CA2047085A1

CA2047085A1 - Hard surface liquid cleaning composition with soil release polymer

Info

Publication number: CA2047085A1
Application number: CA 2047085
Authority: CA
Inventors: Karen L. Wisniewski; Nagaraj S. Dixit; Nandakumar S. Rao
Original assignee: Individual
Current assignee: Colgate Palmolive Co
Priority date: 1990-07-16
Filing date: 1991-07-15
Publication date: 1992-01-17
Also published as: GR1001501B; EP0467472A2; EP0467472A3; GR910100312A

Abstract

WITH ANTI-SOILING POLYMER

Abstract of the Disclosure An aqueous solution of an anti-static cationic quaternized polymer is used to deposit the polymer as a coil releasing agent on hard surface, e.g. bathroom porcelain, tiles, etc. in order to provide easier cleaning of the treated surface during subsequent cleaning operation. A preferred polymer is based on recurring units of beta(trialkyl ammonium) alkyl methacrylate with a molecular weight of from about 5,000 to 50,000 or more.

Description

2 ~ 1 7 ~ S

IR-4874 ¦ HARD SURF~CE LIQUID CLEANINÇ: COMPOSITION
WIT13 ANTI SOILING POLYHeR

¦ This application is a continuation-in-part of our commonly a~signed, copending application Serial No. 07/297,807, filed January 17, 1989.
BACKGROUN~ OF THE INVEN~ION
The present invention relates to an aqueous formulation ¦of an anti-soiling recleaning agent for use on common household ¦hard surface~ to impart soil release propertlee thereto to ¦facilitate subsequent cleaning. The composltions may also ¦include various surface active ingredient~ and/or disinEecting ¦agents to provide effective cleaning and/or disinfecting of the ¦hard surface being treated. More particul~rly, certain cationic, ¦anionic or nonlonic polymeric soil-releaslng agent which is ¦substantive to the treated hard surface iB deposited from an ¦aqueou6 solution, preferably together with various cleaning ¦and/or disinfecting agents or present aleaning/disinfecting, to ¦facilitatè removal of subse~uently deposited soils, such as soap scum, during cleaning or recleaning of the solled surEace.
In our prior application, Ser~al No. 297,807, Eiled January 17, 1989, it was reported that aquecus cleaning compositions with certain nonionic surfactants, characterized by their water solubilities and HLB values gave good performance in preventing the adhesion o soap ~cum on hard household surfaces, such as ceramic tile~, when the tiles are soaked in a 1~ aqueous solution. It was hypothesized that the nonionic surfactant system treatment increased the degree of hydration or water content on the hard surface resulting in preventing tenacious adhesion of the ~oap scum to the tile surface. The prior application al~o disclo~ed that addition of up to 2~ of an acid ~ ~ , ,~"~,.S.7(J8~. ~
¦stable cationic or anionic ~oil release agent enhanced this ¦effect. Example 4 of the prlor appl~cation demonstrated that ¦incorporation of 2.3~ of a 15-2~ solution of poly-[beta~methyl l diethylammonium) ethylmethacrylate] (poly(MDAEM)) in the mixed ¦ nonionic surfactant system aqueou~ ac~dlc d~s~nfectant composition results in significant improvement of ea~e of recleaning soiled tiles. The disclosure of our prior application, Serial No. 297,807, i8 incorporated herein in its ¦entirety by xeference thereto.
¦ However, the efficacy of the soil relea~e polymers, ¦such a~ poly(MDAEM), as a hard surface recleaning or anti-soiling ¦agent, is not limited to the acidic aqueous dlsinfecting cleaning ¦composition of our prior application, or to poly(MD~EM), but ¦appears to a broader range of anionic, catlonlc and nonionic ¦polymers having certain characteristics, and have utility when ¦used alone, or in the presence of other surfactant systems.
¦ SUMMARY OF THE INVENTION
¦ In one aspect of the inventi.on, therefore, there is provided a hard surface treating composit~on for lmproving the soil removal or anti-soLling cllaracteristlc~ of the treated surface, the composition compri~ing an aqueou~ liquld solution or di~per~ion of a water-soluble cationic, anionic or nonionic polymer which is capable of being adsorbed to the hard surface, and which when applied to the hard surface, leaves a residual anti-soiling polymer layer thereon wlllah lncrea~e~ the hydrophilicity thereof, whereby the `nydration of the hard surface from the ambient atmospheric water vapor facilitates removal of soils subsequently deposited thereon, i.e. less work. is required to remove the soil than in the absence of the re~idua]. layer.

: ;' :

~Jf~

n another a~pect, the inventlon provide~ a hard surface treating compo~ition for cleaning the ~urface and for improving tlle ~oil removal characteristics thereof, the l composition comprising an aqueous liquld contalnlng at least one ¦ non-soap synthetic ~urfactant and a aoll release promoting water-soluble cationic, anionic or nonionic polymer which i5 capable of being adsorbed to the hard surface, and which, when ab60rbed to the hard surface, leaves a residual ant~-~oiling polymer layer l thereon which increases the hydrophilicity thereof, whereby the ;-¦ hydration of ~aid hard surface witll ambient atmospheric water vapor facilitates removal of solls subsequently deposlted thereon. .
In still another a~pect of the invention, there i8 l provided a method for improving the soil remo~al property of ¦household hard surfaces which comprises applying to the hard ¦6urface an aqueou~ solution of a ~oil release promoting water-¦~oluble cationic, anionic or nonionic polymer which will bs ¦adsorbed by the ha:rd surface and drying the hard surEace whereby said ad~orbed poly!mer form~ a re~ldual nnt~-eoJling hydrophlllc layer of said soil release promotlng polymer on said surEace, whereby removal of aoils subsequently deposited thereorl requlres les~ work than in the absence of said re~idual layer.
~ ccording to still another aspect of the inverltion, there 18 provided a method for increasing gloss of worn tiles which comprise6 treating the worn tile with an aqueous solution of a cationic quaternized polymer having a molecular weight in the range of from about 4,000 to 100,000, the polymer being adsorbable to the surface of said tlle and, when ad~orbed to said tile, increase6 the hydrophiliclty thereof.

;,, . ' ' .

