CA2055432A1 - Ionizable polymer cleaning compositions and methods for cleaning stains - Google Patents

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

W091/1314~ PCTIUS91/01178 2~3432 IONIZABLE POLYMER CLEANING COMPOSITIONS AND METHODS FOR
CLEANINC STAINS

This invention ls directed to cleaning compositions and methods useful in removing stains.
particularly those of oll and grease or thos~ of oil and grease containing particulakes from ~ur~aoes or fabrlc.

Prlor ark ol@an~n~ composltionr3 hav@ not p~rformed a~ w~ll as ~I@sired ln removLn~ stains, especially hydrophobic oily ones containlng particulates, fro~ ~urfaces ancl fabrics. Problems have included insuPficient lipophilic compatibility Or the cleaning compositions with the stains: lack of wettability sufficient to overcome the work o~ adhesion at the substrate-stain interface; insufficient stabilization of the stain re~oved 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. Sti'l more difficult to clean ars hydrophobic stains containln~
2~ particulates. Prior art compositions ar~ typically ~oo WO91/1314~ PCT/US91/01178 ~5~ ~3~ -2- ~' 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 interrace i5 thought to result f'rom the typical1y hi~hly aqueous nature o~
such compositions.
Insufficient stabilization of the stain removed from a surface or fabric by prior art cleaning compositions has necessitated the u~e of chelating, sequestering, and antiredeposLtion agents. While the agents are efficacious to a certaln d~gre~, th@y are not thought to provld@ the d~ir@~ cl~r~ o~ stabillzatlon with hydrophobio ~ ta ~ ns.
Cleaning e~f`icl~noy of prior art compo~itions may vary accor~ing to pH or ionic content due to their effect upon the chemical composition of prior art anionic ~urfactants. Soaps are subject to formation of insoluble lime salts or loss Or 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.

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WO91/1314~ PCT/US9,1/01178 .~f~ ~3~ 2 ~ 2 2 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 weSting and ~tabilization of stains and compatibility therewith: and an improv~d cleaning co~posltion that offers supèrior 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 buf'fering, antiredeposition, chelating, or sequestering a~ent~. ~urther d~Lrably.
such improved cleaning oompositLons would b@ avallablc in A concentrate~ form sllch a~ ln a ~olid ~iok a~l w@ll as a solution or liclul~. Th0 conc~ntrat~d form not; oflly impart~! synergl~tic cLcanln~ but al~o impay~G~ ~r~at@r efficiency for u c in a pretreatment function.
Accordingly the present invention includes an improved metho~ of cleaning a stain from a surface or fabric characterized by contactin~ 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 presen~ invention also includes an improved method of cleaning a stain from a surfaoe or fabric characterizcd by contacting the ~tai~ with a ..

WO91/1314; PCT/US91/01]78 cleaning composition characterized by an ionizable polymer and a solvent or mixture of solvents.
Accordlngly 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 sur~actant and a solvent or mixture Or solvent(s). Preferably, if the solvent or solvent mixture contains water, the water is present at 0 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 pre~ent up to or equal to 90 weight percent o~ the cleaning compositLon.
~ ccordingly the prcs@nt lnv~n~lon also lnol~ld~
an improved method of pr@trQa~ln~ ~ ~Ea;Ln on a ~ur~ao~
~uch as a fabric charaot@riz@d by oontackin~ th~ Ln 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 2~ 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 1000:1 to 1:4 respectively. More preferably. tne ratio of nonionic surfactant to ionizable polymer will be 200:1 to 1:1. Most preferably. the ratio o~ nonionic surfactant to ionizable polymer will be 100:1 to 1.5~

WO91/1314~ PCT~US91/~1178 ~ ~5~ 2~5~32 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 ls characterized by contacting the stain with a cleaning composition characterized by a pH
0 independent ionizable polymer. a nonionic surfactant and a solvent or mixture of solvent(s). Preferably. if1 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 aleaning composition. if the solvent or solvent mixture contains organi~ solvQnt, the organic solvent can b~ pr~scnt up to or equal to 90 weight percent Or the al~anin~ oompo~l~ion.

Accordingly the pre~@nt inv@ntlon al~o include~
an improved method of pretreating a stain on a surface su~h as a fabric characterlzed 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 lC
weight percent of the composition.
Accordingly the present invention also includes a method o~ cleaning a stain ~rom a surfac or fabric :. . . , ,.: . . ` , ~. :

W0~1/131~; PCT/US91/01178 q ~ 6-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 inclucles a method of cleaning a stain from a surface or fabric which comprise~is oontacting the stain with a composition ?
which comprises a pH independent lonizable 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 lonizable polymer is present at 1 to 40 weight percent based upon th@ total weight o~ the ionizable polymer and the surfactant. and the wel~ht percents of the solvent ar@ bas~d upon th~ w@l~ht o~ khe composition.
Accordin~ly the present inv~ntion also inciludes 20 a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a compo~ition which comprises a pH independent ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer and a nonionlc surfactant.
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 solven~ wherein the organic solvent comprises greater than 10 weight percent o~ the composition. Alternatively. the cleanin~ comp~sition i, may comprise a pH independent ionizable polymer W091/1314~ PCTtVS91/01178 ~ _7_ 2~5~32 i containing a nonionic hydrophobic monomer and a nonionic sur~actant.
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 prei~ent at 1 to 40 welght percent based upon th~ total welght o~ the ioni~able polymer and the surfactant, and the organic solvent comprises greater than 10 weight percent o~ the composition.
Accordingly the present invention also includes a cleaning compoi~ition characterized by a pH ind~pendent ionizable polymer aontaining more than liO weight percenk of a nonlonic hydrophoblc monom@r and A nonionic surf~ctant~ ~
Th~ general cla~ of lonlzabl~ pulym@rs Ui3~U
in the cleaning compoisitlon~ and metho~ of the present invention include the class o~ ionizable polymers represented by Formula I:
A[(B)b~C)C(D)d(E)e]F
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 o~
the types of internally covalently bonded groups. Any one kind of internally covalently bonded group type can occur in a greater number than any other kind of internally covalently bonded group type or not a~ all for example to impart a homopolymer~ More than on~ kind of each type of any aovalently bonded group oan occur 'n . . .- . .. .

WO~1/1314~ PCT/US91/01178 ~3~,2 -8- ~

any copolymer of this invention. For example, the copolymer may contain (D1), (D2)...(Dn) where n is a positive integer and the sum of the subscripts, b+c+d1+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 khe f'orm of branched polymers. or in the form of grafted polymers, or in the ~orm 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 ~uch as those taught in United Stat~ Pat~nt No. 4,llZ7,8l9.
The ionizablc polymer typically ha~ a numb@r av@ra~@
molecular welght rrom l500 to lO,OOO,OOO; pr@~r~bly from 5000 to ~.000.000.

One class of ionizable polymers represented by Formula I is prepared by free radical polymerization o~
ethylenically unsaturated monomers wherein B. C. D. and E in Formula I. are selected frorn 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 acrylamldo-2 methylpropanesul~onic acid: sulfonated aroma~ic . .. -~: . . ~. .. .,. .. ; . .. . . ,; , . .

WO91/1314~ PCT/US91/01178 2~53~32 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 flnal charge to ma9s o~ the ionizable polymer will be at l~aicit 0.1 meq/~. Ir the ioni~able 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 will be at least 0.1 meq/g.
Ethylenically unsaturated monomer representa~i~/e Or C in Formula I contain at lea~t on~
ionizable group that upon ionization 1~ 5@nsltlv~ to th~
pH of the medlum. Examp:L@9 o~ i~uch monom~r.~ lno;lucl~, but are not limLt~d to, monoaarbox~lat@ oontainlnK
monom@rs, ~uoh ai~ ~cryll~ acld and m@kha~ryllo aold;
dlcarboxylate containing monomor , such a itaconic acid, maleic anhydricle: and the like. These monomer units oan 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 tha' either monomer B or C must be Dresent Z5 in a quantity such that final charge to mass of the ~-ionizable polymer will be at least 0.1 meq/~. 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 will be at least 3.1 meq/g.
Ethylenically unsaturate~ monomers representative of D in Formula I do not ~ontain any ionizable groups and are characterized by having nonionic. hydrophobic units. The term hydrophobic unit WO 91/1314~ PCI/VS91/01178 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 20C.
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 t methacrylate, phenyl methacrylate, etc: aromatlc 10 monomers such as styrene, vinyl toluene, t-butyl styrene. etc; alkyl and aryl esters of dicarboxylate containing monomers. such as itaconic acid, maleic anhydride: a-olefin(s); and the like. The minimum value of d is zero. The maximum value o~ d will depend on khe 15 formula weight of th@ monomers cho3en and wlll b@ such that at least 0.1 meq of lonizabl~ charg@ per ~ram of ~inal polymer wLlL be pr@~@nt.
Ethylenioally un.5aturat@d monomer~
20 representative of E in F'ormula 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 alkyi and arylesters o~ 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 30 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-trimethyIaminoethyl methacrylatetdimethyl sulfate (Sipomer;~' Q~ Alcolac): and the lika.

