RU2575131C2 - Product and pollutant-binding agent for surface purification - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to product for surface purification and versions of cleaning system, containing, at least, part of such product and pollutant-binding agent. Product for surface purification contains pollutant-binding agent. Pollutant-binding agent, contains polymer, with polymer containing two or more monomer units, selected from the group, consisting of: a. non-ionic monomer units, with non-ionic monomer units containing non-ionic hydrophilic monomer unit, with non-ionic hydrophilic monomer unit being derived from acrylamide; b. anionic monomer units, with anionic monomer units being derived from monomers, elected from the group, consisting of monomers, which have, at least, one carboxyl functional group; c. cationic monomer units, with cationic monomer unit, being derived from (3-methacrylamidopropyl)trimethylammonium chloride (NATMAC); and d. zwitterionic monomer units, with zwitterionic monomer units being derived from zwitterionic monomers, selected from the group, consisting of sulphobetaine monomers, phosphobetaine monomers and carboxybetaine monomers. Polymer contains, at least, one monomer unit from group a and, at least, one monomer unit, selected from groups b, c and d. At least part of product demonstrates pollutant adsorption index, at least, 75 mg, as measured in accordance with test method of pollutant adsorption. Polymer contains, at least, 69.9 wt % of monomer unit from group a, with polymer containing not more than 30.1 wt % of monomer unit, selected from group, consisting of group b, group c, group d and their mixtures.

EFFECT: obtaining product for surface purification with improved properties of pollutant adsorption in comparison with known materials.

21 cl, 5 tbl

Description

FIELD OF THE INVENTION

The present invention generally relates to a product and a contaminant binding agent for cleaning surfaces.

State of the art

In the past, cleaning products, such as paper towels, have been widely used in combination with liquid cleaning compositions to clean windows, mirrors, countertops, and other hard surfaces. Known cleaning products usually provide cleaning efficiency primarily due to the absorption of a liquid containing a pollutant, therefore, the cleaning efficiency of known cleaning products is limited by the ability of cleaning products to absorb and retain a liquid containing a pollutant.

Improved removal of contaminants from various surfaces is still an important consumer need. Compositioners have attempted to improve the ability of known cleaning products to remove contaminants by incorporating contaminant binding agents in liquid cleaning compositions. There are known liquid cleaning compositions such as cleaning fluids for spraying which comprise a binding agent pollutant, e.g. Mirapol ^® resin (copolymer of acrylic acid and diquaternary ammonium compound) available from Rhodia, and / or a polyacrylamide polymer such as a polymer Hyperfloc ^®, available from Hychem Inc., and / or polymer Lupasol ^® (polyethyleneimine), available from BASF Corporation, are intended to aid in the removal of contaminants from various surfaces by applying to the surface in liquid form.

One of the problems faced by the compilers is that consumers desire improved contaminant adsorption properties of cleaning products compared to those of known cleaning products.

However, there is still a need for a cleaning product and a pollutant binding agent that have improved adsorption properties of pollutants compared to known materials.

SUMMARY OF THE INVENTION

In accordance with one implementation of the product contains an agent that binds a pollutant. The contaminant binding agent contains a polymer. The polymer contains two or more monomer units selected from the group consisting of nonionic monomer units, anionic monomer units, cationic monomer units, and zwitterionic monomer units. The polymer contains at least one monomer unit selected from group a and at least one monomer unit selected from groups b, c and d. At least a portion of the product has a contaminant adsorption index of at least 75 mg, as measured by the contaminant adsorption test method described in this application.

One solution to the problem outlined above is to provide cleaning systems and / or cleaning products containing a contaminant-binding agent that improves the adsorption properties of the pollutant of the cleaning system and / or cleaning products compared to known cleaning systems and / or cleaning products.

According to another embodiment, the cleaning system comprises at least a part of the article and a contaminating agent. The contaminant binding agent contains a polymer. The polymer contains three or more monomer units selected from the group consisting of nonionic monomer units, anionic monomer units, cationic monomer units and zwitterionic monomer units. The polymer contains at least one monomer unit selected from group a and at least two monomer units selected from groups b, c and d. At least two monomer units are present in the polymer at a molar ratio of from about 3: 1 to about 1: 3.

According to another embodiment, the cleaning system comprises at least a part of the article and a contaminating agent. The contaminant binding agent contains a polymer. The polymer contains two or more monomer units selected from the group consisting of nonionic monomer units, anionic monomer units, cationic monomer units, and zwitterionic monomer units. The polymer contains at least one monomer unit selected from group a and at least one monomer unit selected from groups b, c and d. The polymer has a number average molecular weight of from about 500,000 g / mol to about 2,000,000 g / mol and / or from about 1,000,000 to about 1,500,000 g / mol.

According to another embodiment, the surface cleaning product comprises a contaminating agent. The contaminant binding agent contains a polymer. The polymer contains two or more monomer units selected from the group consisting of nonionic monomer units, anionic monomer units, cationic monomer units, zwitterionic monomer units, and mixtures thereof. The polymer has a contaminant adsorption index of about 40 mg or more, as measured according to the test method of contaminant adsorption described in this application.

Although the description ends with a claim specifically indicating and clearly declaring an object that is considered the present invention, it is believed that the present invention will be more apparent from the following description.

DETAILED DESCRIPTION OF THE INVENTION

I. Definitions

As used in this application, the following terms have the meanings indicated below:

"Anionic monomer", as used in this application, means a monomer that has a total negative charge at pH 7 and / or is identified as an anionic monomer in this application. The anionic monomer is typically bound to one or more cations, such as protons or cations of alkali metals or alkaline earth metals, for example sodium, or cationic groups, such as ammonium.

"Anionic monomer unit", as used in this application, means a monomer unit that has a total negative charge at pH 7 and / or is identified as an anionic monomer unit in this application. The anionic monomer unit may be derived from an anionic monomer. The anionic monomer unit is typically associated with one or more cations, such as protons or cations of alkali metals or alkaline earth metals, for example sodium, or cationic groups, such as ammonium.

“Product” as used in this application means any solid material such as a web, sponge, foam structure, co-molded material or particle. In one example, the article is a dry article. In one example, at least a portion of the product has a bulk of about 150 g / m ² or less and / or about 100 g / m ² or less and / or from about 30 g / m ² to about 95 g / m ² . In one example, the article contains material formed from cotton so that at least a portion of the article has an excess anionic charge.

"Bulk", as used in this application, is the mass per unit area of the sample in g / m ² measured according to the test method of the bulk described in this application.

"Cationic monomer", as used in this application, means a monomer that has a total positive charge at pH 7 and / or is identified as a cationic monomer in this application. The cationic monomer is typically associated with one or more anions, such as chloride ion, bromide ion, sulfonate group and / or methyl sulfate group.

"Cationic monomer unit", as used in this application, means a monomer unit that has a total positive charge at pH 7 and / or is identified as a cationic monomer unit in this application. The cationic monomer unit is typically bound by one or more anions, such as chloride ion, bromide ion, sulfonate group and / or methyl sulfate group.

“Cleaning systems” refers to a product and a contaminating agent. Such cleaning systems may include Swiffer brand products and nozzles.

A “dry article”, as used herein, means that the article contains less than about 30% and / or less than about 20% and / or less than 10% and / or less than 5% and / or less than 3% and / or less than 2% and / or less than 1% and / or less than 0.5% by weight of moisture, as measured according to the test method of moisture content described in this application.

"Fiber" and / or "thread", as used in this application, means an elongated particle having a visible length significantly greater than its visible width, that is, the ratio of length to diameter is at least about 10. In one example, "fiber "Is an elongated particle that has a length of less than 5.08 cm (2 inches) and" thread "is an elongated particle that has a length of more than or equal to 5.08 cm (2 inches).

"Fiber structure", as used in this application, means a structure that contains one or more fibrous filaments and / or fibers. In one example, a fibrous structure in accordance with the present invention means an ordered arrangement of filaments and / or fibers within the structure in order to perform a function. Non-limiting examples of fibrous structures may include paper, fabrics (including woven, knitted and non-woven) and absorbent pads (for example, for diapers or feminine hygiene products).

“Film” refers to sheet-like materials in which the length and width of the material far exceed the thickness of the material. “Hard surface” refers to any kind of surface that can usually be found in and around houses, such as bathrooms, kitchens, basements and garages, such as floors, walls, tiles, windows, countertops, sinks, showers, plastic shower curtains , washbasins, toilets, dishes, equipment and devices, etc., which are made of various materials, such as ceramics, enamel, painted and unpainted concrete, gypsum, brick, vinyl, non-wax vinyl, linoleum, melamine, Formica ^® , glass, any plastics, metals, chrome plated overhnosti and the like. The term "surface", as used in this application, also includes household appliances, including, but not limited to, washing machines, automatic dryers, refrigerators, freezers, ovens, microwave ovens, dishwashers, and so on.

“Hydrophilic” and “hydrophobic”. As used in this application, the term "hydrophilic" is used to refer to surfaces that are wetted by aqueous fluids applied to them. Hydrophilicity and wettability are usually defined in terms of the contact angle and surface tension of the fluids and surfaces involved. This is discussed in detail in the publication of the American Chemical Society, Contact Angle, Wettability and Adhesion, edited by Robert F. Gould (Copyright 1964), which is incorporated herein by reference. A surface is called a wettable aqueous fluid (hydrophilic), when the fluid tends to spread spontaneously over the surface. Conversely, a surface is considered “hydrophobic” if the aqueous liquid does not tend to spread spontaneously over the surface.

The "monomer unit", as used in this application, is a constituent unit (sometimes called a structural unit) of the polymer.

"Non-ionic monomer", as used in this application, means a monomer that does not have a total charge at pH 7 and / or is identified as a non-ionic monomer in this application.

"Non-ionic monomer unit", as used in this application, means a monomer unit that does not have a total charge at pH 7 and / or is identified as a non-ionic monomer unit in this application. A non-ionic monomer unit may be derived from a non-ionic monomer.

"Number-average molecular weight," as used herein, means number-average molecular weight M _n , as determined using gel permeation chromatography in accordance with the protocol given in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pp. 107-121.

“Paper product” refers to any product of a fibrous structure that may, but is not necessarily, contain cellulosic fibers. In one embodiment, paper products in accordance with the present invention include paper products in the form of paper towels.

A "polydispersity index" or "PDI", as used herein, means the ratio of the weight average molecular weight to the number average molecular weight, M _w / M _n , as determined using gel permeation chromatography.

“Sanitary product”, as used in this application, means a soft, low density (i.e., approximately <0.15 g / cm ³ ) web that is useful as a means for wiping after discharge from the bladder and intestines (toilet paper), for otolaryngological secretions (face wipes) and multifunction absorbent and cleaning applications (absorbent towels), and folding sanitary products, such as diapers and / or facial wipes, including folding sanitary products distributed from container, for example, out of the box. The sanitary product may be spirally wound on or without a base to form a roll of the sanitary product.

“Contaminant” means organic or inorganic material, often in the form of particles by nature, which may include dirt, clays, food particles, sebum or oily residue, soot, etc.

A “tissue paper towel product,” as used herein, refers to products containing sanitary paper or paper towel technologies in general, including, but not limited to, conventional dry or wet molded sanitary paper , patterned compacted sanitary paper, starch substrates, and high-volume, non-compacted sanitary paper. Non-limiting examples of sanitary towel products include towels, face wipes, bathroom wipes, table wipes, and the like.

"Cloth", as used in this application, means a fibrous structure or film.

"Weight average molecular weight," as used herein, means weight average molecular weight M _w as determined using gel permeation chromatography according to the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pg. 107-121.

"Zwitterionic monomer", as used in this application, means a monomer that has both a negative and a positive charge on the same monomer at pH 7 and / or is identified as a zwitterionic monomer in this application. The zwitterionic monomer is typically associated with one or more cations, such as protons or cations of an alkali metal or alkaline earth metal, for example sodium, or cationic groups, such as ammonium, and one or more anions, such as chloride ion, bromide ion , sulfonate group and / or methyl sulfate group.

"Zwitterionic monomer unit", as used in this application, means a monomer unit that has both a negative and a positive charge on the same monomer unit at pH 7 and / or is identified as a zwitterionic monomer unit in this application. The zwitterionic monomer unit may be derived from the zwitterionic monomer. The zwitterionic monomer unit is typically associated with one or more cations, such as protons or cations of an alkali metal or alkaline earth metal, for example sodium, or cationic groups, such as ammonium, and one or more anions, such as chloride ion, bromide ion, sulfonate group and / or methyl sulfate group.

II. Polymers and binders

A pollutant binding agent, as described herein, provides improved beneficial effects in binding to pollutants. Such contaminant binding agents can be used alone or in combination with other components to form a cleaning solution. In certain embodiments, such contaminant binding agents may contain polymers. Such polymers can contain several monomer units, so they can be called copolymers, rather than homopolymers, which consist of monomer units of the same type. The polymers in accordance with the present invention can be terpolymers (3 different monomer units). The polymers in accordance with the present invention may be irregular copolymers. In one example, the polymer in accordance with the present invention may be water-soluble and / or dispersible in water, which means that the polymer within at least a certain range of pH and concentration does not form a two-phase composition in water at 23 ° C ± 2, 2 ° C and relative humidity 50% ± 10%.

In one example, the polymers in accordance with the present invention have a number average molecular weight of less than 2,000,000 g / mol and / or less than 1,750,000 g / mol and / or less than 1,700,000 g / mol and / or less than 1,500,000 g / mol and / or more than 500,000 g / mol and / or more than 900,000 g / mol. In another example, the polymers have a number average molecular weight of from about 500,000 to 2,000,000 g / mol and / or from about 900,000 to 1,700,000 g / mol.

