WO2014093578A1

WO2014093578A1 - Floor care wipes with improved dirt pick-up

Info

Publication number: WO2014093578A1
Application number: PCT/US2013/074569
Authority: WO
Inventors: Lauren M. HIGHT; Elke FEESE; Kwadwo OWUSU-SARFO; Zhiqiang Song; Ashish TENEJA
Original assignee: Basf Se
Priority date: 2012-12-14
Filing date: 2013-12-12
Publication date: 2014-06-19

Abstract

The present invention is directed to use of dirt-attracting polymers formed from 2-tert- butylaminoethyl (meth)acrylate (tBAEMA) monomers. Cleaning wipes, mop pads, and similar substrates, are treated with the formed polymers to improve dirt pick-up from the cleaned surface. The polymers can be incorporated directly into the non-woven substrates or they can be formulated with a cleaning composition for use with the substrate. The dirt-attracting polymers can be employed to clean hard surfaces such as floors, counter-tops, toilets, windows, and autos.

Description

Floor Care Wipes with Improved Dirt Pick-up

FIELD OF THE INVENTION

The present invention is directed to the use of dirt-attracting polymers formed from tertiary butyl aminoalkyl (meth)acrylate monomers and their use on a cleaning substrate such as cleaning wipes, mop pads, nonwoven and similar substrates. In particular wet and dry nonwoven wipes treated with the dirt-attracting polymers are of particular interest.

BACKGROUND OF THE INVENTION

Household dirt and soil are usually removed from hard and soft surfaces with a cloth, sponge or other similar hand held implement. To facilitate dirt and soil removal, there are numerous commercially available surface cleaning compositions in the prior art. Generally, the liquid cleaners consist of some small percentage of surfactant, such as a nonionic or anionic surfactant, a solvent, such as an alcohol, ammonium hydroxide, a builder, and water.

However, liquid cleaners have limited cleaning efficiency with respect to particular types of soils, and are subject to streaking or re-depositing of soil onto the cleaned surface. Furthermore, certain soils that contain both water soluble ingredients and water insoluble components are very difficult to remove simultaneously from a surface. Thus, there is a need in the art to arrive at formulations for cleaning wipes, mop pads, and similar substrates such as wet and dry nonwoven wipes which act to clean a surface regardless of the nature of the dirt or debris needing removal.

Polycationic polymers are known to provide dirt-pickup in cleaning wipes. For example, U.S. Patent Nos. 7,432,234 and 7,048,806 teach the use of polyethyleneimine polymers in wipes.

Additionally alkylaminoalkyl (meth)acrylate polymers are known to be antimicrobial and are known for use on various fabrics/textiles such as polymeric filters. See for example, PCT application 2002099181 and co-pending U.S Applications Nos. 13/527,972 and 13/528,289. SUMMARY OF THE INVENTION

The present invention is based in part on the discovery that impregnating a cleaning substrate with a particular polymer unexpectedly improves the dirt pick-up of a cleaning wipe. The dirt- attracting polymers can be employed neat or can be mixed with other components of a liquid cleaner. The cleaning wipe may be dry or wet.

Thus one aspect of the application includes a method of removing dirt from a dirt laden hard surface that comprises the steps of a) providing a cleaning substrate wherein the substrate is impregnated or treated with a dirt-attracting polymer comprising the repeat unit of formula I

(I) wherein R is H or CH₃, R² is C1-C5 alkyl bi-radical, and n is a number from 3 to 10,000; and b) optionally a solvent and/or surfactant; c) engaging the dirt laden hard surface with the substrate impregnated or treated with the dirt-attracting polymer of step a) to remove dirt from the dirt laden hard surface, wherein the treated substrate in step c) may be wet or dry.

In another aspect envisioned is a method of removing dirt from a dirt laden hard surface that comprises the steps of: a) providing a cleaning substrate which comprises an absorbent material; b) applying a liquid cleaning solution onto the dirt laden hard surface or onto the cleaning substrate wherein the liquid cleaning solution comprises a polymer comprising the repeat unit of formula (I) defined as above; and c) engaging the dirt laden hard surface in step b) with the cleaning substrate to remove dirt from the dirt laden hard surface.

Further a use is envisioned of the above dirt-attracting polymer in or on wet or dry cleaning substrate for the purpose of removing dirt from hard surfaces.

It is also believed that a nonwoven wipe (wet or dry) comprising about 0.0001 to about 3.0 wt. % of the dirt-attracting polymer comprising the repeat unit of formula (I) is novel and the wt. % is based on the dry weight of the substrate.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Definitions

"Comprising" for purposes of the invention is open ended, that is other components may be included. Comprising is synonymous with containing or including.

When the term "molecular weight" is used this will normally indicate weight average molecular weight (Mw) unless otherwise indicated.

All percentages herein are based on weight unless otherwise noted.

(Meth)acrylate means methacrylate or acrylate and likewise (meth)acrylamide means methacrylamide or acrylamide.

The term "monomer" is used to refer to a compound having at least monoethylenic unsaturation before polymerization. After the monomer is polymerized and becomes part of a polymer, the monomer is referred to as a "monomer unit". For example the repeat unit "n" of polymer of formula (I) is a monomer unit and is used synonymously with the phrase "repeat unit".

"Cleaning formulation" for purposes of this application means a liquid formulation, incorporating the dirt-attracting polymer comprising the repeat unit of formula (I) of this application .

The term "polymer" for purposes of this application means a homopolymer or copolymer.

The term "copolymer" for purposes of this application means a polymer formed from more than one monomer units, In other words a copolymer is form from at least two different monomer units.

Cleaning Substrate

The "substrate" or " cleaning substrate" for purposes of this application is defined as any suitable natural and/or synthetic adsorbent and/or adsorbent material that can be employed to clean hard and soft surfaces by physical contact, e.g, wiping, scrubbing, buffing, polishing, rinsing, and the like.

Wet and dry nonwoven wipes are of special interest as the "substrate" or "cleaning substrate".

Wet nonwoven wipes which are treated with the dirt-attracting polymer may be more typical. A dry nonwoven wipe which has been treated with the dirt-attracting polymer means that the dirt- attracting polymer may be applied to the nonowoven wipe via a liquid dispersion or solution containing surfactants and other adjuvants for cleaning and maintained in the wet state and then used to clean the dirt laden surface.

The cleaning substrate may be any textile or fabric formed from synthetic, natural fibers or some blend of both synthetic and natural fibers.

Preferred "cleaning substrates" are nonwovens which means that the material is formed without the aid of a textile weaving or knitting process. The non-woven material can comprise, for example, non-woven, fibrous sheet materials or meltblown, coform, air-laid, spun bond, wet laid, bonded-carded web materials, and/or hydroentangled (also known as spunlaced) materials. The substrate can also include wood pulp, a blend of wood pulp, and/or synthetic fibers, e.g., polyester, regenerated wood cellulose such as viscose, RAYON, NYLON, polypropylene, polyethylene, and/or cellulose polymers.

The substrate can incorporate a backing member that may be pervious or impervious to a cleaning composition. The backing member provides structural support to the substrate, imparts texture to the substrate, and/or provides a prophylactic barrier. The backing member can be manufactured from any suitable material including, for example, woven or nonwoven material, polymeric material, natural fiber, synthetic fiber, or mixtures thereof.

Woven materials, such as cotton fibers, cotton/nylon blends, or other textiles may also be used in the substrate. Regenerated cellulose, polyurethane foams, and the like, which are used in making sponges, may also be suitable for use herein.