DETAILED DESCRIPTION OF THE INVENTION
Although not wishing to be bound by any apecific theory of operation, it is presently believed that the anti-soiling or soil release polymers which are effective hereln have in common the property of adsorbing to the hard surface being -treated, for example, by associating to tKe sllica groups of ceramic type materials, in such manner that the hydrophilic groups of the polymer are oriented away from the surface whereby the hydrophilic groups are available to attract and trap water molecules. The re~ulting hydrophilic surface can attract and trap ambient atmo~pheric water vapor (e.g. the moisture in a humid room) to more effectively reduce adhee~on of solid (or as referred to by the inventors, to promote "abhesion") by any or all of the followlng mechanisms:
(1) form a barrler (water film) which prevents or reduces the contact of Yoil with the surface (2) form a slip layer that facilitates wiping away of the soil;

(3) for soils, such as soap ~cum, whiall rely on drying out as part of their mechani~m of tenaaious adherence, by preventing the 80il from drying out.
The preferred polymers for providing soil release (abhesion) properties to hard surfaces are the cationic and anionic polymers, and especially the cationic quaternized polymetl)acrylates, such as the beta(tr~Alkyl ammonium) ethylmethacrylate~ described in our prior application, Serial No. 297,807, and having repeating units of the formula .. :. .,. "

`f~

l CE13 S I -CH2~C Rl C00-C2H4-N~2X-l ~3 1 where Rl, R2 and R3, which may bo the ~ame or 10 ¦ different, are each lower alkyl groups of 1 to 4 carbon atoms, preferably methyl or ethyl.
¦ The corresponding acrylates can al~o be used. More ¦generally, the cationic polymers useful herein include ¦homopolymers of unsaturated amines which are at least partially ¦and preferably wholly ~e.g. at least 9S~) quaternized with an ¦appropriate counterion. The preferred unsaturated amines are ¦aminoalkyl esters of acrylic or methacryllc acid, in which the ¦amino group may be ~ubstituted by one or two alkyl, alkenyl, ¦aryl, aralkyl or other suitable group~, or by substituent~ which ¦together with the nitrogen atom form a heterocyclic ring.
¦ The repeating units derived from the aminoalkyl ester ¦is preferably of the formula (I):

R,3 C00-R4-N (I) wherein R1 and R2, wh~ch may be the same or different, are hydrogen or alkyl, or together with the nitrogen atom to which they are attached, form a heterocyclic ring; R4 is an alkylene group containing 1 to 8 carbon atom~; and R3 ls methyl or hydrogen.

: ' ~' '',":

~ 3 Preferably both Rl and R2 are alkyl~ of 1 to 4 carbon atoms, especially methyl or ethyl. When Rl and R2 together with the nitrogen atom form a heterocycllc r~ng, the ring may have from 5 to 7 atoms and may include 1 or 2 addltional hetero atoms, 5 such as N, 5 or O in addition to the amine nitrogen atom to which Rl and R2 are bonded. R3 isrpreferably methyl and R4 preferably has 2 to 4 carbon atoms~ and e~pecially preferably is ethylene.
The units of formula (I) ln the homopolymer are at least partially quaternized by reaction with a suitable alkyl ~alt of an acid, such as, for example, methyl or ethyl chloride, methyl or ethyl sulfate, dlmethyl or diethyl ~ulfate, methyl or ethyl bromide, and the like. The quatern~zed cationic repeating unit in the resulting homopolymer will then have the following formula (II):

-C~2-C- Rl Coo-R4-N+-R2-x- (II) where Rl, R2, R3 and R4 are as defined above, Rs iB a lower alkyl group of from 1 to 4 carbons, preferably methyl or ethyl, e~pecially methyl, and X~ is a monovalent anion or l/m of an m-valent anion.
It is most preferred that at lea~t 50~, preferably at least 80%, more preferably essentially all, i.e. from 95 to 100~, especially preferably 98 to 100% of the repeatlng units of the polymer have the quaternized form of formula (II).

The molecular weight of the polymer is not e~pecially ¦critical so long as the polymer 1) is water-soluble, 2) has some surfaae activity, a~d 3) i~ ad~orbed to th~ hard ~urface from its aqueous solution in such manner as to increase the hydrophilicity of the surface. In general, however, good re~ults will be obtained with the quaternized cationic polymer~ having molecular weight~ in the range of from about 4,000 to 100,000 or higher, preferably from about 5,000 to 50,000, more preferably from about 6,000 to 30,000 and e~peclal~y preferably from about 12,000 to 26,000. At molecular weights below 4,000, the polymers tend to be too water-soluble to adhere to the hard surface while at molecular weight above about 100,000, especially above 50,000, the polymers tend to be in~ufficiently watsr-soluble or are more difficult to process and formulate into stable, pourable formulations.
While the preferred cationic quaternized polymers are the homopolymers as described abo~e, it ~ also within the scope of the invention to use copolymers of the above amines and quaternized salts thereof with, for example, an acrylamide or acrylonitrile, so long as the copolymer retain~ the required surface active propertie~ to adhere to the substrate while xhlblting the appropriate aonformatlon to expo~e the hydrophilic ortion of the polymer to be able to at-traat water and hydrate he surface of the ~ub~trate. Thu~, up to about 25 mol~, specially up to about 20%, for example, up to 5% or 10%, of the nti.re repeating units of the cationic polymer may be comprised f acrylamide unit~ of formula (III):

-CH2~CR6- (III) wllere R6 is hydrogen or methyl;
or acryl.onitrile units of formula IV:

. , . ' ':

2~'17~'? j -CH2 -C~6-~ (IV) where ~6 Ls a~ deflned above.
Other ethylenically un~aturated aopolymerizable comonomers, in amount6 up to about 20 mol%, preferably up to 10 mol~, can also be included in the anionic polymer if they will not adversely impact on the solubility, adhesion and soil release properties of the polymer. A~ examples of such copolymerizable comonomers, mention may be made, for example, to unsaturated monocarboxylic acids, ~uch as acrylic aaid~ methacrylic acid, propionic acid, and the like, un~aturated olefin~, such as ethylene, propylene and butene, alkyl esters of the un6aturated carboxylic acids, such as methylacrylate, ethyl acrylate, methyl methacrylate, hydroxy derivatives of the~e esters, ~uch as, for example, 2-hydroxyethyl metllacrylate, unsaturated aromatic compounds, such as styrene, methyl styrene, vinyl styrene, and heterocyclic compounds, such as vinyl pyrrolidone, and others.
Of these, hydrophilic comonomer~, ~uch as acryllc acid, methacrylic acid, vinyl pyrrolidone, etc., ar~a preEerred.
Other water-aoluble cat~onic polymers such as, Eor example, quaternary nitrogen eub~tituted cellulose ethers, for example Polymer JR-30M, can also impart anti-soiling properties.
The anionic soil release polymers which can be used i.Jl this invention include, for example, the soluble polymeric 6alts disclosed in U.S. Patent 3,696,043 to Labarge, et al., the disclosure of which is incorporated herein by reference thereto.
In particular, soluble polymeric salts may be obta;ned by neutralizing copolymers of 1 to 2 moles of a monovinyl aromatic monomer per mole of an unsaturated dicarboxylic acid or anhydride , .

~ r~
there of to form solubilizing ~alt groups. Preferably the copolymer is an equal molar copolymer.
Solubllizlng ~alt groups include half-amide ~alts formed from the neutralization (interaction) of the anhydride group with ammonia or with a monoamine ha~ing at least one hydrogen attached to the amine nitrogen and having no other groups reactive with an anhydride. Neutralization of the unsaturated dicarboxylic acid copolymers with an alkali metal, ammonia or an amine produces carboxylate ~olubilizing groups O
II-ox by a simple acid-ba~e reaction where X i~ a positively charged ion which may be an alkali metal ion such as sodium or potassium, an ammonium ion or a substituted ammonium ion.
The neutralization of the anhydride group may be illustrated by the reaction of ammonia with a maleic anhydride copolymer (showlng only the anhydride un~t of the copolymer~.