In another example, the polymers of the present invention have a contaminant adsorption index of at least 38 mg and / or at least 40 mg and / or at least 42 mg and / or at least , 45 mg, and / or at least 47 mg, and / or at least 50 mg, and / or at least 53 mg, and / or at least 55 mg, and / or at least 57 mg, and / or at least 60 mg, and / or at least 62 mg, as measured according to the test method for the adsorption of a pollutant described in this application.

In yet another example, the polymers in accordance with the present invention have an excess charge (charge density at pH 4.5) of from about -0.1 meq / g and / or from about -0.05 meq / g, and / or from about - 0.02 meq / g, and / or from about 0 meq / g, and / or up to about +0.1 meq / g, and / or up to about +0.09 meq / g, and / or up to about +0 , 08 meq / g, and / or up to about +0.06 meq / g, and / or up to about +0.05 meq / g, and / or up to about +0.02 meq / g, as measured according to the test method charge density described in this application. In yet another example, the polymers in accordance with the present invention exhibits a charge density of from about -0.1 meq / g to about +0.1 meq / g, and / or from -0.05 meq / g to about +0.1 meq / g, and / or from about 0 to less than +0.1 meq / g, and / or to less than +0.09 meq / g, and / or to less than +0.08 meq / g, and / or up to less than +0.06 meq / g, and / or up to less than +0.05 meq / g, as measured according to the test method of charge density described in this application. In one example, the polymers of the present invention exhibit an excess charge (charge density) of from about 0 to about 0.1 meq / g. In another example, the polymers of the present invention exhibit an excess charge (charge density) of about 0.05 meq / g or less.

In another example, the polymers exhibit a polydispersity index of less than 2.5 and / or less than 2.0, and / or less than 1.7, and / or less than 1.5, and / or less than 1.3.

In one example, the polymer in accordance with the present invention contains two or more monomer units selected from the group consisting of: a. nonionic monomer units; b. anionic monomer units; from. cationic monomer units; d. zwitterionic monomer units; and e. mixtures thereof.

The polymers in accordance with the present invention can exhibit a contaminant adsorption index of at least 38 mg, as measured according to the contaminant adsorption test method described in this application.

In one example, the polymers of the present invention are water soluble.

but. Nonionic Monomer Links

Nonionic monomer units can be selected from the group consisting of: nonionic hydrophilic monomer units, nonionic hydrophobic monomer units, and mixtures thereof.

Non-limiting examples of nonionic hydrophilic monomer units suitable for the present invention include nonionic hydrophilic monomer units derived from nonionic hydrophilic monomers selected from the group consisting of: hydroxyalkyl esters of α, β-ethylene unsaturated acids, such as hydroxyethyl or hydroxypropyl acrylates and α-methacrylates, glyceryl monomethacrylate, α, β-ethylene unsaturated amides such as acrylic amide, N, N-dimethylmethacrylamide, N-methylolacrylamide, α, β-ethylene unsaturated monomers bearing a soluble polyoxyalkylene segment of a poly (ethylene oxide) type, such as poly (ethylene oxide) α-methacrylates (Visomer S20W, S10W, etc., from Laporte) or α, ω-dimethacrylates, SIPomer BEM from Rhodia (ω-behenyl polyoxyethylene methacrylate), Sipomer SEM-25 from Rhodia (ω-tristyrylphenylpolyoxyethylene methacrylate), α, β-ethylenically unsaturated monomers that are precursors of hydrophilic units or segments, such as vinyl acetate, which after polymerization can be hydrolyzed to produce vinyl alcohol units or polyvinyl alcohol segments lpirrolidonov, α, β-ethylenically unsaturated monomers ureido type and in particular 2-imidazolidinone etilmetakrilamid (Sipomer WAM II from Rhodia), and mixtures thereof. In one example, a nonionic hydrophilic monomer unit is derived from acrylamide.

Non-limiting examples of nonionic hydrophobic monomer units suitable for the present invention include nonionic hydrophobic monomer units derived from nonionic hydrophobic monomers selected from the group consisting of: vinyl aromatic monomers such as styrene, alpha-methyl styrene, vinyl toluene, vinyl halides, vinylides vinyl chloride, vinylidene chloride, esters C ₁ -C ₁₂ alkyl esters of α, β-monoethylenically unsaturated acids such as methyl, ethyl or butyl acrylates and methacrylates, 2-etilgeksilak ylate, vinyl esters or allyl esters of saturated carboxylic acids, such as vinyl or allyl acetates, propionates, converts, stearates, α, β-monoethylenically unsaturated nitriles containing from 3 to 12 carbon atoms, such as acrylonitrile, methacrylonitrile, α-olefins, such as ethylene, conjugated dienes, such as butadiene, isoprene, chloroprene and mixtures thereof.

b. Anionic Monomer Links

Non-limiting examples of anionic monomer units suitable for the present invention include anionic monomer units derived from anionic monomers selected from the group consisting of: monomers having at least one carboxy functional group, for example, α, β-ethylene unsaturated carboxylic acids or corresponding anhydrides such as acrylic, methacrylic or maleic acids or anhydrides, fumaric acid, itaconic acid, N-methacroylalanine, N-acryloyl glycine and their water-soluble salts, mon measures that are precursors of carboxylate functional groups, such as tert.-butyl acrylate, which, after polymerization, lead to carboxyl functional groups by hydrolysis, monomers having at least one sulfate or sulfonate functional group, such as 2-sulfooxyethyl methacrylate, vinylbenzenesulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sulfoethyl acrylate or methacrylate, sulfopropyl acrylate or methacrylate, and their water-soluble oli, monomers having at least one phosphonate or phosphate functional group, such as vinylphosphonic acid, etc., esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from Rhodia) and phosphates derived from polyoxyalkylene methacrylates, and their water-soluble salts, and 2-carboxyethyl acrylate (CEA), and mixtures thereof. In one example, the anionic monomer unit is derived from an anionic monomer selected from the group consisting of: acrylic acid, AMPS, CEA, and mixtures thereof. In another example, the anionic monomer unit is derived from acrylic acid.

c. Cationic monomer units

Non-limiting examples of cationic monomer units suitable for the present invention include cationic monomer units derived from cationic monomers selected from the group consisting of: N, N- (dialkylamino-ω-alkyl) -amides of α, β-monoethylenically unsaturated carboxylic acids such as N, N-dimethylaminomethylacrylamide or methacrylamide, 2- (N, N-dimethylamino) ethyl acrylamide or methacrylamide, 3- (N, N-dimethylamino) propyl acrylamide or methacrylamide, and 4- (N, N-dimethylamino ) -butylacrylamide or -methacrylamide, α, β-monoethylenically unsaturated ester in amino acids such as 2- (dimethylamino) ethyl acrylate (DMAA), 2- (dimethylamino) ethyl methacrylate (DMAM), 3- (dimethylamino) propyl methacrylate, 2- (tert-butylamino) ethyl methacrylate, 2- (dipentylamino) -ethyl methacrylate and 2- (diethylamino) -ethyl methacrylate, vinyl pyridines, vinylamine, vinylimidazolines, monomers, which are precursors of amine functional groups, such as N-vinylformamide, N-vinylacetamide, which lead to basic amine functional groups by simple acid or basic hydrolysis acryloyl or acryloxy oxymon iynyh monomers such as chloride trimetilammoniypropilmetakrilata, chloride or bromide trimetilammoniyetilakrilamida or methacrylamide, methylsulfate trimetilammoniybutilakrilamida or methacrylamide, methylsulfate trimetilammoniypropilmetakrilamida, (3-methacrylamidopropyl) trimethyl-ammonium chloride (MAPTAC), (3-methacrylamidopropyl) -trimetilammoniymetilsulfat (MAPTA-MES) , (3-Acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyl trimethylammonium chloride or methyl sulfate, and acryloxyethyltrimethylammonium chloride; 1-ethyl-2-vinylpyridinium or 1-ethyl-4-vinylpyridinium bromide, 0 chloride or methyl sulfate; N, N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC); poly-quaternary monomers such as dimethylaminopropyl methacrylamide chloride and N- (3-chloro-2-hydroxypropyl) -trimethylammonium (DIQUAT or DQ) and 2-hydroxy-N ¹ - (3- (2 ((3-methacrylamidopropyl) -dimethylamino) -acetamido ) -propyl) -N ¹ , N ¹ , N ³ , N ³ , N ³ -pentamethylpropane-1,3-diamine chloride (TRIQUAT or TQ) and mixtures thereof. In one example, the cationic monomer unit contains a quaternary ammonium monomer unit, for example, a mono-quaternary ammonium monomer unit, a dicentric ammonium monomer unit, and a tertiary quaternary monomer unit. In one example, the cationic monomer unit is derived from MARTAS. In another example, the cationic monomer unit is derived from DADMAC. In yet another example, the cationic monomer unit is derived from TQ.

In one example, cationic monomer units are derived from cationic monomers selected from the group consisting of: dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, di-tert.-butylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, ethyleneimine, vinylamine, 2-vinylpyridine, 4-vinylpyridine and vinylimidazole and mixtures thereof.

In another example, cationic monomer units are derived from cationic monomers selected from the group consisting of: trimethyl ammonium ethyl (meth) acrylate bromide, -chloride or-methyl sulfate, dimethyl aminoethyl (meth) acrylate benzyl chloride, 4-benzoyl benzyl dimethyl ammonium methyl bromide chloride or α-methyl sulfate, trimethyl ammonium ethyl (meth) -acrylamide bromide, chloride or methyl sulfate, trimethyl ammonium propyl (meth) acrylamide bromide, chloride or methyl sulfate, vinyl benzyl trimethyl ammonium bromide, chloride or dimethyl methyl ammonium chloride, 1-ethyl-2-vinylpyridinium bromide, -chloride or -methyl sulfate, 4-vinylpyridinium bromide, -chloride or -methyl sulfate, and mixtures thereof.

d. Zwitterionic Monomer Links

Non-limiting examples of zwitterionic monomer units suitable for the present invention include zwitterionic monomer units derived from zwitterionic monomers selected from the group consisting of: sulfobetaine monomers, such as sulfopropyl dimethyl ammonium ethyl methacrylate (SPE from Raschig), sulfoprimpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethylpropyl dimethyl -2-vinylpyridinium (SPV from Raschig), 3 - ((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate (SZ), phosphobetaine monomers such as phosphatoethyltrimethylammon yetilmetakrilat, karboksibetainovyh monomers, N- (carboxymethyl) -3-methacrylamido-N, N-dimethyl-propan-1-aminiyhlorida (CZ). In one example, the zwitterionic monomer unit is derived from CZ, SZ, and mixtures thereof.

In one example, the polymer in accordance with the present invention may contain at least one monomer unit selected from groups a (non-ionic monomer units) and b (anionic monomer units) and at least one monomer unit selected from groups c (cationic monomer units) and d (zwitterionic monomer units).

In one example, the polymer contains at least 69.9 wt. % and / or at least 70 wt. % and / or at least 75 wt. % and / or at least 80 wt. % and / or at least 85 wt. %, and / or at least 90 wt. % and / or at least 95 wt. %, and / or at least 98 wt. %, and / or at least 99 wt. % and / or at least 99.5 wt. % monomer unit from group a. The balance of the polymer (total not more than 30.1 wt.% And / or not more than 30 wt.%. And / or not more than 25 wt.% And / or not more than 20 wt.%. And / or not more than 15 wt.% and / or not more than 10 wt.% and / or not more than 5 wt.%, and / or not more than 2 wt.%, and / or not more than 1 wt.% . and / or not more than 0.5 wt.%) contains one or more monomer units selected from groups b, c and d. In one example, the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from about 0.1 wt. % to about 10 wt. % monomer unit from group b, and from about 0.3 wt. % to about 29 wt. % monomer unit from group c. In another example, the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from about 0.5 wt. % to about 30 wt. % monomer units from groups b and c in total.

In one example, the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from about 0.1 wt. % to about 10 wt. % monomer unit from group b, and from about 0.3 wt. % to about 29 wt. % monomer unit from group d. In another example, the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from about 0.5 wt. % to about 30 wt. % of monomer units from groups b and d in total.

In one example, the polymer contains from about 70 wt. % to about 99.5 wt. % of the monomer unit from group a, and a balance of up to 100% contains from about 0.2 wt. % to about 29 wt. % monomer unit from group C, and from about 0.3 wt. % to about 29 wt. % monomer unit from group d. In another example, the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from about 0.5 wt. % to about 30 wt. % of monomer units from groups c and d in total.

In one example, the polymer contains at least 0.1 wt. % and / or at least 1% and / or at least 5 wt. % and / or at least 7 wt. % and / or at least 10 wt. % and / or up to about 25 wt. % and / or up to about 20 wt. % and / or up to about 15 wt. % monomer unit from group b.

In one example, the polymer contains at least 0.1 wt. % and / or at least 0.3 wt. %, and / or at least 1%. and / or at least 5 wt. %, and / or at least 7 wt. % and / or at least 10 wt. %, and / or up to about 75 wt. %, and / or up to about 70 wt. %, and / or up to about 65 wt. %, and / or up to about 55 wt. %, and / or up to about 40 wt. %, and / or up to about 30 wt. %, and / or up to about 25 wt. %, and / or up to about 20 wt. %, and / or up to about 15 wt. % monomer unit from group c.