WO91/1314' PCT/US91/01178 2~55~2 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 ioni~zble charge per gram of fina' polymer will be prc~ent.
Most prererably. 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 weight range of 2,000 to 200,000 when to be u~ed ln combinatlon wLth an a~ryl~ml~1O sul~onle acLd (3uch a~ 2-acylamido-2-methyl propane ~ulfonlc acld) at a concentration o~ gr~at~r than 5 pr~rably 10 w~l~h~, more pre~erably 20 p@ro~nt b~ n kh~ Eot~l w~1~h~ o~
the composition.
The optimal monomers to prepare the ionizable polymer are chosen to effectuat compatibillty of ~he cleaning compositions with the stains and surfaces fro~, which the stain is to be removed. Selection can be ~ade on the basis of a typical formulation scheme employing, e.g.. known solubility parameters.
Compositions according to the present inventior.
3Q 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 predominantl~ hydrophobic in WO~1/1314; PCT/US91/011~8 2 ~5 ~ 12- ~

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 ar~ selected to compatibillze the nonionic hydrophobic polymer.
Man~ dif'ferent methods of forming these mixtures of polymers can be employed. For example, 0 polymers that have been made independently can be combined in a medium that will dissolve both of the polymers or other appropriate conditions tha~ will giv~
a uni~orm mixture. The e mixtures oould also be for~ed by polymerizing monomers ln the presence o~ an already formed ionizable polymer to form what 1~ hereina~r referrecl to a~ an interpolymer. Th~@ polym~rLzatlon~
could take place in a ~olv~n~ for both the ionlzable polymer and the rcsulting interpolymer or they could ~`
take place in a manner that would lead to the formatlon of a latex stabilized by the ionizabls polymer in water hereinafter referred to as a polymeri^ colloid. These interpolymers may be chemicaily 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.

3 More preferably. the ratio of nonionic surfactant and ionizable polymer will be 200:1 to 1:1. Mos~
preferably. the ratio of nonionic surfactan~ and ionizable polymer will be 100:1 to 1.~:1.

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sl/l3l45 PCTIUS91/01178 -13- 2 05 ~ 43 2 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 ancl methods include but are not limlted to ethylene oxlde 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 1; hereln by reference. PreferrccI sur~actants are @thyl~nn oxide adduct~ o~ aloohol3 ancI alkyl ph~nol~. Pr~forr~
nonionic sur~aotant.~ ~@l~t~cl f'or in~lu~lon Ln compositions cont~Lnln~ an lonlzabl~ polym@r wi-Ll pre~erably h~ve a hydrophill~-llpophllia balano@ (HLB) value in the range of ~rom 8 to 1; and more preferably 8 to 13~ most preferably 9 to 13. Thu~, the preferred nonionic surfactant is water-immiscible. wat~r-insoluble or water-dispersible at room temperatur~. Nonionic 2~ 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 inolude.

Wo91/1314~ PCT/US91/01178 ~ ~ ~S~ 14-but are not limited to linear alkylbenzene sulfonates, alpha olefin sul~onates, alkyl sulfonates, alkyl ether sulfates, alkyl sulfosuccinates, and sul~onate derivatives of nonionic surfactants. Suitable anionic surfactants include those taught in The Encyclopedia of Chemical Technology 3rd Ed., Vol. 22, pp. 347-360, which iC1 incorporated herein by reference. Preferred anionic surfactants are alkylberlzene sulfonates, and a most preferred onc i5 dodecyl benzene sulfonic acid and para-10 toluene sulfonic acid and the like. -Compositions according to the present invention may take the form of a liquid, emulsion. dispersian or solu~ion, ~emi-solld. or a ~oft solld or qtick, Solid ~tick composLtlons may~ be formed by ~isperslng th@
varlou~ dlsclos@d compo~ltions lnto a .~eml-hard ~rrLgr medlum. Sollcl stlok prespoktlng and staln rQmovln~
composltlon5 and methods for m~klng ancl u~ing are ~een in United State~ 4,842.762, Unlted States 4,396.521. and United States 3.66lJ,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 2~ 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 3 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 solver,t such as d-limonene to provide greater hydrophobicity. The oompo~ltlon may comprlse grcat~r .. . . .

W091/1314~ PCT/US91/01178 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 e~her as well as methyl laurate, cotton ~eed oll, dodecyl ben~ene, dibasic esters and mixtures thereof. For purposes of this specification, the nonionic surfactant is not considered an organic solvent because o~ its surface activity.
Compositions according to the present inven~lon as variously taught herein may be Porme~l wLth ai nonlonlc surfactant in lieu of or ln combination with an organlc solvent. In compo~i~lon~ contaLning a nonionio ~urfactant and not an or~anlc 90lvent, th@ compo~ltlon will preferably comprlse greater than 10 weight percent nonionic surfactant.
A specific class of ioniz~ble polymers of the present invention include pH independent ionizable polymers.
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 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 ioni2abls polymers may contain both pH dependent and independent groups~ but are preferably pH independent in overall character. That is~ the mol~ Practlon of a'l B monom@rs .. . .. .. ...

WO91/1314~ PCT/US91/01178 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 pre~erably ha~ a net anlonlc charge upon ionization, and is selected to optlmize stabilization of nonionic hydrophobic mixtures of monomerics. polymerics and particulates in water. Such ionizable polymer comprises a combination of pH independent anionic monomers and nonionie monomers, for example groups B and D in Formula I hereln above. Pre~erred anionic monomers inclucle sulfonated monomers such aq 2~ulfoet,hyl methacrylate (2-SEM), styrene ~ulfonlc acld, 2-acryLamldo-2-m~thyl propane 3ulfonlc aold ~MPS'~), and ~thyl@n@ ~ul~ofllo acid. Pref@r~bly, ~uch ionlzabl~ polym@r aompri~
combinatLons of anionic monomer~ an~ nonionic hydrophobic and hydrophilic monomers. Such ionizable polymers may include pH dependent ionizable monomers such as ca~boxylated monomers, for example from group C
in Formula I, but will contain a greatsr 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 ~ 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 ~ ~17- 20~5~2 greater than 60. and most pre~erably greater than 70 weight percent hydrophobic monomer.
The pH independent ionizable polymer may have a charge density up to 10. The pH independent ionizable polymer preferably has a charge density o~ between 0.1 to 5.0 and more preferably 0.15 to 2.0 milliequivalents per gram.
The pH independent ioni~able polymer may have a 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 weLgh~.
NonlonLc, hydrophobic unlts ~ultabl@ ~or ~`
lncorporation and oopolym~rix~tion into th~ pH
independent ion~z~ble po.lym~r lnoLud~ khose ~@rLv~d ~rom any copolymerlzable eth-ylenically un~a~urate~ monomer which. when in the form of an amorphous homopolymer.
would have a solubility in water of less than 0.l percen' at 20C. Nonionic hydrophobic units inciude.
but are not limited to styrene. t-buty styrene. vinyI
toluene. methyl methacrylate, n-butyl methacrylate.
lauryi methacrylate and 2-ethylhexyl acrylate.
Other monomers such as nonionic~ amphiphilic monomers suitable for incorporation and copolvmerization 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

-18- ~ `
.. . .
2 ~ 3 2 R ~-H2C=C-ZWR ' : .' . ' where R is either H or -CH3; Z is a suitable linking O ' ' group, such as l! ; W is a --C--O--hydrophilic extending group, such as a ~CH2CH2-Otn. with n typically less than 100 and preferably no more than LlO; and ~' is the hydrophobio group, such as -C22H45, or _ ~ ~ , Specific examples CgH19 of monomers of this type are behenyl poly (oxyethylene)[25] methacrylate and nonylphenoxy poly(oxyethylene)~10~methacrylate~
Nonlonlc, hydrophoblo moncmor~ ul ln Eh~
oopolym@rlzation o~ pH ln~p@nd~n~ lonizable polym~r~
include but are not llmlted to qtyrenics. acrylates.
methacrylates. isoprene, butadiene, ethylene. vinyl chloride. and vinyliden~ chloride. ~y copolymerization with a sui~able 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 ~ -3o small amounts (e.g., usually less than 50 weight percent and preferably less than 10 and more preferably less than ~ weight percent based upon the weight of the ionizable polymer) of very hydrophilic but nonionic comonomers represented bv Group ~ in Formula I~ for control of the surface activity and wate~ compatiblli~;

" . ` . . '., ,... ~.. . , ~ , . .. . . . ~ ` ` . ..

