US3716488A - Textile fabric cleaning compositions - Google Patents

Textile fabric cleaning compositions Download PDF

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US3716488A
US3716488A US3716488DA US3716488A US 3716488 A US3716488 A US 3716488A US 3716488D A US3716488D A US 3716488DA US 3716488 A US3716488 A US 3716488A
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water
alkyl
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R Kolsky
V Chase
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Stevens & Co Inc J P
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Stevens & Co Inc J P
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/04Processes in which the treating agent is applied in the form of a foam
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0031Carpet, upholstery, fur, and leather cleansers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite, attapulgite
    • C11D3/1266Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite, attapulgite in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid, cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid, cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid, cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/06Processes in which the treating agent is dispersed in a gas, e.g. aerosols
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/1026Other features in bleaching processes
    • D21C9/1036Use of compounds accelerating or improving the efficiency of the processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/27Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2279Coating or impregnation improves soil repellency, soil release, or anti- soil redeposition qualities of fabric

Abstract

ACCORDING TO THE PRESENT INVENTION, A STABLE AQUEOUS COMPOSITION OF MATTER IS PROVIDED THAT INHIBITS SOILING AND COOPERATES WITH SELECTED DETERGENTS TO PRODUCE SUPERIOR SHAMPOOING AND CLEANING ACTION ON APPLICATION TO TEXTILE FABRICS. THE SOIL PICK-UP INHIBITING EFFECT OF THE FORMULATION IS ATTRIBUTABLE TO AN AQUEOUS COMPOSITION OF MATTER COMPRISING FINELY DIVIDED PARTICULATE CLAY FROM THE SMECTITE GROUP; AN "ESSENTIALLY" WATER-SOLUBLE POLYMER, SUBSTANTIALLY FREE OF CHROMOPHORES, THAT DRIES TO A TACKFREE, NON-STICKY RESIDUE CHARACTERIZED BY ANIONIC PROPERTIES OR THE CAPACITY TO FORM AN ASSOCIATION COMPLEX FOR THE PURPOSE OF CARRYING AN ELECTROLYTIC CHARGE IN THE COMPOSITION; AND IN EFFECTIVE SOIL PICK-UP INHIBITORS A DISPERSE POLYMER WITH A TG OF AT LEAST 15* C. THAT IS NON-FILMFORMING AT AMBIENT TEMPERATURES. THE DETERGENTS THAT EFFECTIVELY COOPERATE WITH THE SOIL PICK-UP INHIBITORS ARE DETERGENTS CHARACTERIZED BY ANIONIC OR NON-IONIC PROPERTIES IN AN ALKALINE MEDIUM RANGING IN PH UP TO ABOUT 11.

Description

Unite d States Patent O US. Cl. 252-155 8 Claims ABSTRACT OF THE DISCLOSURE According to the present invention, a stable aqueous composition of matter is provided that inhibits soiling and cooperates with select detergents to produce superior shampooing and cleaning action on application to textile fabrics. The soil pick-up inhibiting effect of the formulation is attributable to an aqueous composition of matter comprising finely divided particulate clay from the smectite group; an essentially water-soluble polymer, substantially free of chromophores, that dries to a tackfree, non-sticky residue characterized by anionic properties or the capacity to form an association complex for the purpose of carrying an electrolytic charge in the composition; and in effective soil pick-up inhibiting amounts, a disperse polymer with a Tg of at least 15 C. that is non-filmforming at ambient temperatures. The detergents that effectively cooperate with the soil pick-up inhibitors are detergents characterized by anionic or non-ionic properties in an alkaline medium ranging in pH up to about 11.

This is a continuation-in-part of our application Ser. No. 69,948, filed Sept. 4, 1970, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to shampoo compositions of the type adaptable for use in the shampooing and cleaning of textile fabrics, and more particularly to shampoo compositions that inhibit soil redeposition after cleaning.

Shampoo formulations have been previously developed and employed in the cleaning of textile fabrics, including pile fabrics of the type normally found in rugs and carpeting. Many of the prior shampoo formulations involve the use of detergent materials in aqueous or solvent mediums, in which dirt and soil are removed by normal detergent action. Others involve formulations that are applied dry or damp to the touch to the cleaning surface on which soil and dirt particles are, in effect, loosened and removed by mild detergent action. Loosened particles are usually thereafterabsorbed on relatively large particles of filler material and subsequently vacuum drawn from the cleaning surface.

Commercial formulations of the type described above have met with varying degrees of success; however, a disadvantage intrinsic to these prior formulations is manifested by the tendency of the shampooed area to resoil soon after treatment. In many instances the prior formulations appear to promote soiling on the shampooed areas.

Therefore, the present invention provides a shampoo formulation that is simply and easily applied, highly efiicient in cleaning and shampooing action and'is characterized by cooperation between components to inhibit resoil on the shampooed area. More specific advantages of this invention will become apparent from the detailed description that follows.

SUMMARY OF THE INVENTION In accordance with the present invention, a stable aqueous composition of matter is provided that inhibits 3,7l6A8 Patented Feb. 13, 1973 ICO soiling and cooperates with select detergents to produce superior shampooing and cleaning action on application to textile fabrics.

The soilpick-up inhibiting effect of the formulation is attributable to an aqueous composition of matter comprising finely divided particulate clay from the smectite group; an essentially" water-soluble polymer, substantially free of chromophores, that dries to a tack-free, non-sticky residue, characterized by anionic properties or the capacity to form association complexes for the purpose of carrying an electrolytic charge in the composition; and, in effective soil pick-up inhibiting amounts, a disperse polymer with a Tg of at least 15 C. that is non-filmforming at ambient temperatures. The detergents that effectively cooperate with the soil pick-up inhibitors are detergents characterized by anionic or non-ionic properties in an alkaline medium ranging in pH up to about 11.