In one example, the polymer contains at least 0.1 wt. % and / or at least 0.3 wt. %, and / or at least 0.5%, and / or at least 1%, and / or at least 5 wt. %, and / or at least 7 wt. %, and / or at least 10 wt. %, and / or up to about 75 wt. %, and / or up to about 70 wt. %, and / or up to about 65 wt. %, and / or up to about 55 wt. %, and / or up to about 40 wt. %, and / or up to about 30 wt. %, and / or up to about 25 wt. %, and / or up to about 20 wt. %, and / or up to about 15 wt. % monomer unit from group d.

In another example, the polymer contains not more than 30.1 wt. % monomer unit selected from the group consisting of: group b, group c, group d, and mixtures thereof.

In one example, the polymer may contain a monomer unit from group a and a monomer unit from group b.

In one example, the polymer may contain a monomer unit from group a and a monomer unit from group c.

In another example, the polymer in accordance with the present invention may contain a monomer unit from group a and a monomer unit from group d.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group b and a monomer unit from group c.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group b and a monomer unit from group d.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group c and a monomer unit from group d.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group a, a monomer unit from group b, and a monomer unit from group c.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group a, a monomer unit from group b, and a monomer unit from group d.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group a, a monomer unit from group c, and a monomer unit from group d.

In another example, the polymer in accordance with the present invention may contain a monomer unit from group b, a monomer unit from group c, and a monomer unit from group d.

In yet another example, the polymer in accordance with the present invention may contain a monomer unit from group a, a monomer unit from group b, a monomer unit from group c, and a monomer unit from group d.

In one example, the monomer unit from group b and the monomer unit from group c, if present in the polymer, are present in a molar ratio of from about 3: 1 to 1: 3 and / or from about 2: 1 to 1: 2, and / or from about 1.3: 1 to 1: 1.3. and / or about 1: 1 or less, or about 1: 1 or more.

In another example, the monomer unit from group b and the monomer unit from group d, if present in the polymer, are contained in a molar ratio of from about 3: 1 to 1: 3 and / or from about 2: 1 to 1: 2, and / or from about 1.3: 1 to 1: 1.3, and / or about 1: 1 or less, or about 1: 1 or more.

In another example, the monomer unit from group c and the monomer unit from group d, if present in the polymer, are contained in a molar ratio of from about 3: 1 to 1: 3, and / or from about 2: 1 to 1: 2, and / or from about 1.3: 1 to 1: 1.3, and / or about 1: 1 or less, or about 1: 1 or more.

In another example, the polymer contains a monomer unit from group a and a monomer unit from group c. For example, the polymer may comprise an acrylamide monomer unit and a quaternary ammonium monomer unit. The quaternary monomer unit can be selected from the group consisting of: mono-quaternary ammonium monomer units, dicervice quaternary ammonium monomer units, and tertiary quaternary ammonium monomer units. In one example, the polymer may contain at least 69.9 wt. % monomer unit from group a and not more than 30.1 wt. % monomer unit from group c.

In yet another example, the polymer contains a monomer unit from group a and a monomer unit from group b. For example, the polymer may comprise an acrylamide monomer unit and an acrylic acid monomer unit. In one example, the polymer may contain at least 69.9 wt. % monomer unit from group a and not more than 30.1 wt. % monomer unit from group b.

In yet another example, the polymer contains a monomer unit from group b and a monomer unit from group c. For example, the polymer may contain an anionic monomer unit derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, carboxyethyl acrylate and mixtures thereof, and a quaternary ammonium monomer unit. The quaternary ammonium monomer unit may be derived from a quaternary monomer selected from the group consisting of: mono-quaternary ammonium monomer units, dicentric ammonium monomer units, tertiary quaternary ammonium monomer units, and mixtures thereof. In one example, the polymer contains an anionic monomer unit derived from acrylic acid and a quaternary ammonium monomer unit derived from MARTAS. In one example, the polymer may contain no more than 25 wt. % monomer unit from group b and not more than 75 wt. % monomer unit from group c.

In another example, the polymer contains a monomer unit from group a, a monomer unit from group b, and a monomer unit from group c. For example, the polymer may contain an acrylamide monomer unit and an anionic monomer unit derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, carboxyethyl acrylate and mixtures thereof, and a quaternary ammonium monomer unit . The quaternary ammonium monomer unit may be derived from a quaternary monomer selected from the group consisting of: mono-quaternary ammonium monomer units, dicentric ammonium monomer units, tertiary quaternary ammonium monomer units, and mixtures thereof. In one example, the polymer comprises a nonionic monomer unit derived from acrylamide, an anionic monomer unit derived from acrylic acid, and a cationic monomer unit derived from MARTAC. In another example, the polymer comprises a nonionic monomer unit derived from acrylamide, an anionic monomer unit derived from acrylic acid, and a cationic monomer unit derived from DADMAC. In yet another example, the polymer comprises a nonionic monomer unit derived from acrylamide, an anionic monomer unit derived from acrylic acid, and a cationic monomer unit derived from TQ. In another example, the polymer contains a non-ionic monomer unit derived from acrylamide, an anionic monomer unit derived from CEA, and a cationic monomer unit derived from MARTAS. In yet another example, the polymer comprises a nonionic monomer unit derived from acrylamide, an anionic monomer unit derived from AMPS, and a cationic monomer unit derived from MARTAS. In one example, the polymer may contain at least 69.9 wt. % monomer unit from group a and not more than 30.1 wt. % monomer units from groups b and c in total. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from 0.1 wt. % to about 30 wt. % monomer unit from group b, and from about 0.1 wt. % to about 30 wt. % monomer unit from group c. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a and from about 0.5 wt. % up to 30 wt. % monomer units from groups b and c in total.

In another example, the polymer contains a monomer unit from group a, a monomer unit from group c, and a monomer unit from group d. For example, the polymer may contain an acrylamide monomer unit, a quaternary ammonium monomer unit, and a zwitterionic monomer unit selected from the group consisting of: CZ, SZ, and mixtures thereof. The quaternary ammonium monomer unit may be derived from a quaternary monomer selected from the group consisting of: mono-quaternary ammonium monomer units, dicentric ammonium monomer units, tertiary quaternary ammonium monomer units, and mixtures thereof. In one example, the polymer comprises a nonionic monomer unit derived from acrylamide, a cationic monomer unit derived from MARTAS, and a zwitterionic monomer unit derived from CZ. In another example, the polymer comprises a nonionic monomer unit derived from acrylamide, a cationic monomer unit derived from MARTAS, and a zwitterionic monomer unit derived from SZ. In one example, the polymer may contain at least 69.9 wt. % monomer unit from group a and not more than 30.1 wt. % combined monomer units from groups c and d. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from 0.1 wt. % to about 30 wt. % monomer unit from group C, and from about 0.1 wt. % to about 30 wt. % monomer unit from group d. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a and from about 0.5 wt. % up to 30 wt. % combined monomer units from end groups.

In another example, the polymer contains a monomer unit from group a, a monomer unit from group b, and a monomer unit from group d. For example, the polymer may contain an acrylamide monomer unit, an anionic monomer unit derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, carboxyethyl acrylate and mixtures thereof, and a zwitterionic monomer unit selected from the group consisting of CZ, SZ and mixtures thereof. In one example, the polymer comprises a nonionic monomer unit derived from acrylamide, an anionic monomer unit derived from acrylic acid, and a zwitterionic monomer unit derived from CZ. In another example, the polymer comprises a non-ionic monomer unit derived from acrylamide, an anionic monomer unit derived from acrylic acid, and a zwitterionic monomer unit derived from SZ. In one example, the polymer may contain at least 69.9 wt. % monomer unit from group a and not more than 30.1 wt. % of monomer units from groups b and d in total. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from 0.1 wt. % to about 30 wt. % monomer unit from group b, and from about 0.1 wt. % to about 30 wt. % monomer unit from group d. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a and from about 0.5 wt. % up to 30 wt. % of monomer units from groups b and d in total.

In yet another example, the polymer contains a monomer unit from group a and a monomer unit from group d. For example, the polymer may contain an acrylamide monomer unit and a zwitterionic monomer unit selected from the group consisting of CZ, SZ and mixtures thereof. In one example, the polymer comprises a nonionic monomer unit derived from acrylamide and a zwitterionic monomer unit derived from CZ. In another example, the polymer contains a nonionic monomer unit derived from acrylamide and a zwitterionic monomer unit derived from SZ. In one example, the polymer may contain at least 69.9 wt. % monomer unit from group a and not more than 30.1 wt. % monomer unit from group d. In another example, the polymer may contain from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from 0.5 wt. % to about 30 wt. % monomer unit from group d.

In one example, the polymer of the present invention comprises a nonionic hydrophilic monomer unit. Non-limiting examples of suitable hydrophilic monomer units are derived from nonionic hydrophilic monomers selected from the group consisting of: hydroxyalkyl esters of α, β-ethylene unsaturated acids, α, β-ethylene unsaturated amides, α, β-ethylene unsaturated monoalkylamides, α , β-ethylene-unsaturated dialkylamides, α, β-ethylene-unsaturated monomers bearing a water-soluble polyoxyalkylene segment of a poly (ethylene oxide) type, α, β-ethylene-unsaturated monomers that are precursors of hydrophilic units or segments, vinylpyrrolidones, α, β-ethylene unsaturated monomers of the ureide type, and mixtures thereof. In one example, a nonionic hydrophilic monomer unit is derived from acrylamide.

In another example, the polymer in accordance with the present invention contains a nonionic hydrophobic monomer unit. Non-limiting examples of acceptable non-ionic hydrophobic monomer units come from non-ionic hydrophobic monomers selected from the group consisting of: vinyl aromatic monomers, vinyl halides, vinylidene halides, C ₁ -C ₁₂ alkyl esters of α, β-monoethylenically unsaturated acids, saturated vinyl esters of saturated carbon esters, allyl esters of saturated carboxylic acids, α, β-monoethylenically unsaturated nitriles containing from 3 to 12 carbon atoms, α-olefins, conjugated dienes and mixtures thereof.

In one example, the polymer contains an anionic monomer unit. Non-limiting examples of suitable anionic monomer units are derived from anionic monomers selected from the group consisting of: monomers having at least one carboxy functional group, for example, α, β-ethylene unsaturated carboxylic acids or the corresponding anhydrides, monomers that are precursors carboxylate functional groups, monomers having at least one sulfate or sulfonate functional group, monomers having at least one phosphonate or phosphate functional group, esters of ethylenically unsaturated phosphates and mixtures thereof. In one example, the anionic monomer unit is derived from an anionic monomer selected from the group consisting of: acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, carboxyethyl acrylate, and mixtures thereof.

In one example, the polymer contains a cationic monomer unit. Non-limiting examples of suitable cationic monomer units are derived from cationic monomers selected from the group consisting of: acryloyl or acryloxy ammonium monomers, 1-ethyl-2-vinylpyridinium or 1-ethyl-4-vinylpyridinium bromide, -chloride or -methyl sulfate, N, N dialkyl diallylamine monomers, poly-quaternary monomers, N, N- (dialkylamino-ω-alkyl) -amides of α, β-monoethylenically unsaturated carboxylic acids, α, β-monoethylenically unsaturated esters of amino acids, vinyl pyridines, vinylamine, vinyl imidazones, m yavl are precursors of amine functional groups which lead to primary amine functional groups by a simple acid or base hydrolysis, and mixtures thereof. In one example, the cationic monomer unit is derived from MARTAS. In another example, the cationic monomer unit is derived from DADMAC. In another example, the cationic monomer unit is derived from 2-hydroxy-N ¹ - (3- (2 - ((3-methacrylamidopropyl) dimethylamino) acetamido) propyl) -N ¹ , N ¹ , N ³ , N ³ , N ³ -pentamethylpropane-1,3-diaminium chloride.

The method of producing polymers

The polymers in accordance with the present invention can be obtained by any suitable method known in the art. For example, a polymer can be prepared by radical polymerization.

The polymers in accordance with the present invention can be obtained by a wide variety of methods, including bulk, in solution, emulsion or suspension polymerization. Polymerization methods and methods are described generally in Encyclopedia of Polymer Science and Technology, Interscience Publishers (New York), Vol. 7, pp. 361-431 (1967), and Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol. 18, pp. 740-744, John Wiley & Sons (New York), 1982, both incorporated herein by reference. See also Sorenson, W.P. and Campbell, T.W., Preparative Methods of Polymer Chemistry. 2nd edition, Interscience Publishers (New York), 1968, pp. 248-251, incorporated by reference in this application for general reaction methods acceptable to the present invention. In one example, polymers are prepared by free radical copolymerization using water-soluble initiators. Suitable free radical initiators include, but are not limited to, thermal initiators, redox pairs, and photochemical initiators. Redox and photochemical initiators can be used for polymerization processes that begin at temperatures below about 30 ° C (86 ° F). Such initiators are generally described in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, John Wiley & Sons (New York), Vol. 13, pp. 355-373 (1981), incorporated by reference in this application. Typical water-soluble initiators that radicals can provide at 30 ° C or lower include redox pairs such as potassium persulfate / silver nitrate and ascorbic acid / hydrogen peroxide. In one example, the method uses thermal initiators in a polymerization process that is conducted at a temperature above 40 ° C (104 ° F). Water soluble initiators that can provide radicals at 40 ° C (104 ° F) or higher can be used. These include, but are not limited to, hydrogen peroxide, ammonium persulfate, and 2,2′-azobis- (2-amidinopropane) dihydrochloride. In one example, the water-soluble starting monomers are polymerized in an aqueous-alcoholic medium at 60 ° C (140 ° F) using 2,2′-azobis (2-amidinopropane) dihydrochloride as an initiator. The solvent should typically contain at least about 10% by volume of alcohol to prevent gelation of the polymerization reaction medium. Suitable alcohols for use in such a reaction include low molecular weight alcohols, such as, but not limited to, methanol, ethanol, isopropanol and butanol.