WO91/1314~ PCTtVS91/~1178 _19_ :
'';'~2~5 ~
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.
Low concentrations of monomers with weak acid (Group C in Formula I) or weak base groups ~Group ~ in Formula I) and salts thereo~ may also b0 used provided that the pH independence o~ the ionlzable polymer backbone i5 m~lntaln~d. ~.g., a mlnor amoun~ o~ a vinyl monomcr ~uch as acryllo a~ld or amlno~thyl m~thaoryl~@
(or the hydrochlorid~ ~alt th~r~Q~) could b~ Includ~ EQ
promote adhesion. s~rv~ r~ac~iv~ sit~ and th~ lik@.

Compositions according to the p~l independent ionizable polymer may employ mixture~ of two or more polymers as similarly described herein above for ionizabie polymers.

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 surfactan~ 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 ar the ionizable polymer and the nonionic aosurfac~ant.

WO91/1314~ PCTIUS91/01178 2 ~ ~ r ~ s~ ~

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, diL~persion or solution, seml-solid, or a ~oft solid or stlck a5 discussed herein above.
Cleaning compositions of the presen~ invention utilizing pH independent polymers may contain one or more solvents as discussed herein above. The composltlons will preferably comprlse up to about 40, more preferably about 2~ or less, ancl moqt pr~rabLy about 15 or leqs weight pero@nt watar ba9@d upon th~
welght of the compo~ltlon.
Compositions according ~o the present invention utilizing pH independent polymers as variously taught herein may be forrned 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 staln resides in addition to directly upon the stain itself. The term stain includes any substance which is embedded or not `
embedded, solid or llquid. wet or dry~ and at or beneath WO91/1314~ PCT/US91/01178 ~ -21- 2~

the surface or fabric. and is not to be construed as limiti n g.
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 subqtantially aqueous medla. In the case of fabric, the composltion-treate~ stain i~ preferably laundered with water and more preferably with an aqueous solution of mostly water and a conventional laundry detergent.
Thus, it is possib}e to formulate a cl@anlng composition offerlng 3uperl0r cleanln~ ln accorclance with the preqent invention without th@ incluslon ~
prior ar~ ~cquest@ring or che:Latln~ ag~nt~ ~sllch as ED'rA.
phoqphate~, nit,rLloac~at@.c~1 and aminopo:lycarboxyllo acid~. Inclu~lon o~ ~uoh prlon ar~ ag~nt~ rnay how~v@r, be appropriate in use a~ a co~equestran~1 as a sequestrant for substanc~s not efficiently sequestrable by the present compositions. or as an a~ent for some other purpose.
27 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 mav be included as coagents for the same purposes or as an agent for some other purpose.
The composltions and methods according to the present invention may be utilized e~fectively to clean soils and oily stains such as motor oii~ co~king oil.

:,,, .. ,.,.,, ,.. ,.. , ~:.:. , , . ; ~ . ,:. . . . .

WOgl/1314~ pcr/us91/oll78 ~ 22-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 dircy motor or diesel oil. Such compositions and methods may also be utilized effectively to clean stains of lesser hydrophobicity tharl oil and grease such as grass, blood, an~ carbohydrates such as starch on surfaces and fabrics.
Compositions and methods according to the present inven~ion may be effectively utilized in laundry pretreating, stain removing. industrial and household degreasing, metal cleanlng. paint stripping, and g~neral purpose industrial and household cleaning.
Th@ inventLun i~ ~urth~r lllu~traE@d but nok limited by th~ ~ollowlng exampl~ wh~r@Ln all par~ ar@
by weight unleqs oth@rwi~e specLfied.
Examples:
The following examples t~st the cleaning effectiveness of various test compositions comprisin~ an ionizable polvmer with and without hydrophobic polymer.
2~ and/or nonionic surfactants as a pretreat stain remover on fabric using varyin~ conditions in a subsequent laundry cycle. Various types of ionizable polymers.
hydrophobic polymers, and nonionic surfactants are utilized.
Fabrics utilized in the following examples include lO0 percent po~yester, a 65/35 percent polyester-cotton (polycotton) blend. and lO0 percent cotton.

w~s1/l3l4~ PCT/US91/01178 2 ~ 3 ~ `

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 ~tain is alLowed to sit overnight.
About 1.5 grams of each of the test compositions is placed in the form of a thln 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 speclrle~l) at 100 rpm, The ~watche5 are launcler@c1 with an aqll@Oll~
~olution of a heavy c~uty eomm~rel~l laundry deter~ent (hereinafter r~ferre(1 to ln thg Ex~mple~ a~ "d@t~rg~nt") or with water only~ The ternp@ratur@ of lal1nderlng is around 50C unless otherwise indicated, The water is tap water from the City of Mi~land. Michigan or deionized water unless otherwise indicate~. Wher@
detergent solution is utilized, the detergent concentration is about 1.0 gm/liter of water. After Z5 laundering, the swatches are rinsed for 5 minutes. and allowed to air-dry overnight.
The swatches were analyzed along wlth unstained swatches on a Hunter Labscan 45/0 D25-PC2 Colorimeter 3 of Hunter Associates Laboratory. Inc. usin_ the CIE 1931 standard source illuminant C. Alternatively on a MiniScan'~ Spectrocolorimeter version MS450C~ with a 45~0~ geometry and large viewing area opticn using the :: . : . .: : ~ .. . , :.,, : . . .: -. . .. ..

.. . . . . . ... . . - .
: : ~, . : . . . :., W09}/1314~ PCI'/US9l/Ol17g 2~ 24- ~

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 MinlScan is flrst calibrated using a factory issued whl te tile; the blaok ~anclard ls lnternal. The swatches are read by set1ng the one lnch diameter 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 per¢ent clean) and stalned. unwashed fabric (100 percent dirty) were analyzed to determlne the range of cleaning. Percent cleaning i5 dctermin@d on ba~ o~
hue and brightn@9~.

Example 1~: Preparation of_an Ionizable Polymer An ionizable aopolymer comprising 97.6 percent MMA, 2.4 percent ~-SEM (2-sulfoethyl methacrylate) by weight is prepared according to the following procedure.
The 2-SEM will provide a charge of 0.127 meqig of this polymer.
The poly~erization is achieved by adding 133.33 parts of methyl ethyl ketone (MEK) to a stirred 3 reactor provided with a nitrogen atmospnere. a condenser. and inlets for monomer and initiator addition. The reactor is purged with nitrogen and heated to 80C by a constànt temperature water bath.
Two solutions are prepared for addition Co this reactior.
flask: a~ the solution of monomers prepared in ME~ and , : .. . .. ,., ~ .. , . :,. . . . .