Most preferably the nonwoven is formed at least partially from synthetic polymers which are selected from the group consisting of polyolefin, polyester, polyamide and mixtures thereof, especially for example, polypropylene, polyethylene, polypropylene/polyethylene copolymers, PET, PET/Viscose blends, PEN, Nylon and the like.

Polyolefins for example, include polypropylene, polyethylene, copolymers of ethylene and propylene, polybutylene, styrenic polymers and copolymers, metallocene-catalyzed polyolefins and mixtures thereof.

More than one type of synthetic polymer may be present. Naturally occurring polymers may also be present.

The dirt-attracting polymer does not need to be chemically attached (covalently bonded) to the cleaning substrate. This is one of the clear benefits of the particular polymer disclosed in this application. The application of the dirt-attracting polymer in a solution or dispersion directly to the cleaning substrate via a simple dipping, spraying or coating step will insure sufficient binding of the dirt-attracting polymer to the substrate and may prevent wash-off even under exposure to fluids.

Furthermore, the substrate, for example a nonwoven impregnated or treated with a solution or liquid dispersion of the dirt-attracting polymer of formula (I) engages a dirt laden hard surface with the impregnated or treated substrate to remove dirt from the hard surface, wherein the treated substrate may be wet or dry and used in the wet or dry form to remove dirt from the dirt laden hard surface. Preferably, there is no covalent attachment of the dirt-attracting polymer to the cleaning substrate or nonwoven. However, the polymer continues to reside on the cleaning substrate and remain substantive to the substrate even if formulated with surfactants and the like. Thus the dirt-attracting polymer on the substrate has the advantage of not losing its effectiveness even after rinsing and the like.

The dirt-attracting polymer may be for example, pre-formed before applied to the cleaning substrate. Of course, it is possible for a monomer which would polymerize and form the monomer unit of formula (I) to be polymerized in the presence of the cleaning substrate. But most typically the polymer of formula (I) is not formed in the presence of the cleaning substrate or is not covalently bound or grafted to the cleaning substrate.

The dirt-attracting polymer on the cleaning substrate may be protonated, partially protonated or not protonated. This will depend on the pH of the formulation. But it is not required that the dirt- attracting polymer be formulated in an acidic environment on the cleaning substrate.

The present invention relates to a cleaning implement that includes a substrate that has been impregnated with a dirt-attracting polymer comprising the repeat unit of formula (I). In addition, the invention relates to methods of cleaning hard surfaces using the so-impregnated substrate or using a non-impregnated substrate on a hard surface on which dirt-attracting polymer has been applied in the form of a liquid cleaner.

Loading of the Substrate with The Cleaning Formulation Containing the Dirt-Attracting Polymer

The substrate for example the non-woven, will typically be loaded with a cleaning formulation anywhere from 0.5 to 10 times the dry weight of the substrate. The cleaning formulation comprises the dirt-attracting polymer comprising the repeat unit of formula (I) and any other ingredients such as solvents, water, surfactants and other additives such as colorants, preservatives and fragrances.

The substrate will normally comprise from about .0001 to about 3 wt. % of the dirt-attracting polymer based on the weight of the dried substrate. Thus dirt-attracting polymer comprises about 0.0001 % to about 3 wt.%, preferably about 0.01 % to about 2.0 wt. %, most preferably about 0.01 to about 1.75 wt. % of the total weight of the dry weight of the substrate.

Dirt-Attracting Polymer The dirt-attracting polymers of the present application comprising the repeat unit n of formula (I):

wherein R-i is H or CH₃, R₂ is C C₅ alkyl bi-radical, and n is a number from 3 to 10,000.

Preferably,

R₂ is C^-C₃ alkyl bi-radial.

Most preferably,

R₂ is C₂ alkyl bi-radical.

The polymer of formula (I) may be protonated or unprotonated. Thus if protonated the polymer will carry a positive charge.

The dirt-attracting polymer may be a copolymer or homopolymer.

The polymer is formed from at least 2-tert-butylaminoethyl (meth)acrylate (tBAEMA) and may contain in addition to repeat units "n" repeat units different than repeat unit "n". The polymer of formula (I) may be a homopolymer containing only the repeat unit "n".

Alternatively, the polymer of formula (I) may additionally contain other repeat units. For example, the polymer may be a copolymer formed from in addition to tert-butylaminoethyl (meth)acrylate (tBAEMA) other monomer including cationic, nonionic monomers and/or anionic monomers different from tBAEMA.

It may be more advantageous to form the dirt-attracting polymer from say for example hydrophilic monomers such as cationic monomers containing amines and non-ionic monomers which are comparatively more hydrophilic than for example alkyl esters of (meth)acrylate or amides of (meth)acrylamide. For example hydroxyl alkyl (meth)acrylates or hydroxyl alkyl (meth)acrylamides are generally more hydrophilic then C₁-C4 alkyl (meth)acrylate esters and thus may positively impact the cleaning effectiveness of the dirt-attracting polymer on the substrate or nonwoven. Further additional cationic monomers such as those listed below may also polsitively impact the cleaning effectiveness of the dirt-attracting polymer on the substrate or nonwoven.

Cationic Monomers

Examples of suitable cationic monomers are esters or amides of a, β-ethylenically unsaturated mono- and dicarboxylic acids with C₂-Ci₂ amino alcohols or C₂- to C₁₂ diamines respectively.

These will be Ci-C₈-monoalkylated dialkylated or quaternized at the amine nitrogen. Suitable acid components of these esters or amides are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are most typical.

Thus suitable cationic monomers would include for example cationic monomers selected from the group consisting of N,N-dimethylaminomethyl(meth)acrylate, N,N- dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N- diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N- diethylaminopropyl(meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate, N,N-diethylamino- butyl(meth)acrylate, Ν,Ν-dimethyl aminomethyl(meth)acrylamide, N,N- dimethylaminoethyl(meth)acrylamide, N,N-diethylaminomethyl(meth)acrylamide, N,N- diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N- diethylaminopropyl(meth)acrylamide, N,N-dimethylaminobutyl(meth)acrylamide, N,N-dimethyl aminobutyl(meth)acrylamide, mixtures thereof and the quaternization products thereof with Ci- C₄ -alkyl chlorides, Ci-C₄-dialkyl sulfates, C₁-C4 -epoxides or benzyl chloride.

Other suitable cationic monomers envisioned are N-vinylimidazoles, alkylvinylimidazoles, in particular methylvinylimidazoles, such as 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridines and quaternized products of these monomers.

Further suitable monomers are allylamine, dialkyldiallylammonium chlorides, in particular dimethyldiallylammonium chloride and diethyldiallylammonium chloride.

Accordingly the cationic comonomers may be selected from the group consisting of N,N- dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N- diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide, mixtures thereof and the quaternization products thereof with C₁-C4 -alkyl chlorides, CrC₄-dialkyl sulfates, C₁-C4 -epoxides or benzyl chloride; N-vinylimidazoles, alkylvinylimidazoles, in particular methylvinylimidazoles, such as 1-vinyl-2-methylimidazole, 2- and 4-vinylpyridines and quaternized products of these monomers, allylamine, dialkyldiallylammonium chlorides, in particular dimethyldiallylammonium chloride and diethyldiallylammonium chloride, preferably N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide, more preferably N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N- diethylaminopropyl(meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate, N,N-diethylamino- butyl(meth)acrylate, most preferably N,N-dimethylaminoethyl(meth)acrylate and N,N- diethylaminomethyl(meth)acrylate.