-~ CH3 1H2 ~ .~NH3 ~ CH fll }
0-- - C C _ 0 0 = C~ 0 \0 H21 1H
(half-amide) Tlle half-amide may be further neutralized by further reaction with ammonia or another base to form A half-amide salt, ~f 3 T 2 ~

=f T--. .: ..
. . .

~ 7 ~
where X iB the same as above. An N-substituted half-amide salt is formed when said amine is used in place of the ammonia.
By a soluble polymeric salt lt ~ meant to include any of the unsaturated dlcarboxylic acid or anhydrlde copolymer neutralization products which contain a sufflcient number of salt group~ to render said copoly~er soluble ~n the concentrations employed. It is to be understood that complete neutralization of all the acid groups or anhydride groups may not be required to obtain the desired solubility, however, complete or substantially complete, e.g. at least 95%~ neutralization is preferred.
Any primary or secondary monoamlne may be employed to neutralize the anhydride copolymers provided the amine has no other group reactive with an anhydride and providing it forms a salt group capable of solubilizing the ~opolymer. While a variety of aliphatic, cycloaliphatic, heterocyclic and like ¦amines may be employed certain amine~ are preferred from the ¦human toxicity and handling standpoint, since the products are principally intended for use by humans, and from the availability and cost standpoint. The lower alkyl amine~ ~uch as ¦diethylamine, dimethylamine and the like are frequently used.
¦ Alkali metal base~ include hydroxides of sodium, ¦potassium, lithlum or the corresponding carbonates, bicarbonates, ¦etc. are the most preferred neutrallzing agents, especially the ¦sodium salts. Ammonium hydroxide is the u~ual form of ammonia employed. ~ny amine may be used provlded it forms a carboxylate salt group capable of solubillzing tlle polymer. Certain amines are prefèrred for the previously stated reasons. Typical amines for forming substituted ammonium ion-carboxylate salt groups include the mono-, dl- and tri-alkyl amines (trimethyl amine, ; ` .' : . ' ". "., " . :

~ ~ ~i r~

diethylamine, i60propylamine, etc.); mono-, di- and tri-alkanol amines (triethanolamine, diiaopropanolamine, monoethanolamine, ~tc.); cycloaliphatic amines such a~ cyclohexylam~ne;
heterocyclic amine~ suah as morpholine; and like amlnes.
For complete neutraliæation of the copolymers at least about 2 moles of base per mole unit of dicarboxylic acid or anhydride iB required. As indicated complete neutrallzation i~
not always needed and in many caaes excess base i~ beneficial.
The copolymers themselves and thelr methods of preparation are well known to the art and need no detailed de~cription herein. Briefly one widely uaed method is to prepare the polymers by ~olution polymerization employing a solvent which is a solvent for both the monomer~ and the polymer. Suitable free radical catalysts such as benzoyl peroxide may be used to initiate the polymerization which can be run over a wide temperature range. The monomers tend to polymerLze readily in equal molar proportions. U.S. 3,336,267 d~scloses how to make non-equal molar copolymera. A variety of other patent~
disclose methods of polymerization by batch or continuoua techniques or to produce low molecular weight or high moleaulax weight copolymers. It i~ also taught to employ solvents for the monomer only. Other patents which may be consulted include Re.
23,514; U.S. 2,606,891; V.S. 2,675,370; V.S. 2,838,475; U.S.
2,971,939; U.S. 3,178,395 and U.S 3,418,292.
The molecular weight of the copolymers may vary quite widely from about four thousand up to as high aa 500,000 or more, 80 long as the criteria a~ described above for the cationic polymer~ are satisfied.
Monomers which may be uaed to prepare the copolymers include unaaturated dicaxboxylic acid~ such as maleic acid, . ,, ,', chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid and tha like. Any of the anhydrides of the unsaturated acids may be employed. Aromatic monomer3 include styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene and similar well known monomer~. Preferredcopolymers are sodium salt of ~-tyrene-maleic anhydride or styrene-maleic acid.
While the cationic and anionic polymers are preferred, nonionic polymer~ which adsorb to the hard surface and increase the hydration thereof aan also be used. For example, polyvinyl pyrrolidone (PVP), poly(vinyl pyrrolidone-C0-dlmethylaminoetllyl methacrylate) (also known as polyquatern~um II), polyethylene glycols, ethylene oxide polymers, and the llke provide anti-soiling benefits to hard surface treated therewith.
Conversely, not all water-~oluble ~nd adherent or surface-active polymers can provide the des~red anti-~oiling propertiea to harcl ~urfaces. For example, ~ilicone-based polymers, fluorocarbon polymere, polyvinyl alcohol, copolymer~ of methyl vinyl ether and maleic anhydride ~i.e. Gantrez ~N) and polyacrylates wers tested as descrlbed below a~ neat 0.5~ wt.
aqueous solutions on ceramic tiles but dld not confer any anti-soiling benefits or facilitate recleaning. A1BO, a copolymer inyl pyrrolldone and vinyl acetate (60/40) did not coner recleaning beneflts, thereby showing that whereas PVP homopolymer provides a residual anti-soiling hydrophillc layer, the amount of hydropllobic comonomer is limited to no more than about 25 mol~.
~ 8 described above, many different types of cationic, anionic and nonionic polymer~ can be u~ed ae the anti-soiling, abhesion promoting agents in this inventlon. However, the best results have been obtained with the cationic quaternized polymers f~ . J

of formula (II) and e~pea~ally wlth poly(MDAEM). Furthermore, a~
de~cribed below, even better performance can be obtained when. the cationi.c polymer is present a~ it~ complex with an anionic surface active agent, the amount of the anionic surfactant being ~ufficiently low such that the complex ~s Also water-soluble and a significant proportion of..~he quaternized ammonium groups are not complexed.
The amount of the soil-releasing agent to promote abheSiOtl i8 not particularly crltical ~o long as thin residual anti-soiling layer of the polymer remains adhered to the hard surface after the aqueous solution thereof 1~ dried or wiped off.
Generally, however, at lea~t, and usually no more than, a monomolecular layer of the polymer i8 sufflcient to exhibit the full anti-soiling effect of the polymer since a monomolecular layer of the polymer ~hould be adequate to form a hydrated water .
layer on the treated surface. Such monomolecular residual film or coating layer can be achieved with aqueou~ solutions containing as llttle a~ 0.02 weight percent of the ~oil release polymer, especial].y for new or unsoiled hard ~urfaces. ~
referred concentr.ation range ls from about 0.04 to ~, more referably 0.08 to 1%, by weight of the composltlon, of the soil elease polymer.
As u~ed herein and in the appended claims, the expression "less work" in reference to the anti-soiling or recleaning property of the treated hard surfAce having a re~idual layer of polymer thereon mean~ that deposlted 80il can be removed from the treated ~urface with les~ scrubbing or wiping when using the same cleanlng composition or with a milder . cleaning compo~ition and le~s chemical action than for the same . , . : . .
,' ,. ~' .',' ,' ,' ,''' ','.:

20 r~7oB~
similarly solled hard surface which ha~ not been treated with a soil-relea~e polymer according to the Lnvention.
While the 80il relea~e polymer~ can be u~ed as such to provide easier "next time" cleaning performance, it ~8 generally 5 preferable for the consumer to formula-te the soil relea~e polymer recleaning agents together with one or more compatible surface active cleaning agents and/or germiclde~, a~ in conventional all-purpose cleaning products or a bathroom or kitchen or general hard surface cleaning compositions, as are well known in this 10 art, including, for example, the germiaidal acldic hard ~urface cleaning compositions of our prior application Serial No.
297,807.
Such cleaning compositions have ln common the presence of one or more ~urface active detergent compound~, u6ually 15 ~ynthetic anionic (non-~oap), ca-tionic, nonionic, amphoteric or zwitterionic ~urfactant~. Other common ingredlent~ often present in ~uch type6 of aqueous cleaning composition~ include, for example, detergent builder ~alts; solvents; acids, bases and pH
buffer~; germiclde~, bactericides, and preservatives; th:ickeners;
20 coloring agents and perfume~; and the 11ke. Any of these ingredients whlch do not interfere with the solubility and adherence of the anti-soiling polymer may be pre~ent: in the hard ~urface cleaning and anti-solllng compo~.itlons of thi.s invention although it i~ often preferred to exclude detergent builder salt~
25 which are often associated with ~potting or streaking of hard ~urface~.
Organic 601vents are often a preferred additive where needed to llelp solubilize the anti-~oilinq polymer or any other ingredient pre~ent in the composition. For instance, tlle 30 poly(MDAEM) anti-soiling polymer may often form a ~lightly haæy . : ., : , - :

~ 2 0 ~
a~ueous composition and the lncorporation of a ~mall amount of isopropanol, for example, or other low molecular weight alcohol, can clarify the composition. Generally, amount~ of solvent, wllen present, will be in the range of from about 0.5 to 5~ by weight, preferably about 2~ by weight.
The polymeric anti'so11ing agent~ w~ll, by themselves, provide a small contrlbution toward~ inc~easing the visco~lty of the aqueous composition~ however, in view of the low "~olids"
concentrations in the typical hard ~urface treating or combined hard surface treating and cleaning compo~itlon~, the viscos~ties, even with the polymeric additive tend to be as low a~ about 7 cps or less. Without the polymer or added thickener viscosities of the aqueou`s composition tend to be less than 5 Cp8, or example, about 3 cps. For many types of applicat~ons, for instance, for treating/cleaning vertical surface, for r~pray dispensers, and the like, product viscosities in exces~ o~ about 10 centipoises, for instance, from about 10 to 100 Cp5 for wlpe-on products and from about 10 to 20 cps for spray-on product~, are de~irable. The increase in viscosity can be accomplished by addition of conventional polymeric thicken~ng agent~ ~uch as polyacrylntes, guar gum, Irish Moss, carrageenan, polycarboxy vinyl ethers and the like.
In selecting the polymeric thickening agent, as well as other additives, the ionic nature of the additive must be taken into con~ideration. Thus, when the anti-soiling polymer is anionic in nature, then cationic additives ~hould be avoided.
Similarly, fox a cationic anti-soiling polymer, anionic polymeric thickeners, coloring agents, suractant (except a~ discusised ~ below in connection with cationic polymer/anionic complexes), ~hould be avoided.

~ .. I

With these caveat~ ln mind, any of the surface active detergent cleaning compound~ usually used ln hard surface, all purpo~e or bathroom/kitchen cleaning product~, can be used in the present invention. Cation~c, amphoteric or zwitterionic surfactant may also be used (except that cationic surfactant should be avoided in combina~ion with anionic soil release polymers) although they are less preferred.
Suitable nonionic surfactant detergent cleaning compounds include, but are not limited to those disclosed in our prior applLcation Serial No. 297,807. More generally, mention can be made, for example, of polyethylene oxide and polypropylene oxide etl)ers of fatty alcohols, fatty acids, fatty amide~, alkyl phenols and the like. For instance, the conden~ation products of fatty alcohols or fatty acids whereLn the alkyl group thereof has from 8 to 22 carbon atom~, preferably from 10 to 18 carbons, with from about 1 to 50, preferably from about 3 to 15 moles of ethylene oxide or propylene oxide or mixturos thereof;
olyoxyethylene oxide ethers of alkyl phenols, wherein the alkyl has Erom 6 to 16, preferably 8 to 14 carbon, and the number of repeating ethylene oxide unitB 1B from about 6 to 25, preferably from 8 to 15; and the condensat.ion reaction product of ethylene oxide and/or propylene oxide with a C8 to C22 alkyl or C6 to Cg aryl (lncluding alkaryl) amine or amide or (Cl-C6) alkanolamide, can be used as the nonionic surfactant.
Suitable surface active anionic detergent cleaning compounds include, for example, the water-~oluble salts, e~pecially the alkali metal salts, of sulfate~ and sulfonates of fatty acids and alcohols and the water-soluble alkali metal salts . of the alkyl aryl sulfonate~. More specifically, the anionic 3Q includes, in the sale form, alkyl sulfate~ of 8 to 22 carbons, :' ' : ' , , ` ~ i`7~

preferably 12 to 18 carbons; alkoxy (polyalkoxy) sulfa-te6 wherein the alkyl portion has between 12 and 18 carbon atom~ and the alkoxy portion has from 1 to about 10 repeating un~ts, the alkoxy portion most preferably being ethoxy of from 1 to 5 repeating units; alkyl phenoxypolyalkoxy sulfates wherein the alkyl portion has from about 8 to about 16rcarbon atoms and the alkoxy portion is selected from the group of ethoxy and propoxy, the number of repeating units thereof being between 1 and 10, the alkoxy portion preferably belng ethoxy of 1 to 5 repeating unit6;
~ulfonate alkyl and alkylaryl alkoxylate~ wherein the alkyl portion and the alkoxy portlons are a~ previously aet forth for the alkoxy (polyalkoxy) sulfate~ and alkyl phenoxypolyalkoxy sulfate~, respectively; hydroxy alkane sulfonatea wherein tlle alkane is from 12 to 18 carbon atoms; alpha-olefln sulfonates and alkyl benzene sulfonates, espeaially linear alkyl benzene sulfonates, the alkyl of which has from 10 to 18 carbon atoms;
sulfated monoglycerides, and ~ulfosuccinates, for example, the reaction product oE malic acid esters with sodium bi~ulfate.
Most preferably, the anlonia surfaatant 18 aodium lauryl sulfate or dodecylbenzene sulfonate.
Mixtures of anionic and nonionic surfactants can also be used with anionic anti-soiling polymers and mixtures of cationic and nonionia ~urfactants can eimilarly be used with cationic anti-60iling polymers. ~mphoterlc or zwitterionic aurfactants can alao be used along or with the anionic, cationic or nonionic surfactants. Of course, for the nonionic anti~
soiling polymers any of the type~ of surfactants may be used.
The amount of surfactant which will be included in the composition for cleaning purposes may vary widely depending on the intended use, type of surfactant, other ingredients in the :..... , . . , - . `, '. . :