W091/1314~ PCT/US91/01178 2053~32 b) an initiator solution is prepared by adding 2.5 parts of VAZ0~ 64 initlator (marketed by E. I. duPont deNemours & Co.) to 133.33 parts of MEK. These two solutions are added by syringe to the heated ME~ 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 50lutions are added. the mixture iq heated to achieve ~reater than 90 percent conversion which typically requlres 3 addltlonal hours to complete the polymerization. The final product is a clear amber solution.
A test composition is prepared by adding 3 parts Or NIS-5 (nonionic urfactant with an average of 5 ethy~ene oxide adducts) to a copolymer solution containin~ 1 part of the copolymer as de~oribe~ ~bove. Th@ MEK olv~ng is removed ~rom this ~olutlon by roto@vaporatlon und@r vacuum at 50C to obtaln a mixture that aon~l~t~ o~ 98 percent soLids. Stained fabrlc~ utlllzing the test composition are laundered at 50C for 1~ minutes as indicated with the detergent solution. Percent cleaning on cotton is 62.2, and percent cleaning on polycotton ls 48.8.
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 accordinc 3 to the procedure above. Solids content is determined to be 98.0 percent. Stained fabrics utilizing the test composition are laundered at 50C for 15 minutes as indicated with the detergent solution. Percent cleanin~

WOgl/1314~ PCT/US91/01178 ~ ~25-2~ 3~3:~
on cotton is 85.0, and percent cleaning on polycotton is 66.2.
ExamDle 1B:
An ionizable copolymer is prepared by free radical polymerization of 82.4 percent MMA, and 17.6 acrylamido-2-methylpropanesulfonic acid (~MpsQ') by welght ~imilarly to Example lA except 33 ~rams o~ water is added to each o~ the MEK or ME~ 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 lA. Solids content i5 determine~ to be 99 percen~.
Stained fabrics utilizing the test composltion are laundered at 50C ~or 15 minutes as lndieated with th~
detergent solution. Percent cleanin~ on oo~ton 13 53.0, and percent cleanlng on polycot~on 1~ 36~0.
Comparatlve ExamPle I (control fabnio):
Stained fabrics not utili~ing a test composition ~control) are ~aundered in the detergent solution for 15 minutes at 50C. 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 lA and 1B.
Pretreatment ComDarative ExamDle . .
Stained fabrics utilizing a commercial soil and stain remover composition (Spray'n Wash~Stain Stick Tough Stain Remover for Laundry. DowBrands Inc.) as 2 control are laundered in the detergent solution for 1 .

.~ , ,, .... : .. : ;: : : : : : :
:" . :: : .
`.. ` ` ` `.. . :; ~!; .. .` : ~ ' . : ` ' . .::` , `, WO91~1314; PCT/US91/01178 ~ -27- %~432 minutes at 50C. Percent cleaning on cotton is 27. and percent cleaning on polycotton is 27.
Example 1C:
SPS: Partially sul~onate 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%) ls cooled to 0C.
The chlorosulfonic acid in chloroform ls slowly added 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 po~entiometrlc tltration.
Stained fabric~ utillzlng the te~t eompo~Ltlon~
lndicated in the following Table~ ar@ laundered ~t 50~C
for 15 minuteq as indlcate~ with the water and/or detergent solution. These test compositions are prepared by comblning the indicated ionizable copolymers and NIS-5 in an amount required to give the weight percent solids of the ionizable polymer based on the lonizable copo]ymer plus NIS-~ shown in the Tables. In 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 50C under at least 25 inches of vacuum for two hours.
When water is initially present in the formulations they are additionally heated at 80C for one hour to assure removal of the water. The resulting percent cleaning on cotton and on polycotton are given in the ~ables indicated that a wide variety of ioniæabl~ homopol~mer3 W091/1314~ P~T/US91tO1178 ~55~
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 ~cld) ~lxtllre wlth c~ulfonlc acid (either dodecylbenzene sulfonlc aci~ or toluene sulfonic acid monohydrate) with a polymer weight average molecular weight between 1800 and 4i50.000 and concentrations between 0.~ wt% and 17 wt% and sulfonic acid concentrations between 1.5 ancl 50 wt%.
3. Sulfonated poly(styrene) with weight av~rage molecular wei~ht b~tween 6500 ancl 70,000. d~r~@~ o~
sulfonation betw~n 10 mol@% an~l 100 rn~l~% ~ncl concentratlon~ b@tw~@n lj wt'h ~n~ 2~.5 wt~hl al~o lncluding blend9 of ~ulfonat~d poly(.~kyren@) wlth poly(methyl methaorylat~).
4. Miscellaneous polymers with concentrations from 4.4 to 24.3 wt~ including methyl cellulose (MOC).
chondroitin sulfate. dextran sulfate. sulfoethyl cellulose. and polymethacrylic acid).
2~ --. . . : . .-:,, : , .. :: .

WO91/1314~ PCT/US91/01178 203a~32 TABLE I
(1) Pol~(Acrylic Acid) in NIS-5 -weight percents are based on total formulation weights Percent Cleaning ___ P~AA) P(AA) Aqueous In Water MolecularConcentration Detergent 1Weight (wt% ) _ CottoncoPtOtloyn Cotton coPtOtlyn :
. ~ . ~ _______ 1, 80 0 40 40 18 .
1 1,800 42 42 18 _ . _. . .
5,000 11 30 1 6 26 11 ~ _ _ _ . . . _ 5,000 S0 42 22 43 l 5 50,000 S 50 31 ~9 17 __ ___ _ . - - - ~ _ 250,000 1-O~ 73 _ 62 l 7 50,000 _ _ 72 29 67 16 __ _ _ _ S0,000 20 78 29 64 l7 50,000 25 5 1 26 1 50,000 1 1 77 30 .
~ ................. _ .. . _ _ 450,000 3 8 1 36 -~4,000,000 ___ 58 26 _ ..
4,000,000 O.S 39 25 .
_ _ _ 2 1 1 8 7 2 3' Wo91~1314~ ~.k PCT/US9l/01178 ,, , -. . :

TABLE II
(2) Poly(Acrylic Acid) and Dodecyl Benzene Sulfonic Acid in NIS-5 .. . _ . . . , . . "
Percent Cleaning Dodecyl , .~ _ Mwlec hlar tratlonSulfonic Aci~l Detergent In w rter elg t (wt. %)centration ~
1 C . ~wt. % ) Cotton cc~ttonCotton Cotton . .. .
1,800 11 13.5 42 31 45 13 - . , . __ __ __ __ _.
5,000 11 13.5 4131 65 24 , . .. ~ .. __ __ __ __ 50,000 2.S 13.5 43 36 65 32 1 ___ _ : __ : .__~ __ __ 50,000 2 5 25 46~ ~6 29 S0,000 2.5 50 ~428 39 2 __ __ __ __ __ 50,000 5 25 68 3l 56 2 50,000 5 50 30 21 29 21 , _ ~ __ __ __ 2 50,000 5.5 7 6355 49 40 50,000 5 5 l4 6650 67 37 __ _~ __ __ __ 50,000 11 5.5 67 4165 39 50,000 11 25 59 4454 33 2 50,000 11 13.5 66 4056 40 90,000 11 13.5 68 3838 25 . .
150,000 11 13.5 49 2640 13 _ . ._ __ .
450,000 0.5 5 48 47 28 19 .,_ , .
3 450,000 ~.5 1.5 58 19 15 450,000 1.5 5 34 21 , _ _ ......

450,000 3 5 73 49 15 __ _ _~ _ 450,000 3 10 ~838 .
. ,, . . . __ . __ __ 450,000 1.5 25 ~8 ~2 . .
__. .__ __ __ _ __ __ 50,000 l7 l3 5 53 3253 2 W091/1314~ ~ PCT/US91/Olt78 ~" 31 TABLE II Continued Poly(Acrylic Acid) and Toluene Sulfonic Acid in NIS-5 50,000 ~ 35 62 42 30 23 =
50,000 11 7.8 67 38 25 1 0 _ __ __ ..
SO,OOO 11 15,5 62 39 33 18 _ _ _ _ _._ _ 7.8 40 41 21 19 =