The soil pick-up inhibitors may be formulated for separate application to textile fabrics; however, they are particularly effective in cooperation with the select detergents. The clean appearance of shampooed textile fabrics endures for unexpected lengths of time, even during periods of frequent use.

The smectite group of clays, as characterized in Clay Minerology, second edition, by Ralph E. Grim, published in '1968 by McGraw-I-Iill, includes, among others, the following species, reported as having the typical formula indicated:

nontronlte OH) I (Si .r4-1}lo.ta

hectorite (011)4(Sl5ME5-14-{11M6 010 Name and

The montmorillonite species is well known as the main component of bentonite clays.

The Na in smectite group clays is exchangeable as indicated by the typical species formulas, and the montmorillonite species, in particular, may be magnesium modified by substitution of sodium for magnesium. In general, the smectite group clay lattice structure is expandable between silicate layers and expands several times its dry volume when soaked in water. The manner in which smectite group clays interact with other components of the composition to improve performance is unknown; however, clays of other groups are essentially ineffective as soil inhibitors or to enhance shampoo performance.

The montmorillonite species, which is readily available, is particularly effective in the practice of this invention, however, an admixture of smectite group clays provides the best results. A preferred admixture of smectite group clays, in terms of resoil and shampoo performance, predominantly contains the montmorillonite and hectorite species.

It is found that clay or other powdered material which contains a minor but significant amount of clay from the smectite group is also effective, the degree of effectiveness being apparently directly related to the content of smectite group clay. For instance, bentonite clay, which consists predominantly of the montmorillonite species is extremely useful in the practice of this invention, particularly when the montmorillonite content of the bentonite is at least 80 weight percent or when the bentonite is admixed with additional montmorillonite to provide at least 80 weight percent montmorillonite based on the admixture.

The essentially water-soluble polymers employable in this invention are substantially free of chromophores, dry to a tack-free, non-sticky residue and exhibit anionic properties or form association complexes for the purpose of carrying an electrolytic charge in the aqueous composition. f-Essentially water-soluble polymers include polymers that are, of course, water-soluble and polymers that are capable of being solubilized by well-known conventional techniques; for example, acidic polymers that are solubilized by conversion to the salt form using conventional titration techniques with an alkali base, such as sodium hydroxide. In general, polymers free of chromophores do not contain conjugated double bonds or azo groups, and are not readily oxidized or degraded to form conjugated double bonds. Polymers that dry to a tackfree, non-sticky residue are usually not viscous or oily in the dry state and, preferably, dry to a powdery form.

The manner in which the polymers complex for the purpose of carrying an electrolytic charge is not completely understood; however, it is believed that the acceptable normally non-ionic polymers introduced into the composition undergo molecular association with other components of the system which substantially alters the ionization constant of the association product. Whether molecular association occurs through intermolecular association with ionic species or other polymers is not known; however, these associations are generally attributed to hydrogen bonding effects. Although the manner in which polymer associations occur within the composition is unknown, it is clear that polymers which are normally nonionic in aqueous solutions, and are incapable of forming such associations, do not coact with other components of the composition to inhibit resoil or enhance shampoo performance.

Polymers conforming to the above criteria that may be employed in the present invention include acrylic acid and methacrylic acid polymers and copolymers such as poly- (acrylic acid), poly(methacrylic acid), copolymers of acrylic acid and acrylamide and copolymers of acrylic acid and maleic acid; alginic acid and its salts such as potassium alginate, sodium alginate, ammonium alginate and propylene glycol alginate; carboxylated cellulose derivatives and their salts such as sodium carboxy methyl cellulose; polymeric sulfonic acid derivatives such as poly (vinyl sulfonic acid) and poly(styrene sulfonic acid); sulfuric acid ester salts of polyglycol ether compounds; gum karaya; poly(alkylene oxide) such as poly(ethylene oxide); polyvinylpyrrolidone; guar gum; poly(vinyl alcohol); polymeric maleic acid or maleic anhydride derivatives such as styrene-maleic acid copolymer and vinyl methyl ether-maleic acid copolymer; gum arabic; gum ghatti; locust bean gum; pectin; carboxy methyl starch; and polypeptides such as poly(glutamic acid). Particularly outstanding results are obtained with copolymers of acrylic acid and acrylamide.

The usable polymers and copolymers are water-soluble or at least capable of being solubilized in water by the addition of a compound which neutralizes or complexes the polymer or copolymer. The polymers and copolymers can be solubilized in water by reaction with a base having a dissociation constant of at least 1.07

As previously indicated, some of the suitable essen tially water-soluble polymers are normally non-ionic in aqueous solutions and are formed into association complexes for the purpose of carrying an electrolytic charge. Of the polymers listed above the following must be formed into complexes: poly(alkylene oxide), poly(vinyl-pyrrolidone), poly(vinyl alcohol), and guar gum. These complexes are formed by known procedures. As a specific illustration, the manner in which poly(ethylene oxide) complexes to form an intermolecular association product within the context of this invention is described by K. L. Smith, A. E. Winslow, and D. E. Petersen in the article Association Reactions for Poly(alkylene oxides) and Polymeric Poly (carboxylic acids) at 51 Ind. Eng. Chem. 1361- 64 (November 1959).