Nonionic Monomer Components

Suitable neutral or nonionic monomers which may be copolymerized to form a copolymer of formula (I) are, for example, esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with d-C₄-alkanols and esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids C₂-C₄-alkanediols, amides of α,β-ethylenically unsaturated monocarboxylic acids and N- vinyl formamide derivatives.

Esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with CrC₄-alkanols are, for example, methyl(meth)acrylate, methyl ethacrylate, ethyl(meth)acrylate, ethyl ethacrylate, n- butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate and mixtures thereof.

Esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with C₂-C₄-alkanediols,are for example are 2-hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2- hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4- hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, etc. and mixtures thereof.

Also suitable neutral comonomers are acrylamide, substituted acrylamides, methacrylamide, substituted methacrylamides, such as, for example, acrylamide, methacrylamide, N- methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-(n- butyl)(meth)acrylamide, tert-butyl(meth)acrylamide, and mixtures of said monomers.

Thus, the dirt-attracting polymer may be formed from 2-tert-butylaminoethyl (meth)acrylate (tBAEMA) and cationic, non-ionic monomers and/or anionic monomers wherein the cationic monomers are selected from the group consisting of group consisting of N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N- diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide, mixtures thereof and the quaternization products thereof with C₁-C4 -alkyl chlorides, CrC₄-dialkyl sulfates, C₁-C4 -epoxides or benzyl chloride; N-vinylimidazoles, alkylvinylimidazoles, in particular methylvinylimidazoles, such as 1-vinyl-2-methylimidazole, 2- and 4-vinylpyridines and quaternized products of these monomers; allylamine, dialkyldiallylammonium chlorides, in particular dimethyldiallylammonium chloride and diethyldiallylammonium chloride preferably N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide, more preferably N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N- diethylaminopropyl(meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate, N,N-diethylamino- butyl(meth)acrylate, most preferably N,N-dimethylaminoethyl(meth)acrylate and N,N- diethylaminomethyl(meth)acrylate; wherein the nonionic monomers are selected from the group consisting of methyl(meth)acrylate, methyl ethacrylate, ethyl(meth)acrylate, ethyl ethacrylate, n- butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate,

2-hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl(meth)acrylate, 3- hydroxypropyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6- hydroxyhexyl(meth)acrylate, (meth)acrylamide, N-methyl(meth)acrylamide, N- ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide, tert- butyl(meth)acrylamide, and N-vinyl formamide, preferably 2-hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2- hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4- hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, more preferably 2- hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl(meth)acrylate, 3- hydroxypropyl(meth)acrylate and mixtures thereof and most preferably 2- hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate and 3-hydroxypropyl(meth)acrylate and mixtures thereof.

Anionic Monomers Components

The anionic possible monomer components are a, β-ethylenically unsaturated mono- and dicarboxylic acids.

For example acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride and mixtures thereof are typical and more preferably acrylic acid, methacrylic acid and mixtures thereof .

The additional monomers not forming the repeat unit "n" however, should not interfere with the dirt-pick up effect resulting from the polymer comprising the repeat unit of formula (I).

While the polymers comprising the repeat unit of formula (I) may be a co-polymer, it is believed that there should be significant repeat units "n" of formula (I). For example, if the polymer comprising the repeat unit of formula (I) is a co-polymer, the co-polymer may be a block copolymer containing at least one block formed from the repeat unit "n". Alternatively, a suitable random copolymer can be a random copolymer preferably with molar ratio of repeat unit "n" of at least 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 80%, 90% or 95%. The percent is based on the total number of repeat units of the (co)polymer. Generally the dirt-attracting copolymer will contain from 10 to about 95 mol %, about 15 to about 95 mol %, about 20 to about 80 mol % of repeat unit n.

Thus the dirt-attracting polymer may be a copolymer and the copolymer may be formed from at least 5 mol % , more typically 10, 20% or 30 % by mol % of repeat unit "n". Most typically the polymer of formula (I) will contain from about 5 to about 100 mol %, about 10 to about 90 or about 15 to about 85 mol % of repeat unit "n". The percent is based on the total number of repeat units of the (co)polymer or homopolymer.

The co-polymer could have a grafted or a brush architecture wherein the co-polymer contains pendant graft monomer repeat units of formula (l)along a linear polymer chain. Hyperbranched architectures are also envisioned wherein a central multifunctional acrylate may be polymerized with repeat units "n" giving a star like or hyperbranched configuration wherein the monomer repeat units of formula (I) radiate around the central multifunctional acrylate.

Accordingly, the dirt-attracting polymer may have most any architecture and can be a linear polymer of formula (I), a graft, brush or comb co-polymer having pendant monomer repeat units of "n" or a star like polymer configuration wherein the repeat units of formula (I) radiate outward from a central multifunctional (meth)acrylate.

The dirt-attracting polymer may be water soluble or water insoluble. Preferably, however, the dirt-attracting polymer on the cleaning substrate is substantially water-insoluble.

Water-insoluble for purposes of this application means < 5%, preferably < 1 % soluble in deionized water at room temperature (25 °C) and pressure.

The term substantially "water-insoluble" for purposes of this application means that less than 5 wt. %, preferably less than 3 wt. %, most preferably less than 1 wt. % and especially 0.5 or 0.1 wt. %, most especially < 100 ppm or < 10 ppm of the dirt-attracting polymer is soluble in deionized water at room temperature (25 °C) and pressure. For example, the dirt-attracting polymer according to formula (II) may be < 10 ppm soluble in deionized water at room temperature.

The dirt-attracting polymers may exhibit a net positive charge at a pH range of 1 to 13, which is influenced by the pH of the cleaning composition described herein.

Molecular Weight of Dirt-attracting Polymer

The dirt-attracting polymer has a weight average molecular weight ranging from about 500 to 10,000,000 g/mole, preferably from about 1000 to about 500,000g/mole, more preferably about 1000 to about 250,000 g/mole, most preferably about 500 to about 100,000 g/mole and especially about 500 to about 30,000.

Even more typically the dirt-attracting polymer is a low weight average molecular weight (MW < 50, 000) with a narrow MW distribution (polydispersity Mw/Mn < 4). For example, the dirt- attracting polymer may have a Mw ranging from about 500 to about 30,000 or about 500 to about 25,000.

The average molecular weights of polymers formed from formula (I) are measured by gel permeation chromatography (GPC) using poly(methyl methacrylate) narrow molecular weight standards.

The dirt-attracting polymers can be employed as salts. In general any counterion may be employed, including, for example, halides, organic carboxylates, organic sulfonic acid anions and the like.

Preparation of the Dirt-Attracting Polymers

The dirt-attracting alkylaminoalkyl polymers can be prepared by virtually any conventional random radical polymerization, controlled radical polymerization (CRP), anionic polymerization and cationic polymerization with reaction conditions aimed for virtually any molecular weight polymers known to the art skilled. The preparation can be carried out using various

polymerization techniques such as solution, emulsion, microemulsion, inverse emulsion, and/or bulk polymerizations, as well as other technologies that are available to those who are skilled in the art.

Molecular weights of polymers synthesized by radical polymerization, anionic polymerization and cationic polymerization can be controlled by varying reaction conditions such as initiator type and concentration, monomer concentration, reaction temperature, chain transfer agent type and concentration. Generally, high concentration of initiator, low concentration of monomer, high reaction temperature and addition of a chain transfer agent are used to achieve low molecular weights for the dirt-attracting polymers.