7 ~ ~ ~
composition, and other factors known in the art. However, for many types of hard surface, all purpose, and bathroom or kltchen cleaning compositions, the total amount of surface active detergent cleaning compounds will usually be in the range of from about 0.1 to 10% by weight, preferably 0.2 to 4% by weight.
As noted above, an~onic ~urfaatant~ ln combination with cationic 80il release polymer~ form complexe~ whLch modLfy the solubility of the polymer and, dependlng on the amount, as well as type of the anionic surfactant, these complexes can adversely or beneficially impact on either or both of the adsorption of the polymer to the hard surface and the abheslon performance of the polymer. For any particular cationic 80il release polymer, the positive, negative, or neutral lmpact on adheslon and/or abhesion characteristics can be determined by routine experimentation.
The preferred anionic surfactant~ for complexing with the cationic polymers for improving adhesion and facilitating recleaning are the alkali metal C10 to Clg alkyl sulfates or carboxylates, preferably C12 to C14 alkyl, ~uch as ~odium lauryl sulfate, the ethoxylated (2 to 10 moles ethylene oxide) C14 to C20 fatty acld ~OapB~ and the ethoxylated (2 to 10 mole~ etllylene oxide) C10 to Clg fatty alcohol sulfates~ ~uch as sodlum stearate condensed with 2 to 10 moles ethylene oxlde, and sodium C14 to C16 alkyl ether (2 to 10 moles ethoxylatlon) ~ulfate.
However, the anlon~cs are not l~m~ted to these but also include, for example, the mono and divalent alcohol sulfates and sulfonates, anionic carboxylates, olefln sulfonates, aryl sulfonates and the corre~ponding ethoxylated anlonic surfactants.
In general, any of the anionic ~urfactant~ mentioned above for the anionic detergent cleaning compound when used in amounts ,: .-; ~ , , , : . . -. .. ~ ~ . :

which will not cau~e the cationic polymer complex to precipitate can be u3ed.
Although not wishing to be bound by any particular theory as to why the complexes can often provlde further improvements in anti-soiling properties, it i~ believed that the complex become~ slightly moré hydrophobic and can, therefore, more readily deposit on and adhere to the hard surface without changing the orientation of the hydrophillc portion of the polymer with re~pect to the hard surface.
In general, however, ba~ed on the experiment~ conducted by the inventor~ for poly[MDAEM] (mol.26. approximately 20,000) at a molar ratlo of at lea~t 3, and preferably 4 or more, cationic group~ in the polymersl anionia ~urfactant head group the best performance for both promoting adhe~on and increasing abhesion of soap ~cum are achieved with the Clo to Cl4 alkyl sulfate salts, especially ~odium lauryl sulfate and moderately ethoxylated (5 to lO moles ethylene oxide) Cl2 to Cl6, especially Cl4, alkyl sulfate or alkyl carboxylate.
The balance of the novel liquld hard surface anti-soiling/treating or anti-~oillng/aleaning composLtion is water, preferably dLstLlled water, reduced by any optlonal ingredient6 which may be pre~ent. Generally, the proportion of water in the compositions i~ about 80~ to 94~ by weight~ preferably 85 to 92 by weight of the composit1On. Those ~kllled ~n the art will readily appreciate that minor amounts of addltional ingredient3 may be optionally pre~ent to prov~de cosmetically appealing products and increa~e con~umer acceptability. Examples of 8uch adjuvants include coloring agent~, fragrances, perfumes, . viscosifier3, germicides, bactericides, dis1nfectants, and p~l adju~ting agent~.

:. .
' . - '-, ' ~

~ 5 the acidic compound~ for modifying pH~eTtt~i~n- ~an be made of the organic acid~, ~uch as lower aliphatic monocarboxylic acids, hydroxycarboxylic acids and dicarboxylic acids. Examples of the aliphatic monocarboxylic and dicarboxylic acids include Cl-C6 alkyl and alkenyl monobasic and dlbasic acids, such a~
glutaric acid, succinic acid, propionic acld, adipic acid, acetic acid and the like. Examples of the hydroxy carboxylic acids include hydroxyacetic acid and citric acid. Mixtures of saturated aliphatic dicarboxylic acids, and e~pecially mlxtures oE adipic, glutaric and succinic aclds are ~ommercially available and are conveniently used. These mixtures are described in greater detail in our prior application Serial No. 297,807.
Of course, inorganLc acids, such as HCl, HN03, H2S04, can also be used, but usually in comblnatlon with organic acids, or appropriately diluted.
Similarly, organic and inorgan~c bases, ~uch as ammonia, ammonium hydroxide and various amlnes, amides and alkanolamines and alkanolamides, can also bo added to raise the H were necessary or desired to formulate less acidia or more alkaline formulations.
In this regard, it is well understood by the practitioner that product pH not only affects cleaniny performance against specific soil types~ but that the pH will also have an affect on the form and stability of the cationic or anionic soil abhesion promoting polymers. It i8 also well understood that the choice and selection of the surfactant component and other optional additives, such as, coloring ager-ts, thickening agents (viscosifiers) and the l~ke will be made in consideration of the ionic nature of the ant~-soiling polymer.

It should also be apparent to tho~e of ordinary ~kill in the art that when, for example, a aationic germicidal or surfactant compound 1B to be included ln the composition, the complex of the catlonic antl-soiling polymer with the anionic surface active agent ~hould be ~ormed out of the presence of the cationic compound since, othérwise, the cationic compound and anionic compound may form a complex rather than the desired anionic surfactant-cationic polymer complex.
For example, for the preferred catlonic polymers, anionic surfactants, except as descrlbed above, and anionic coloring agents or thickening agents, and other anionic additives should be avolded ~ince they tend to form insoluble complexes with the cationic polymer. Anionic surfactant concentrations in cationic polymer embodiments should, in any case, be limited to about 0.25~ by weight, while anionic polymer thickening agents or other anionic polymers ahould be altogether avoided.
In addition to the improvement in facilitating recleaning of surfaces treated with the aomposltions of this invention, it ha~ been surprisingly di~covered that the appearance (gloss) o damaged ceramic ti~e~ or similar household hard surfaces, e.g. porcelains, to which the compositions of this invention are applied can be improved (e.g. gloss readings are increased) as compared to tiles treated with the same compositions, excluding the cationic polymer. For example, an acidic (pH=2.5) aqueous composition containing 0.4 weight percent of poly[MD~EM~ of 20,000 molecular weight complexed with C14 alkyl sulfate condensed with 7 moles ethylene oxide when applied 1 in a laboratory test to a ceramic tile etched for 15 minutes by ¦immersion in a 1.3~ }3F bath (BUCh that the g10BB iB reduced from . . ~ . ,:

?~ ~7' 3 ;
an initial value of 90 to a value between 30 and 50 - ~imulating ¦older tile~ washed with abrasive cleaners for sevexal year~) lmproves the gloss of the surface by 1 glo~s unit when measured l with a Gardner 20 glo~ meter.
¦ Even more signLficant, however, iB that ln consumer ¦panel te~ts, almost all of t~e panelists ~ndicated that they ¦attribute higher shine to the tiles treated with the invention compositions. The appearance of higher shine is most pronounced 1 with acidic treating composit~ons, presumably because the acid ¦treatment itself provides better soap scum removal and cleaning.
¦However, even at p~ values of about 6 or more, the paneli~t~
¦still report a higher shine for -tiles treated with the ¦compositions of the invention.
1 In comparison, when the same tlle~ are treated with a ¦similar composition but without the poly[MDAEM], no differences ¦in gloss are measured. This effect on ~urface appearance i~ on]y ¦observed for worn tile~, that is, glo~ difference~ are not measured after treating a new tile surface. However, recleaning performance is obtained on both new and old tlles and other hard surfaces.
ExamPle 1 An anti-soiling polymer according to the invention is ~ed in the fo110wiDg bathroom o1e~ning oompo~ition:

,~ ,n ~ , Amount Inqredient (Wt.~ L

Acid mixturel) 5.0 Neodol 91-82) 1.5 Neodol 91-2.53) 0 7 Cationic disinfectant4) 0 2 Poly(MDAEM)5) 0.4 I~opropanol 2.0 Perfume and color 0.21 10 Water r Q S
(ph = 2.5) 1) Mixture of 57.5~ glutaric, 11.6~ adlpia and 27~ succinic acids in the form of water so]uble white flakea, a product of E.I. Du Pont de Nemour~ & Co.
2) A nonionic surfactant from Shell Chemlcal Co. which is tlle conden6ation product of Cg-Cll fatty alaohol with 8 moles, on average, of ethylene oxide.
3) A nonionic aurfactant from Shell Chemical Co. which iB the condensation product of Cg-Cll fatty alcohol with 2.5 mole~, on average, of ethylene oxide.

4) Variquat 50hC disinfectant, from Sherex Chemical Co.

5) A commercially available preparation containing 15-20~
polymer, average mol.wt of 20,000, 5-10% i~opropanol, 3-5% N-octanol, 3-5% sodium acetate, 1-3% terpene hydrocarbons and 3-5 of either sodium lauryl sulfate or AEOS (7 mole~ ethoxylated C14 alkyl sulfate).
The anti-soiling performance of the composition is tested on each of a new white ceramic tlle and of a ~oap scum soiled new or etched white aeramic tile. One-half of the new tile i8 immersed and the other half 18 ~mmer~ed ln the same formulation but without the poly(MDAEM). After removal from the bath, the tile i~ gently wiped dry with a soft paper towel.
The soap scum soiled tiles are prepared by spraying the tiles with a 250 g/l solutlon of CaC12-H20 followed by a red dyed 5~ 60dium oleate ~olutlon. The tlle~ are allowed to dry for one hour at 30C and the 60iling procedure i8 repeated. The gO11 90 PrOd.]Ced 1B uniform and reproducible within accepted limits.

One-half of each 60ap ~cum solled tllff is cleaned witl iO Ithe ven-ion ~ompoaition deacribed above a d the other half ia ~ r~ 3 j ~
cleaned with the ~ame compo~ition excluding the poly(MDAEM). The tiles are cleaned by hand until all the ~oap scum is removed. ,1 After the treatment of the new or soiled tiles with the cleaning composition w~th or without the anti-~olling polymer the tile~ are rinsed and a~r-dr~ed and the entlre tlle surface i~ re-soilsd with soap scum by ther~ame procedure as described above.
The re-soiled tile is then washed with a m~ld cleaning consisting of a 1~ aqueous Eolution of a 1:1 w/w mlxt~re of Neodol 91-6/Neodol 91-2.5. This mild cleaning solutton wlll provide a minimum amount of chemical cleaning action. The tiles are cleaned according to 5tandard Practice In~truction 8173 u~ing the mild cleaner and 10 cycles on a Gardner Abras~on Tester. In thls test, the tiles are mounted in the Tester equipped ~ith two cellulose sponge~ measuring 5 cm x 5 cm x 5 cm. Three grams of the mild cleaner are pipetted onto the ~ponges wetted with 5 gm water. A xeflectometer is u~ed to mea~ure the reflectance before and after the 10 abrader cycle~ and the percent 80il removal is determined. The results are shown in the following table.
New Tile Percent Soil ~emoval Treated halfa) 90-100 Untreated half 0-30 Soap Scum Soiled New Tile Treated halfa) 90-100 Untreated half 15 Soap Scum Soiled Etched Tile Treated halfb) 55 Untreated half 15~

a) poly~MDAEM) with sodium lauryl sulfate b) poly( MDAEM) with AEOS

Wllen the above test iB repeated by treating the tiles with a similar composition according to the lnvention except that . .

~ l' ;` ~s) ~
the pH is increased to 6 by addition of sodlum hydroxide, the tile-half treated with the poly(MDAEM)-AEOS containing composition, gave l00~ soil removal after 5 cycles on the Gardner Abrasion tester using the same mild cleanlng ~olution whereas the untreated tile gave 55% soil removal.
Example 2 r The procedure of Example 1 i~ repeated on soap scum ~oiled new tiles prepared as described ln Example 1 using the following composition:

Amount Inqredient Acid Mixtur2e1) 3.0 Neodol 91-8 ) 1.5 Neodol 91-2.53) 0.7 Isopropyl Alcohol 3.0 Cationic disi~fectant4) 0.2 Poly(MDAEM)5)6) 0 4 Perfume and color 0.21 Water Q.S.

1), 2), 3), 4), 5) - ~ee footnote~ in Example 1 6) _ Complexed to sodlum lauryl ~ulfate.
After recleaning with the same mild cleaning composition as in Bxample 1, the untreated side showed essentially no clean~ng (<10~ floil removal) wherea~ ~he poly(MD~EM) treated side showed an average of 90~ soil removal.

Example 3 Tlli~ example demonstrates that the treating composition~ of this Lnvention can be applled to various types of ard surfaces commonly found in the home.

~5 ,.

2~ ''3 . ~

The following formulation i8 prepared:

~mount Inqredient (Wt.%) Mixed Acidl) 3.5 Neodol 91-82) 1 5 Neodol 91-2.53) 0 7 Isopropyl alcohol 3.0 Poly(MDAEM)5)7) 0.4 Perfume and color 0.21 Water Q.S.

11, 2J, 3), S) _ see footnotes in Example 1 7) - Complexed with ~EOS
The ~ame test as described in ExRmplra 1 i8 carried out on unsoiled polymethacrylate test plates, except that only 5 cycles are applied on the Gardner ~brasion tester using 'che same mild cle~ner as used Ln Example 1. The average 80il removal on the poly(MDAEM) treated side 18 66% and on the untreated side is 45%. No significant difference in the shine or glos~ of the surface is observed.

Example 4 The test procedure of Example 1 ~ repeated orl new white ceramic tiles treated with neat 0.5~ aqueous ~olu~.ion~ oE
either poly(MD~EM) or the following polymerss polyvinyl pyrrolidone (avg. mol. 26. 360,000); Gafquat 755N (vinyl pyrrolidone/dimethylam~noethylmethacrylate copolymer, polyquaternium II), Polymer J~-30M (a quaternary nitrogen substituted cellulose ether, where 30M is the designation of viscosity at 1~ concentration, sodium salt of styrene-maleic anhydride copolymer, Sokalan (CP7) (sodium salt of copolymer of methacrylic acid and maleic anhydride), polyethylene . ¦terephthalate/polyethylene oxide terephthalate copolymer, and polyethylelle oxide (mol. wt. 4,000,000). The best recleaning - . . : ~: .
~ , , ~ ...

~J~ P~ 'J
performance (least amount of work required for given 50il removal or most soil removal for a given amount of work) was provided by the poly(MDA~M) treated surface, with le~er improvements in the order given (from good to adequate) for the remaining polymers.
Accordingly, it can be appreciated that the present invention provides a compo~i~ion and method for treatlng hard surfaces, ~uch aa ceramic tiles, porcelaln, enamel, Formica, polymethacrylate~, and the like, ~uch as found in bathrooms (sinks, tubs, shower stall~, walls, ~loor~, vanities, etc.), whereby the treated ~urface i~ modified to lncrease its hydrophilicity, with or without simultaneou~ aleaning of exi~ting 80il. As a result of thls treatment any further ~oiling becomes easier to clean during ~ubsequent cleaning (wi~h the same or different cleaning solution) because the built-up ~oil will not adhere as tenaclou~ly to the treated surfaae as it would to the same surface which has not been treated with an anti-soiling polymer according to the invention.
Lt should be noted that the performance of the 9011 release polymer containlng compo~i~ione of thi~ lnverltion is dependent on the prevailing humidlty of the ambient Atmosphere:
lf there is little moisture in the air the degree of llydration of the treated surface becomes insufficient to adequately prevent soll adhe~lon by whichever of the above proposed theories or other mechani~m is in operation. Generally, humidity level~ of at least about 35~ RH at 70F will provlde the best re6ult~ upon subsequent recleanlng. For most area~ of application, such as bathrooms and kitchens, the prevailing atmospherlc moisture levels will be equivalent to at lea~t 35~ RH.
It ~hould al~o be understood that the treating compo~itions of this invention are not llmited to hou~ehold hard ~urfaces but can al~o be used to facil~tate recleaning for other types of hard surfacea, such a~ automobiles (e.g. vinyls, metals, painted ~urfaces, etc.), window ca~ement~ and the like.
In final form, the aqueou~ llqu~d hard surface modifying compos~tLon~, including the treatlng and cleaning compositions are typically hormogeneous compositions which exhibit stability at both reduced and increased temperatures. More specifically, such compo~itions remaln st~ble in the range of 5C
to 40C. The liquids are readlly pourable and free flowing from any suitable container or may be sprayed from a pump-type sprayer. Another advantage of the composlt~on~ of this invention is that by virtue of the increase in viscoslty from the polymer anti-soiling agent, especially the cationlc polymer-anionic surfactant complex, the products can be formulated with viscositieis between about 10 to 20 cp~ which allows the products to be sprayed with most conventional pump ~pray no~zles with substantially less misting than for lower vi~co~itie~ but without logging the spray nozzle aa would tend to occur with hlgher viscosities.
The compositions are directly ready for use. Only minimal rinslng 1B needed and substantially no reaidue or streaks re left bèhind on the cleaned surface. Becau~e the preferred ompo~itlon~ are free of detergent bullder~, such as alkali metal olyp}-osphates they provide a better "~hine", i.e. less streaklng, on cleaned hard surfacea.
Typically, the inventive compositions are prepared ~imply by combining all of the ingredient~ in a suitable mixing vessel or container. Generally, the various ingredient~ can be added sequent~ally, or all at once, to form an aqueous solutlon of each or all of the essential ingredient~, care being taken -to ;: :

~ ! S ~

avoid mixing together any anionic and cationic components as described previou~ly. Preferably, when a fragrance i8 preSerlt, the fragrance ls flrst dlssolved Ln a water disperslble nonionic surfactant which ls then added to the other ingredlents in aqueous acid solution. When the ~urfactant/fragrance mixture is added to the aqueous acld sorution contain~ng the remaining ingredients, the solution may become slightly hazy. If a cationic disinfectant compound 18 added to the aqueous mixture, the fragrance becomes completely ~olubil~zed and the final mixture is clear as well as stable. Additional base may then be added, if de~ired, to lncrease product pH. The compositions may be prepared at room temperature.
In use, the composltions of this invention are applied to the surfaces to be modlfied/cleaned w~th a cloth or sponge or by spraying onto ceramic or other surfaces which may have been soiled by accumulations of insoluble soaps~ mlneral deposits, and oily soil~. The compositlons, without added th~akeners, other than the soil-releasing polymer, are of somewhat higher viscosity than water, generally up to about 3-10 cps or higher, the polymer complexes providing higher viscoslty in general. ~he material will usually be allowed to remain on the surface to be modified ~or a period from 10 seconds to 5 or 10 minutes, but preferably such contQct time will be from about 30 seconds to five minutes or from 1 to 3 mioutes. The liquid composit~on may then be removed either by wlping or rln~ing wlth water. Depending on the degree of soiling of a hard surface not prev~ously treated with the invention composition more or less strenuous wiping and rinsing may be required. However, in all cases subsequent . recleaning requires substantially less work to remove any 3~ subsequently deposited soils. These compositions leave ~ '6~

substantially no ~pots or streaks whether or not ttley are rinsed from the cleaned surface.
Tlle foregoing description and specific examples are intended merely as illustrations of speclflc and preferred embodiments for the practice of tlle inventlon. It is to be understood, however, that ot~er expedient~ known to those skilled in the art or disclosed herein may be employed without departing from the spirit of the invention or ~cope of the appended claims.

, . , .:

Claims

1. A hard surface modifying composition for increasing the hydrophilic nature thereof to thereby facilitate removal of soils deposited thereon, said composition comprising an aqueous solution of an anti-soiling water-soluble anionic, cationic or nonionic polymer, said polymer being adsorbed on said hard surface from said aqueous solution and forming a residual anti-soiling polymer layer thereon, said residual layer being hydrophilic and capable of attracting atmospheric water vapor thereto, whereby soil deposited on said residual layer in the presence of atmospheric water vapor can be removed from said surface with less work than in the absence of said residual layer.