Disperse polymers suitable for use in the present invention are colorless or light colored, are non-filmforming at ambient temperatures and have glass transition temperatures (Tg) of at least 15 C. The amount of disperse polymer used in the composition will vary within wide limits and will depend to a great extent on the activity of the disperse polymer selected for use in the composition, as well as other constituents in the complete formulation. The amount employed will also depend to some extent on the nature and characteristics of the ma terial being cleaned, or whether the fabric is cotton, rayon, acetate, wool, polyester, acrylic or of other origin or mixtures thereof, the purpose for which the fabric is intended, the degree of cleanliness desired and other variables. For most purposes, it has been found that from about 0.1 to about 19% by weight based on the weight of a complete shampoo formulation is satisfactory and with amounts of from about 0.2 to 7% by weight of a formulation being preferable.

As specific examples of various polymers, the following are illustrative:

(a) homopolymers and copolymers of lower alkyl methacrylates, lower alkyl acrylates, phenylethylene, chloroethylene; and

(b) copolymers of poly(vinylchloride) and acrylate derivatives.

Disperse polymers suitable for use in the practice of this invention are dispersible in water. The aqueous dispersion may be made by methods already known to the art; for example, by emulsion polymerization techniques.

Among the numerous detergents that are anionic or non-ionic in an alkaline medium ranging in pH up to about 11, its being understood throughout the specification and claims that the alkaline medium is aqueous, the preferred detergents include:

(a) Fatty acid amides of alkylol amines of the general formula wherein R is alkyl with a chain length of 5 to 21 carbon atoms. Compounds of this general class are described in U.S. Pat. 2,089,212. In addition, these compounds are described in some detail by I. P. Sisley and P. J. Wood in the Encyclopedia of Surface-Active Agents, volume II (1964), Chemical Publishing (10., pp. 148150, as Kritchevsky reaction products.

In a preferred member of this class of compounds R is derived from coconut oil fractions which vary from C to about C the dominant fraction being C (b) Inner salts of substituted aminoacetic acid of the general formula wherein R is selected from the group consisting of alkyl and alkylene radicals with a chain length of 1 to 22 carbon atoms and acyl derivatives containing up to 22 carbon atoms and wherein R is selected from the group consisting of hydrogen and alkyl radicals containing up to 22 carbon atoms. Compounds of this class are described and the preparation therefor disclosed in U.S. Pat. 2,217,846. The compounds of this class are generally referred to as substituted betaines. Preferred members of this class in the practice of the present invention include: C-cetyl betaine, C-decyl betaine, N-lauryl betaine,

N-coconut oil-amido propyl dimethyl betaine, and N-cetyl betaine.

(c) Tertiary amine oxides of the general formula R3R4R5N wherein R is alkyl with a chain length of 6 to 22 carbon atoms, and R and R are selected from the group consisting of lower alkyl and lower hydroxyalkyl radicals.

Methods for the preparation of this class of compounds are well-known to the art and are described, for example, in U.S. Pat. 2,169,976. A particularly preferred member of this class in the practice of the present invention is N,N-bis(2-hydroxy ethyl)decylamine oxide.

(d) Alkali metal salts of hydroxy alkyl sulfates wherein the alkyl group contains from to 20 carbon atoms. Compounds of this class are described in U.S. Pat. 2,452,943. Illustrative examples of suitable sulfates within this class include sodium, lithium or potassium sulfate salts of lauryl, myristyl, and cetyl alcohols. In addition, magnesium lauryl sulfate is found to be particularly effective in the practice of this invention, although magnesium is sometimes considered to be an alkaline earth metal.

(e) N-acylated sarcosinates wherein the acyl group has a chain length of 10 to 20 carbon atoms. Members of this class of compounds generally found to be most effective in the practice of this invention are represented by the general formula CH (CH CON(CH CH COOB wherein n is an integer from 4 to 20 and B represents a cationic salt-forming nucleus. These effective sarcosinates may be prepared by treating the acid or sarcosine form of the compound with an organic or inorganic base. A preferred member of the particularly effective group of sarcosinates is sodium lauroyl sarcosinate.

(f) Alkali metal salt of an alkanoyl alkyl amine sulfonic acid of the formula wherein R is alkyl, cycloalkyl or alkenyl with a chain length of 5 to 21 carbon atoms, R" is alkyl with a chain length of 6 to 22 carbon atoms, and A is an ion derived from an alkali metal. Compounds of this class, usually referred to as taurates, are described in general, together with methods for their preparation in U.S. Pat. 1,932,180 and U.S. Pat. 2,542,385. As specific examples of various members of this class, the following are illustrative: sodium N-methyl-N-oleoyl taurate, sodium N-cyclohexyl- N-palmitoyl taurate, sodium N methyl N palmitoyl taurate, sodium N-methyl-N-coconut oil acid taurate, the long-chain alkyl substituent being derived predominantly from the C and C fractions of coconut oil. Sodium N-methyl-N-tallow .acid taurate is found to be especially effective, wherein the long-chain substituent is derived from saturated and unsaturated C to C fractions of tallow acid.

At least one, and preferably at least two, suitable detergents are included in the shampoo composition of this invention to achieve satisfactory performance. In one preferred embodiment of the shampoo composition small but effective amounts of a tertiary amine oxide and fatty acid amide of an alkylol amine, both detergents being chosen from the above-defined classes, are included in the composition. In another preferred embodiment of the shampoo composition small, but effective amounts of The chelating agents which may be introduced into the composition are generally of the type that soften hard water by sequestering divalent and trivalent hard Water ions. Tetrasodium (ethylenedinitrilo) tetraacetate is found to be a particularly effective chelating agent.