TA~LE III
Toluenesulfonic Acld (3) Sulfonated Poly(Styrene) in NIS-5 Percen~ :ler nin~
2 Polymer type and its Concentration Det r~ent In Water Molecular Weight (wt-%) . ~ __ , .cot~onCotton cottonco~ton 210% Sulfonated-60,00025 78 60 34 2g . . ..... _ 100% Sulfonated - 70,000 4.5 44 30 17 10 __ 100% Sulfonated- 70,000 10.0 61 35 44 10 ~:
100% Sulfonated-70,000 17.5 78 42 44 36 . . . . ~ ~ . .
100% Sulfonated-70,000 29.5 42 13 63 12 :
3~ __ .
100% Sulfonated - 70,000 4 65 46 30 1 8 PMMA 12,000 1 3.5 . _ 100% Sulfonated 6,5001 0 45 3 6 29 30 ~ _ _ _ ~ ~ _ _ . . ~ ~

wosl/l3l4; PCr/VS91/01178 ,.2,a~s43'l ., .
TABLE IV
(4) Miscellaneous ... . ~

Concen. Addltlve Aadltlve Percent Oeanlng M~teoiJI trarlon Con. .... __ .. ,_ wt ~ centr~lr)no~ C/AD PclAD C'Vv PC/W
___ _ _ MOC 1; I 1 D35 13.5 37 39 66 46 .. _ _ .... .
1 C MOC 2 5 1 1 D3S 1 3 . 5 3 7 3 7 6 5 4 5 MOC400 1 1 DBS 13.5 37 38 59 47 ... . _ . _ ....... __ __ _.
Chondrolon 14. 8 3 5 3 7 3 6 31 Sul~are _ . _ . . - ,.. ___ __ _. __.
Cnondrol~ln 4 4 . . 29 28 29 20 1 ~ 5UIfdtr3 ~ ~ __ ___ - ~ L ~
Dextrdn lO.3 . 35 37 36 37 Su1~3t@
_ __ _ ___ __ __ ~ _ ~...,.._.., 0~.~
Sullo~thyl 17.8 . ~ 24 30 7 2 Cellulose ___ ___ __ __ __ 2 C Sultoetnyl 24. 3 . 34 34 7 2 Cellulose _ _ , , .. .. __ ___ __ ... ,. _ P~MAA) 12 D~S 7 50 57 52 l 9 _ _ . .. ,. .. . .. __ . ~ .
~ ~M~ _ 12 D35 14 51 48 50 46 versa~ 15 54 29 59 28 ._ . _ .
2- ~arlex~ D-a2 15 44 19 oO 19 ~.......... ... _ ~ .

C = Cotton 3 AD - Aqueous Detergent PC = Poly/Cotton W _ Water ., ~ , , . . . .. . . , ~ . -WOgl/1314~ PCr/USgl/01178 P~MAA) = Poly(methacrylic acid).
Versa~ TL4 = Sulfonated styrene maleic anhydride copolymer by National Starch and Chemical, weight average molecular weight=20.000.
Narlexr~ D82 - Sulfonated vinyl toluene maleic anhydride copolymer by Nation~l St~rch and Chemical, weight average molecular wei~ht-25.000.
DBS = dodecylbenzene sulfonic acid.
MOC - methyl cellulose MOC 15 - methyl cellulose with 2% aqueou~ solutLon having a viscosity of 15 centipoi~e.
MOC 25 - methyl cellulo~@ wlkh 2~ aqu~ou~ ~olutlon having a viscosity o~ 25 c@ntipol~.
MOC 400 - methyl cellulose with 2% aqueous solution having a vi cosity of 400 centlpolse.
Sample Description:
A. Sulfonated poly(styrene) 6500 was 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 aqueous solution from Polyscience (Warrington PA).

WO91/1314~ PCT/US91/01178 . -34-20~543~
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% solicls in water 1150~000 powder 4,000.000 powder 3o .

- , . ., .;, : .. ; , .

WO91tl3145 PCT/US91/01178 205a~32 .. ....
Sources f~r Other Polymers Polymer Source Form -Sul~oethyl CelluloseAmerican Tokyo Kasei Powder ~0.15 meq/g) . _ .
-P~ly(methyl meth~crylat~) Polyscienc0s Pow~er 'P~MMA) -Cho~droitin Suleate Sigma P~d~r ?
-Dextran Sul~2te Sigma Powder -Poly(methacrylic Acid)Polysciences Powder P(MAA) -Methyl CelluLos~ ~M0C) 2~ Aqu~us .Solution 15 cp ~ldrich Powdor 25 cp 1100 cp ~
-~V~r~ TL~ Nati~nul St~rch 25~ S~ a nnd Chamie~l ifl wnGor -~NarLex' D-82 N,ltl~naL St~rch Powder ~nd Ch~mic~l ~These samples were conv~rted to the hydrogen ion ~orm by stirring ~or ~ hr, with a ~1 (wt,-wt.) ~xcess oE Dowex 50W Ion exch~nge Resin in an ~queous slurry. The "Dowex" was r~mov~d by filtration and the process was repe~ted. , 2~ 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 lA. The 2-SEM will provide a charge of 0.925 meqig of the copolymer. A test ~:
3 composition is formed from the same charged polymer and a variety of nonylphenol ethoxylate (Igepal~ nonionic surfactants from CAF Chemicals and Tergito~e surfactants from Union Carbide) and alcohol ethoxylate nonionic surfaatants (Neodol'~i nonionia sur~actants from Shell) according to the procedure o~ E.xample lA. 5tained ~, . . :

WO91/1314; PCT/US91/01178 2~5~32 fabrics utilizing the test compositions are laundered at 50C for l~ minutes as indicated with the detergent solution. P~rcent cleaning on cotton and percent cleaning on polycotton are ~iven 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 ethoxylate~ ~e.g., Neodol'~ 23.5). These data al~o ~ho~J that the cleaning for a ~iven formulatlon will depend on the HLB of the nonlonic 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'7 25-3 and 23 percent of Neodol'~ 25-9, bLend 2 contains 50 percent of Neodol~' Z3-3 and 50 peraent of Neodol0 23-6.5, blend 3 contain~ 32 p~ra~nt of Nco~ol'~
25-3 and 68 percent of Neodol'~J 25-9.

WO91/1314~ PCT/US91/01178 2~5~3~
~able Y
The Effect o~ Nonionic on Cleaning Nonionic Sur~actant Percent Percent sur e~ tant HLB
C~on Po1ycott~n IGEPAL~ C0-630 13 42.5 20.9 IGEPAL'~J CO-610 lZ.2 64.9 37.0 TE~GITOL'~ NP-6 10.9 67.5 35.7 IGEPAL'~ C0-520 10 77.8 43.8 ~ERGITO~ NP-4 8.9 59.7 18.
N~odol~) 23-5 lO, 7 5~1. 7 ~4 . 2 N~odol~ 23-6.5 12.1 ~.7 31.7 Naodol'~ 25-9 13.1 35.1 ~7.
Ne~dol~ ~lend 1 9 62.5 2l.6 Neodol~ Blend 2 10 60.6 36.0 Neodol~ Sl~nd 3 ll.4 53.} 39.3 ~xamDls 1E~ Preparation o~ Ionizable Polyme~

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 50C while continuously adding ~ .
reactants from five separate sources with proportionate 3 feeds over 120 minutes and the resulting polymerization is allowed to continue ~or an additional 2 hours. Feed ~.
compositions are as follows~
After polymerization, 3,333 parts of deionized water are added and 1,715 parts o~ volatile IPA and W O 91/1314~ PCr/US91/01178 - ~ r ~ ~ ~

Feed PartsComp~nent l 333Dei~nized water 333Isopropanol 5002-Acrylamido-2-methyl p~op~ne s~ onic acid ~ AMPS ) 2 46$ Mcthyl m~th~cryl~t~
35Allyl methacrylat~
3 2.8i2-Mercaptoethanol 80Deionized water 4 2.00Tertiary butyl hy~rop~o~id~
80D~i~niz~ w~e~

water are r~moved by vaouum dlstLLl~tion at. ~bout 50C.
The devolatlli~cl polym~r~ ~ollltlon m@a~lJr~ I7.8 percent olids arld 2.LI m~l of strong ancl wQak aci~ p@r 6ram of polymer 901id~.
ExamQ 1 e _1~e~_19~3~