2. The hard surface modifying composition of claim 1 wherein said anti-soiling polymer is a cationic polymer at least 50 mole%
of the repeating units of which comprise quaternized ammonium alkyl methacrylate groups.

3. The hard surface modifying composition of claim 2 wherein said cationic polymer comprises at least 80 mole% of repeating units of formula (II):

(II) wherein R1 and R2, which may be the same or different, are hydrogen or lower alkyl, or R1 and R2 together with the nitrogen atom to which they are bonded may form a heterocyclic group;

R3 is hydrogen or methyl;
R4 is alkylene of 1 to 8 carbon atoms;
R5 is a monovalent anion or l/m of an m-valent anion

4. The hard surface modifying composition of claim 3 wherein R1 and R2 are, independently, methyl or ethyl, R3 is methyl, R4 is ethyl and R5 is methyl.

5. The hard surface modifying composition of claim 1 wherein said anti-soiling polymer is an anionic copolymer salt of a monovinyl aromatic monomer and an unsaturated dicarboxylic acid or anhydride thereof.

6. The hard surface modifying composition of claim 3 wherein said cationic polymer is present as a water-soluble complex with an anionic surfactant at a molar ratio of the quaternized ammonium groups to the anionic surfactant of at least about 3:1.

7. The hard surface modifying composition of claim 6 wherein the molar ratio of quaternized ammonium groups to anionic surfactant is from about 3.5:1 to 6:1.

8. The hard surface modifying composition of claim 6 wherein said anionic surfactant is selected from the group consisting of alkali metal alkyl sulfate wherein the alkyl group has from about 10 to 16 carbon atoms, a C12 to C18 alcohol sulfate ethoxylated with from about 2 to 7 moles ethylene oxide per mole of the alcohol, and an alkali metal C16 to C20 fatty acid soap ethoxylated with from about 2 to 7 moles ethylene oxide per mole of fatty acid.

9. A hard surface modifying and cleaning composition comprising an aqueous solution of non-soap synthetic surface active detergent compound and a surface modifying anti-soiling water-soluble polymer which is adsorbed from said solution by said hard surface and which when adsorbed by said hard surface forms a residual anti-soiling polymer layer which increases the hydrophilic property thereof, whereby said surface becomes capable of attracting atmospheric water vapor thereto, such that when said composition is applied to a soiled hard surface the soil can be cleaned with the assistance of the surface active detergent compound and a residual anti-soiling polymer layer is formed said hard surface such that soil subsequently deposited on said surface can be removed therefrom with less work than in the absence of said residual layer.

10. The hard surface modifying and cleaning composition of claim 9 wherein said surface active detergent compound comprises at least one nonionic surface active compound and said anti-soiling polymer comprises a quaternized cationic polymer.

11. The hard surface modifying and cleaning composition of claim 10 wherein said quaternized cationic polymer is present as a water-soluble complex with a minor amount of an anionic surfactant compound.

12. The hard surface modifying and cleaning composition of claim 11 wherein said quaternized cationic polymer contains at least 50 mole% of repeating units of formula (II):

(II) wherein R1 and R2, which may be the same or different, are hydrogen or lower alkyl, or R1 and R2 together with the nitrogen atom to which they are bonded may form a heterocyclic group;
R3 is hydrogen or methyl;
R4 is alkylene of 1 to 8 carbon atom;
R5 is a monovalent anion or l/m of an m-valent anion.

13. The hard surface modifying and cleaning composition of claim 12 wherein the water-soluble complex comprises at least about 3 moles of the group of formula (II) for each mole of the anionic surfactant.

14. The hard surface modifying and treating composition of claim 13 wherein said anionic surfactant is selected from the group consisting of alkali metal alkyl sulfate wherein the alkyl group has from about 10 to 16 carbon atoms, a C12 to C18 alcohol sulfate ethoxylated with from about 2 to 7 moles ethylene oxide per mole of the alcohol, and an alkali metal C16 to C20 fatty acid soap ethoxylated with from about 2 to 7 moles ethylene oxide per mole of fatty acid.

15. The hard surface modifying and treating composition of claim 10 wherein said quaternized cationic polymer contains at least 50 mole% of repeating units of formula (II) (II) wherein R1 and R2, which may be the same or different, are hydrogen or lower alkyl, or R1 and R2 together with the nitrogen atom to which they are bonded may form a heterocyclic group;
R3 is hydrogen or methyl;
R4 is alkylene of 1 to 8 carbon atoms;
R5 is a monovalent anion or l/m of an m-valent anion.

16. The hard surface modifying and treating composition of claim 15 having a pH in the range of from about 2 to 9.

17. A stable aqueous hard surface modifying and cleaning composition comprising by weight:
(a) about 0.5-4% of a mixture of acid stable nonionic surfactants, said mixture consisting essentially of a water soluble nonionic surfactant and a water dispersible nonionic surfactant in a weight ratio of water-soluble to water-dispersible surfactant of from about 4:1 to 4:3;
(b) about 3-7% of an organic acid selected from the group consisting of lower aliphatic monocarboxylic acids, lower aliphatic hydroxycarboxylic acids, lower aliphatic dicarboxylic acids and mixtures thereof (c) from about 0.04 to 2% of a water-soluble cationic or anionic polymer soil releasing agent;
(d) from 0 to about 5% of aliphatic alcohol solvent;
and (e) the balance water, said liquid cleaning composition having a pH of about 2-9.

18. The composition according to claim 17 comprising 0.06-1% of said water-soluble polymer soil releasing agent selected from the group consisting of poly(bet? trialkyl ammonlum ethyl methacrylates) having ethyl or methyl groups attached to the ammonium moiety.

19. A method for modifying the hydrophilic properties of a household hard surface to facilitate removal of soil deposited thereon, said method comprising contacting the hard surface to be modified with an aqueous solution of an anti-soiling water-soluble cationic, anionic or nonionic polymer which will be adsorbed by and hard surface, and drying said hard surface whereby said adsorbed polymer forms a residual anti-soiling hydrophilic layer on said surface, whereby soil deposited on said residual layer can be removed therefrom with less work than in the absence of said residual layer.

20. The method of claim 19 for treating ceramic, enamel or porcelain hard surfaces.

21. The method of claim 19 wherein said aqueous solution further comprises a detersive amount of an anionic, cationic or nonionic surface active detergent compound, with the proviso that said detergent compound is cationic or nonionic or both when said polymer is cationic, and said detergent compound is anionic or nonionic or both when said polymer is anionic.

22. The method of claim 21 wherein said polymer is cationic, said surface active detergent compound is nonionic and said cationic polymer is present as a water-soluble complex with a minor amount of an anionic surfactant compound in an amount of no more than one mole of anionic surfactant for each 3 moles of cationic group in said cationic polymer.