Another method is solution polymerization, as described in US Pat. No. 3,317,370 to Kekish, issued May 2, 1967 and US Patent No. 3,410,828 to Kekish, issued November 12, 1968, which are incorporated herein by reference. According to this method, acrolein, or another aldehyde monomer, is copolymerized with a non-nucleophilic, water-soluble, nitrogen-heterocyclic polymerizable monomer in the presence of a redox initiator system. The copolymer is then converted to cationic form by reacting the copolymer with a water-soluble amine or amine quaternary derivative. Suitable amines, including amine quaternary derivatives, include, but are not limited to, primary, secondary, and tertiary amines such as ethylenediamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, or partially or fully quaternized derivatives of any of the foregoing, hydrazides and their quaternary derivatives such as betainhydrazide chloride, N, N-dimethylglycine hydrazide, asymmetric dimethyl hydrazides, polymers, for example, formed by the interaction of urea and polyalkylene polyamide ins, guanidines, biguanides, guanylureas, mono- and polyhydroxypolyamines and their quaternary derivatives, etc. When using this emulsion copolymerization method, it will be necessary to control the molecular weight within the ranges presented in this application.

In one example, a method for producing a polymer in accordance with the present invention includes the steps of:

i. provide two or more monomer units selected from the group consisting of:

a. nonionic monomer units;

b. anionic monomer units;

c. cationic monomer units;

d. zwitterionic monomer units; and

e. mixtures thereof; and

ii. two or more monomer units are polymerized in such a way that a polymer is obtained which exhibits a contaminant adsorption index of at least 38 mg, as measured by the contaminant adsorption test method described herein. In one example, the polymerization step includes a step in which two or more monomer units or monomers from which they are prepared are mixed with water to form a monomer solution, and the monomers are polymerized to form a polymer solution. The monomer solution and / or the polymer solution may be deoxygenated. Additionally, the monomer solution and / or the polymer solution can be subjected to temperature (heated) at least 25 ° C, for example 60 ° C. The temperatures used to form the polymer can be any suitable temperature in order to produce the polymer in accordance with the present invention. The monomer solution and / or the polymer solution can be exposed to this temperature for a time sufficient to polymerize the monomer units into the polymer, for example at least 10 minutes, and / or at least 18 hours, depending on the reaction conditions. An initiator, such as a free radical initiator, may be added to the monomer solution and / or polymer solution to polymerize the monomer units (monomers) in the monomer solution to form a polymer in accordance with the present invention. The levels of free radical initiator (s) used to produce the polymer can be any acceptable level in order to produce the polymer of the present invention. The levels of the various monomer units (monomers) used to make the polymer can be any acceptable level in order to make the polymer in accordance with the present invention.

Non-limiting Synthesis Examples

Sample Retrieval

Obtaining a solution of initiator

10 ml of water was added to a flask with 1 gram of 2,2′-azobis- (2-methylpropionamidine) dihydrochloride (available from Wako Chemicals), referred to herein as V-50. This solution was purged with gaseous argon to remove oxygen.

Monomer production

Synthesis of 2-hydroxy-N ¹ - (3- (2 - ((3-methacrylamidopropyl) -dimethylammonio) -acetamido) propyl) -N ¹ , N ¹ , N ³ , N ³ , N ³ -pentamethylpropane-1,3 -diaminium chloride (referred to in this application as TQ)

340.6 grams of dimethylaminopropyl methacrylamide (DMAPMA, available from Sigma-Aldrich), 238.8 grams of methyl chloroacetate (available from Sigma-Aldrich), 0.5 grams are placed in a round bottom flask with a jacket equipped with a mechanical stirrer, gas inlet, refrigerator and thermometer. 4-methoxyphenol (available from Sigma-Aldrich) and 423 grams of methanol (available from Sigma-Aldrich). The round bottom flask was heated at 70 ° C for 5 hours. The reaction was cooled to room temperature and then 0.5 grams of 4-methoxyphenol (available from Sigma-Aldrich) and 225 grams of dimethylaminopropylamine (available from Sigma-Aldrich) were added uniformly over 2 hours. After 2 hours, the reaction mixture was heated to 65 ° C for 2 hours, after which methanol was distilled off at 50 ° C in vacuo. To this was added 690 grams of (3-chloro-2-hydroxypropyl) -trimethylammonium chloride (available as a 60% aqueous solution from Sigma-Aldrich). The temperature is maintained at 65-70 ° C for 2 hours. During these 2 hours, methanol was distilled off and water was added to obtain a 55% aqueous solution by weight. The reaction is continued in water at 65-70 ° C for another hour to obtain a TQ monomer.

Synthesis of 3 - ((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate (referred to in this application as SZ)

26.4 grams of anhydrous acetonitrile (available from Sigma-Aldrich) and 15.5 grams of propanesultone (available from Sigma-Aldrich) were placed in a round bottom flask and stirred for 30 minutes. After 30 minutes, add a solution of 25.6 grams of DMAPMA in 56.5 grams of acetonitrile. The mixture is stirred and heated to 35 ° C. A white precipitate forms quickly. After the white precipitate has taken up the volume of the flask, the liquid is decanted. The solid is washed once with acetonitrile and again the liquid is removed by decantation. The solids are then washed with a double volume of diethyl ether. Then they are filtered through a funnel and washed abundantly on the filter with diethyl ether. The NMR structure is consistent with the structure of the target SZ molecule.

Synthesis of N- (carboxymethyl) -3-methacrylamido-N, N-dimethylpropane-1-aminium chloride (referred to in this application as CZ)

16.5 grams of methyl bromoacetate (available from Sigma-Aldrich), 74 grams of tetrahydrofuran (THF, available from Sigma-Aldrich) and 16.5 grams of DMAPMA are placed in a round bottom flask. The solution was stirred for 16 hours at 25 ° C and then stirring was stopped. After delamination, the top layer of THF is discarded. The bottom layer is washed with 50 ml of hexane (available from Sigma-Aldrich) twice and it becomes a viscous material. The material is then dissolved in 15 ml of methanol (available from Sigma-Aldrich) and precipitated with 150 ml of diethyl ether (available from Sigma-Aldrich). The precipitate is washed several times with diethyl ether until it becomes a viscous semi-solid. It is then dried overnight in high vacuum at room temperature. A small portion is selected for NMR analysis. The remaining intermediate is placed in a glass desiccator containing calcium chloride, until the next step.

3.3 grams of the intermediate obtained above is dissolved in 10 ml of deionized water and passed through a column consisting of 50 ml of Dowex Marathon A hydroxide ion exchange resin (available from VWR Scientific) in a 2.5 cm diameter glass column at 2.7 ml / min The effluent was collected and 13 ml of 1N hydrochloric acid (available from Sigma-Aldrich) was added. The water is dried in vacuo at room temperature. The sample was then dried overnight under high vacuum at room temperature. Material is removed from vacuum and a small portion is taken for NMR analysis. 2.71 g of deionized water is added to the material to form the finished product CZ, which is stored as a solution in water.

Polymer Production

Monomers in the amounts listed for the examples in Table 1 below and 456 g of water are placed in the reaction vessel. Monomers - acrylamide (referred to as AAM in this application), acrylic acid (referred to as AA in this application), diallyldimethylammonium chloride (referred to as DADMAC in this application), 2-carboxyethyl acrylate (referred to as CEA in this application), 2-acrylamido-2-methylpropanesulfonic acid ( referred to in this application as AMPS) and [3- (methylacryloylamino) propyl] trimethylammonium chloride (referred to as MAPTAC in this application), all available from Sigma Aldrich. MAPTAC is used as a solution in a concentration of 50 wt. % TQ, SZ and CZ are used as described above. The reaction vessel is purged with nitrogen to remove oxygen from the system and a nitrogen atmosphere is maintained in the vessel. The reaction vessel and contents are heated to a temperature of 60 ° C.

After the temperature of the contents has reached 60 ° C, 1 ml of the V-50 initiator solution obtained as described above is added as a 10% solution (except for Example 1.17, where 0.0562 g of pure V-50 is used). The reaction was maintained at 60 ° C for 48 hours.

The following tables represent non-limiting examples of polymers that have been prepared in accordance with the present invention.

Test methods

Determination of the percentage of solids

An empty weighing tray (VWR disposable aluminum corrugated cups with pendants, VWR catalog No. 25433-010; or equivalent tray) was weighed to an accuracy of ± 0.1 mg (Weight _Tray ). An aliquot of a polymer solution, for example, a polymer solution obtained as described above, 2.5 ± 0.5 grams, was placed in a tray and weighed to the nearest ± 0.1 mg (Mass _{Tray + Polymer solution} ). An open polymer tray was placed in a ventilated oven at 80 ° C. for 12 hours. After cooling to room temperature, the tray and polymer solids were then weighed to an accuracy of ± 0.1 mg (Mass _{Tray + Polymer solid} ). The percentage of solids was calculated as follows:

Obtaining a 0.02% polymer solution

When using the amounts indicated in Table 2, the polymer solutions obtained above must be diluted to a solids content of 0.02% deionized water, and any other polymer solution intended for testing in which more than 0.02% solids must be diluted deionized water to 0.02% solids using the following equation:

If the polymer solution contains less than 0.02% solids, then dilution is not necessary.

Weigh the receiving vessel large enough to hold the diluted solution. The desired amount of the starting polymer solution is placed in the receiving vessel and the mass (solution only) is recorded with an accuracy of ± 1 mg (Mass _{Polymer solution} ). The polymer solution is then diluted to 0.02% with deionized water and the mass is recorded with an accuracy of ± 0.01 g (Mass _{Polymer solution + water} ). The diluted solutions are closed and allowed to settle for 24 hours, stirring from time to time until use to ensure dissolution of the polymers. The concentration is calculated as follows:

Determination of the molecular weight of the polymer

The molecular weight of the polymer is determined using GPC SEC / MALS. HPLC is a Waters Alliance 2695 auto-injector HPLC equipped with a battery of two µStyragel HT linear speakers at room temperature. The flow rate is 1.0 ml / min., And the mobile phase is dimethyl sulfoxide (DMSO) with 0.1% (w / v) LiBr. The detectors are a Wyatt Dawn EOS light scattering detector calibrated with toluene and normalized with 25 K dextran in the mobile phase, and a Wyatt Optilab rEX refractive index detector at 30 ° C.

Samples for analysis were obtained at a known concentration in the range from 1 to 5 mg / ml. Samples were filtered using 0.2 μm polypropylene membrane filters. The injection volume is 100 μl. Data was collected and analyzed using ASTRA 5.3.4.14. Values for dn / dc were calculated from RI traces, assuming 100% mass recovery. The number average molecular weight and polydispersity index are calculated and reported.

Receiving a processed product

Rectangular 3.00 × 4.00 inches pieces of commercial products (see description below) were obtained using a 3 × 4 inch die cutter, resulting in samples having a bulk of 19 g / m ² to 33 g / m ² for sheets of handmade paper less than or equal to 100 g / m ² for paper towels, paper towels, napkins, sponges, floor nozzles removed from mops, and for a cleaning (contacting the surface) base and / or not contacting the surface the basis of other multilayer cleaning systems, and less than or equal to 150 g / m ² for samples mainly made of cotton, such as gauze, cotton pads and rags (samples outside this range are discarded). For paper towels, at least the first and last 5 towels are discarded, as they may be contaminated with glue, which is commonly used to bond paper towels. Samples of paper towels are cut so that the perforations between the towels are perpendicular to the 4-inch wide section. Samples of paper towels are cut so that they are free of perforations. Samples of napkins are cut without first unwrapping napkins, thereby preserving the original layer of the sample. For mops and other multi-layer cleaning systems, a base that contacts the floor or surface to be cleaned is removed and used as a test sample. In the case when the substrate is hydrophobic, the next adjacent layer (s) (different g / m ²⁾ can also be used in conjunction with a base floor. The Swiffer WetJet Refills nozzle is cut along the outer edges. The upper base web and the adjacent core layer are discarded, and the floor nozzle base and the adjacent core layer are used. Clorox Ready Mop Mop Absorbers are also cut along the outer edges. All other layers, with the exception of the base of the floor nozzle, are discarded. Any sample that is pre-moistened is first air dried before being cut, except for sponges. The sponge is slightly moistened and cut using a Berker Deli slicer (model 823 E, South Bend, Indiana) set at a thickness level of 2.5, after which a 3x4 inch rectangle is cut out (resulting in a mass of 0.58 g ± 0 15 g after conditioning at a temperature of 70 ° F ± 2 ° F and a relative humidity of 50% ± 2% for at least 2 hours, preferably overnight). All samples were obtained from a portion of the test material spaced at least 0.5 inches from any edges.

Samples mentioned above are marked with the name of the sample using a ballpoint pen or equivalent marker. Samples are conditioned at a temperature of 70 ° F ± 2 ° F and a relative humidity of 50% ± 2% for at least 2 hours, preferably overnight. After conditioning, each of the samples is weighed to an accuracy of ± 10 mg (mass _basis ) while maintaining the conditioning conditions. The rest of the work is performed in the laboratory at a temperature of 73 ° F ± 3.5 ° F and relative humidity <70%. The sample is placed on a grate (23.75 x 47.75 inches polystyrene light panel manufactured by Plaskolite, Inc., Columbus, Ohio, available from Home Depot as model No. 1425005A, or equivalent grating).

If the sample has been pretreated, it can be tested without further adding any polymer solution or water. Thus, a 3 × 4 inch piece is simply cut out of the sample.

If the sample has not been pretreated with a polymer solution, the sample is treated with a total of 3.8 ml (in 1-4 aliquots to avoid oversaturation if necessary) of a polymer solution containing 0.02% solids obtained as described above or the polymer solution that is tested contains less than 0.02% solids, the total amount of polymer solution that must be added to each sample (in 1-4 aliquots to avoid supersaturation if necessary) is determined using the following equation :

The polymer solution is then applied only to the upper (processed) side of the entire sample. Between aliquots, time (at least 1.5 hours) is given to allow the sample to partially dry. After applying the entire polymer solution, the samples are allowed to air dry for at least 4 hours, usually overnight on a wire rack.

When evaluating the index of adsorption of the pollutant, manifested only by the polymer, a sheet of paper of manual casting is used as the basis.

A. Scott Paper Towels Mega Roll Choose-a-Size, Kimberly-Clark, Neenah, Wisconsin (6 rolls, 102 paper towels per roll, 1 layer, 11.0 x 7.3 inches, available from Walmart).

B. White paper towels by Bounty, manufactured by Procter & Gamble, Cincinnati, Ohio (1 roll, 52 sheets per roll, 2-ply, 11 × 11 inches, available from Walmart).

C. Kleenex Viva Paper Towel White Big Roll, Kimberly-Clark, Neenah, Wisconsin (1 roll, 59 sheets, 1-ply, 11 x 10.4 inches, available from Walmart).

D. Bounty white quilted wipes from Procter & Gamble, Cincinnati, Ohio (1 pack, 220 wipes, 1 ply, 12.1 x 12 inches, available from Walmart).

E. Swiffer Sweeper wet mop inserts manufactured by Procter & Gamble, Cincinnati, Ohio (12 wet fabric inserts, 10 × 8 inches, available from Walmart).

F. Swiffer WetJet insert nozzles manufactured by Procter & Gamble, Cincinnati, Ohio (24 cleaning nozzles available from Walmart).

G. Clorox Ready Mop Absorbent Nozzle Nozzles, manufactured by Clorox Company, Oakland, California (16 liner tips, 8.5 × 11.5 inches, available from Walmart).

H. O-Cel-O sponge, manufactured by 3M (3 sponges, 5.9 × 3.0 × 0.9 inches, available from Walmart).

I. Lysol Sanitizing Wipes, Citrus Fragrance, manufactured by Reckitt Benckiser (35 wet wipes, 7 × 8 inches, available from Walmart).

J. Clorox Sanitizing Wipes, Lemon Freshness, manufactured by The Clorox Company, Oakland, California (35 wet wipes, 7 × 8 inches, available from Walmart).

K. Napkins for various surfaces Clean Wipe, manufactured by Procter & Gamble, Cincinnati, Ohio (62 pre-moistened wipes, 7 × 8 inches are available at http://www.amazon.com/Mr-Clean-Multi-surface-Disinfecting-62-Count/dp/B000UD09JO )

L. Glass and surface wipes Windex Original, manufactured by SC Johnson & Son, Racine, Wisconsin (28 pre-wetted wipes, 7 × 10 inches, available from Walmart).

M. Pampers Sensitive Baby wipes manufactured by Procter & Gamble, Cincinnati, Ohio (1 box, 64 wipes, 7 × 7 inches, available from Walmart).

N. Huggies Sensitive Baby Wipes manufactured by Kimberly-Clark, Neenah, Wisconsin (1 box, 64 wipes, 7.7 × 6.7 inches, available from Walmart).

A. Clorox Handi Wipes, manufactured by The Clorox Company, Oakland, California (6 wipes, 21 × 11 inches, available from Krogers).

P. Shout color preserving agent, manufactured by SC Johnson & Son, Racine, Wisconsin (24 sheets, 9.8 x 4.7 inches, available from Walmart).

Q. VWR Gauze Wipes, manufactured by Fisher Scientific (100% cotton, white, 200, 4 x 4 inch packs, available from VWR No. 21910-107).

R. VWR cotton pads distributed by VWR International (100% cotton, 100, 4 x 4-inch pack, available from VWR No. 21902-985).

S. Mainstays dust bags distributed by Walmart (100% cotton, white, 5 packs, 28 × 29 inches, available from Walmart).

T. Sheets of paper of a manual ebb - as received below.

Obtaining a sheet of paper for manual casting - In order to test the adsorption properties of a contaminant of a material such as a polymer, a sheet of paper for manual casting is prepared as follows and then used in the test method for the adsorption of a pollutant described above.

A sheet of handmade paper is a hand made sample of the fibrous structure. Sheets of handmade paper are obtained with a target bulk of 26.8 g / m ² but not less than 19 g / m ² and not more than 33 g / m ² using the following procedure.

but. Pulp Preparation — A Northern Softwood Kraft (NSK) cellulosic suspension is prepared as follows. Using an analytical balance capable of weighing with an accuracy of ± 0.0002 g, 30 g of dry pulp NSK is weighed. The mass of dry pulp NSK is fixed. The percentage of absolutely dry pulp or mass consistency is recorded. Place 500 ml of water in Cincinnati, Ohio (or equivalent, having the following properties: total hardness = 155 mg / L per CaCO ₃ ; calcium content = 33.2 mg / L; magnesium content = 17.5 mg / L; phosphate content = 0.0462) with a temperature of 23 ± 2 ° C in a 2000 ml polypropylene glass. Add suspended NSK dry pulp to the water in the glass immediately after adding water to the glass. After the NSK pulp is completely wetted (approximately 50-60 seconds), remove it from the beaker and manually tear it into small pieces of approximately 2 cm ² or less. Place small pieces of wet NSK pulp back into the glass in a glass. The wet pulp is soaked in water for at least 1 hour, usually 1-2 hours. At the end of the soaking period, transfer the contents of the beaker (water and pulp) to the disintegrator tank of the pulp disintegrator, which is commercially available from Testing Machines, Inc. under the trademark 73-18 Pulp Disintegrator, or equivalent. Follow manufacturer's instructions for operating, calibrating, and cleaning the disintegrator, as needed. The disintegrator must comply with the TAPPI T-205 Standard. Using additional water from Cincinnati, Ohio (or equivalent water as described above), supplied in a polyethylene rinse bottle, wash the remaining pulp and stick to the glass and remove it into a disintegrator tank. An additional amount of water from Cincinnati, Ohio (or equivalent water as described above) is added to the disintegrator tank, giving a total of 1,500 ml of total volume in the disintegrator tank.

Next, place a disintegrator tank containing pulp and water in Cincinnati, Ohio (or equivalent water, as described above) with a temperature (23 ± 2 ° C), on the platform of the disintegrator and place it under the shaft and impeller blade of the disintegrator. Fix the disintegrator tank tightly in its place on the platform of the disintegrator. Lower the impeller blade to its original position and fix it in place in accordance with the manufacturer's instructions. Place the lid of the disintegrator tank in its place on the disintegrator tank. Set the timer to shut off exactly 10 minutes later. They turn on the disintegrator and start the timer with a sound signal so that the sound signal sounds and the disintegrator automatically turns off after exactly 10 minutes of operation. Turn off the beep. Use a cellulosic suspension (pulp plus water from Cincinnati, Ohio (or equivalent water, as described above)) in the disintegrator within an hour after 10 minutes of operation. Do not allow the cellulosic suspension to stand idle for more than 1 hour before using it to make a manual sheet of paper.

b. Pulp Dispensing - After receiving the pulp in the disintegrator tank as described above, the pulp suspension is then placed in a dispenser such as a Noble and Wood Handsheet Forming Machine or a dispenser and hand sheet machine that is commercially available from Adirondack Machine Corporation, in the following way.

Cincinnati, Ohio (or equivalent water as described above) is introduced into a dispenser having a 19-21 liter stainless steel tank (or equivalent water as described above) to fill the tank approximately half (approximately 9-10 liters). The dispenser agitator is turned on, and the agitator speed is set at 23 ± 2 revolutions per minute to ensure good mixing after adding the cellulosic suspension. The mixing quality is judged by seeing that the cellulosic suspension is evenly mixed with water from Cincinnati, Ohio (or equivalent water, as described above), which is added to the tank. Then, the cellulosic suspension obtained above is added to the tank in an amount equivalent to 30 g of absolutely dry pulp. After adding the cellulose suspension to the tank, the slider of the dispenser volume scale is set at 19 l. Add additional water to Cincinnati, Ohio (or equivalent water, as described above) to bring the liquid level to the top of the slider on the meter scale.

c. Formation of sheets of paper of manual casting - A sheet of paper of manual casting was obtained from the cellulosic suspension present in the dispenser described above, as follows.

A sheet of manual cast paper is prepared using a 12 ″ × 12 ″ stainless steel sheet mold commercially available from Adirondack Machine Corporation. First, open the drain valve on the sheet-shaped inlet box and completely empty the inlet box. The inlet box must be clean and free from contamination. Close the drain valve and open the inlet box. Provide water to the city of Cincinnati, Ohio (or equivalent water, as described above), allowing the overflow of the inlet box. Place a clean forming mesh (84M plastic fabric made from 14 ″ × 14 ″ polyester monofilament commercially available from Appleton Wire Co.) on a coarse rough wire inlet box to prevent air bubbles from trapping under the forming mesh. If air bubbles continue to exist, they are removed by rubbing the net gently with your hands before closing the inlet box. Air bubbles under the forming grid, if not removed, will lead to holes in the sheet of manual paper and make the sheet of paper manual plastic unacceptable for use in the tests described in this application.

After the forming net has been thoroughly moistened with water, close and seal the inlet box, allowing water to rise up to 8½ ″ from the forming net in the inlet box. The mark on the inside of the inlet box should be used to constantly indicate this volume. Add 2543 ml of cellulosic suspension from the dispenser to the water in the inlet box using a sampling vessel. Using the perforated metal piston of the inlet box, the cellulosic suspension is distributed evenly, moving the piston from the top of the cellulosic suspension to the bottom of the cellulosic suspension in the inlet box and back for three full cycles up and down. Do not touch the forming grid during downward movements. After the third cycle, the piston is lifted up and stopped, holding the piston plate directly below the surface of the pulp suspension for two seconds (to eliminate wave motion), and then slowly removed. Make sure that the cellulosic suspension in the inlet box is at rest.

Press the switch to activate the time-controlled opening of the inlet drain valve. The drain valve closes automatically after water has completely drained from the inlet box. Most devices empty completely in about 20-25 seconds. After closing the bleed valve, open the inlet box and carefully form a mesh with a fibrous sheet on it from the box. Immediately place the forming grid with the fibrous sheet on top, on the surface of the vacuum chamber (vacuum chamber table) having a flat surface with a vacuum gap (13 ″ × 1/16 ″, opening angle 90 °), over which the forming grid with the fibrous sheet passes. Leave the edge of the forming grid, which is next to the operator, in the same relative position during this transfer from the inlet box to the table of the vacuum chamber.

Vacuum valves in the table of the vacuum chamber are installed in such a way that a low level vacuum (forevacuum) is achieved at a pressure of 4.0 ± 0.5 ″ Hg, and a high level vacuum is reached at a pressure of 10.0 ± 0.5 ″ Hg. Art. Based on the Ashcroft 1189 gauge, a 0-15 ″ Hg range commercially available from Ashcroft Inc.

The vacuum pump is turned on (a Nash H4 pump with an extract of 106 cubic feet / min. With a 10 HP model engine, 1745 rpm, three-phase, 60 Hz, available from ECM Inc.) connected to the vacuum chamber table. Establish a low level vacuum (forevacuum). Lay the forming mesh with the fibrous sheet turned upward on the table of the vacuum chamber so that the front edge of the forming mesh (the edge next to the operator) protrudes approximately ¼ ″ -½ ″ beyond the boundaries of the vacuum gap. A forming grid with a fibrous sheet is passed over the vacuum gap in 1 ± 0.3 seconds at a uniform speed. The pressure gauge should indicate 4.0 ± 0.5 ″ Hg. This stage is called the fore-vacuum stage.

Then turn off the low level vacuum and open the high level side of the vacuum system. A transfer grid is placed (44M plastic fabric made from 16 ″ × 14 ″ polyester monofilament commercially available from Appleton Wire Co., with a rough side that is a sheet side and marked with an arrow indicating the longitudinal direction) with the nodded side up on the vacuum table chambers behind the vacuum gap. The transfer grid is placed on the table of the vacuum chamber so that the 16 ″ side is perpendicular to the vacuum gap. Carefully turn the forming mesh with the fibrous sheet, keeping the edge of the forming mesh that was next to the operator in the same relative position. Gently place the forming grid with the fibrous sheet in the center of the transfer grid, forming a “sandwich” so that the front edge of the transfer grid (closest to the operator) extends approximately ¼ ″ -½ ″ beyond the vacuum gap. The direction of movement of the fibrous sheet through the vacuum gap should be identical to the direction of movement of the forming network with the fibrous sheet during the fore-vacuum step described above. A “sandwich” is pulled through a vacuum gap in 1 ± 0.3 seconds at a constant speed. The pressure gauge should indicate 10.0 ± 0.5 ″ Hg. This stage, in which the fibrous sheet is transferred from the forming network to the transfer network, is called the vacuum transfer stage.