The solwtion of Example IE 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 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 WO91/1314~ PCT/US91/01178 _39_ 20~3~ :~
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.
E~ 3~ti~ L~`~55~ a~ a~3~
Ionlzable Polvmer Colloi,d and Nonionic Surfactants The final liquid-solid mixture oP Example lF is blended with nonionic surfactants in a quantity to ' produce test compositions comprising 75 parts by weight nonionlc surfactant to 25 part~ oi~ the poly~eric colloid. The water content l~ reduced to about 5 perc~nt by vacuum dl~tlllation at 80C. Th~ nonlonio ~urfaot~nts u~d ar~ elth~r nonyl ph@nol wi~h 5 mol~.~ Or ethylene oxld~ adduct ~NIS-5) ~r a 111 to 15 ciarbOn alcohol with 7 mole~ of ~thylene oxld@ adduct (45-7). ', Comparatlve Example: , Standard fabrics not utilizing a test ' composition (control) are laundered in the detergent ,' solution for 15 minutes at 50C. 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 Lxample -~
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 Por 15 WO91/1314; PCT~US91/01178 2 ~
minutes at 50C. Percent cleaning on cotton is 26 and percent cleaning on polycotton is 26.
Example 1H:
Stained fabrics utilizing test compositions of Example lG are laundered in detergent solution for 15 minutes at 50~C. Percent cl~aning on cotton ~or the combination~ with NI5~5 and 45-7 15 82 and 70 respectively. Percent cleaning on polycotton with the same order of nonionic combinations is ~4 and 38.
Examcle lHa: Preparation of Compositions of an QR-1265, ~ carboxylated deker~@nt polymer ~rom Rohm & Haas, United State~ Patent 4,797.Z23, havln~ an ionlzable content o~ 3.75 meq of' char~ p~r ~ram o~
polymer, i~ blended incllvldually wLth tll~f~r~nt nQnlofllo surfactants in a quantity for testing comprLsing 75 parts by weight of nonionic surfactant and 25 parts polymer solids. The water content is reduced to about percent by vacuum distillation at 80C. The nonionic surfactants are nonyl phenol with 4 or 5 or 6 ethylene oxide adducts or Neodol'~ 45-7 (product by Shell Chemical 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 -as 45-7- . .

.

WO91/1314~ PCT/US91/01t78 2~53~32 ComDarative ExamDle:
I

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

... . . .. .

... .. . . . . . .. ... .

WO91/131~ PCT/US91/01178 2~ 2 -42- ~

cotton is 29. and percent cleaning on polycotton is 11.
Fabrics of the same manufacture were used in Examples lHb and the following comparative nonionic examples and 1He.
Pretreatment Comparative Exam3le:
Stained fabrics utilizing a commercial soil and stain remover composition (Spray'n Wash0Stain Stick Tough S~ain Removcr for Laur1dry, DowBrands Inc.) as a control are laundered in ~he detergent solution for 15 minutes at 50C. Percent cleaning on cotton is 26 and percent cleaning on polycotton is 26.
Example_1Hb:
Stained ~abrics utlllzin~ test compo~Ltlon Or Example~ 1~{a are laundcr~d Ln det~rg~nt ~olution for 15 minute at 50C. Percent ~leaning on cotton ~or kh~
~omblnatlon wl~h NIS-II, N~S-5. NIS-6? an~ 1l5-7 1~ ~l9, 29, 23, and 47 re~p~ctively. Pcroent cl~nlng on polycotton with same order of' nonionic combination is 15, 2C. 19. and 29.
Comparative ExamPIe:
Stained fabrics utilizing nonionic surfactants withaut charged polymers are laundered in the detergent solution for 15 minutes at 50C. Percent cleaning on :. :
cotton with NIS-4. NIS-5, NIS-6 and 45-7 is 19, 25, 18, 30 and 30 respectively. Percent cleaning on polycotton .
with the same order of nonionic combinations is 7, 9, 12, and 23.

' ,`~; ; ,'',, "' .` '~,, . : `

WO91/1314~ PCTIUS91/01178 205a~32 Exam~le lHc:_ Preparation of Colloid with Ionizable Polvmer 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 styren~ and 2-cthylhexyl acrylate ~nd emulsion polymerized u~ing the procedure of' Example lF. An aliquot reveals (a) 24.2 percent solids indicating the reaction to be essentially complete. (b) approximately 1.9 meq weak acid per gram so].ids, and (c) the colloid average particle dlameter is about 0.1 micron. The resulting polymeric solids are abowt 50 peroent Q~-1265 ~, charged polymer and about 25 percent ctyren~ and 25 percent 2-ethylhexyl aorylate.

b~:9~ D~!L_~L ~ L~on o~ IonLzabl~Gollold andi Nonlonic Surfactant~_ The liquid-solid colloid of Example 1Hc (hydrophobic modi~ioation of water soluble detergent polym~r) blended with different nonionic surfactants in a quantity for testing 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 80C. The nonionic surfactants are nonyl phenol with 5 ethylene oxide adducts or Neodol~
45-7 ~product from Shell Chemlcal Company) depending on example. The nonyl phenol 5 moles ethylene oxide surfactant is designated as NIS-5 and the 14 to 15 carbon alcohol with 7 moles ethylene oxide as 45-7.

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W091/1314~ PCT/US91/01178 . . . ~ .
, .. .

Examp1e 1HeD:~J ~ 3 ~
Stained fabrics utilizing test compositions of Example d are laundered in detergent solution for 1i~
~inutes at 50C. 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 Ionlzable Polymer (The following examples are additional examples Or pH
independent ionizable polymers; some of the examples of Set I also include pH independent ionizable polymers) Example 2A~
Polvmer An ionizable polym@r is prepared by addin~ 1000 parts of 130propanol and 650 parts o~ dQionized wat@r to a stirred reactor provid@d wlth a nltro~n atmosph@re and maintalned at 50C while continuouqily 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:
. :

.

,`,., . . '` ' ' .;:. .. . .~ ~ .'.. : . . ..

WO91/l3l4~ PCr/US91/01178 ~3 _45_ . .............. .

Feed Parts Component l lO00 Deionized Water 384 2-Sulfoethyl Methacrylate (2-SEM) 62.2 Dimethylaminoethyl methacrylate (DMAEMA) 2 554 Methyl methacrylate (MMA) .
3 6.18 2~Mercaptoethanol 114 Deioni~ed Water 4 2.00 Tertiary(t)-butyl `
Hydroperoxide 118 Deionized Water 1.50 Sodium Formaldehyde Sulfoxyl~te 118.5 Deioni~,ecl Water :3_~ou~ _D~-!Do~D~ti~on of a ~Solu _ n IonLzahl~
~ @
The solution formed in Example 2B is added to 2500 parts delonlzcd wat~r followed by devolatilization of 1700 parts. The devolatized solution o~ ionlzable polymer is mixed with 56.3 parts of glycidyl methacrylate (GMA) while heating for two hours at 50C.
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 25C, pH of about 2, --~
and a viscosity of 15 cp at 25C. The ionizable polymer has a total acid content of about l.9 meqijg and an :~: average molecular weight of less than 40.000.

W091/1314~ PCTt~S91/~1178 . . ,, . ~ .
ExamD_e 3B: PreDaration of HydroDhobic CoDolvmers The solution of Example 2B is used as the water based stabilizer ~or the emulsion polymerization of hydrophobic copolymers.
Hydrophobic styrene/2-ethyl hexyl acrylate copolymer~ are prepared by copolymerization in the prei~enc~ a portion of th~ lonlz~ble polymer-~lycidyl methacrylate isolution. 100 parts each o~ 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 mcthacrylate ~olutlon of Example 2~ (22 perc~nt ~olid~ by mat@rial balanc~).
This mixture i~ heated to and malntaln~d at 50C und@r a nitrogen atmoi~phero whll~ addlne proportlonately ~rom separate feed ~yi~tems of 0.1l0 part t~butyl hydropgr~xlt in 50 part~ of water and 0.30 p~rti~ ~odlum ~ormal~ehyd~
sulfoxylate in 50 parts water over about 30 minutes.
After co~pleting 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 percer.t 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.

. . .. : ,` " , . ~ , . . . , . : , , . 1! . .

wosl/l314~ PCT/US91/01178 ~ _47- 20~432 ExamDle 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 sy~tem. The water content is lowered by vacuum ~istillatlon at 80C to about 5 percent. The nonionlc 5urfactant i~ a nonyl phenol with 5 or 9 ethylene oxide adducts depending upon the example. The nonionic surfactant with an average o~ 5 .
ethylene oxide adducts is designated as NIS-5. and the one with 9 as NIS-9.
The following example~ t~st the cleaning effectlvene~s of var.ious test compo~lt.ion~ o~ thc ionLzable po;lym~r with ancl wlthout hydroph~blc polym~r, and/or nonionic ~ur.~aatant~ a~ a pr~kr~k ~taln r~mov~r on fabrlc using varying oondltion~ in a ~ub~qu@nt laundry cycle. Various types of ionizable polymers, hydrophobic polymers, and nonionic ~urfactants are utilized.
Com~arative ExamDle 1B:
Stained fabrics not utilizing a test composition (control) are laundered in the detergent - solution for 15 minutes at 50C. Percent cleaning on cotton is 32, and percent cleaning on polycotton is 12.
: 30 Fabrics of the same manufacture were used in Examples 5B-9B.

WO9l/1314~ PCT/US91/01178 -48- ~
"
~ ~ ., ExamDle 5B:
Stained fabrics utilizing the test composition ~ -of Example 4B having NIS-5 are laundered as indicated with the detergent solutionv Percent cleaning on polyester is 86.8 at 8 minutes of laundering and 89.5 at 15 minutes of laundering. Percent cleaning on polycotton i~ 29.0 at 8 minutes ~nd 33.1 at 15 minutes.
Percent cleaning of cotton i~ 47.9 at 8 minutes and 47.0 at 15 minutes.
ExamDle 6B: ;
Stalned fabrics utilizing the test composition of Example IIB havlng NIS-9 are laundered as indicated with water only. Percent cleaninK efflclen~y on polye~ter is 60.8 a~ 8 mlnutc~ of launderin~ ~ncl 67.6 at 15 mlnute3 o~ laund@r.ing. P~ro~n~ aning on polycotton i~ 17.1l at 8 mlnut~ an~ 20.5 a~ 15 mlnut~.
Percent cleaning on cotton 1~ 30.0 at 8 minutes and 31.8 at 15 minutes.

ExamDle 7B

Stained fabrics utilizing the test composition 25 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 12.8C respectively. Percent cleaning on polycotton is ~ :
3 20.5, 18.0, and 10.9 at launderins temperatures of 50, 26.7. and 12.8C respectively. -WO91/1314~ PCT/USgl/01178 2 0 ~ ~ ~ 3 2 `
Example 8B
Stained fabrics utilizing the test composition of Example 48 having NIS-9, and laundered for 15 minutes as indicated with water only at various temperatures:
Percent cleanlng on cotton is 31.8. 23.0, and 20.3 at laundering temperatures of 50, 26.7. and 12.8C
respectively.
Examole 9B

Stained ~abrics utilizing the test composition of Example 4 having NIS~5 are laundered at 50C for 15 minute~ as indicated with hard water preparecl by addlng 300 ppm of a CaC03/MgC03 mlxture (2/1 w~1ght ratlo) to tap water. Peroent cl~anln~ on ootton ls 36.9, and percent oleaning on polycotton 19 29.LI.
Example 10B
An ionizable polymer comprising MMA/2-SEM/DMAEMA in wei~ht proportions of 55.3/38.2/6.5 is prepared in accordance with Example 2~. A hydrophoblc copolymer comprising GMA/S/2-EHA in weight proportions of 5.3/83.0/11.7 is polymerized in the presence of the ~:
ionizable polymer as in Example 3B. The poiymer mixture contains equal proportions by weight of the ionizable polymer and the hydrophobic copolymer. The polymer mixture is blended with a nonionic surfactant, and 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 ratlo ., WO~1/1314; PCT/US9l/01178 2055~2~
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.

59~ Lf~ Le:
Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 1~ minutes at 50C. Percent cleaning on cotton i5 23, and percent cleaning on polycotton Ls 14.
Methodology i5 the ~ame as ln prevlou~ exampl@s exo~pt;
that fabrics utlllzed arc Or the ~am~ bl@nd~ bu~ Or dlfferent manufaetur@. Th~ fabrlc~ w@r~ o ul;lli~
in Example 11~-18~, Example 11B:
Stained ~abrics utllizing the test compo~ition of Example 10B are laundered at 50C for 15 minutes with a commercial laundry detergent. Percent cleaning on cotton is 100, and percent cleaning on polycotton is 92.
25 When laundered at 50C for 15 minutes with water, -percent cleaning on cotton is 99.8. and percent cleaning on polycotton is 92.4. ~;
~xample 12B: PreDaration of an Ionizable Polvmer and a Composition of Said Ionizable Polvmer and a Nonionic Surfactant An ionizable polymer with a weight average molecular weight of about 10tOOO is prepared by free radical polymerl~ation of methyl methacrylat@ (MMA) and 2-W091/1314~ PCI/IJS91/0117X

-51- 2 05 5 ~3 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 80C by a constant temperature water bath.
Two solutions are prepared for addition to this reaction flask: ~ solution of monomers is prepared by adding 23.26 part~ of 2-SEM an~ 102.08 part~ of MMA to 133.33 parts of MEK. An initiator solutlon is prepare~ by adding 2.5 parts of VAZ0'~ 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 reactlon flask in 18 equal volumes once every 10 minuteQ over a total tLme of about 3 hours. After all of the monomer ~nd inltlator 30lution~ arc add~c1, the mlxture i~ heatcd ~or 3 ~ddltLonal hour~ to oompl~t~
the polym~rlzation. Th@ ~ln~l produot 1~ a el~ar amb~r ~olution. The wei~ht pera@n~ ~olld~ o~ thls .olutlon l~
determined to be 24 8. Thus, the conversion of the monomer to copoly~er is essentially 100 percent. The composltion of this copolymer is 89.5 mole peraent MMA
and 10.5 mole percent 2-SEM. The 2-SEM will provide a 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 solution by rotoevaporation under vacuum at 50C 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.

. ~

I ~,, ~
20~3~3~ -52-ExamDle 13B
Stained f`abrics utilizing the test composition of Example 12B are laundered at 50C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 75.2, and percent cleaning on polycotton is L15.8.
E mple 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 Z-SEM wlll provide a charge of 0.948 m~g/gram of this ¢opolymer. A test composLtion is formec1 rrom the same lonlzable p~lymer and NIS-5 acoordln~ to th@ prooedure o~ E.xampl@ 12~.
Solids oon~ent ~s det~rmLn~d to be 98.1 pera0nt.
StRin0d ~abrlcs utLlizing the t~t oompo~ltion arc laundered at 50C Eor 15 mlnut@~ as indicated with the Z 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 (NP10MAj by weight is prepared according to the procedure of ~ -Example 12B. The 2-SEM will provide a charge of 0.933 3 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 a~
50C for 15 minutes as indiaated with the detergent .. .. . . . : ~ : , . ............................. .
: : :: . . . : : . . , . . : , , ;: : " - ; . .
, ~ : . . : . .. . :.: :: ... : . ... . . .

W091/1314~ PCT/US91/01178 ~, .
_53_ ~55~2 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 accordlng to the procedure of Example 12B. The 2-SEM
will provide a charge of 0.8011 meg/gram of this copolymer. A test composltion 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 50C for 15 minutes as indlcated wlth the detergent 30lutlon. Percent cl~anlng on cotton ls 58.7, and percent cleanlng on po.lyootton 1~ 47.6.

~a~l3 An ionlzabl@ polymer oompri~Lng 89.5 p~rcent methylmethacrylate, 10.5 percent 2-SEM by welght ls 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 o~ 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 DowanolW DPM comprises 75.1 percent by weight of the test composition. Stained fabrics utilizing the test composition are laundered at 50C for 15 minutes as indicated with the detergent solution.
Percent cleaning on cotton is 34.5, and percent cleaning on polycotton is 37.9.

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W091/1314~ PCT/US91/01178 ~ . -54-$~
Example 18B
The test composition o~ 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 28Ø
Gompara~
Stained fabrics utlli~ing a test composition consisting only of Dowanol'~' DPM (The Dow Chemical Company) brand dipropylene glycol monomethyl ether are laundered at 50C for 15 minutes as indicated with detergent solution or with water. Peroent cleaning on cotton ls 25, and percent cleanlng on polycotton .Is 11 when laundered in the detergent solution. Percenk cleaning on cotton .i~ 17, and percenk cleanLn~ on polyootton 1~ 4 when laundered in water.

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W09t/1314~ PCTIUS91/01178 ExamDle 19B
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 proportions, is formulated in a stick form in the followlng manner:

Comoonent~ and Concentra~lon Grams 10 First Mixture 24 d-Limonene 30 PEG-900 1.3 ~ater ll.7 15 Sodium ~orate Decahydrate 2.3 50 percent NaOH in water 2.5 Stearlc Aoid 8 Dodecyl Benzen0 Sulfonlo ~al~ ~l.5 (LAS) The ionizable polymer MMA/2-SEM/DMAEMA and hydrophobic copolymer GMa/S/2~EHA of Example 3B ls mixed wlth NIS-5 according to the method o~ Example 4B to form a first mixture. The first mixture and d-Limonene were mixed together and heated to 60C to form a second mixture. Polyethylene glycol of about 900 average molecular weight is added and heated to 65C . 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 heated to 77C to form a fourth mixture. Stearic acid ((70 percent C1g) is then mixed to~ether with the fourth mixture and heated to 77C to form a fifth mixture. The fifth mixture is allowed to drop in temperature to 70C under constan~ a~ltation. When the 70C temperature level i5 reaohed. the LAS is mixed ; . :.. , . .. .. , , ~. .... .. . .... .

WO9l/l3l4; PCT/US91/~1l78 ~.
20~ 2 ~ 56-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 lB. Methodology is consistent with previous examples.
Example 20B
Stained fabrics utilizing the test composition of Example 19B are laundered for 15 minutes at 50C in water only. Percent cleaning on cotton is 67. and percent cleaning on polyootton i~ 53.
Example 21B
Stained f`abrici~ utl.lLæin~ th@ t~irJ~ compo~ikloR
of Example 19B ~r~ launder~3d in d0t~rg~nt ~oluELon for 20 15 mlnutes at 50C. Percent cleanin~ on cotton ls 76 and percent cleanlng on polycotton is 72.
~m~ :
Stained fabrics utilizing the test composltion of Example 19B are laundered in hard water for 15 minutes at 50C. The hard water prepared by adding 300 -ppm of a CaC03/MgC03 mixture (2/1 weight ratio~ to tap water. Percent cleaning on cotton is 77.8. and percen~
cleaning on polycotton is 6~.o.

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W091/1314~ PCT/US91/~1178 ~ 59 ~ 2~ 3 2 ExamDle 23B: Hydrophilic Surface Modification of Hydroehobic 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 aopolymer of Example 2B with shell monomers of ~tyren~ pluq me~hyl 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 determlnation of perc~nt gel (90 percent non-extractable polymer) and swell lndox (15 s.i., mea~ure of Lmblbitlon of solvent by t~t polym~r).
A method for determlnlng th~ pr~nt ~@l and ~w~llln~
index i9 disclosed in Unlt~d state9 Pat~nt 11,146,589.
The rubber latex particles ar0 ~tyr~ne-butadiene copolymer (7 percent styrene, 93 percent butadiene) and stabillzed 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 3 grams of VAZ0~ 64 (2,2'-Azobis (2-Methylpropanenitrile)) from DuPont is added to the stirred (150 rpm) reactor.
The head space in the reactor is continuously ~lushed with nitrogen and the contents heated to 70C.

, ,.. , :. .. ., . . .,:, ~ . :, , WO91/1314; PCT/US91/01]78 2055~2 905 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.
5 During the remaining 80 percent feed additions over 90 minutes, the reactor temperature is increased to 80C
and maintained for another 120 minutes. An aliquot reveali~ 32.9 percent ~olids and 0.38 milliequivalents 10 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 Composltlon~ O~ ?n rrsotRnt9 The ~inal llqui~ olids ~ollol~ o~ Ex3mpl~ 23 20 ii~ blcnd~d lndivldually with di~P~ran~ nonlonic isiur~actants in a quantlty for tei~ting comprising 75 parts by weight of nonlonic i~urfactant and 25 parts ?
polymer solids. The water content is reducsd to about 5 percent by vacuum distillation at 80C. The nonionic 25 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 3 15 carbon alcohol with 7 moles ethylene oxide adduct as 45~7.

WO91/1314~ . PCT/US91/~}178 2~aL~3~
Comparative Example:
Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50C. Percent cleaning on cotton is 23, and percent cleaning on polycotton is 13.
Fabric.s 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 minute~ at 50C. Pero~nt cleaning on cotton ~or the combination~ with NIS-5, NIS-6! ~nd ~15-7 l~ 1l7~ 53, an~l 63 re~pectlvely. P~rc~nt ~ n~n~ on PO1YOOttOFI wlth the ~ame ord~r o~ nonlonio aomblnatlon~ l~ 36, ll9, ancl 5ll .

Example 26B:
Stalned f~brics utilizing test compositions of Example 24B are laundered in water only for 15 minutes at 50C. 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.
ExamDle 27B
3o A copolymer comprising 33.6 percent by weight styrene (S), 61.0 percent by weight 2-ethylhexyl acrylate (EHA) and 5.4 percent by weight 2,3-dihydroxypropyl methacrylate (HPMA) i5 prepared aocording to the prooedure o~ ~xample 12B~

W091/1314; PCT/US91/01178 ~,~ .
2 ~ 5 5 4 ? ~ -62-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. Stalned fabrics utilizing the test compo~ition are laundered at 50C for 1~ minutes as indicated with the deterKent solution. Percent cleaning on cotton is 38.7, and percent cleaning on polycotton is 25.5 A test compo~ition ls ~ormed by combining 0.5 parts of the hydrophobic, non-ioni~able copolymer prepared in this example plu3 0, 5 part~ of the pol~m~r prepared in Exampl~ 1~B and 3 parts of NIS-5. The M~K
~olvent is remove~ from thl~ 30lution ~y roto~vaporatLon at 80 C to obtain a mixture that ha~ 100 percent ~ollds. These solids consist of the nonionic surfactant and the copolymer in a 3 to 1 weight ratio, respectlvely. St~ined fabrics utilizing the test composition are laundered at 50C 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 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 oopolymer in a 3 to 1 weight ratio, respectively. Stained ~abrics utilizing the test composition are laundered at 50C for 15 W~9l/1314~ PCT/US91/01178 2 ~ 3 2 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. I'c further illustrates that a blend o~ thi~ hy~rophoblc non-ionlzable 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 followlng lllustration demon~trates the synergy of the nonionio sur~aotant and poly~er interaction a~ a ~unctlon o~ diluent conoontratlofl. The graph ~hows the lmprov~d cleaning e~flcaoy Eo oocur wh~n the water conoentration i~ lc~ than 80 wel~ht perc~nt ~ the total cleanlng compo~ltlon. Creater lmprovement in cleaning occurs at less than 60 percent water and continues to increase as the water concentration decrease~ to about 20 percent.

.

WO91/1~14; PCT/US91/01178 ~1 2 0 ~ ~ ~ 3 ~ --64--Cleanin~ Versus Water Content .

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

TableVI
__ .
Cleaning Efficacy of Poly(Acrylic Acid) Pretreatment Percent Cleaning When Laundered in PercentAqueous DetergentSolutions . Cot~n . . ~ .. . I -0 ~7.~ 5.8 ___ ...... .. ... , ~. .,., . . ~ .
2~.7 7.3 __ 3~.~ 6.2 _ :

W091/1314~ PCT/US91/01178 2Q~5~32 Cleaning Versus Water Content ~ .

Influence of water content of pretreatment composition formulation on percent cleaning of soil on swatches laundered in aqueous deter~ent solutions 80 _ o g 60 ~ ~ o f.~
~ 40 _ a . , 20 _ O _ ~

Wat~r Cont~nt ~W~ight P~rc~nt) Samples: 1.5 wt percent poly~acrylic acid) weight average molecuar weight = 450,000 ~ ~A~
2 5 wt, percent Dodecylbenzenesulfonic Acid Remainder Igepal~ C0-520 J
Curve represents mixtures of "A" with deionized water, plotting cleaning versus water content ~ Igepal C0-520 ~onionic Surfactant ~ "B"

Curve represents mixtures of "8" with deionized water, plotting cleaning versus water content Samples prepared by mixing "A" or "8" with deioni~ed water in the desired ratios.

Claims (53)

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 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.

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

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 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 per-cent 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, 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 anionic surfactant.

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

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 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 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.