Conventional random radical polymerization provides a simple way to make the dirt-attracting polymers. The source of free radicals required to initiate the polymerization of the radically polymerizable monomers is a free radical initiator. The free radicals may be formed by thermal or photoinduced decomposition of the initiator or by a redox reaction with the initiator. Typical free radical initiators include, but not limited to, azo and peroxide compounds. Typical azo initiator include azobis(isobutyronitrile) (AIBN), dimethyl 2,2'-azobisisobutyrate (MAIB), 1 , 1 '- azobis(l-cylcohexanenitrile), 2,2'-azobis(2,4,4-trimethylpentane), and azobis-2,4- dimethylvaleronitrile, polymeric or oligomeric materials comprising azo,— N=N— , groups. Water soluble azo initiator may be used in emulsion polymerization and selected from the group consisting of 2,2-azobis-(N,N'-dimethylene-isobutyramidine) dihydrochloride, 2,2'-azobis-(2- amidinopropane) dihydrochloride, 4,4'-azobis-(4-cyanopentane-carboxylic acid); 2,2'-Azobis[2- (5-methyl-2-imidazolin-2-yl)propane]dihydrochloride; 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]tetrahydrate; 2,2'-Azobis[2-(3,4,5,6-tetrahydropyrimidin- 2-yl)propane] dihydrochloride; and 2,2'-Azobis{2-methyl-N-[2-(1-hydroxybuthyl)]propionamide.

Typical peroxide radical initiator may include acyl and diacyl peroxides, alkyl peroxides, dialkyl peroxydicarbonates, hydroperoxides such as tert.-butylhydroperoxide, peresters, and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate, benzoyl peroxide (BPO) or a peroxy acid such as peroxyacetic acid or

peroxybenzoic acid. The redox initiator in combination with reducing agents is selected from the group consisting of, for example, an acyl peroxides with tertairyamine such as triethylamine, and tert.-butylhydroperoxide or persulfate with iron(ll)-ammonium sulfate, ascorbic acid, sodium methyl sulfinate, disodium disulfite, sodium hydrogen sulfite, sodium phosphite, potassium phosphate, hydrogen phosphite, sodium hypophosphite or potassium hypophosphite.

Azo initiator such as AIBN may be used at high concentration from 1 % to 20% based on monomer to achieve low molecular weight using radical polymerization to prepare the dirt- attracting low molecular weight polymers. Lower concentration of initiator may be used in combination with an effective chain transfer agent to obtain low molecular weight.

Suitable chain transfer agents may include mercaptans such as dodecyl mercaptan, octyl mercaptan, hexyl mercaptan and ethanolmercaptan and halogen-containing compounds such as carbon tetrabromide.

However, controlled living polymerization methods may also be used for preparing the dirt- attracting polymers. Living polymerization techniques have been traditionally used for the synthesis of well-defined polymers where polymerization proceeds in the absence of irreversible chain transfer and chain termination, i.e. nearly ideally in anionic polymerization and less ideally in cationic polymerization. Anionic living polymerization is initiated by nucleophilic addition to the double bond of the monomer using an organo-metallic initiator such as an alkyl lithium or Grignard reagent. An alternative means of initiation is electron transfer which occurs when alkali metals or similar species are the initiators. Cationic polymerization, on the other hand, is initiated by electrophilic agents such as a protonic acid and a Lewis acid. Examples of Lewis acid initiators include AICI₃, SnCI₄, BF₃, TiCI₄, AgCI0₄, and l₂ in combination with a co-initiator such as H₂0 or an organic halogen compound.

Although most of the ionic living polymerization techniques are not tolerant towards primary and secondary amino functional groups in the monomers to be polymerized, anionic polymerization of t-butylaminoethyl methacrylate is possible because of its relatively low basicity. Tertiary butyl amino ethyl methacyrlic polymers can be prepared by anionic polymerization method described in "Living anionic homo- and block copolymerization of 2-(ferf-butylamino)ethyl methacrylate " by Serge Creutz, Philippe Teyssie and Robert Jerome, J. Polymer Science (part A), vol 35 (10), 1997, 2035-2040 using a monomer to initiator molar ratio of from 5 to 100. Preferred initiators are diphenylmethyllithium with lithium chloride.

Typical controlled radical polymerization is provided by recent methods such as atom transfer radical polymerization (ATRP), nitroxide-mediated radical polymerization (NMP), reversible addition-fragmentation chain transfer polymerization (RAFT) and other related processes involving a degenerative transfer, such as macromolecular design via interchange of xanthates (hereinafter referred as MADIX).

Dirt-Attracting Polymer in Use

In use, the dirt-attracting polymers can be applied directly onto the cleaning surface of a substrate. Thereafter, the substrate can be used in its "dry" form to clean surfaces. The dry substrate can also be used in conjunction with a liquid cleaner that has been applied to the surface to be cleaned. Alternatively, a "wet" substrate can be formed when an aqueous cleaning composition, which contains the polymers and one or more additional components, is incorporated into the substrate.

When incorporated onto the substrate, either "dry" (dry wipe) or as part of a "wet" substrate (a wet wipe), the dirt-attracting polymer typically comprises about 0.0001 % to about 3 wt.% and aout preferably about 0.01 % to about 2.0 wt. %, most preferably about 0.01 to about 1.75 wt. % of the total weight of the dry weight of the substrate. The cleaning substrate's liquid loading capacity should be at least about 50%-1000% of the dry weight thereof, most preferably at least about 200%-800%. Thus the cleaning substrate is treated with a loading of cleaning formulation of 1/2 to 10 times the weight (or, more accurately, the mass) of the substrate.

The substrate varies without limitation from about 0.01 to about 1 ,000 grams per square meter, most preferably 25 to 120 grams/m.sup.2 (referred to as "basis weight") and typically is produced as a sheet or web, which is cut, die-cut, or otherwise sized into the appropriate shape and size.

The dirt-attracting polymers can be incorporated into the substrate neat or in combination with one or more cleaning components and/or adjuncts for example with a solvent and/or surfactant. Alternatively, the dirt-attracting polymers can be incorporated as part of an aqueous cleaning composition. Finally, the non-impregnated substrates can be employed to cleaning surfaces onto which the cleaning composition has been applied.

Cleaning Composition

The following are components for formulating suitable aqueous cleaning solutions containing the dirt-attracting polymers. It is understood that the choice of components for the composition depends on the surface to be cleaned. Water typically will be the predominant ingredient and it should be present at a level of about 40% to 99.5% and preferably about 90% to about 98% of the cleaning composition. As is apparent, concentrated forms of the cleaning composition will have significantly less water.

Surfactants

Because the dirt-attracting polymer functions as a cleaning aid, it is possible to exclude nonionic or cationic surfactants.

But it may be more typical to use surfactants in combination with the dirt-attracting polymer in the instance when the cleaning formulation is applied to the surface to be cleaned or when the cleaning formulation is applied directly to the cleaning substrate.

The cleaning composition applied to the cleaning substrate directly or be applied to the surface to be cleaned and then engaged with a substrate. The cleaning composition on the substrate may or may not contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. Where present, ampholytic, amphotenic and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants. The surfactants are preferably present at a level of from 0.1 % to 60% and preferably from 0.5% to 5% of the composition.

