 60 weight percent of the cleaning composition.

3. The method according to Claim 1 wherein if the solvent(s) contains water, the water is present at equal to or less than 40 weight percent of the cleaning composition, if the solvent(s) contains organic solvent, the organic solvent can be present up to or equal to 90 weight percent of the cleaning composition.

4. A method of cleaning a stain from a surface or fabric by contacting the stain with a composition characterized by a) an ionizable polymer and b) a nonionic surfactant.

5. The method according to Claim 4 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively.

6. The method according to Claim 4 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 200:1 to 1:1 respectively.

7. The method according to Claim 4 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 100:1 to 1.5:1 respectively.

8. The method according to Claim 4 wherein the composition is additionally characterized by solvent(s).

9. The method according to Claim 8, wherein if the solvent(s) contains water, the water is present at equal to or less than 60 weight percent of the cleaning composition.

10. The method according to Claim 8 wherein if the solvent(s) contains water, the water is present at equal to or less than 40 weight percent of the cleaning composition, if the solvent(s) contains organic solvent, the organic solvent can be present up to or equal to 90 weight percent of the cleaning composition.

11. The method according to Claims 4-8, wherein the solvent is organic solvent(s) present in an amount greater than 10 weight percent but less than 90 weight percent of the cleaning composition.

12. The method according to Claim 4-8, wherein the ionizable polymer is characterized by a copolymer containing a nonionic hydrophobic monomer.

13. The method according to Claim 12, wherein the copolymer is further characterized by a sulfonated monomer.

14. The method according to Claim 13, wherein the sulfonated monomer is chosen from 2-sulfoethyl methacrylate or 2-acrylamido-2-methyl propane sulfonic acid.

15. The method according to Claim 8, wherein the nonionic hydrophobic monomer is methyl methacrylate.

16. The method according to Claim 8, wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively.

17. The method according to Claim 8 wherein the nonionic surfactant and ionizable polymer are present in 5 a weight ratio range of 200:1 to 1:1 respectively.

18. The method according to Claim 8 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 100:1 to 1.5:1 respectively. 0

19- The method according to Claim 12, wherein the ionizable polymer contains more than 40 weight percent of the nonionic hydrophobic monomer.

_c- 20. The method according to Claim 1-20, wherein the ionizable polymer contains more than 60 weight percent of the nonionic hydrophobic monomer.

21. The method according to Claim 1-20, wherein 0 the composition is further characterized by an anionic surfactant.

22. The method according to Claims 1-21, wherein the composition is dispersed in a semi-hard carrier medium.

23. A method of pretreating a stain on a fabric by: a) contacting the stain with a cleaning composition of Claims 1-22, and b) washing the fabric.

24. The method according to Claim 23, wherein the fabric is washed in an aqueous solution of a laundry detergent.

25. A method of cleaning a stain from a surface or fabric by contacting the stain with a composition characterized by a) a ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer, b) a nonionic surfactant, the ionizable polymer being present at 1 to 40 the weight percent based upon the total weight of the ionizable polymer and the surfactant, and c) 0 to 10 weight percent of an organic solvent based upon the weight of the composition, and d) 0 to 25 weight percent of water based upon the weight of the composition.

26. A method of cleaning a stain from a surface or fabric of Claims 1-25 wherein the ionizable polymer is a pH independent ionizable polymer.

27. The method according to Claim 26, wherein the ionizable polymer contains more than 60 weight percent of the nonionic hydrophobic monomer.

28. A cleaning composition, characterized by: a) an ionizable polymer and b) solvent(s).

29. The cleaning composition of Claim 28 wherein if the solvent(s) contains water, the water is present at equal to or less than 60 weight percent of the cleaning composition.

30. The cleaning composition of Claim 28 wherein if the solvent(s) contains water, the water is present at equal to or less than 40 weight percent of the cleaning composition, if the solvent(s) contains organic solvent, the organic solvent can be present up to or equal to 90 weight percent of the cleaning composition.

31. A cleaning composition characterized by a) an ionizable polymer and b) a nonionic surfactant.

32. The cleaning composition of Claim 31 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively.

33. The cleaning composition of Claim 31 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 200:1 to 1:1 respectively.

34. The cleaning composition of Claim 31 wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 100:1 to 1.5:1 respectively.

35. The cleaning composition of Claim 31 wherein the composition is additionally characterized by solvent(s) .

36. The cleaning composition of Claim 35 wherein if the solvent(s) contains water, the water is present at equal to or less than 60 weight percent of the cleaning composition.

37. The cleaning composition of Claim 35 wherein if the solvent(s) contains water, the water is present at equal to or less than 40 weight percent of the cleaning composition, if the solvent(s) contains organic solvent, the organic solvent can be present up to or equal to 90 weight percent of the cleaning composition.

38. The cleaning composition of Claim 31 and 35, wherein the ionizable polymer is characterized by a copolymer containing a nonionic hydrophobic monomer.

39. The cleaning composition of Claim 38, wherein the copolymer is further characterized by a sulfonated monomer.

40. The cleaning composition of Claim 39, wherein the sulfonated monomer is chosen from 2- sulfoethyl methacrylate or 2-acrylamido-2-methyl propane sulfonic acid.

41. The cleaning composition of Claim 38, wherein the nonionic hydrophobic monomer is methyl methacrylate.

42. The cleaning composition of Claim 38, wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively.

43. The cleaning composition of Claim 38, wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 200:1 to 1:1 respectively.

44. The cleaning composition of Claim 38, wherein the nonionic surfactant and ionizable polymer are present in a weight ratio range of 100:1 to 1.5:1 respectively.

45. The cleaning composition of Claim 38, wherein the ionizable polymer contains more than 40 weight percent of the nonionic hydrophobic monomer.

46. The cleaning composition of Claim 38, 10 wherein the ionizable polymer contains more than 60 weight percent of the nonionic hydrophobic monomer.

47. The cleaning composition of Claim 28-46, wherein the composition is further characterized by an

15 anionic surfactant.

48. The cleaning composition of Claims 28-47, wherein the composition is dispersed in a semi-hard carrier medium.

20

49. A pretreatment for a stain on a fabric with a cleaning composition of Claims 28-48.

50. The cleaning composition of Claims 28-47 -r wherein the ionizable polymer is a pH independent ionizable polymer.

51. The cleaning composition of Claim 50, wherein the composition is dispersed in a semi-hard

30 carrier medium.

52. A cleaning composition, characterized by: a) an ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer, b) a nonionic surfactant, the ionizable polymer being present at 1 to 40 the weight percent based upon the total weight of the ionizable polymer and the surfactant, and c) 0 to 10 weight percent of an organic solvent based upon the weight of the composition, and d) 0 to 25 weight percent of water based upon the weight of the composition.

53. A cleaning composition of Claim 52 wherein the ionizable polymer is pH independent.