Wetting agents may be added to the composition in effective wetting amounts. The amount of wetting agent employed will depend to a great extent on the surface activity of the agent in the formulation. A particularly effective group of surfactants that may be employed in the present invention are the dialkyl sulfosuccinates.

DESCRIPTION OF PREFERRED EMBODIMENTS Satisfactory resoil results are obtained when the aqueous composition of this invention contains up to about 40% water insoluble solids and is formulated to include from about 0.1 to about 8 Weight percent of the smectite group clays, from about .02 to about 19 weight percent of the essentially Water-soluble polymer, and from about 0.1 to about 19 Weight percent of the disperse polymer. When about 0.1 to about 15 weight percent of at least one synthetic detergent, of the type previously described, is employed in the formulation, effective cleaning and shampoo performance is obtained.

An improvement in the effectiveness of the shampoo composition is observed when the average disperse polymer particle size is not more than 10 microns, and preferably the average particle size does not exceed 5 microns. When disperse polymer particles are within the contemplated size range, they may be uniformly dispersed throughout the aqueous shampoo composition to insure homogeneity within the composition for substantial periods of time. To further insure that the dispersion is homogeneous, a small but effective amount of surfactant of the type described in U.S. Pat. 2,441,341 may be added to the shampoo composition.

Although satisfactory performance is observed when the weight percent of components is formulated as above, the preferred compositions contain from about 0.2 to about 7 weight percent disperse polymer, from about 0.05 to about 2.5 weight percent essentially water-soluble polymer, from about 0.2 to about 10 weight percent synthetic detergent and 0.1 to 6% smectite group clays. Additionally, in a particularly preferred embodiment of the shampoo composition, formulated for aerosol use, the water-insoluble solids content of the composition does not exceed about 15% based on the formulation.

'Usually the aqueous dispersion or composition of this invention will contain up to about 20% water-insoluble solids by weight, generally identifiable as disperse polymer and clay material and will have a pH of about 8.0 to about 11.0. A significant attribute of aqueous dispersions formulated according to this invention is their stability against separation for substantial periods of time. Any separation that may occur is readily corrected by agitating the container in which the composition is stored. Mild agitation should restore the composition to its original homogeneous state.

The shampoo formulations can be applied in liquid form or as an aerosol spray. When applied in liquid form, e.g., with a sponge, the formulations are normally diluted with water prior to use to maximum concentrations of water-insoluble solids of up to about 10%, the solids being constituted principally by the disperse polymer and clay particles. Employing the formulation in such solids concentration results in excellent cleaning action and minimizes resoil on the clean area. When used as an aerosol spray, the formulations are packaged in a pressure container, along with a liquified, normally gaseous propellant.

The composition of the present invention finds principal use as a shampoo for pile textile fabrics. It 'has, generally, greater application to heavy, durable fabrics having a nap or pile of the type not usually dry cleaned or laundered. More particularly, the present invention, in

its narrowest application, is directed to the shampooing of rugs and carpets. The textile fabrics may be vegetable, synthetic or of animal origin, including mixtures of these. Synthetic tfibers, as the term is used herein, includes viscose rayon, acetate rayon, nylon, polyester and acrylic type fibers. The vegetable fibers contemplated include cotton, jute and the like. Wool is illustrative of suitable animal fibers.

For the application of the present invention to a textile fabric, the formulation of the present invention is applied by suitable applicator, for example by aerosol spray, sponge, sponge mop, or other suitable device to the surface to be Shampooed. Effective results are obtained when the formulation is evenly distributed over the -fabric surface to provide an add-on of .005 to 2 oz. of

solids per sq. yard of textile fabric. In shampooing of pile fabrics it is preferred that the add-on be about .05 to 1 oz. of solids/sq. yd. of pile fabric.

It is an important feature of the formulation of the present invention that its application does not result in significant modification of hand of the fabric treated, nor does it significantly change or modify the color thereof.

In order to illustrate the present invention, the following examples are given primarily by way of illustration. Specific enumerations and details found therein should not be construed as limitations on the present invention, except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specified.

EXAMPLE 1 An admixture was prepared containing 2.0 parts mag nesium montmorillonite and 0.33 part tetrasodium (ethylenedinitrilo) tetraacetate. The admixture was reduced to a blend during the addition of 73:14 parts water under conditions of agitation in an Eppenbach mixer. When the blend was substantially homogenous, parts of an aqueous composition containing 30% by weight of active ingredients were added under conditions of mild agitation to minimize the amount of air incorporated therein, the active ingredients were methyl methacrylate polymer (dispersed in the water) and acrylamide-acrylic acid copolymer (dissolved in the water) with the relative weight ratio of polymer to copolymer in the aqueous composition being about 8 to 1.

A separate admixture was prepared containing 3.3 parts of a 45% aqueous solution of 2,2'-decyl diethanol amine oxide and 2.0 parts of an aqueous 37% solution containing a fatty acid amide of an alkylol amine, as herein described, distributed by GAF Corp. and generally available under the tradename Antaron FC-34. Fatty acid amides of alkylol amines of the Antaron FC-34 type are generally prepared by reacting coconut oil with 2-[(2-aminoethyl)amino] ethanol. Dispersed in this mixture was 0.1 part of Fluorescent Brightening Agent C.I. 185. The admixture was then blended with 8:13 parts of water, and to the aqueous blend 1.0 part of admixed sodium l,4-bis(2-ethylhexyl) sulfosuccinate-sodium ben zoate was added.

When the aqueous blend of surfactants was homogenous, it was added to the magnesium montmorillonite dispersion with mild agitation to minimize the incorporation of air therein.

EFFECTIVENESS OF THE FORMULATION AS AN ANTISOILANT A portion of the above prepared concentrate was diluted with water to about 4 times its volume. The formulation, in diluted form, was sprayed on l-meter squares of new, unused carpet to provide substantially even distribution thereupon and a solids add-on of about 0.32 oz. solids/sq. yd. of the fibers. The phrase face weight of the fibers is herein defined as the weight of the carpet minus the weight of the jute backing. The carpets treated in this manner were all prepared from unbleuded synthetics including acrylic, nylon, polyester, polypropylene and modified acrylic fibers. New, unused wool carpet samples were treated in similar fashion except that the solids add-on was increased to about 0.9 oz. solids/ sq. yd.

The pretreated carpet samples were air dried. No change in appearance was observed, either with respect to color or to hand.

For purposes of control, l-meter squares of the same kinds of materials as treated above were treated with each of three leading commercial carpet shampoos. In separate tests l-meter swatches of carpet samples were treated with the formulation disclosed in US. Pat, 3,433; 666, particularly the formulation set forth in Example 9 therein, i.e., an aqueous dispersion of methyl methacrylate polymer and sodium polyacrylate with a trace amount of sodium cetyl sulfate included therein.

Visual comparisons of the samples tested were made after the treated samples were dry, The samples treated with the formulation of Example 1 demonstrated resoil inhibiting qualities. The samples were exposed to pedestrian traffic. The samples were subjected to daily cleaning procedures utilizing an upright beater-bar type vacuum sweeper. With respect to test comparisons made on beige acrylic carpets, the formulation of Example 1 was observed to be more effective than the formulation disclosed in US. Pat. 3,433,666 in reducing the soiling rate and more effective than the best of the three leading carpet shampoos currently on the market. Two other lead EFFECTIVENESS OF THE FORMULATION AS A CLEANSING AGENT One-meter square carpet samples prepared from acrylic fibers dyed to a red or gold shade were treated with the formulation of. Example 1 providing for uniform distribution of a solids add-on of about 1.6% 1 and submittted to uniform soiling conditions of pedestrian traffic for two weeks. An aliquot portion of shampoo concentrate was diluted to about 8 times its volume by addition of water and applied to the soiled samples. The dilute dispersion was manually distributed in a substantially uniform marmer over the samples with a nylon brush and air dried. The treated samples were rotated and their location changed every two days.

For purposes of establishing a control, l-meter squares of acrylic carpeting, soiled by the same procedure as set forth above, were shampooed by manually distributing each of three leading commercial carpet shampoos, with a nylon applicator, over the fiber surface in a substantially uniform manner. The carpet samples treated had been previously dyed to a red or gold shade.

The formulation prepared according to Example 1 readily restored carpet luster and color tone. The formulation of Example I appeared to be more effective in restoring the aesthetic qualities of the original carpeting than the other commercial formulations tested. In particular, after removal of the Example 1 formulation the carpet sample did not have'a whitish cast or hue. All comparative testing in this procedure was made with observation by the human eye.

Shampooed carpet samples were exposed to radiation of the ultraviolet and visible spectra types in a Fadeometer for 20 hours. The degree of yellowing observed with respect to carpet samples treated with the Example 1 formulation was within aesthetically acceptable limits.

1 On the face weight of the fibers.

9 EXAMPLE 2 Shampoo concentrate was prepared in the manner described in Example 1; however, the amount of admixed sodium 1,4-bis(ethylhexyl) sulfosuccinate and sodium benzoate added to the aqueous blend was increased to 2.4 parts and the total amount of water added to the blend was reduced to 79.87 parts.

Samples were tested in the same manner and under the same conditions for resoiling and cleaning qualities as heretofore described in Example 1 with substantially the same results.

EXAMPLE 3 Shampoo concentrate was prepared in the manner described in Example 1, except that the amount of decyl diethanol amine oxide solution therein was increased to 6.6 parts, the amount of Antaron FC-34 was increased to 4.0 parts and 0.3 part of Triton X-100 dispersant was substituted for the admixed sodium l,4-bis(ethylhexyl) sulfosuccinate-sodium benzoate. In addition, tetrasodium (ethylenedinitrilo) tetr-aacetate was eliminated from the concentrate and the total amount of water in the concentrate was reduced to 77.0 parts.

Samples were tested in the same manner and under the same conditions for resoiling and cleaning qualities as heretofore described in Example 1 with substantially the same results.

EXAMPLE 4 Shampoo concentrate was prepared in the manner described in Example 1, except the amount therein of Antaron FC-34 was increased to 2.50 parts, the amount of aqueous decyl diethanol amine oxide was increased to 4.12 parts, and the amount of water added was reduced to 79.95 parts.

Samples were tested in the same manner and under the same conditions for resoiling and cleaning qualities as heretofore described in Example 1, with better results than achieved in Examples 1-3.

EXAMPLE 5 Shampoo concentrate was prepared in the manner described in Example 3, except the amount of the composition containing methyl methacrylate polymer and acrylamide-acrylic acid copolymer was increased to 15.0 parts; magnesium montmorillonite was excluded from the formulation, and replaced therewith by an alumina silica clay, represented by the formula Al O -2SiO and distributed under the trade name Glomax LL; and the amount of water added to the blend was decreased to 64.0 parts.

Samples were tested in the same maner and under the same conditions for resoiling and cleaning qualities as heretofore described in Example 1, and said samples demonstrated poor resistance to resoiling under the conditions effected therein.

EXAMPLE 6 Shampoo concentrate was prepared in the manner described in Example 4, except that the composition containing methyl methacrylate polymer and acrylamideacrylic acid copolymer was excluded from the formulation; the amount of Antaron FC-34 was increased to 2.80 parts; the amount of aqueous decyl diethanol amine oxide was increased to 4.75 parts; admixed sodium 1,4- bis(2-ethylhexyl) sulfosuccinate and sodium benzoate was excluded from the formulation and replaced therewith by 0.20 part of Triton X-100 dispersant; the amount of Fluorescent Brightening Agent 185 was increased to .15 part; and the amount of water added to the aqueous blend was increased to 89.77 parts.

Samples were tested in the same manner and under the same conditions for resoiling and cleaning qualities as heretofore described in Example 1, and said samples demonstrated poor resistance to resoiling under the conditions effected therein.

10 EXAMPLE 7 Shampoo concentrate was prepared in the manner described in Example 6, except that the amount therein of Antaron FC-34 solution was reduced to 1.3 parts; the amount of aqueous decyldiethanol amine oxide was reduced to 2.2 parts; the amount of Triton X-100 dispersant was reduced to 0.1 part; the amount of disperse Fluorescent Brightening Agent 185 was increased to 0.2 part; tetrasodium (ethylenedinitrilo) tetraacetate was excluded from the formulation; and the amount of required water therein was increased to 94.2 parts.

Samples were tested in the same manner and under the same conditions for resoiling and cleaning qualities as heretofore described in Example 1, and said samples demonstrated poor resistance to resoiling under the conditions effected therein.

What is claimed is:

1. An aqueous composition capable of inhibiting soil pickup by textile fabrics comprising, based on the total weight of the composition, 0.1 to 8 weight percent of finely divided particulate smectite group clay selected from montmorillonite, beidelite, nontronite, hectorite, saponite and mixtures thereof; 0.02 to 19 weight percent of essentially water soluble polymer substantially free of chromophores, that dries to a tack-free residue, characterized by anionic properties or the capacity to form association complexes for the purpose of carrying an electrolytic charge in the composition, said essentially water soluble polymer being selected from the group consisting of acrylic acid and methacrylic acid polymers and copolymers, alginic acid and its potassium, sodium, ammonium and propylene glycol salts; carboxylated cellulose derivatives and salts thereof; poly(vinyl sulfonic acid); poly (styrene sulfonic acid); sulfuric acid ester salts of polyglycol ether compounds; gum karaya; poly(alkylene oxide); polyvinylpyrrolidone; guar gum; poly(vinyl alcohol); polymeric maleic acid and maleic anhydride derivatives; gum arabic; gum ghatti; locust bean gum; pectin; carboxymethyl starch and poly(glutamic acid) and 0.1 to 19 weight percent of a disperse polymer, dispersible in water, with a Tg of at least 15 C. that is non-film forming at ambient temperatures, said disperse polymer being selected from the group consisting of homopolymers and copolymers of lower alkyl methacrylates, lower alkyl acrylates, phenylethylene and chloroethylene and copoly wherein R is alkyl of 5 to 21 carbon atoms; '(b) inner salts of substituted aminoacetic acid of the general formula wherein R is selected from the group consisting of alkyl and alkylene radicals of 1 to 22 carbon atoms and acyl derivatives containing up to 22 carbon atoms and R is selected from the group consisting of hydrogen and alkyl radicals containing up to 22 carbon atoms;

(c) tertiary amine oxides of the general formula wherein R is alkyl with a chain length of 6 to 22 carbon atoms, and R and R are selected from the group consisting of lower alkyl and lower hydroxyalkyl radicals;

(d) alkali metal salts of hydroxyalkyl sulfates wherein the alkyl group contains to 20 carbon atoms;

(e) N-acylated sarcosinates wherein the acyl group contains 10 to 20 carbon atoms; and

(f) alkali metal salts of the formula wherein R contains 5 to 21 carbon atoms and is an alkyl, cycloalkyl or alkenyl group, R" is alkyl of 6 to 22 carbon atoms and A is an ion derived from an alkali metal.

3. The composition of claim 2 including a dialkyl sulfosuccinate wetting agent.

4. The composition of claim 2 wherein said smectite group clay is montmorillonite.

5. The composition of claim 2 wherein said smectite group clay is an admixture of montmorillonite and hectorite.

6. A shampoo composition for textile fabrics which is an aqueous dispersion comprising, based on the weight of the dispersion. 0.1 to 8 weight percent of finely divided particulate smectite group clay selected from montmorillonite, beidelite, nontronite, hectorite, saponite and mixtures thereof; 0.02 to 19 weight percent of essentially water soluble polymer substantially free f chromophores, that dries to a tack-free residue, characterized by anionic properties or the capacity to form association complexes for the purpose of carrying an electrolytic charge in the composition, said essentially water soluble polymer being selected from the group consisting of acrylic acid and methacrylic acid polymers and copolymers; alginic acid and its potassium, sodium, ammonium and propylene glycol salts; carboxylated cellulose derivatives and salts thereof; poly (vinyl sulfonic acid); poly (styrene sulfonic acid); sulfuric acid ester salts of polyglycol ether compounds; gum karaya; poly(alkylene oxide); polyvinyl pyrrolidone; guar gum; poly(vinyl alcohol); polymeric maleic acid and maleic anhydride derivatives; gum arabic; gum ghatti; locust bean gum; pectin; carboxyl methyl starch and poly(glutamic acid); 0.1 to 19 weight percent of a disperse polymer, dispersible in water, with a Tg of at least C. that is non-filmforming at ambient temperatures, said disperse polymer being selected from the group consisting of homopolymers and copolymers of lower alkyl methacrylate, lower alkyl acrylates, phenylethylene and chloroethylene and copolymers of polyvinyl chloride and acrylate derivatives; and 0.1 to 15 weight percent of at least one synthetic detergent selected from the group consisting of (a) fatty acid amides of alkylol amines of the general formula RC O) NHCH CH NHCH CH OH wherein R is alkyl of 5 to 21 carbon atoms;

(b) inner salts of substituted aminoacetic acid of the general formula wherein R is selected from the group consisting of alkyl and alkylene radicals of 1 to 22 carbon atoms and acyl derivatives containing up to 22 carbon atoms and R is selected from the group consisting of hydrogen and alkyl radicals containing up to 22 carbon atoms;

(0) tertiary amine oxides of the general formula wherein R is alkyl with a chain length of 6 to 22 carbon atoms, and R and R are selected from the group consisting of lower alkyl and lower hydroxyalkyl radicals;

(d) alkali metal salts of hydroxyalkyl sulfates wherein the alkyl group contains 10 to 20 carbon atoms;

(e) N-acylated sarcosinates wherein the acyl group contains 10 to 20 carbon atoms; and

(f) alkali metal salts of the formula wherein R contains 5 to 21 carbon atoms and is an alkyl, cycloalkyl or alkenyl group, R" is alkyl of 6 to 22 carbon atoms and A is an ion derived from an alkali metal.

7. A process for inhibiting the soil pickup of textile fabrics by applying to said fabrics the composition of claim 1.

8. A textile fabric possessing antisoiling properties, said fabric having been treated with the composition of claim 1 to apply on said fabric a solids add-on of said smectite group clay, said essentially water soluble polymer and said dispersed polymer, the total add-on being equal to from 0.005 to 2 ounces of solids per square yard of textile fabric.

References Cited UNITED STATES PATENTS 2,976,112 3/1961 Yonkers 8-157 X 3,206,408 9/1965 Vitalis et a1. 252-163 X 3,433,666 3/1969 Moyse et al. 117139.5 F

MAYER WEINBLATT, Primary Examiner US. Cl. X.R.

7 UNITED STATES PATENT OFFICE CE'I-EFICATE OF (IORRE THON Patent No. 3,716,488 Dated February 1-3, 1973 Inventor-(s) Rodger E Kolsky and Vernon Lindsay Chase It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shgwn below:

Col pmn 5, line 74, "filters" should read fillers 7' Claim 2, Column 11, line 10, R'c(=,o)NH"cH c H so A should read R'C (=O)NR" CH2CH2SO3A Signed and sealed this 3rd day of July 1973.,

(SEAL) Attest:

EDWARD M.PLETCHER,JR. Rene Tegtmeyer- Attesting Officer. Acting Commissioner of Patents-

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DE2412837A1 (en) * 1973-04-13 1974-10-31 Henkel & Cie Gmbh A method for washing and cleaning the surfaces of solid materials, in particular of textiles, as well as means for performing the method
US3862058A (en) * 1972-11-10 1975-01-21 Procter & Gamble Detergent compositions containing a smectite-type clay softening agent
USB305417I5 (en) * 1972-11-10 1975-01-28
US3933425A (en) * 1972-07-01 1976-01-20 Henkel & Cie Gmbh Method of cleaning textiles
US3948790A (en) * 1974-01-31 1976-04-06 The Procter & Gamble Company Detergent compositions containing short chain quaternary ammonium clays
US3959155A (en) * 1973-10-01 1976-05-25 The Procter & Gamble Company Detergent composition
US3979314A (en) * 1973-08-15 1976-09-07 Lever Brothers Company Detergent compositions
US3985668A (en) * 1974-04-17 1976-10-12 The Procter & Gamble Company Scouring compositions
US3994744A (en) * 1973-10-01 1976-11-30 S. C. Johnson & Son, Inc. No-scrub cleaning method
US4002571A (en) * 1972-03-08 1977-01-11 S. C. Johnson & Son, Inc. Cleaning compositions
US4035148A (en) * 1976-05-06 1977-07-12 The Procter & Gamble Company Carpet cleaning and soil repellent compositions
US4051056A (en) * 1974-09-09 1977-09-27 The Procter & Gamble Company Abrasive scouring compositions
US4062647A (en) * 1972-07-14 1977-12-13 The Procter & Gamble Company Clay-containing fabric softening detergent compositions
US4105574A (en) * 1975-01-24 1978-08-08 American Cyanamid Company Process for formulating a non-caustic oven cleaner which will remove pyrolyzed fat efficaciously
WO1985005294A1 (en) * 1984-05-10 1985-12-05 Gaf Corporation Surface cleaning process
US4561992A (en) * 1982-02-20 1985-12-31 Vorwerk & Co. Interholding Gmbh Aerosol cleaning agent for textile surfaces
US4599186A (en) * 1984-04-20 1986-07-08 The Clorox Company Thickened aqueous abrasive scouring cleanser
US4657692A (en) * 1984-04-20 1987-04-14 The Clorox Company Thickened aqueous abrasive scouring cleanser
US4725319A (en) * 1985-09-20 1988-02-16 Henkel Kommanditgesellschaft Auf Aktien Cleaning preparations for hard surfaces
US5049311A (en) * 1987-02-20 1991-09-17 Witco Corporation Alkoxylated alkyl substituted phenol sulfonates compounds and compositions, the preparation thereof and their use in various applications
US5429684A (en) * 1990-12-10 1995-07-04 Henkel Kommanditgesellschaft Auf Aktien Water-based carpet cleaning composition and method
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US5968203A (en) * 1997-02-28 1999-10-19 Sybron Chemicals Inc. Clay-containing textile material treating composition and method
US6010539A (en) * 1996-04-01 2000-01-04 E. I. Du Pont De Nemours And Company Cleaning formulations for textile fabrics
WO2001044425A1 (en) * 1999-12-16 2001-06-21 Unilever Plc Stain and soil removal in the laundering of textile fabrics
US20020151634A1 (en) * 2001-01-30 2002-10-17 Rohrbaugh Robert Henry Coating compositions for modifying surfaces
US20040121928A1 (en) * 2002-12-19 2004-06-24 The Procter & Gamble Company Anti-filming materials, compositions and methods
US20060051512A1 (en) * 2004-08-13 2006-03-09 Orosz Gary R Apparatus and systems for coating objects
US20060223731A1 (en) * 2005-03-30 2006-10-05 Carling Philip C Monitoring cleaning of surfaces
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US20080223596A1 (en) * 2007-03-14 2008-09-18 Ryan Ezell Aqueous-Based Insulating Fluids and Related Methods
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US4002571A (en) * 1972-03-08 1977-01-11 S. C. Johnson & Son, Inc. Cleaning compositions
US3933425A (en) * 1972-07-01 1976-01-20 Henkel & Cie Gmbh Method of cleaning textiles
US4062647A (en) * 1972-07-14 1977-12-13 The Procter & Gamble Company Clay-containing fabric softening detergent compositions
US3862058A (en) * 1972-11-10 1975-01-21 Procter & Gamble Detergent compositions containing a smectite-type clay softening agent
USB305417I5 (en) * 1972-11-10 1975-01-28
US3915882A (en) * 1972-11-10 1975-10-28 Procter & Gamble Soap compositions
DE2412837C3 (en) * 1973-04-13 1989-10-12 Henkel & Cie Gmbh Means for washing or bleaching fabrics using water-insoluble crystalline silicates, their preparation and their use
DE2412837A1 (en) * 1973-04-13 1974-10-31 Henkel & Cie Gmbh A method for washing and cleaning the surfaces of solid materials, in particular of textiles, as well as means for performing the method
US3979314A (en) * 1973-08-15 1976-09-07 Lever Brothers Company Detergent compositions
US3994744A (en) * 1973-10-01 1976-11-30 S. C. Johnson & Son, Inc. No-scrub cleaning method
US3959155A (en) * 1973-10-01 1976-05-25 The Procter & Gamble Company Detergent composition
US3948790A (en) * 1974-01-31 1976-04-06 The Procter & Gamble Company Detergent compositions containing short chain quaternary ammonium clays
US3985668A (en) * 1974-04-17 1976-10-12 The Procter & Gamble Company Scouring compositions
US4051056A (en) * 1974-09-09 1977-09-27 The Procter & Gamble Company Abrasive scouring compositions
US4105574A (en) * 1975-01-24 1978-08-08 American Cyanamid Company Process for formulating a non-caustic oven cleaner which will remove pyrolyzed fat efficaciously
US4035148A (en) * 1976-05-06 1977-07-12 The Procter & Gamble Company Carpet cleaning and soil repellent compositions
US4561992A (en) * 1982-02-20 1985-12-31 Vorwerk & Co. Interholding Gmbh Aerosol cleaning agent for textile surfaces
US4586962A (en) * 1983-09-27 1986-05-06 Gaf Corporation Surface cleaning process
US4599186A (en) * 1984-04-20 1986-07-08 The Clorox Company Thickened aqueous abrasive scouring cleanser
US4657692A (en) * 1984-04-20 1987-04-14 The Clorox Company Thickened aqueous abrasive scouring cleanser
WO1985005294A1 (en) * 1984-05-10 1985-12-05 Gaf Corporation Surface cleaning process
US4725319A (en) * 1985-09-20 1988-02-16 Henkel Kommanditgesellschaft Auf Aktien Cleaning preparations for hard surfaces
US5049311A (en) * 1987-02-20 1991-09-17 Witco Corporation Alkoxylated alkyl substituted phenol sulfonates compounds and compositions, the preparation thereof and their use in various applications
US5429684A (en) * 1990-12-10 1995-07-04 Henkel Kommanditgesellschaft Auf Aktien Water-based carpet cleaning composition and method
US6010539A (en) * 1996-04-01 2000-01-04 E. I. Du Pont De Nemours And Company Cleaning formulations for textile fabrics
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US5968203A (en) * 1997-02-28 1999-10-19 Sybron Chemicals Inc. Clay-containing textile material treating composition and method
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US20090042757A1 (en) * 2005-03-30 2009-02-12 Carling Philip C Monitoring Cleaning of Surfaces
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US7718395B2 (en) * 2005-03-30 2010-05-18 Kleancheck Systems, Llc Monitoring cleaning of surfaces
US20080224087A1 (en) * 2007-03-14 2008-09-18 Ezell Ryan G Aqueous-Based Insulating Fluids and Related Methods
US20080227665A1 (en) * 2007-03-14 2008-09-18 Ryan Ezell Aqueous-Based Insulating Fluids and Related Methods
US20080223596A1 (en) * 2007-03-14 2008-09-18 Ryan Ezell Aqueous-Based Insulating Fluids and Related Methods
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