Suitable anionic surfactants include, but are not limited to, fatty alcohol sulfates of fatty alcohols having from 8 to 22, and more preferably from 10 to 18, carbon atoms, e.g., C₉-Cn alcohol sulfates, C₁₂-C₁₄ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate, tallow fatty alcohol sulfate, and combinations thereof. Further non-limiting examples of suitable anionic surfactants include alkanesulfonates, such as C₈-C₂4 alkylsulfonates, soaps such as alkali metal salts of C₈-C₂4 carboxylic acids, C₉-C₂o linear alkylbenzenesulfonat.es, and C₉-C₂₀ linear alkyltoluenesulfonat.es. Still further, the anionic surfactant may include C₈-C₂₄

olefinsulfonates and di-sulfonates, mixtures of alkene- and hydroxyalkane-sulfonates or di- sulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glyceryl sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffinsulfonates having from 20 to 50 carbon atoms, alkyl phosphates, acyl isothionates, acyl taurates, acyl methyl taurates, alkylsuccinic acids, alkenylsuccinic acids and corresponding esters and amides thereof, alkylsulfosuccinic acids and corresponding amides, mono- and di-esters of sulfosuccinic acids, acyl sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates, hydroxyalkyl sarcosinates, and combinations thereof. The anionic surfactant may be a salt such as an alkali metal salt and/or an ammonium salt such as a hydroxyethylammonium,

di(hydroxyethyl)ammonium, and/or tri(hydroxyethyl)ammonium salt. In one embodiment, the anionic surfactant is present in the cleaning formulation in an amount of from 0.01 to 30% by weight.

Suitable non-ionic surfactants include, but are not limited to, alkylphenol alkoxylates, alkyl polyglucosides, hydroxyalkyl polyglucosides, N-alkylglucamides, alkylene oxide block copolymers, polyhydroxy and polyalkoxy fatty acid derivatives, and combinations thereof. The alkylphenol alkoxylates may include alkylphenol ethoxylates having C₆-Ci₄ alkyl chains and from

5 to 30 moles of alkylene oxide added to the alkyl chains. The alkyl polyglucosides and/or hydroxyalkyl polyglucosides may have from 8 to 22 carbon atoms in an alkyl chain and have from 1 to 20 glucoside units. The N-alkylglucamides may have C₆-C₂₂ alkyl chains and may be formed from acylation of reductively aminated sugars with corresponding long-chain carboxylic acid derivatives. Further, the alkylene oxide block copolymers may include block copolymers of ethylene oxide, propylene oxide and/or butylene oxide. Still further, the polyhydroxy and/or polyalkoxy fatty acid derivatives may include polyhydroxy fatty acid amides, N-alkoxy- and/or N- aryloxy-polyhydroxy fatty acid amides, fatty acid amide ethoxylates, and also fatty acid alkanolamide alkoxylates. In one embodiment, the non-ionic surfactant is present in the cleaning formulation in an amount of from .01 to 20% by weight.

In addition to the anionic and/or non-ionic surfactants, the additional surfactant may alternatively include cationic surfactants. Suitable cationic surfactants include, but are not limited to, interface-active compounds including ammonium groups such as alkyldimethylammonium halides and compounds having the chemical formula RR'R"R"'N⁺ X^" wherein R, R', R", and R'" are independently selected from the group of alkyl groups, aryl groups, alkylalkoxy groups, arylalkoxy groups, hydroxyalkyl(alkoxy) groups, and hydroxyaryl(alkoxy) groups and wherein X is an anion. In one embodiment, the cationic surfactant is present in the cleaning formulation in an amount of from 0.01 to 25 percent by weight.

Further, the additional surfactant may include ampholytic surfactants. Suitable ampholytic surfactants include, but are not limited to, aliphatic derivatives of secondary and/or tertiary amines which include an anionic group, alkyldimethylamine oxides, alkyl- and/or

alkoxymethylamine oxides, and combinations thereof. In one embodiment, the ampholytic surfactant is present in the cleaning formulation in an amount of from 0.1 to 25 percent by weight of the cleaning formulation.

Solvent

The cleaning composition may include organic solvents which solubilize hydrophobic materials as well as some of the cleaning components. The solvent is preferably present at a level of from 0% to 10% and preferably from 0.05% to 5% of the composition. Suitable solvents include, but are not limited to, C₁-6 alkanols, Ci-₆ diols, d-io alkyl ethers of alkylene glycols, C₃-₂4 alkylene glycol ethers, polyalkylene glycols, short chain carboxylic acids, short chain esters, isoparafinic hydrocarbons, mineral spirits, alkylaromatics, terpenes, terpene derivatives, terpenoids, terpenoid derivatives, formaldehyde, and pyrrolidones. Alkanols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, and hexanol, and isomers thereof. Diols include, but are not limited to, methylene, ethylene, propylene and butylene glycols. Alkylene glycol ethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, di- or tri-polypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and propionate esters of glycol ethers. Short chain carboxylic acids include, but are not limited to, acetic acid, glycolic acid, lactic acid and propionic acid. Short chain esters include, but are not limited to, glycol acetate, and cyclic or linear volatile methylsiloxanes. Water insoluble solvents such as isoparafinic hydrocarbons, mineral spirits, alkylaromatics, terpenoids, terpenoid derivatives, terpenes, and terpenes derivatives can be mixed with a water soluble solvent when employed.

Additional Adjuncts

The cleaning composition optionally contains one or more of the following adjuncts: stain blocking agents, stain and soil repellants, enzymes, lubricants, insecticides, miticides, anti- allergen agents, odor control agents, fragrances and fragrance release agents, brighteners or fluorescent whitening agents, oxidizing or reducing agents polymers which leave a film to trap or adsorbs bacteria, virus, mite, allergens, dirt, dust, or oil.

The cleaning composition typically will include additional adjuncts. The adjuncts include, but are not limited to, fragrances or perfumes, waxes, dyes and/or colorants, solubilizing materials, stabilizers, thickeners, defoamers, hydrotropes, lotions and/or mineral oils, enzymes, bleaching agents, cloud point modifiers, preservatives, and other polymers. The waxes, when used, include, but are not limited to, carnauba, beeswax, spermacet, candelilla, paraffin, lanolin, shellac, esparto, ouricuri, polyethylene wax, chlorinated naphthaline wax, petrolatu,

microcrystalline wax, ceresine wax, ozokerite wax, and/or rezowax. The solubilizing materials, when used, include, but are not limited to, hydrotropes (e.g. water soluble salts of low molecular weight organic acids such as the sodium and/or potassium salts of xylene sulfonic acid). The acids, when used, include, but are not limited to, organic hydroxy acids, citric acids, keto acid, and the like. Thickeners, when used, include, but are not limited to, polyacrylic acid, xanthan gum, calcium carbonate, aluminum oxide, alginates, guar gum, methyl, ethyl, clays, and/or propylhydroxycelluloses. Defoamers, when used, include, but are not limited to, silicones, aminosilicones, silicone blends, and/or silicone/hydrocarbon blends. Lotions, when used, include, but are not limited to, achlorophene and/or lanolin. Enzymes, when used, include, but are not limited to, lipases and proteases, and/or hydrotropes such as xylene sulfonates and/or toluene sulfonates. Bleaching agents, when used, include, but are not limited to, peracids, hypohalite sources, hydrogen peroxide, and/or sources of hydrogen peroxide.

Preservatives, when used, include, but are not limited to, mildewstat or bacteriostat, methyl, ethyl and propyl parabens, short chain organic acids (e.g. acetic, lactic and/or glycolic acids), bisguanidine compounds (e.g. DANTAGARD and/or GLYDANT) and/or short chain alcohols (e.g. ethanol and/or IPA).

