Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3776—Heterocyclic compounds, e.g. lactam
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

• the present invention relates to an aqueous formulation of an anti-soiling recleaning agent for use on common household hard surfaces to impart soil release properties thereto to facilitate subsequent cleaning.
• the compositions may also include various surface active ingredients and/or disinfecting agents to provide effective cleaning and/or disinfecting of the hard surface being treated. More particularly, certain cationic, anionic or nonionic polymeric soil-releasing agent which is substantive to the treated hard surface is deposited from an aqueous solution, preferably together with various cleaning and/or disinfecting agents for present cleaning/disinfecting, to facilitate removal of subsequently deposited soils, such as soap scum, during cleaning or recleaning of the soiled surface.
• Example 4 of the prior application demonstrated that incorporation of 2.3% of a 15-20% solution of poly-[beta(methyl diethylammonium) ethylmethacrylate] (poly(MDAEM)) in the mixed nonionic surfactant system aqueous acidic disinfectant composition results in significant improvement of ease of recleaning soiled tiles.
• poly(MDAEM) poly-[beta(methyl diethylammonium) ethylmethacrylate]
• the efficacy of the soil release polymers is not limited to the acidic aqueous disinfecting cleaning composition of our prior application, or to poly(MDAEM), but appears to a broader range of anionic, cationic and nonionic polymers having certain characteristics, and have utility when used alone, or in the presence of other surfactant systems.
• a hard surface treating composition for improving the soil removal or anti-soiling characteristics of the treated surface, the composition comprising an aqueous liquid solution or dispersion of a water-soluble cationic, anionic or nonionic polymer which is capable of being adsorbed to the hard surface, and which when applied to the hard surface, leaves a residual anti-soiling polymer layer thereon which increases the hydrophilicity thereof, whereby the hydration of the hard surface from the ambient atmospheric water vapor facilitates removal of soils subsequently deposited thereon, i.e. less work is required to remove the soil than in the absence of the residual layer.
• the invention provides a hard surface treating composition for cleaning the surface and for improving the soil removal characteristics thereof, the composition comprising an aqueous liquid containing at least one non-soap synthetic surfactant and a soil release promoting water-soluble cationic, anionic or nonionic polymer which is capable of being adsorbed to the hard surface, and which, when absorbed to the hard surface, leaves a residual anti-soiling polymer layer thereon which increases the hydrophilicity thereof, whereby the hydration of said hard surface with ambient atmospheric water vapor facilitates removal of soils subsequently deposited thereon.
• a method for improving the soil removal property of household hard surfaces which comprises applying to the hard surface an aqueous solution of a soil release promoting water-soluble cationic, anionic or nonionic polymer which will be adsorbed by the hard surface and drying the hard surface whereby said adsorbed polymer forms a residual anti-soiling hydrophilic layer of said soil release promoting polymer on said surface, whereby removal of soils subsequently deposited thereon requires less work than in the absence of said residual layer.
• a method for increasing gloss of worn tiles which comprises treating the worn tile with an aqueous solution of a cationic quaternized polymer having a molecular weight in the range of from about 4,000 to 100,000, the polymer being adsorbable to the surface of said tile and, when adsorbed to said tile, increases the hydrophilicity thereof.
• the anti-soiling or soil release polymers which are effective herein have in common the property of adsorbing to the hard surface being treated, for example, by associating to the silica groups of ceramic type materials, in such manner that the hydrophilic groups of the polymer are oriented away from the surface whereby the hydrophilic groups are available to attract and trap water molecules.
• the resulting hydrophilic surface can attract and trap ambient atmospheric water vapor (e.g. the moisture in a humid room) to more effectively reduce adhesion of solid (or as referred to by the inventors, to promote "abhesion") by any or all of the following mechanisms:
• the preferred polymers for providing soil release (abhesion) properties to hard surfaces are the cationic and anionic polymers, and especially the cationic quaternized polymethacrylates, such as the beta(trialkyl ammonium) ethylmethacrylates described in our prior application, Serial No. 297,807, and having repeating units of the formula where R i , R 2 and R 3 , which may be the same or different, are each lower alkyl groups of 1 to 4 carbon atoms, preferably methyl or ethyl.
• the corresponding acrylates can also be used.
• the cationic polymers useful herein include homopolymers of unsaturated amines which are at least partially and preferably wholly (e.g. at least 95%) quaternized with an appropriate counterion.
• the preferred unsaturated amines are aminoalkyl eaters of acrylic or methacrylic acid, in which the amino group may be substituted by one or two alkyl, alkenyl, aryl, aralkyl or other suitable groups, or by substituents which together with the nitrogen atom form a heterocyclic ring.
• the repeating units derived from the aminoalkyl ester is preferably of the formula (I): wherein R 1 and R 2 , which may be the same or different, are hydrogen or alkyl, or together with the nitrogen atom to which they are attached, form a heterocyclic ring; R 4 is an alkylene group containing 1 to 8 carbon atoms; and R 3 is methyl or hydrogen.
• both R 1 and R 2 are alkyls of 1 to 4 carbon atoms, especially methyl or ethyl.
• the ring may have from 5 to 7 atoms and may include 1 or 2 additional hetero atoms, such as N, S or O in addition to the amine nitrogen atom to which R 1 and R 2 are bonded.
• R 3 is preferably methyl and R 4 preferably has 2 to 4 carbon atoms, and especially preferably is ethylene.
• the units of formula (I) in the homopolymer are at least partially quaternized by reaction with a suitable alkyl salt of an acid, such as, for example, methyl or ethyl chloride, methyl or ethyl sulfate, dimethyl or diethyl sulfate, methyl or ethyl bromide, and the like.
• a suitable alkyl salt of an acid such as, for example, methyl or ethyl chloride, methyl or ethyl sulfate, dimethyl or diethyl sulfate, methyl or ethyl bromide, and the like.
• the quaternized cationic repeating unit in the resulting homopolymer will then have the following formula (II): where Ri, R 2 , R 3 and R 4 are as defined above, R 5 is a lower alkyl group of from 1 to 4 carbons, preferably methyl or ethyl, especially methyl, and X- is a monovalent anion or 1/m of an m-valent anion.
• At least 50%, preferably at least 80%, more preferably essentially all, i.e. from 95 to 100%, especially preferably 98 to 100% of the repeating units of the polymer have the quaternized form of formula (II).
• the molecular weight of the polymer is not especially critical so long as the polymer 1) is water-soluble, 2) has some surface activity, and 3) is adsorbed to the hard surface from its aqueous solution in such manner as to increase the hydrophilicity of the surface.
• the quaternized cationic polymers having molecular weights in the range of from about 4,000 to 100,000 or higher, preferably from about 5,000 to 50,000, more preferably from about 6,000 to 30,000 and especially preferably from about 12,000 to 26,000.
• the polymers tend to be too water-soluble to adhere to the hard surface while at molecular weight above about 100,000, especially above 50,000, the polymers tend to be insufficiently water-soluble or are more difficult to process and formulate into stable, pourable formulations.
• the preferred cationic quaternized polymers are the homopolymers as described above, it is also within the scope of the invention to use copolymers of the above amines and quaternized salts thereof with, for example, an acrylamide or acrylonitrile, so long as the copolymer retains the required surface active properties to adhere to the substrate while exhibiting the appropriate conformation to expose the hydrophilic portion of the polymer to be able to attract water and hydrate the surface of the substrate.
• the entire repeating units of the cationic polymer may be comprised of acrylamide units of formula (III): where R 6 is hydrogen or methyl; or acrylonitrile units of formula IV: where R 6 is as defined above.
• ethylenically unsaturated copolymerizable comonomers in amounts up to about 20 mol%, preferably up to 10 mol%, can also be included in the anionic polymer if they will not adversely impact on the solubility, adhesion and soil release properties of the polymer.
• Such copolymerizable comonomers mention may be made, for example, to unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, propionic acid, and the like, unsaturated olefins, such as ethylene, propylene and butene, alkyl esters of the unsaturated carboxylic acids, such as methylacrylate, ethyl acrylate, methyl methacrylate, hydroxy derivatives of these esters, such as, for example, 2-hydroxyethyl methacrylate, unsaturated aromatic compounds, such as styrene, methyl styrene, vinyl styrene, and heterocyclic compounds, such as vinyl pyrrolidone, and others.
• hydrophilic comonomers such as acrylic acid, methacrylic acid, vinyl pyrrolidone, etc., are preferred.
• water-soluble cationic polymers such as, for example, quaternary nitrogen substituted cellulose ethers, for example Polymer JR-30M, can also impart anti-soiling properties.
• the anionic soil release polymers which can be used in this invention include, for example, the soluble polymeric salts disclosed in U.S. Patent 3,696,043 to Labarge, et al., the disclosure of which is incorporated herein by reference thereto.
• soluble polymeric salts may be obtained by neutralizing copolymers of 1 to 2 moles of a monovinyl aromatic monomer per mole of an unsaturated dicarboxylic acid or anhydride there of to form solubilizing salt groups.
• the copolymer is an equal molar copolymer.
• Solubilizing salt groups include half-amide salts formed from the neutralization (interaction) of the anhydride group with ammonia or with a monoamine having at least one hydrogen attached to the amine nitrogen and having no other groups reactive with an anhydride.
• Neutralization of the unsaturated dicarboxylic acid copolymers with an alkali metal, ammonia or an amine produces carboxylate solubilizing groups by a simple acid-base reaction where X is a positively charged ion which may be an alkali metal ion such as sodium or potassium, an ammonium ion or a substituted ammonium ion.
• the neutralization of the anhydride group may be illustrated by the reaction of ammonia with a maleic anhydride copolymer (showing only the anhydride unit of the copolymer).
• the half-amide may be further neutralized by further reaction with ammonia or another base to form a half-amide salt, where X is the same as above.
• An N-substituted half-amide salt is formed when said amine is used in place of the ammonia.
• a soluble polymeric salt it is meant to include any of the unsaturated dicarboxylic acid or anhydride copolymer neutralization products which contain a sufficient number of salt groups to render said copolymer soluble in the concentrations employed. It is to be understood that complete neutralization of all the acid groups or anhydride groups may not be required to obtain the desired solubility, however, complete or substantially complete, e.g. at least 95%, neutralization is preferred.
• Any primary or secondary monoamine may be employed to neutralize the anhydride copolymers provided the amine has no other group reactive with an anhydride and providing it forms a salt group capable of solubilizing the copolymer. While a variety of aliphatic, cycloaliphatic, heterocyclic and like amines may be employed certain amines are preferred from the human toxicity and handling standpoint, since the products are principally intended for use by humans, and from the availability and cost standpoint.
• the lower alkyl amines such as diethylamine, dimethylamine and the like are frequently used.
• Alkali metal bases include hydroxides of sodium, potassium, lithium or the corresponding carbonates, bicarbonates, etc. are the most preferred neutralizing agents, especially the sodium salts.
• Ammonium hydroxide is the usual form of ammonia employed. Any amine may be used provided it forms a carboxylate salt group capable of solubilizing the polymer. Certain amines are preferred for the previously stated reasons.
• Typical amines for forming substituted ammonium ion-carboxylate salt groups include the mono-, di- and tri-alkyl amines (trimethyl amine, diethylamine, isopropylamine, etc.); mono-, di- and tri-alkanol amines (triethanolamine, diisopropanolamine, monoethanolamine, etc.); cycloaliphatic amines such as cyclohexylamine; heterocyclic amines such as morpholine; and like amines.
• copolymers themselves and their methods of preparation are well known to the art and need no detailed description herein. Briefly one widely used method is to prepare the polymers by solution polymerization employing a solvent which is a solvent for both the monomers and the polymer. Suitable free radical catalysts such as benzoyl peroxide may be used to initiate the polymerization which can be run over a wide temperature range. The monomers tend to polymerize readily in equal molar proportions. U.S. 3,336,267 discloses how to make non-equal molar copolymers. A variety of other patents disclose methods of polymerization by batch or continuous techniques or to produce low molecular weight or high molecular weight copolymers. It is also taught to employ solvents for the monomer only.
• the molecular weight of the copolymers may vary quite widely from about four thousand up to as high as 500,000 or more, so long as the criteria as described above for the cationic polymers are satisfied.
• Monomers which may be used to prepare the copolymers include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid and the like. Any of the anhydrides of the unsaturated acids may be employed.
• Aromatic monomers include styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene and similar well known monomers.
• Preferred copolymers are sodium salt of styrene-maleic anhydride or styrene-maleic acid.
• nonionic polymers which adsorb to the hard surface and increase the hydration thereof can also be used.
• polyvinyl pyrrolidone PVP
• poly(vinyl pyrrolidone-CO-dimethylaminoethyl methacrylate) also known as polyquaternium II
• polyethylene glycols ethylene oxide polymers, and the like provide anti-soiling benefits to hard surface treated therewith.
• silicone-based polymers fluorocarbon polymers, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride (i.e. Gantrez AN) and polyacrylates were tested as described below as neat 0.5% wt. aqueous solutions on ceramic tiles but did not confer any anti-soiling benefits or facilitate recleaning.
• the amount of the soil-releasing agent to promote abhesion is not particularly critical so long as thin residual anti-soiling layer of the polymer remains adhered to the hard surface after the aqueous solution thereof is dried or wiped off. Generally, however, at least, and usually no more than, a monomolecular layer of the polymer is sufficient to exhibit the full anti-soiling effect of the polymer since a monomolecular layer of the polymer should be adequate to form a hydrated water layer on the treated surface.
• Such monomolecular residual film or coating layer can be achieved with aqueous solutions containing as little as 0.02 weight percent of the soil release polymer, especially for new or unsoiled hard surfaces.
• a preferred concentration range is from about 0.04 to 5%, more preferably 0.08 to 1 %, by weight of the composition, of the soil release polymer.
• the expression "less work” in reference to the anti-soiling or recleaning property of the treated hard surface having a residual layer of polymer thereon means that deposited soil can be removed from the treated surface with less scrubbing or wiping when using the same cleaning composition or with a milder cleaning composition and less chemical action than for the same similarly soiled hard surface which has not been treated with a soil-release polymer according to the invention.
• soil release polymers can be used as such to provide easier "next time” cleaning performance
• Such cleaning compositions have in common the presence of one or more surface active detergent compounds, usually synthetic anionic (non-soap), cationic, nonionic, amphoteric or zwitterionic surfactants.
• surface active detergent compounds usually synthetic anionic (non-soap), cationic, nonionic, amphoteric or zwitterionic surfactants.
• Other common ingredients often present in such types of aqueous cleaning compositions include, for example, detergent builder salts; solvents; acids, bases and pH buffers; germicides, bactericides, and preservatives; thickeners; coloring agents and perfumes; and the like.
• any of these ingredients which do not interfere with the solubility and adherence of the anti-soiling polymer may be present in the hard surface cleaning and anti-soiling compositions of this invention although it is often preferred to exclude detergent builder salts which are often associated with spotting or streaking of hard surfaces.
• Organic solvents are often a preferred additive where needed to help solubilize the anti-soiling polymer or any other ingredient present in the composition.
• the poly(MDAEM) anti-soiling polymer may often form a slightly hazy aqueous composition and the incorporation of a small amount of isopropanol, for example, or other low molecular weight alcohol, can clarify the composition.
• amounts of solvent, when present will be in the range of from about 0.5 to 5% by weight, preferably about 2% by weight.
• the polymeric anti-soiling agents will, by themselves, provide a small contribution towards increasing the viscosity of the aqueous compositions, however, in view of the low "solids" concentrations in the typical hard surface treating or combined hard surface treating and cleaning compositions, the viscosities, even with the polymeric additive tend to be as low as about 7 cps or less. Without the polymer or added thickener viscosities of the aqueous composition tend to be less than 5 cps, for example, about 3 cps.
• product viscosities in excess of about 10 centipoises for instance, from about 10 to 100 cps for wipe- on products and from about 10 to 20 cps for spray-on products, are desirable.
• the increase in viscosity can be accomplished by addition of conventional polymeric thickening agents, such as polyacrylates, guar gum, Irish Moss, carrageenan, polycarboxy vinyl ethers and the like.
• the ionic nature of the additive must be taken into consideration.
• the anti-soiling polymer is anionic in nature, then cationic additives should be avoided.
• anionic polymeric thickeners, coloring agents, surfactant except as discussed below in connection with cationic polymer/anionic complexes, should be avoided.
• any of the surface active detergent cleaning compounds usually used in hard surface, all purpose or bathroom/kitchen cleaning products can be used in the present invention.
• Cationic, amphoteric or zwitterionic surfactant may also be used (except that cationic surfactant should be avoided in combination with anionic soil release polymers) although they are less preferred.
• Suitable nonionic surfactant detergent cleaning compounds include, but are not limited to those disclosed in our prior application Serial No. 297,807. More generally, mention can be made, for example, of polyethylene oxide and polypropylene oxide ethers of fatty alcohols, fatty acids, fatty amides, alkyl phenols and the like.
• Suitable surface active anionic detergent cleaning compounds include, for example, the water-soluble salts, especially the alkali metal salts, of sulfates and sulfonates of fatty acids and alcohols and the water-soluble alkali metal salts of the alkyl aryl sulfonates.
• the anionic includes, in the sale form, alkyl sulfates of 8 to 22 carbons, preferably 12 to 18 carbons; alkoxy (polyalkoxy) sulfates wherein the alkyl portion has between 12 and 18 carbon atoms and the alkoxy portion has from 1 to about 10 repeating units, the alkoxy portion most preferably being ethoxy of from 1 to 5 repeating units; alkyl phenoxypolyalkoxy sulfates wherein the alkyl portion has from about 8 to about 16 carbon atoms and the alkoxy portion is selected from the group of ethoxy and propoxy, the number of repeating units thereof being between 1 and 10, the alkoxy portion preferably being ethoxy of 1 to 5 repeating units; sulfonate alkyl and alkylaryl alkoxylates wherein the alkyl portion and the alkoxy portions are as previously set forth for the alkoxy (polyalkoxy) sulfates and alkyl phenoxypolyal
• anionic and nonionic surfactants can also be used with anionic anti-soiling polymers and mixtures of cationic and nonionic surfactants can similarly be used with cationic anti-soiling polymers.
• Amphoteric or zwitterionic surfactants can also be used along or with the anionic, cationic or nonionic surfactants.
• nonionic anti-soiling polymers any of the types of surfactants may be used.
• the amount of surfactant which will be included in the composition for cleaning purposes may vary widely depending on the intended use, type of surfactant, other ingredients in the composition, and other factors known in the art. However, for many types of hard surface, all purpose, and bathroom or kitchen cleaning compositions, the total amount of surface active detergent cleaning compounds will usually be in the range of from about 0.1 to 10% by weight, preferably 0.2 to 4% by weight.
• anionic surfactants in combination with cationic soil release polymers form complexes which modify the solubility of the polymer and, depending on the amount, as well as type of the anionic surfactant, these complexes can adversely or beneficially impact on either or both of the adsorption of the polymer to the hard surface and the abhesion performance of the polymer.
• the positive, negative, or neutral impact on adhesion and/or abhesion characteristics can be determined by routine experimentation.
• the preferred anionic surfactants for complexing with the cationic polymers for improving adhesion and facilitating recleaning are the alkali metal C 10 to C 18 alkyl sulfates or carboxylates, preferably C 12 to C 14 alkyl, such as sodium lauryl sulfate, the ethoxylated (2 to 10 moles ethylene oxide) C 14 to C 20 fatty acid soaps, and the ethoxylated (2 to 10 moles ethylene oxide) C 10 to C 18 fatty alcohol sulfates, such as sodium stearate condensed with 2 to 10 moles ethylene oxide, and sodium C 14 to C 16 alkyl ether (2 to 10 moles ethoxylation) sulfate.
• alkali metal C 10 to C 18 alkyl sulfates or carboxylates preferably C 12 to C 14 alkyl, such as sodium lauryl sulfate, the ethoxylated (2 to 10 moles ethylene oxide) C 14 to C 20 fatty
• the anionics are not limited to these but also include, for example, the mono and divalent alcohol sulfates and sulfonates, anionic carboxylates, olefin sulfonates, aryl sulfonates and the corresponding ethoxylated anionic surfactants.
• any of the anionic surfactants mentioned above for the anionic detergent cleaning compound when used in amounts which will not cause the cationic polymer complex to precipitate can be used.
• the complexes can often provide further improvements in anti-soiling properties, it is believed that the complex becomes slightly more hydrophobic and can, therefore, more readily deposit on and adhere to the hard surface without changing the orientation of the hydrophilic portion of the polymer with respect to the hard surface.
• the balance of the novel liquid hard surface anti-soiling/treating or anti-soiling/cleaning composition is water, preferably distilled water, reduced by any optional ingredients which may be present.
• the proportion of water in the compositions is about 80% to 94% by weight, preferably 85 to 92% by weight of the composition.
• additional ingredients may be optionally present to provide cosmetically appealing products and increase consumer acceptability.
• adjuvants include coloring agents, fragrances, perfumes, viscosifiers, germicides, bactericides, disinfectants, and pH adjusting agents.
• the acidic compounds for modifying pH mention can be made of the organic acids, such as lower aliphatic monocarboxylic acids, hydroxycarboxylic acids and dicarboxylic acids.
• the aliphatic monocarboxylic and dicarboxylic acids include C i -C e alkyl and alkenyl monobasic and dibasic acids, such as glutaric acid, succinic acid, propionic acid, adipic acid, acetic acid and the like.
• the hydroxy carboxylic acids include hydroxyacetic acid and citric acid. Mixtures of saturated aliphatic dicarboxylic acids, and especially mixtures of adipic, glutaric and succinic acids are commercially available and are conveniently used. These mixtures are described in greater detail in our prior application Serial No. 297,807.
• inorganic acids such as HCI, HN0 3 , H 2 S0 4
• organic acids can also be used, but usually in combination with organic acids, or appropriately diluted.
• organic and inorganic bases such as ammonia, ammonium hydroxide and various amines, amides and alkanolamines and alkanolamides, can also be added to raise the pH were necessary or desired to formulate less acidic or more alkaline formulations.
• product pH not only affects cleaning performance against specific soil types, but that the pH will also have an affect on the form and stability of the cationic or anionic soil abhesion promoting polymers. It is also well understood that the choice and selection of the surfactant component and other optional additives, such as, coloring agents, thickening agents (viscosifiers) and the like will be made in consideration of the ionic nature of the anti-soiling polymer.
• the complex of the cationic anti-soiling polymer with the anionic surface active agent should be formed out of the presence of the cationic compound since, otherwise, the cationic compound and anionic compound may form a complex rather than the desired anionic surfactant-cationic polymer complex.
• anionic surfactants except as described above, and anionic coloring agents or thickening agents, and other anionic additives should be avoided since they tend to form insoluble complexes with the cationic polymer.
• Anionic surfactant concentrations in cationic polymer embodiments should, in any case, be limited to about 0.25% by weight, while anionic polymer thickening agents or other anionic polymers should be altogether avoided.
• An anti-soiling polymer according to the invention is used in the following bathroom cleaning composition:
• the anti-soiling performance of the composition is tested on each of a new white ceramic tile and of a soap scum soiled new or etched white ceramic tile.
• One-half of the new tile is immersed and the other half is immersed in the same formulation but without the poly(MDAEM). After removal from the bath, the tile is gently wiped dry with a soft paper towel.
• the soap scum soiled tiles are prepared by spraying the tiles with a 250 g/I solution of CaCb. H20 followed by a red dyed 5% sodium oleate solution. The tiles are allowed to dry for one hour at 30°C and the soiling procedure is repeated. The soil so produced is uniform and reproducible within accepted limits.
• each soap scum soiled tile is cleaned with the invention composition described above and the other half is cleaned with the same composition excluding the poly(MDAEM).
• the tiles are cleaned by hand until all the soap scum is removed.
• the tiles are rinsed and air-dried and the entire tile surface is re-soiled with soap scum by the same procedure as described above.
• the re-soiled tile is then washed with a mild cleaning consisting of a 1% aqueous solution of a 1:1 w/w mixture of Neodol 91-6/Neodol 91-2.5. This mild cleaning solution will provide a minimum amount of chemical cleaning action.
• the tiles are cleaned according to Standard Practice Instruction 8173 using the mild cleaner and 10 cycles on a Gardner Abrasion Tester.
• the tiles are mounted in the Tester equipped with two cellulose sponges measuring 5 cm x 5 cm x 5 cm.
• Three grams of the mild cleaner are pipetted onto the sponges wetted with 5 gm water.
• a reflectometer is used to measure the reflectance before and after the 10 abrader cycles and the percent soil removal is determined. The results are shown in the following table.
• Example 1 The procedure of Example 1 is repeated on soap scum soiled new tiles prepared as described in Example 1 using the following composition:
• the untreated side showed essentially no cleaning ( ⁇ 10% soil removal) whereas the poly(MDAEM) treated side showed an average of 90% soil removal.
• Example 2 The same test as described in Example 1 is carried out on unsoiled polymethacrylate test plates, except that only 5 cycles are applied on the Gardner Abrasion tester using the same mild cleaner as used in Example 1.
• the average soil removal on the poly(MDAEM) treated side is 66% and on the untreated side is 45%. No significant difference in the shine or gloss of the surface is observed.
• Example 1 The test procedure of Example 1 is repeated on new white ceramic tiles treated with neat 0.5% aqueous solutions of either poly(MDAEM) or the following polymers: polyvinyl pyrrolidone (avg. mol. 26. 360,000); Gafquat 755N (vinyl pyrrolidone/dimethylaminoethylmethacrylate copolymer, polyquaternium II), Polymer JR-30M (a quaternary nitrogen substituted cellulose ether, where 30M is the designation of viscosity at 1% concentration, sodium salt of styrene-maleic anhydride copolymer, Sokalan (CP7) (sodium salt of copolymer of methacrylic acid and maleic anhydride), polyethylene terephthalate/polyethylene oxide terephthalate copolymer, and polyethylene oxide (mol.
• poly(MDAEM) polyvinyl pyrrolidone
• Gafquat 755N vinyl pyrrolidone/
• the present invention provides a composition and method for treating hard surfaces, such as ceramic tiles, porcelain, enamel, Formica, polymethacrylates, and the like, such as found in bathrooms (sinks, tubs, shower stalls, walls, floors, vanities, etc.), whereby the treated surface is modified to increase its hydrophilicity, with or without simultaneous cleaning of existing soil.
• any further soiling becomes easier to clean during subsequent cleaning (with the same or different cleaning solution) because the built-up soil will not adhere as tenaciously to the treated surface as it would to the same surface which has not been treated with an anti-soiling polymer according to the invention.
• the performance of the soil release polymer containing compositions of this invention is dependent on the prevailing humidity of the ambient atmosphere: if there is little moisture in the air the degree of hydration of the treated surface becomes insufficient to adequately prevent soil adhesion by whichever of the above proposed theories or other mechanism is in operation.
• humidity levels of at least about 35% RH at 70 F will provide the best results upon subsequent recleaning.
• the prevailing atmospheric moisture levels will be equivalent to at least 35% RH.
• treating compositions of this invention are not limited to household hard surfaces but can also be used to facilitate recleaning for other types of hard surfaces, such as automobiles (e.g. vinyls, metals, painted surfaces, etc.), window casements and the like.
• the aqueous liquid hard surface modifying compositions including the treating and cleaning compositions are typically homogeneous compositions which exhibit stability at both reduced and increased temperatures. More specifically, such compositions remain stable in the range of 5°C to 40°C.
• the liquids are readily pourable and free flowing from any suitable container or may be sprayed from a pump-type sprayer.
• compositions of this invention are that by virtue of the increase in viscosity from the polymer anti-soiling agent, especially the cationic polymer-anionic surfactant complex, the products can be formulated with viscosities between about 10 to 20 cps which allows the products to be sprayed with most conventional pump spray nozzles with substantially less misting than for lower viscosities but without clogging the spray nozzle as would tend to occur with higher viscosities.
• compositions are directly ready for use. Only minimal rinsing is needed and substantially no residue or streaks are left behind on the cleaned surface. Because the preferred compositions are free of detergent builders, such as alkali metal polyphosphates they provide a better "shine", i.e. less streaking, on cleaned hard surfaces.
• the inventive compositions are prepared simply by combining all of the ingredients in a suitable mixing vessel or container.
• the various ingredients can be added sequentially, or all at once, to form an aqueous solution of each or all of the essential ingredients, care being taken to avoid mixing together any anionic and cationic components as described previously.
• the fragrance is first dissolved in a water dispersible nonionic surfactant which is then added to the other ingredients in aqueous acid solution.
• the surfactant/fragrance mixture is added to the aqueous acid solution containing the remaining ingredients, the solution may become slightly hazy.
• a cationic disinfectant compound is added to the aqueous mixture, the fragrance becomes completely solubilized and the final mixture is clear as well as stable. Additional base may then be added, if desired, to increase product pH.
• the compositions may be prepared at room temperature.
• compositions of this invention are applied to the surfaces to be modified/cleaned with a cloth or sponge or by spraying onto ceramic or other surfaces which may have been soiled by accumulations of insoluble soaps, mineral deposits, and oily soils.
• the compositions, without added thickeners, other than the soil-releasing polymer are of somewhat higher viscosity than water, generally up to about 3-10 cps or higher, the polymer complexes providing higher viscosity in general.
• the material will usually be allowed to remain on the surface to be modified for a period from 10 seconds to 5 or 10 minutes, but preferably such contact time will be from about 30 seconds to five minutes or from 1 to 3 minutes.
• the liquid composition may then be removed either by wiping or rinsing with water.
• compositions Depending on the degree of soiling of a hard surface not previously treated with the invention composition more or less strenuous wiping and rinsing may be required. However, in all cases subsequent recleaning requires substantially less work to remove any subsequently deposited soils. These compositions leave substantially no spots or streaks whether or not they are rinsed from the cleaned surface.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• 1991
  • 1991-07-15 CA CA 2047085 patent/CA2047085A1/en not_active Abandoned
  • 1991-07-15 EP EP19910201866 patent/EP0467472A3/en not_active Withdrawn
  • 1991-07-16 GR GR910100312A patent/GR1001501B/el unknown

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