Turn off the high level vacuum and turn off the entire vacuum system. By this time, the fibrous sheet becomes a manual sheet of paper. Next, place the “sandwich” on the table of the vacuum chamber. The forming mesh is separated from the sheet of paper of manual casting and the transfer grid, carefully lifting one of the corners of the forming grid and removing it, leaving the sheet of paper of manual casting on the transfer grid. Hold the edge of the grid closest to the operator in the same relative position as the sheet of manual paper during the transfer stage under vacuum. Draw the arrow with a chemical pencil (a watercolor pencil commercially available from Dick Blick Art Supplies) at the corner of a sheet of hand-eased paper to indicate the direction of movement through the vacuum gap. This determines the longitudinal direction of the sheet of paper manual tide.

Then, a transfer net with an attached sheet of manual cast paper is passed through an E-100 drum dryer commercially available from Adirondack Machine Corporation, with a transfer net facing the drum dryer, and while the operator is holding the edge that is last into the drum dryer. Pass the transfer grid with an attached sheet of manual paper through a drum dryer a second time with a sheet of paper of manual paper facing the drum dryer.

A sheet of manual tide paper is removed immediately after the second exit from the drum dryer, while it is still warm.

Formed sheet of paper manual casting should have a target bulk of 26.8 g / m ² , but not less than 19 g / m ² and not more than 33 g / m ² acceptable for testing. If the bulk is less than 19 g / m ² or more than 33 g / m ² , this means that the amount of pulp is either too small or too large, and the method requires adjustment accordingly to obtain sheets of paper of manual tide with a target bulk of 26, 8 g / m ² , but not less than 19 g / m ² and not more than 33 g / m ² .

Obtaining a pollutant solution

A centrifuge tube (VWR brand 50 ml ultra-transparent ultra-efficient stand-alone centrifuge tube with flat caps, VWR catalog No. 82018-052; or an equivalent tube) is marked with the name of the sample and weighed to the nearest ± 1 mg (weight _{tube + cap} ). Then, 0.1784 g ± 0.0005 g of model pollutant is weighed (Black Todd Clay, available from Empirical Manufacturing Co., 7616 Reinhold Drive, Cincinnati, Ohio 45237-3208) (Mass of _{added pollutant} ), which is then placed in a centrifuge tube. Deionized water, 25.0 ± 0.2 ml, is added slowly to the centrifuge tube using an acceptable dispenser. Deionized water is added to the centrifuge tube carefully to avoid the formation of a plume of model pollutant dust. In the event of a dust loop, the tube is discarded and a new tube is prepared. The tube is then re-weighed to an accuracy of ± 1 mg (weight of _{tube + cap + dispersion} ).

The Petri dish (VWR sterile Petri dish, Simport plastic, 60 × 15 mm, volume 28 ml, VWR catalog No. 60872-306; or equivalent) is marked with the name of the sample and weighed to the nearest ± 1 mg (weight of the _cup ).

Pollutant Adsorption Test Method

A 3 × 4 inch sample is folded in half with the machined side inward, so that it is 1.5 inches long and 4 inches wide. An accordion folding technique (paper fan) is then used to fold the sample 5 times to obtain a sample containing 6 segments, each approximately ⅔ inch wide. A closed centrifuge tube containing a model contaminant and water is mixed / shaken to disperse the contaminant in water to form a dispersion of the contaminant. The centrifuge tube is then opened, allowing the folded sample to completely immerse in the dispersion of the model contaminant and water in the centrifuge tube so that the folds run parallel to the length of the centrifuge tube. The tube is immediately resealed and shaken in a WS 180 ° shaker for 60 ± 1 seconds. The WS 180 ° shaker (Glas-Col No. 099AWS18012; or equivalent shaker) is set at a speed of 50% so that it turns the sample 160-170 degrees every second.

After shaking, the folded sample is carefully removed over the Petri dish using laboratory tweezers. Care must be taken to ensure that all dispersion is contained either in the original centrifuge tube or in the appropriate Petri dish. The dispersion is squeezed out of the sample using a “squeezing” movement and collected in a Petri dish (≥85% of the dispersion of the contaminant should be collected if the sample is a paper towel, paper towel, napkin, base for mopping the floor for the squeegee, cleaning (contacting the surface) base other multilayer cleaning systems, or a rag; ≥60% of the dispersion of the contaminant should be collected if the sample contains an absorbent nozzle, such as a mop containing an absorbent layer similar to Swiffer Wet Jet nozzles, a sponge or cotton pad). After the dispersion has been removed from the sample, the sample is discarded. The remaining dispersion is poured from the centrifuge tube into the Petri dish after shaking the mixture in order to redisperse the model contaminant in water, thereby ensuring that no amount of model contaminant is accidentally left in the centrifuge tube. Petri dish containing a mixture model contaminant to water, is weighed to within ± 1 mg (weight _{+ cup effluent).} The Petri dish is then placed in a laboratory ventilated drying oven at 60 ° C until the sample dries, preferably overnight.

After the sample has dried, it is removed from the oven and cooled to room temperature (73 ± 3.5 ° F). A Petri dish containing a dried model contaminant is re-weighed to an accuracy of ± 1 mg (Weight _{cup + dried contaminant} ).

Calculations

To calculate the amount of residual model pollutant (mass of _{residual pollutant} ) remaining in the Petri dish, the following equation was used:

_Residual mass of _pollutant = Mass of _{cup + dried pollutant -} Mass of _cup

The amount of residual model pollutant was indicated in mg.

To calculate the amount of adsorbed pollutant (retained pollutant) in the sample, the following formula was used:

Retained pollutant = Weight of _{added pollutant -} Mass of _{residual pollutant}

The amount of adsorbed contaminant was indicated in mg.

To calculate the percentage of retained pollutant (% retained pollutant), the following formula was used:

The test is performed on four samples, and the average amount of adsorbed pollutant (also known as the index of adsorption of the pollutant) and the average percentage of retained pollutant (% of retained _{environmental} pollutant) are calculated for the product.

Charge density test method

The charge density of a polymer, for example, a polymer adsorbing a pollutant, can be determined using a Mutek PCD-04 particle charge detector, available from BTG, or an equivalent device. Use the following guidelines provided by BTG.

Start with a 0.1% solution (0.1 g of polymer + 99.9 g of deionized water) (sample). Depending on the consumption of titrant, the polymer content is increased or decreased, if necessary. The pH of the solution is adjusted until the final dilution, since the charge density of many polymers and / or additives depends on the pH of the solution. This application uses a pH of 4.5.

1. Place 20 ml of sample in the PCD measuring cell and insert the piston.

2. Place the measuring cell with the piston and sample in the PCD, the electrodes facing the back wall. Move the cell along the guide until it touches the back wall.

3. Lift the piston up and turn it counterclockwise to lock the piston in place.

4. Turn on the engine. Stream potential is shown on the touch panel. Wait 2 minutes until the signal becomes stable.

5. An oppositely charged titrant is used (for example, an anionic titrant is used for a cationic sample having a positive flow potential). Titrants are available from BTG and are 0.001N PVSK solution or 0.001N PolyDADMAC solution.

6. Use an automatic titrator available from BTG. After selecting the appropriate titrant, the tube washing regime is established in the titrator by dispersing 10 ml of the solution, ensuring the removal of all air bubbles.

7. Place the tip of the tube below the surface of the sample and begin titration. The automatic titrator is set so that it automatically shuts off when the potential reaches 0 mV.

8. The titrant consumption is recorded, ideally it should be between 0.2 and 10 ml; otherwise, the polymer content should be reduced or increased.

9. Repeat titration of a second aliquot of a 20 ml polymer sample.

10. Calculate the charge consumption of the solution or charge consumption of dry matter

The charge consumption (charge density) of the polymer is indicated in meq / g.

Bulk Test Method

A 3.00 × 4.00 inch rectangular sample cut as described above in a test method for adsorbing a contaminant was held in an air conditioning chamber at 70 ± 2 ° F and a relative humidity of 50% ± 2% for at least 2 hours, usually during the night. The sample is weighed to an accuracy of ± 10 mg ( _basis weight) while maintaining the conditioning conditions. The bulk of the sample is then calculated as follows:

Moisture Test Method

The moisture content present in the product is measured using the following moisture content test method.

The product or part thereof (“sample”) is placed in an air conditioning chamber at a temperature of 73 ± 4 ° F (approximately 23 ± 2.2 ° C) and a relative humidity of 50 ± 10% for at least 24 hours before testing. The mass of the sample is recorded when no further mass changes are detected for at least a 5-minute period. This mass is recorded as the "equilibrium mass" of the sample. The sample is then placed in a drying oven for 24 hours at 70 ° C and a relative humidity of approximately 4% to dry the sample. After 24 hours of drying, remove the sample from the drying oven and immediately weigh. This mass is recorded as the "dry mass" of the sample. The moisture content in the sample is calculated as follows:

% moisture in the sample for 3 samples is averaged to obtain a fixed% moisture in the sample.

III. Products

This application further relates to cleaning products for cleaning surfaces (e.g., hard surfaces). Such products may include dry material, for example, a dry fibrous structure such as a dry paper towel, mop, sponge; or a pre-moistened, liquid composition towel or napkin or pad showing improved contaminant adsorption indices, as measured by the contaminant adsorption test method described in this application, compared to known products using the contaminant binding agent described in this application. It will be appreciated that the article may include the entire article or part of the article on which a contaminating agent is applied or in contact with and / or a cleaning composition. In certain implementations, a part of the product may include a separate layer or part of the product, including, for example, a part of the product tested by the test method of adsorption of the pollutant described in this application.

In certain embodiments, at least a portion of the article may exhibit a contaminant adsorption index of at least 75 mg; in certain embodiments, approximately 85 mg or more; in certain embodiments, about 100 mg or more; in certain embodiments, about 120 mg or more; and in certain embodiments, approximately 140 mg or more as measured according to the test pollutant adsorption test method described herein.

In one example, the article comprises a web. The canvas may include one or more non-woven or woven fabric, or a combination thereof. In certain embodiments, the web may include multiple cellulosic fibers. In certain embodiments, the web may include a fibrous structure.

Non-limiting examples of methods for making fibrous structures include known wet spinning methods, such as wet spinning methods for making paper, and dry methods, for example, dry paper making methods. Wet forming methods and / or dry paper making methods typically include a step in which a composition is prepared containing a plurality of fibers that are suspended in a medium, either a moist, more specifically aqueous medium, or a dry, more specifically gaseous medium, such as air. The aqueous medium used for wet spinning processes is often referred to as fiber suspension. The fibrous composition is then used to deposit a plurality of fibers onto a forming network or tape so that a germinal fibrous structure is formed, after which drying and / or bonding of the fibers to each other results in a fibrous structure. Further processing of the fibrous structure can be carried out in such a way that a finished fibrous structure is formed. For example, in typical papermaking processes, the finished fibrous structure is a fibrous structure that is wound on a spool at the end of the papermaking process and can subsequently be converted into a finished product, for example, a hygiene paper product.

Another method that can be used to produce fibrous structures is a blown melting method and / or spin bonding method, where the polymer composition is spun to form filaments and assembled on a tape to obtain a fibrous structure. In one example, a plurality of fibers may be blended with the yarns prior to joining them on the tape and / or a plurality of fibers may be applied to another fibrous structure containing the yarns.

The fibrous structures may be uniform or may be layers in a direction perpendicular to the longitudinal direction. If they are laminated, the fibrous structures may contain at least two and / or at least three and / or at least four and / or at least five layers.

Fibers are generally considered discontinuous in nature. Non-limiting examples of fibers include wood pulp fibers and synthetic staple fibers such as polyester fibers.

Threads are generally considered continuous or substantially continuous in nature. Threads are relatively longer than fibers. Non-limiting examples of yarns include yarns obtained by blowing and / or spinning. Non-limiting examples of materials that can be spun into yarns include natural polymers such as starch, starch derivatives, cellulose and cellulose derivatives, hemicellulose, hemicellulose derivatives, and synthetic polymers, including, but not limited to, polyvinyl alcohol threads and / or threads polyvinyl alcohol derivatives and thermoplastic polymer yarns such as polyesters, nylon, polyolefins such as polypropylene yarns, polyethylene yarns and biodegradable or compostable Hovhan thermoplastic fibers such as polylactic acid filament or filaments of polyhydroxyalkanoate and polycaprolactone filaments. The yarns may be unicomponent or multicomponent, for example, two-component yarns.

The paper-forming fibers used in the present invention may include cellulose fibers, commonly known as wood pulp fibers. Suitable wood pulps include chemical pulps, such as kraft pulp, sulfite and sulfate pulps, as well as mechanical pulps, including, for example, chopped wood, thermomechanical pulp and chemically modified thermomechanical pulp. Chemical celluloses, however, may be preferred since they give a strong tactile softness to sheets of paper made from it. Cellulose obtained from deciduous trees (also referred to as “hardwoods” in this application) and conifers (also referred to as “conifers” in this application) can be used. Hardwood and coniferous fibers can be blended, or alternatively, can be layered to provide laminated webs. Also used in the present invention are fibers made from recycled paper, which may contain some or all of the above categories, as well as other non-fibrous materials, such as fillers and adhesives, used to facilitate the initial paper manufacturing process.

In addition to various wood pulp fibers, other cellulosic fibers, such as cotton tow, viscose, lyocell and pulp, can be used in the present invention. Other sources of cellulose in the form of fibers or capable of spinning into fibers include herbs and grain sources.

In certain embodiments, the sanitary product may include a fibrous structure. Sanitary products (as well as other cleaning products or parts thereof) may have a bulk of from about 10 g / m ² to about 120 g / m ² and / or from about 15 g / m ² to about 110 g / m ² and / or from about 20 g / m ² to about 100 g / m ² and / or from about 30 to 95 g / m ² . It should be borne in mind that acceptable cleaning products, as described in this application, may have a bulk of approximately 150 g / m ² or less; in certain embodiments, the bulk is about 100 g / m ² or less; and in certain embodiments, the bulk is from about 30 g / m ² to about 95 g / m ² based on the test pollutant adsorption method described in this application (for example, the bulk is measured relative to the size of the sample). It should be borne in mind that some products, such as cotton pads, rags, gauze, will have a higher base mass based on the test method of adsorbing contaminants than paper towels, paper towels, napkins, sponges, or floor nozzles removed from the mop .

The fibrous structure in accordance with the present invention may contain many cellulose fibers. In addition, the fibrous structure in accordance with the present invention may contain single-layer or multi-layer sanitary products, such as a paper towel.

In another implementation, the material in accordance with the present invention may contain a cloth, for example a fibrous structure, in the form of a cleaning nozzle suitable for use with a cleaning device, for example, a floor cleaning device, for example Swiffer ^® cleaning nozzle.

The fibrous structures in certain embodiments may be co-molded fibrous structures. Such acceptable examples of co-formed fiber structures are described in US Pat. No. 4,100,324.

In yet another embodiment, the article may comprise a foam structure or sponge. Suitable foam structures or sponges are described in US Pat. Nos. 4,638,017, 4,738,992 and 4,957,810; US Patent Publications No. 2007/0061991 A1, 2007/0161533 A1 and 2009/0163598 A1.

As described in this application, the cleaning product may contain an agent that binds the contaminant, applied to the product before use or applied to the surface before using the product. For example, an agent that binds a contaminant can be pre-applied (for example, embedded) on the surface of the product before using it to clean the surface of the object. In alternative embodiments, a contaminant binding agent may be applied to a surface to be cleaned (e.g., a table surface), and then the article is brought into contact with the surface to remove the contaminant.

In certain embodiments, a contaminant binding agent may be present in and / or on at least a portion of the cleaning product at a level of more than 0.005% and / or more than 0.01% and / or more than 0.05%, and / or more than 0.1% and / or more than 0.15% and / or more than 0.2% and / or less than 5% and / or less than 3% and / or less than 2%, and / or less than 1%, by weight of the product. In one example, a contaminant binding agent is present in and / or on the product at a level of from about 0.005% to about 1% by weight of the product.

In certain embodiments, a cleaning system including both the article (or part of the article) and the contaminant binding agent may contain from about 0.00001 mass fraction to about 0.001 mass fraction of the contaminant binding agent. In another embodiment, the cleaning system may contain from about 0.0005 mass fraction to about 0.003 mass fraction of the contaminating agent.

In another example, a contaminant binding agent may be present in and / or on the cleaning product in the form of a pattern, for example, a regularly repeating pattern and / or present in and / or on areas of different densities, different ground weights, different heights and / or different textures material.

The cleaning product may contain other ingredients in addition to a contaminating agent, such as a surfactant. Additional surfactants may be desirable in this application, as they further increase the cleaning efficiency and / or beneficial gloss effect of the compositions in accordance with the present invention. Surfactants for use in this application include anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. Such surfactants may be present in the material at a level of from about 0.01% to about 0.5% by weight of the article (or part of the article). Examples of such acceptable surfactants are described in US Patent Application Publication No. 2010/0154823 A1 and PCT Application No. PCT / US2011 / 042644.

Other suitable additives may also be included with the contaminating agent. For example, additives such as perfumes, bleaching agents, brighteners, fabric tinting agents, chelating agents, and other active ingredients may be included with the contaminating agent. Suitable examples of such additives are described in PCT application No.PCT / US2011 / 042644.

In one example, in accordance with the present invention, a kit comprising a non-woven base that may contain a contaminating agent, for example, a cleaning composition that is present on and / or in a non-woven base, and / or a non-woven base and a separate, discrete cleaning composition that may be applied to the surface and / or to a non-woven base prior to use by the consumer.

Kits containing non-woven backing and compositions

In one embodiment, the present invention also relates to a kit comprising a non-woven base and a cleaning composition comprising a contaminating agent. The cleaning composition may be an aqueous cleaning composition, and may also contain other ingredients selected from surfactants, surface tackifiers, and mixtures thereof. Means for reducing surface stickiness are materials that regulate the adhesion of a contaminating agent. The cleaning composition may be pre-applied to the non-woven base to form a pre-moistened wipe or pad. Alternatively, the kit may comprise a separate dry base, with or without a pollutant binding agent, and an aqueous composition, with or without a pollutant binding agent, at least one of which contains a pollutant binding agent. In a final embodiment of the invention, the user can, for example, by spraying, apply the cleaning composition to the surface to be cleaned and then use a non-woven base to clean and absorb the cleaning composition and agglomerated contaminant. Alternatively, the composition may be applied directly to the substrate by the user. There are several advantages to using a contaminant binding agent in combination with a disposable (pre-moistened or dry) pad / napkin. First, a disposable pad / napkin acts as a means of fixing the copolymer, especially if the napkin / pad contains at least some amount of cellulose. Not wishing to be limited by any theory, it is believed that ionic interactions (binding of cationic copolymer fragments to negatively charged cellulose regions of a pad / wipe), molecular weight effects (a high molecular weight polymer will be fixed better than a low molecular weight polymer) or a combination of ionic and molecular mass interactions leads to the fact that the agent that binds the pollutant adheres strongly to the non-woven base. This limits the transfer of the copolymer to the surface to be treated, reducing the need for, or level of, a means of reducing surface stickiness. The non-woven base also acts as a medium for the agglomerated contaminant, limiting re-deposition of the contaminant on the treated surface. By limiting re-deposition of the contaminant, a disposable pad and a fixed agglomerating copolymer provide improved cleaning of the treated surface. Finally, an agglomerated contaminant bound to a contaminating agent will contaminate the cleaning cloth / pad, providing consumers with evidence that the product is working and giving a visual signal when to replace the used pad. This last effect of the pollutant binding agent is only useful if the pad / napkin is intended to be discarded after limited use (i.e., are disposable). Darkening of the base due to agglomeration of contaminant particles is a compelling advertising demonstration.

Compositions of pre-moistened wipes and pads:

Pre-wetted wipes and pads in accordance with the present invention (defined as pre-wetted laminate wipes for the purposes of the present invention) contain a cleaning composition containing a contaminating agent. In one example, the composition of pre-wetted wipes further comprises a means of reducing surface stickiness. Pre-moistened wipes are widely used in the European household cleaning products industry and are used for treating hard surfaces, including, but not limited to, kitchen countertops and household appliances, bathroom sinks, home windows and mirrors, blinds, external surfaces of toilets, living room tables, cleaning household floors, including particles and hair, the interior and exterior of the car, glasses, and hard surfaces that require cleaning in industry, such as cars. Pre-moistened wipes can be used manually for cleaning, or they can be attached to the handle, which limits the contact of consumers with the water composition and helps to provide improved access, or inserted into it. Wipes containing dry, twisted into a bundle of fibers are already used in the industry for dusting, for example Swiffer Duster ^® . Compositions in accordance with the present invention include wet / wet dust milling compositions, optionally containing twisted fibers and preferably containing a certain level of hydrophilic fibers. When using compositions for wet / wet wiping dust is optional, although it is preferable to use a handle. The handle can have any length, for example, from 15 cm to 1 meter and can be made of any material. Pre-wetted wipes containing the agglomerating copolymer in accordance with the present invention can also be used to remove contaminants, especially contaminant particles, which are usually removed with dry dusting sheets and dust removers. Compositions can also be used to remove contaminant particles from upholstery and other fabrics, including carpet.

The chemical composition of the nonwoven backing used in the present invention can vary from 100% synthetic to 100% non-synthetic fibers. Preferably, the chemical composition of the base contains a mixture of synthetic and non-synthetic fibers. More preferably, the synthetic material in this application includes polypropylene, nylon or polyester, or mixtures thereof. Non-synthetic bases used in this application are treated or untreated cellulose fibers that are hydrophilic and typically include anionic sites. Examples of such fibers include wood pulp, Rayon ^® and Lyocell ^® . The base composition preferably contains at least 10%, more preferably at least 15%, more preferably at least 20% non-synthetic fibers. The incorporation of cellulosic fibers into a non-woven base predominantly secures the agglomerating polymers of the present invention through an anion-cation bond; this is useful because it reduces the possibility of the release of the agglomerating copolymer on the solid surface to be treated, thereby reducing slippage and stickiness problems and sludge formation.

The distribution of synthetic and non-synthetic fibers in the canvas can be homogeneous or heterogeneous. When the fiber distribution is not uniform, it is preferable that the areas acting on the hard surface to be treated contain more synthetic fiber than is present in the entire base composition. Such a structure retains a fluid reservoir in a non-synthetic structure with greater absorption capacity and is sandwiched between two regions of the wipe, which are more hydrophobic; this leads to a more controlled release of the aqueous composition and an overall increase in the life of the wipes. Alternatively, the fiber distribution can preferably be made so that only one surface of the base has more hydrophobic fibers than in the entire composition. In this case, the base will combine functions, providing a low coefficient of friction with a high content of synthetic substances, and the second, more ordinary surface, is made of cellulose or processed cellulose derivatives. The presence of an increased amount of hydrophobic material on the surface (s) of the substrate also is known to improve the lubrication or sliding of the substrate, since many hard surfaces are wiped with it. This allows you to be sure of “easier cleaning” for consumers.

In accordance with the present invention, the base can be obtained by any method known in the art. For example, nonwoven fabric substrates can be formed using dry forming techniques such as air laying or wet laying, for example, on a paper machine. Other non-woven fabrication methods, such as hydro-entangling, blown melting, spinning, needle punching and other methods can also be used.

In one example, the non-woven base has a bulk of from about 20 g / m ² to about 200 g / m ² and / or at least 20 g / m ² and / or less than 150 g / m ² and / or from about 20 g / m ² to 110 g / m ² and / or from about 20 g / m ² to 80 g / m ² and / or from about 25 g / m ² to 60 g / m ² .

Compositions in accordance with the present invention can be applied to the substrate at any time after it has been dried. For example, the composition may be applied to the substrate before calendaring or after calendaring and before it hits the roll. Typically, the application will be on a base unwound from a roll having a width substantially equal to the number of wipes to be produced. The base coated with the composition is then sequentially perforated using standard methods to obtain the desired line of perforations.

In one example, compositions are applied in an amount of from 1.0 gram (g) to 10.0 gram (g) per gram (g) of dry basis (i.e., 1-10-fold load factor), preferably from 1.25 g to 8.5 g per g of dry base, most preferably from 1.5 g to 7.0 g per g of dry base. In one embodiment, a single layer base with a low bulk, from 20 gm ^-2 to 55 gm ^-2 , more preferably from 30 gm ^-2 to 45 gm ^-2 , is impregnated with an aqueous composition containing a pollutant binding agent at a load factor of 1 , 0 g to 2.5 g per g of dry basis; In this scenario, the cleaning is carried out by wet wiping dust from surfaces. A commercially available example of this type of composition and application is Swiffer Shine ^® sold in Europe.

In another example, a kit is provided containing a dry article, for example, a dry cleaning pad, and a separate cleaning composition containing a contaminating agent. The dry cleaning pad may be a dry dust remover (with or without an optional handle), laminate from nonwoven substrates without a superabsorbent polymer, or laminate from substrates containing a superabsorbent polymer. The aqueous chemical may be placed in any suitable container and may be applied to the surface to be treated by any method known in the art. For example, solution application can be achieved using a separate spray gun, aerosol can, or trigger spray system. Alternatively, the water chemical container may also be housed in or integrated into the container directly attached to the cleaning device (i.e., the head or handle of the mop). The feed mechanism may then be actuated by the operator, or may be an induced battery or electric.

The cleaning pad may be absorbent. An example of an acceptable commercially available absorbent pad is set to nozzle, which is sold under the trademark Clorox Ready Mop ^®. In a preferred embodiment, the absorbent pad further comprises superabsorbent material. Superabsorbent materials are particularly useful with the compositions of the present invention since they help to keep the side of the pad facing the floor free from the water cleaning composition, reducing the amount of polymer agglomerating the contaminant left after cleaning with a mop. This simultaneously reduces the stickiness of the surface and keeps the floor substantially free of rain.

Cleaning pads may have an absorbent capacity measured under a limiting pressure of 0.09 psi (psi = psi) after 20 minutes (1200 seconds) (referred to as “tj200 absorbent capacity” in this application), and a component of at least approximately 10 g of deionized water per 1 g of cleaning pad. The absorbent capacity of a pad is measured 20 minutes (1200 seconds) after exposure to deionized water, as it is a typical time during which a consumer cleans a hard surface such as a floor. The limiting pressure is a typical pressure applied to the pad during the cleaning process. As such, the cleaning pad should be able to absorb significant amounts of the cleaning solution during these 1200 seconds at a pressure of 0.09 psi. The cleaning pad may have an absorbent capacity of t ₁₂₀₀ of at least about 15 g / g, more preferably at least about 20 g / g, even more preferably at least about 25 g / g and most preferably at at least about 30 g / g. The cleaning pad may have an absorbent capacity of t ₉₀₀ of at least about 10 g / g, more preferably an absorbent capacity of t ₉₀₀ of at least about 20 g / g. Values for the absorbency of t ₁₂₀₀ and t ₉₀₀ are measured by the method of working under pressure (referred to as “PUP” in this application), described in detail in the Test Methods section of US Pat. No. 6,045,622, which application is incorporated herein by reference in its entirety. This application contains a more detailed description of the pads, tools, etc. that are used in this application.

In one example, the cleaning pad comprises an absorbent layer containing a thermally bonded dry formation web of cellulose fibers (Flint River, available from Weyerhaeuser, Wa) and AL Thermal C (thermoplastic, available from Danaklon a / s, Varde, Denmark), and a swellable superabsorbent hydrogel forming polymer. The superabsorbent polymer is preferably incorporated in such a way that the discrete layer is located near the surface of the absorbent layer remote from the cleaning layer. Preferably, a thin layer of, for example, cellulosic fibers (optionally thermally bonded) is located above the superabsorbent gelling polymer to increase retention.

In another example, the cleaning pad comprises a cleaning layer. The cleaning layer is part of the cleaning pad that comes in contact with the contaminated surface during cleaning. Thus, materials useful as a cleaning layer must be strong enough so that the layer retains its integrity during the cleaning process. In addition, when a cleaning pad is used in combination with a solution, the cleaning layer must be able to absorb liquids and contaminants, and transfer these liquids and contaminants to the absorbent layer. This ensures that the cleaning layer is constantly able to remove additional material from the surface to be cleaned. Whether it is used with a cleaning solution (i.e., in a wet state) or without a cleaning solution (i.e. in a dry state), the cleaning layer, in addition to removing particles, facilitates other functions, such as polishing, dusting and sanding, to be cleaned.

The cleaning layer may be a single layer or multi-layer structure, one or more layers of which may have gaps to facilitate cleaning of the contaminated surface and absorption of particles. This cleaning layer, as it passes through the contaminated surface, interacts with the contaminant (and with the cleaning solution when used), loosening and emulsifying solid contaminants, and allows them to pass freely into the absorbent layer of the pad. The cleaning layer preferably contains openings (eg, slots) that provide an easy path so that larger particles of contaminant can move more freely into and be captured in the absorbent layer of the pad. Low density structures are preferred as a cleaning layer in order to facilitate the transport of particles to the absorbent layer of the pad. In order to provide the desired integrity, materials particularly suitable for the cleaning layer include synthetic materials such as polyolefins (e.g. polyethylene and polypropylene), polyesters, polyamides, synthetic cellulose derivatives (e.g. Rayon ^® ), and mixtures thereof. Such synthetic materials can be made using a known method, such as hydro-entangling, spinning, melt blown, dry method, needle punching and the like.

The cleaning pads in accordance with the present invention optionally comprise an attachment layer that allows the pad to be attached to the handle or tool head in preferred embodiments of the invention. The attachment layer will be necessary in those implementations where the absorbent layer is not acceptable for attaching the pads to the support head of the handle. The attachment layer may also function as a means to prevent fluid from flowing out through the upper surface (i.e., the surface in contact with the handle) of the cleaning pad and may further provide improved pad integrity. As with cleaning and absorbent layers, the attachment layer may consist of a single-layer or multi-layer structure to the extent that it meets the above requirements. The attachment layer may comprise a surface that is capable of mechanically attaching to the support head of the handle by using known hook and loop technology. In such an embodiment, the attachment layer will comprise at least one surface that is mechanically attached to hooks that are permanently attached to the lower surface of the handle support head.

The present invention also includes methods for cleaning a surface, preferably a solid surface, comprising the step of contacting, preferably wiping, the surface using an aqueous composition containing a contaminating agent and preferably a means of reducing surface stickiness. For floor cleaning, compositions can be used in combination with a conventional mop / rag and / or broom cleaning systems. These include sponges, rope and tape mops. Alternatively, the floor cleaning process may be performed using a disposable, pre-moistened wipe or nozzle containing an aqueous composition comprising a contaminating agent. Examples of such systems include Pledge Wet ^® and Swifer Wet ^® . In yet another embodiment, the cleaning process is carried out using a kit containing a cleaning device, dry cleaning nozzles that are attached to the cleaning device, and an aqueous composition containing a contaminating agent. Examples of such a system include Clorox Ready Mop ^® and Swiffer Wet Jet ^® (for Wet Jet ^®, disposable dry nozzles also include a superabsorbent polymer). The cleaning process in each case consists of thoroughly wetting the floor with an aqueous composition. The preferred wiping order consists of overlapping up and down movements starting from the lower left side (or right side) of the section to be cleaned and continuing to wipe across the floor using up and down movements. The wiping is then continued, starting in the upper right (or left) side of the section to be cleaned and changing the wiping direction using side-to-side movement. Another preferred wiping order consists of wiping up and down, followed by a wiping up and down in the opposite direction. All preferred wiping procedures described above can be transferred to the consumer through the instructions for use listed in the drawing in a kit or package.

For cleaning smaller solid surfaces, including, but not limited to, tiles, windows, shutters and curtains for windows and doors, sinks, showers, car interiors, travel bags, walls, countertops, appliances and tables, compositions are preferably used in ready-to-use spray or aerosol can. Accordingly, the composition containing the copolymer in accordance with the present invention, is brought into contact with the surface to be processed, and then distributed and wiped using a cleaning device. Examples of cleaning devices in this context include cotton fabrics, sponges, paper towels, and suede. Alternatively, a composition comprising a contaminant binding agent may be included in pre-moistened wipes or pads. In this case, the surface to be cleaned and the contaminated area (s) are wiped with pre-moistened wipes or pads, preferably using wiping movements from side to side. Contaminant removal is visually observed due to visible agglomeration of the contaminant on a tissue.

The method of cleaning a solid surface or object

The present invention further includes a method for cleaning a hard surface or object.

This method may include the steps of: applying a cleaning composition comprising a contaminating agent to a solid surface or object; leaving said composition on said hard surface or said object to act on it; optionally wiping said solid surface or object and / or providing mechanical stirring and then rinsing said solid surface or said object. In other embodiments, a contaminant binding agent may be applied to the article before being applied to a solid surface or object.

Cleaning systems (e.g. product and contaminant binding agent) are particularly suitable for treating hard surfaces located inside and around a house, in particular in bathrooms, toilets, garages, driveways, basements, gardens, kitchens, etc. .

Other suitable uses of the product in combination with the contaminant binding agent described herein for the purpose of binding the contaminant will be apparent to those skilled in the art.

The dimensions and values described in this application should not be understood as strictly limited in accuracy to the values given. Instead, unless otherwise indicated, each such dimension shall indicate both the quoted value and the functionally equivalent range surrounding this value. For example, a dimension disclosed as “40 mm” is intended to mean “approximately 40 mm”.

For clarity, the sum of the values "wt. % "Does not exceed 100 wt. %

All documents cited in the detailed description, in the relevant part, are incorporated into this application by reference; the citation of any document should not be construed as an assumption that it is a prior art in relation to the present invention. To the extent that any meaning or definition of a term in this application is contrary to any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to this term in this application prevails.

While specific embodiments of the present invention have been illustrated and described, it should be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, all such changes and modifications that are within the scope of the present invention are intended to be encompassed by the appended claims of the present invention.

Claims (21)

1. Product for cleaning the surface, while the product contains an agent that binds a pollutant, and the agent that binds a pollutant contains a polymer, while the polymer contains two or more monomer units selected from the group consisting of:
a. nonionic monomer units, wherein the nonionic monomer units contain a nonionic hydrophilic monomer unit, wherein the nonionic hydrophilic monomer unit comes from acrylamide;
b. anionic monomer units, the anionic monomer units derived from monomers selected from the group consisting of monomers having at least one carboxyl functional group;
c. cationic monomer units, wherein the cationic monomer unit is derived from (3-methacrylamidopropyl) trimethylammonium chloride (MARTAS); and
d. zwitterionic monomer units, wherein the zwitterionic monomer units come from zwitterionic monomers selected from the group consisting of sulfobetaine monomers, phosphobetainic monomers and carboxybetaine monomers;
moreover, the polymer contains at least one monomer unit from group a and at least one monomeric unit selected from groups b, c and d, while at least part of the product exhibits an index of adsorption of the pollutant, at least , 75 mg, as measured according to the test method of adsorption of the pollutant;
moreover, the polymer contains at least 69.9 wt. % of the monomer unit from group a, and wherein the polymer contains not more than 30.1 wt. % monomer unit selected from the group consisting of group b, group c, group d and mixtures thereof. 2. The product according to p. 1, characterized in that the polymer contains at least 69.9 wt. % monomer unit from group a, not more than 30.1 wt. % monomer unit from group b and not more than 30.1 wt. % monomer unit from group c. 3. The product according to p. 2, characterized in that the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a, from about 0.1 wt. % to about 10 wt. % monomer unit from group b and from about 0.3 wt. % to about 29 wt. % monomer unit from group c. 4. The product according to p. 2, characterized in that the polymer contains from about 70 wt. % to about 99.5 wt. % monomer unit from group a and from about 0.5 wt. % to about 30 wt. % of the monomer unit from group b and the monomer unit from group c in total. 5. The product according to claim 1, characterized in that the monomer unit from group b and the monomer unit from group c are present in the polymer with a molar ratio of from about 3: 1 to about 1: 3. 6. The product according to claim 1, characterized in that the polymer exhibits an excess charge of from about 0 to about 0.1 meq / g. 7. The product according to claim 1, characterized in that the polymer exhibits a polydispersity index of less than about 2.5. 8. The product according to claim 1, characterized in that the polymer is water soluble. 9. The product according to claim 1, containing a fibrous structure. 10. The product according to p. 9, characterized in that the fibrous structure contains many cellulose fibers. 11. The product according to p. 9, characterized in that the fibrous structure contains a sanitary-hygienic product. 12. The product according to claim 1, characterized in that it further comprises a cleaning composition, wherein the contaminating agent is in the cleaning composition. 13. The product according to claim 1, characterized in that the product is a dry product. 14. A cleaning system comprising at least a portion of an article and a contaminating agent, the contaminating agent comprising a polymer, wherein the polymer comprises three or more monomer units selected from the group consisting of:
a. nonionic monomer units, wherein the nonionic monomer units contain a nonionic hydrophilic monomer unit, wherein the nonionic hydrophilic monomer unit comes from acrylamide;
b. anionic monomer units, the anionic monomer units derived from monomers selected from the group consisting of monomers having at least one carboxyl functional group;
c. cationic monomer units, wherein the cationic monomer unit is derived from (3-methacrylamidopropyl) trimethylammonium chloride (MARTAS); and
d. zwitterionic monomer units, wherein the zwitterionic monomer units come from zwitterionic monomers selected from the group consisting of sulfobetaine monomers, phosphobetainic monomers and carboxybetaine monomers;
wherein the polymer contains at least one monomer unit from group a and at least two monomer units selected from groups b, c and d, and wherein at least two monomer units are present in the polymer at a molar ratio from about 3: 1 to about 1: 3;
moreover, the polymer contains at least 69.9 wt. % of the monomer unit from group a, and wherein the polymer contains not more than 30.1 wt. % monomer unit selected from the group consisting of group b, group c, group d and mixtures thereof. 15. A cleaning system according to claim 14, characterized in that the polymer contains at least 69.9 wt. % monomer unit from group a, not more than 30.1 wt. % monomer unit from group b and not more than 30.1 wt. % monomer unit from group c. 16. A cleaning system according to claim 14, characterized in that the agent that binds the contaminant is applied to at least part of the product before use. 17. The cleaning system according to p. 14, characterized in that the agent that binds the contaminant is applied to the surface to be cleaned before use. 18. A cleaning system according to claim 14, characterized in that it exhibits a contaminant adsorption index of at least 75 mg, as measured according to a test method for contaminant adsorption. 19. A cleaning system comprising at least a portion of an article and a contaminant binding agent, wherein the contaminant binding agent comprises a polymer, the polymer comprising two or more monomer units selected from the group consisting of:
a. nonionic monomer units, wherein the nonionic monomer units contain a nonionic hydrophilic monomer unit, wherein the nonionic hydrophilic monomer unit comes from acrylamide;
b. anionic monomer units, the anionic monomer units derived from monomers selected from the group consisting of monomers having at least one carboxyl functional group;
c. cationic monomer units, wherein the cationic monomer unit is derived from (3-methacrylamidopropyl) trimethylammonium chloride (MARTAS); and
d. zwitterionic monomer units, wherein the zwitterionic monomer units come from zwitterionic monomers selected from the group consisting of sulfobetaine monomers, phosphobetainic monomers and carboxybetaine monomers;
wherein the polymer contains at least one monomer unit from group a and at least one monomer unit selected from groups b, c and d, and wherein the polymer has a number average molecular weight of from about 500,000 g / mol to about 2,000,000 g / mol;
moreover, the polymer contains at least 69.9 wt. % of the monomer unit from group a, and wherein the polymer contains not more than 30.1 wt. % monomer unit selected from the group consisting of group b, group c, group d and mixtures thereof. 20. A cleaning system according to claim 19, characterized in that the agent that binds the contaminant is applied to at least part of the product before use. 21. The cleaning system according to claim 19, characterized in that the agent that binds the contaminant is applied to the surface to be cleaned before use.