The mildewstat or bacteriostat includes, but is not limited to, mildewstats (including non- isothiazolone compounds) include Kathon GC, a 5-chloro-2-methyl-4-isothiazolin-3-one, KATHON ICP, a 2-methyl-4-isothiazolin-3-one, and a blend thereof, and KATHON 886, a 5- chloro-2-methyl-4-isothiazolin-3-one, all available from Rohm and Haas Company;

BRONOPOL, a 2-bromo-2-nitropropane 1 ,3 diol, from Boots Company Ltd., PROXEL CRL, a propyl-p-hydroxybenzoate, from ICI PLC; NI PASOL M, an o-phenyl-phenol, Na⁺ salt, from Nipa Laboratories Ltd. , DOWICIDE A, a 1 ,2-Benzoisothiazolin-3-one, from Dow Chemical Co. , and I RGASAN DP 200, a 2,4,4'-trichloro-2-hydroxydiphenylether, from Ciba-Geigy A.G.

Antimicrobial Agent

It is also possible to treat the cleaning substrate with antibacterial ingredients. Bactericides or bacteriostatic agents (component (d)), which influence the germ flora and kill off or inhibit the growth of bacteria, may also be present in the formulations. Many biocides are known for decades, such as silver, silver salts, triclosan, chlorohexidene, quaternary ammonium salts, polydimethyldiallylammonium chloride and polyhexamethylen-biguanid compounds. Typical examples are, in particular, phenoxyethanol. 5-Chloro-2-(2,4-dichlorophenoxy)-phenol, which is marketed by BASF SE Ludwigshaven, Germany under the name of Irgasan® (Triclosan) is particularly effective.

Other non-limiting examples would be quaternary compounds that function as antimicrobial agents include benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C₆- C₁₄)alkyl di short chain (Ci_₄ alkyl and/or hydroxyalkl) quaternaryammonium salts, N-(3- chloroallyl) hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride. The quaternary compounds useful as cationic antimicrobial actives are preferably selected from the group consisting of dialkyldimethyl ammonium chlorides, alkyl dimethylbenzylammonium chlorides, dialkylmethylbenzylammonium chlorides, and mixtures thereof. Biguanide antimicrobial actives including, but not limited to polyhexamethylene biguanide hydrochloride, p-chlorophenyl biguanide; 4-chlorobenzhydryl biguanide, halogenated hexidine such as, but not limited to, chlorhexidine (1 , 1 '-hexamethylene-bis-5-(4-chlorophenyl biguanide) and its salts are especially preferred. Typical concentrations for biocidal

effectiveness of these quaternary compounds, especially in the low-surfactant compositions, range from about 0.001 % to about 0.8%

The wipe or cleaning pad can be used for cleaning, disinfectancy, or sanitization on inanimate, household surfaces, including floors, counter tops, furniture, windows, walls, and automobiles. Other surfaces include stainless steel, chrome, and shower enclosures. The wipe or cleaning pad can be packaged individually or together in canisters, tubs, etc. The package may contain information printed on said package comprising a instruction to use the more abrasive side to remove soil followed by using the less abrasive side to wipe the soil away. The wipe or cleaning pad can be used with the hand, or as part of a cleaning implement attached to a tool or motorized tool, such as one having a handle.

EXPERIMENTAL

Preparation of Tertiary-butyl aminoethylmethacrylate homopolymer Example 1

Following the procedure described in Example 1 of U.S. Patent 6,096,800 using

azobisisobutyronitrile (AIBN) initiator and tetrahydrofuran (THF) solvent, a tBAEMA

homopolymer was prepared and characterized by GPC to have a weight average molecular weight (Mw) of 174,000 and a number average molecular weight of 63,000 (polydispersity index Mw/Mn = 2.75).

Example 2

Preparation of high M_w tBAEMA homopolymer with narrow molecular weight distribution by conventional radical polymerization process

40 g of t-butylaminoethyl methacrylate (tBAEMA) monomer (M) and 160 g of tetrahydrofuran (THF) solvent are charged to a 500 mL reactor equipped with overhead condenser and agitator. The reactor content with overhead condenser is heated to 65 °C under agitation and nitrogen sparging for 1 hour. After 1 hour nitrogen sparging and the reaction temperature reaches 65 °C, an initiator solution (I) comprising 0.4 g of AIBN (azobisisobutyronitrile) and 10 g of THF are added to the reactor slowly over about 60 minutes. The reactor is maintained at 70 °C under nitrogen blanket overnight. The reactor content is cooled down to room temperature. The final reaction product is added to 1 L of heptane under agitation. The polymer product is removed by filtration and wash with 300 ml. of fresh heptane. The product is dried in a vacuum oven at 50 °C for 12 hours. The polymer product is analyzed with gel permeation chromatography (GPC) to have a number average molecular weight (Mn) of 54,000 g/mole and a weight average molecular weight (Mw) of 135,000 g/mole using poly(methyl methacrylate) monodisperse molecular weight standards from Polymer Labs. The molecular weight polydispersity index (PDI = Mw/Mn) is 2.62.

Example 3

Preparation of low MW TBAEMA homopolymer with narrow molecular weight distribution by conventional radical polymerization process .

4800 g of tetrahydrofuran (THF) solvent is charged to a 10 L reactor equipped with overhead condenser and agitator. The reactor content with overhead condenser is heated to 65 °C under agitation and nitrogen sparging for 1 hour. After 1 hour nitrogen sparging and the reaction temperature reaches 65 °C, 1200 g of t-butylaminoethyl methacrylate (tBAEMA) monomer (M) and an initiator solution (I) comprising 150 g of AIBN (azobisisobutyronitrile) and 1500 g of THF are added to the reactor slowly over about 180 minutes. The reactor is maintained at reflux temperature under nitrogen blanket and agitation during the M and I feeds and for additional 3 hours after the feeds. Monomer conversion is more than 95% after the polymerization reaction. The reactor content is heated to distill out about 5000 g of solvent. Fresh THF solvent (2000g) is added to the reactor and distillation of solvent out of the reactor is repeated until residual monomer is less than 1 %. The reactor content is cooled down to room temperature. The final solution polymer product contains 75% polymer solids. The polymer product is analyzed with gel permeation chromatography (GPC) to have a number average molecular weight (Mn) of 2,850 g/mole and a weight average molecular weight (Mw) of 6,900 g/mole using poly(methyl methacrylate) monodisperse molecular weight standards from Polymer Labs. The molecular weight polydispersity index (PDI = Mw/Mn) is 2.42.

TABLE 1

Surface Cleaning Substrate Formulations for Wet Wipes

*Dipropylene Glycol n-Propyl Ether

*Glucopon® 425N is an Alkyl

Polyglycoside, C8-16 available from BASF

Corporation

1 and 2. Weight percent of polymer based

on dry weight of substrate.

Note: - Loading ratio is 4:1 by weight ( ratio of total formulation to dry weight of substrate) - Non-woven is a PET/Viscose blend, Item No. 3043059-32.250 from Non-woven Solutions

Preparation of Tertiary-Butylaminoethylmethacrylate Copolymer Abbreviations

M1 is Tertiary-butyl aminoethylmethacrylate (TBAEMA)

M2 is Methyl methacrylate (MMA)

M3 is hydroxyethyl methacrylate

M4 is dimethylaminoethyl methacrylate

M5 is vinylformamide

Example 4

Synthesis of TBAEMA/MMA copolymer

TABLE 2 - Synthesis of Various TBAEMA/MMA copolymers

THF 120 120 120 120

Polvmer purification

Heptane (~ 2.5 liters) (~ 2.5 liters) (~ 2.5 liters) (-2.5 liters)

Procedure

Charge the RC to a 1 L reactor. Heat the reactor content with overhead condenser to 65 °C under agitation and nitrogen sparging for 1 hour. After 1 hour nitrogen sparging and the reaction temperature reaches the reflux temperature (65 °C), start to feed the initiator solution (I) to the reactor uniformly over 45 minutes and the monomer solution over 90 minutes. Maintain the reactor at reflux temperature (65 to 68 °C) under nitrogen blanket and agitation during feeding (M) and (I) and for additional 3 hours after the both feeds are completed. Continue to hold the reaction at reflux temperature (~ 68 °C) for additional 3 hours after both feeds are completed. Heat up and distil out enough solvent out of the reactor to concentrate the reactor content to about 75% polymer solid.

Final product purification: Add (slowly) the final reaction product to at least 5 times (-2.0 L) of heptane under agitation at room temperature (20 °C). The polymer product is removed by filtration or decantation and wash with fresh heptane (0.5L). Dry the product in vacuum oven at 50 °C for 16 hours. The purified products are analyzed for molecular weight by GPC and copolymer composition by NMR.

The copolymers of TBAEMA and a second monomer were essentially synthesized as above (TBAEMA/MMA copolymers) except that the MMA was replaced by hydroxyethyl methacrylate (M3), dimethylaminoethyl methacrylate(M4) or vinylformamide (M5).

TABLE 3- Copolymers of Tertiary-Butyl aminoethylmethacrylate

22/88 12, 100 2.15 8.5

M1/M3 74/26 14,500 2.5 9.6

51/49 12,900 3.87 9.8

32/68 15,800 1.86 9.6

15/85 9,000 3.3 9.8

M1/M4 76/23 15,800 2.01 9.2

66/44 1 1 ,600 2.34 9.4

36/64 82,800 3.13 9.2

27/83 14,200 2.32 9.6

M1/M5 60/40 NA NA 8.8

36/64 NA NA NA

20/80 NA NA (7.8)

9/91 NA NA (8.4)

pH*, *0.1 % aqueous dispersion or solution

Application Examples

Tests are carried out using a non-woven for floor care and cleaning formulations that contained the dirt-attracting polymer of example 3 at concentrations of 0.0074% and 0.02%. The wipes are used to clean vinyl tiles stained with orange juice containing solids (pulp), and the average number of swipes required to remove the stain/ solids is recorded. An internally developed test protocol was used to measure the cleaning ability of these formulations. Tropicana High Pulp orange juice was added in 4 g aliquots to each 4-inch square vinyl tile. A 1" diameter O-ring was used to contain the stain to the middle of the plate during addition of the juice to the tile. Once the stains had dried and set for the desired number of days, the wipes (comprised of the non-woven and the formulations developed) are used to clean the stain tiles on a scrubbing apparatus that applies constant pressure during cleaning strokes.

Objective: Study various co-polymers and of TBAEMA and copolymers of pTBAEMA polymers in improving the dirt pick-up by floor care wipes (wet and dry). TABLE 4-Description of copolymers tested

Evaluation via Wet Floor Wipes

Test Method: Tests are carried out using a non-woven for floor care and cleaning formulations that contain test polymers at test concentrations. The wipes are used to clean vinyl tiles stained with orange juice containing solids (pulp). Tropicana High Pulp orange juice is added in 4 g aliquots to each 4-inch square vinyl tile. A 1 " diameter O-ring is used to contain the stain to the middle of the plate during addition of the juice to the tile. The stains are dried and set for four days at room temperature. Using a Gardener Scrubber (a scrubbing apparatus that applies constant pressure during cleaning strokes), the average number of swipes required to remove the stain/ solids are recorded. The wipes (comprised of the non-woven and the formulations developed) are used to clean the stain tiles. The loading ratio (weight of formulation that is used to impregnate the wipe to the weight of dry wipe) used is 4: 1. Each wipe contains approximately 0.8 mg/1g of dry substrate (or .08 wt. % polymer based on dry weight of substrate).

Results:

TABLE 5-Various formulations of dirt-attracting polymers tested. Base Soln

Formulations Base Soln with Polymer¹

Water qs to 100 qs to 100

Dowanol® DPnP* 1 1

Glucopon® 425N 1.25 1.25

pTBAEMA (2% soln in

Ethanol) 0 1

PH 7 7

*Dipropylene Glycol n-Propyl Ether

Note: - Loading ratio is 4:1.

Non-woven is a PET/Viscose blend, Item No. 3043059-32.250 from Non-woven Solutions 1. Wipes with polymer contain approximately 0.08 wt. % of the active polymer based on the dry weight of the substrate.

TABLE 6-Performance of various polymers tested.

87

68 81.3

129

110

4D 81 106.7

72

70

5A 68 70.0

58

61

5B 60 59.7

62

63

5C 57 60.7

61

73

5D 72 68.7

58

59

6A 61 59.2

54

67

6B 52 57.7

54

61

6C 64 59.7

50

62

6D 61 57.7

Evaluation via Dry Floor Wipes Apparatus and Materials

1. Straight Line Washability Apparatus, Gardner Abrasion Tester

2. 8"x16" Armstrong Excelon Vinyl Composition Tile

3. Spray Head with output of 0.5 ml. per pump

4. Zip Lock Bags 8"x8" or larger

5. Olfa Fabric Rotary Cutter

6. Dritz 24"x36" Gridded Cutting Mat

7. Scrap fabric

8. 3.5"x4" VWR Brand Cat#58540-047 Sponges— 1 hydrated (dry), 2 Dehydrated (dry)

9. U.S. Standard Sieve Series #30, 600 microns

10. Arizona Dirt

Procedure:

Preparation of nonwovens: The nonwoven material is cut into 4.25"x10.5" strips. Two strips for each formulation are placed onto a flat surface, and the formulation is sprayed onto the cut strip using the head of a windex bottle that is unused. A 2% solution of polymer in ethanol is sprayed on to the nonwoven with initial loading ratio kept at 0.5. These nonwovens are left in the hood, so as to evaporate the ethanol. Approximatelyl O mg of active polymer is deposited on 1g of nonwoven. To test the nonwovens, strips are cut in half lengthwise to size 4.25"x5.25".

Preparation of Washability Scrubber and Soil: One 8"x16" Armstrong Excelon Vinyl Composition Tile was placed into the bed of the washability scrubber, and the US Standard Sieve #30, 600 microns was placed over the tile on the arm of the washability scrubber. Two dehydrated 3.5"x4" VWR Brand Cat#58540-047 sponges are placed into the head of the large washability scrubber (weight 280 ± 10 g).

The soil (Arizona Dirt) is weighed to approximately 0.11 grams on a clean watch glass. Using the sieve on the scrubber arm, the soil is gently tapped from the watch glass through the sieve and onto the tile directly above the first socket on the wash ability scrubber arm.

Testing of the Polymer: Arizona Dirt is used to test the effectiveness of the polymers. Each nonwoven is pre-weighed, and the weight recorded. After pre-weighing the nonwoven, the nonwoven is placed directly on top of the soil, ensuring that no extra pressure is exerted. The head of the washability scrubber is placed directly above the treated nonwoven. The head of the scrubber is passed over the soil and tile a single time at a speed of approximately 1 pass/15 seconds. The head of the scrubber is removed from the nonwoven and the nonwoven is picked up, ensuring that no soil excess soil is picked up in the process or soil is lost. The weight of the nonwoven is weighed again to determine the amount of soil picked up on the nonwoven.

This test is performed for each soil multiple times using each polymer, and the results are recorded.

Claims

We claim:

1. A method of removing dirt from a dirt laden hard surface that comprises the steps of a) providing a cleaning substrate wherein the substrate is impregnated or treated with a dirt-attracting polymer comprising the repeat unit of formula I

2. The method according to claim 1 , wherein

R₂ is C1 -C3 alkyl bi-radial.

3. The method according to either claim 1 or 2, wherein

R₂ is C₂ alkyl bi-radical and R is methyl.

4. The method according to any one of the preceding claims, wherein the treated substrate in step c) is a textile, fabric or nonwoven.

5. The method according to claim 4, wherein the treated substrate in step c) is a nonwoven

6. The method according to claims 5, wherein the nonwoven is formed at least partially formed from synthetic polymers which are selected from the group consisting of polyolefin, polyester, polyamide and mixtures thereof, especially polypropylene, polyethylene,

polypropylene/polyethylene copolymers, PET, PET/Viscose blends, PEN, Nylon and the like

7. The method according to either claim 5 or 6, wherein the nonwoven is a dry wipe or a wet wipe.

8. The method according to anyone of the preceding claims, wherein the dirt-attracting polymer comprising the repeat unit of formula (I) is a copolymer and the copolymer is formed from about 5 to about 100 mol %, about 10 to about 90 or about 15 to about 85 mol % of repeat unit "n" and the mol % is based on the total mol % of repeat units of the copolymer.

9. The method according to any one of claims 1 to 7 , wherein the dirt-attracting polymer comprising the repeat unit of formula (I) is a homopolymer.

10. The method according to any one of claims 1 to 8, wherein the dirt-attracting polymer comprising the repeat unit of formula (I) is a copolymer and is formed from 2-tert- butylaminoethyl (meth)acrylate (tBAEMA) and a cationic monomer , a nonionic monomer and/or anionic monomer different than 2-tert- butylaminoethyl (meth)acrylate (tBAEMA).

1 1. The method according to claim 10, wherein the dirt attracting polymer is a copolymer and the cationic monomer is selected from the group consisting of of N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N- diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide,

quaternization products thereof with C₁-C4 -alkyl chlorides, CrC₄-dialkyl sulfates, C₁-C4 - epoxides or benzyl chloride; N-vinylimidazoles, 1-vinyl-2-methylimidazole, 2- and 4- vinylpyridines and quaternized products thereof, allylamine, and dialkyldiallylammonium halides, preferably N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide, more preferably N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N- diethylaminopropyl(meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate, N,N-diethylamino- butyl(meth)acrylate, most preferably N,N-dimethylaminoethyl(meth)acrylate and N,N- diethylaminomethyl(meth)acrylate, and the nonionic monomer is selected from the group consisting of methyl(meth)acrylate, methyl ethacrylate, ethyl(meth)acrylate, ethyl ethacrylate, n- butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate,

2-hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl(meth)acrylate, 3- hydroxypropyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6- hydroxyhexyl(meth)acrylate, (meth)acrylamide, N-methyl(meth)acrylamide, N- ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-(n-butyl)(meth)acrylamide, tert- butyl(meth)acrylamide, N-vinyl formamide and mixtures thereof, preferably 2- hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl(meth)acrylate, 3- hydroxypropyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 6- hydroxyhexyl(meth)acrylate, more preferably 2-hydroxyethyl(meth)acrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate and mixtures thereof and most preferably 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate and 3- hydroxypropyl(meth)acrylate and mixtures thereof;

and the anionic monomer is selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride and mixtures thereof and more preferably acrylic acid, methacrylic acid and mixtures thereof .

12. The method according to claim 1 1 , wherein the copolymer is a polymer formed from formed from 2-tert-butylaminoethyl (meth)acrylate (tBAEMA) and

2-hydroxyethyl(meth)acrylate or N,N-dimethylaminoethyl(meth)acrylate.

13. The method according to anyone of the preceding claims, wherein the dirt-attracting polymer comprising the repeat unit of formula (I) has an weight average molecular weight ranging from about 500 to 10,000,000 g/mole, preferably from about 1000 to about 500,000g/mole, more preferably about 1000 to about 250,000 g/mole, most preferably about 500 to about 100,000 g/mole and especially about 500 to about 30,000.

14. The method according to any of the preceding claims, wherein the dirt-attracting polymer comprises about 0.0001 % to about 3 wt.%, preferably about 0.01 % to about 2.0 wt. %, most preferably about 0.01 to about 1.75 wt. % of the total weight of the dry weight of the substrate.

15. A method of removing dirt from a dirt laden hard surface that comprises the steps of: a) providing a cleaning substrate which comprises an absorbent material; b) applying a liquid cleaning solution onto the dirt laden hard surface or onto the cleaning substrate wherein the liquid cleaning solution comprises a polymer comprising the repeat unit of formula (I) defined in claim 1 ; and c) engaging the dirt laden hard surface in step b) with the cleaning substrate to remove dirt from the dirt laden hard surface.

16. Use of the dirt-attracting polymer defined in any one of claims 1 to 14 in or on a wet or dry cleaning substrate for the purpose of removing dirt from hard surfaces.

17. A nonwoven wipe (wet or dry) comprising about 0.0001 to about 3 wt. % of the dirt- attracting polymer comprising the repeat unit n of formula (I)

(I) wherein R is H or CH₃,

R² is C1-C5 alkyl bi-radical, and n is a number from 3 to 10,000; and the wt. % is based on the dry weight of the substrate, wherein the dirt-attracting polymer is a homopolymer of repeat unit n or a copolymer formed from in addition to repeat unit n, a monomer unit derived from a cationic monomer, anionic monomer or nonionic monomer.

18. The nonwoven wipe according to claim 17, wherein the dirt attracting polymer is a copolymer and the cationic monomer is selected from the group consisting of of N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N- diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide,

quaternization products thereof with C₁-C4 -alkyl chlorides, CrC₄-dialkyl sulfates, Ci-C₄ - epoxides or benzyl chloride; N-vinylimidazoles, 1-vinyl-2-methylimidazole, 2- and 4- vinylpyridines and quaternized products thereof, allylamine, and dialkyldiallylammonium halides, preferably N,N-dimethylaminomethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N- dimethylaminopropyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, N,N- dimethylaminobutyl(meth)acrylate, N,N-diethylaminobutyl(meth)acrylate, Ν,Ν-dimethyl amino- methyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N- diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N- dimethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, N,N- dimethylaminobutyl(meth)acrylamide, Ν,Ν-dimethyl aminobutyl(meth)acrylamide, more preferably N,N-dimethylaminoethyl(meth)acrylate, N,N-diethylaminomethyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, N,N- diethylaminopropyl(meth)acrylate, N,N-dimethylaminobutyl(meth)acrylate, N,N-diethylamino- butyl(meth)acrylate, most preferably N,N-dimethylaminoethyl(meth)acrylate and N,N- diethylaminomethyl(meth)acrylate, and the nonionic monomer is selected from the group consisting of methyl(meth)acrylate, methyl ethacrylate, ethyl(meth)acrylate, ethyl ethacrylate, n- butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate,