WO2000078906A1

WO2000078906A1 - Spot cleaning compositions useful for cleaning garments and textiles

Info

Publication number: WO2000078906A1
Application number: PCT/GB2000/002385
Authority: WO
Inventors: Kathleen Elizabeth Landy; Jeanne Marie Lesica; Thomas Michael Papasso; Anthony Domenick Sidoti
Original assignee: Reckitt Benckiser Inc; Reckitt Benckiser (Uk) Limited
Priority date: 1999-06-23
Filing date: 2000-06-19
Publication date: 2000-12-28
Also published as: GB9914622D0; GB2353288A; AU5549000A; GB0014742D0

Abstract

Improved spot cleaning compositions particularly useful for the localized cleaning of stains from garments and textiles are presented.

Description

SPOT CLEANING COMPOSITIONS USEFUL FOR CLEANING GARMENTS AND TEXTILES

The present invention relates to improved spot cleaning compositions particularly useful for the localized cleaning of stains from garments and textiles.

The prior art has suggested many types of spot cleaning compositions which are intended to be used in the localized cleaning of stains on garments or textiles. Such spot cleaning is typically done shortly before a subsequent laundering step wherein the garment or textile is immersed in an aqueous bath.

The performance of these spot cleaning compositions is known to vary considerably, based upon the types of stains which are to be removed as well as on the type of textiles from which the garments are made. Frequently, while known spot cleaning compositions are effective for many types of stains, they are not necessarily effective in the removal of a test soil, bandy black clay, or grease stains, both of which are notoriously difficult to remove.

Another shortcoming of many of the known spot cleaning compositions is that they frequently need to be formulated, or reformulated, for use in a specific type of container or dispensing device (for example, a trigger spray, an aerosol, a gel, a "push/pull" and a solid stick). Thus, one looking to make such a product may need to produce several different formulations of one product, which is costly and inconvenient.

The present invention overcomes these shortcomings.

The present invention provides an aqueous cleaning composition, which may or not be thickened, which is particularly useful in the spot cleaning of stains and soils on garments and textiles. The composition comprises:

at least one detersive surfactant selected from anionic, nonionic, cationic, amphoteric, zwitterionic, and mixtures thereof; at least one organic solvent selected from alcohols, diols, glycols, glycol ethers, 1-methyl-2-pyrrolidone, C₆-C₁₈ methyl esters, aliphatic solvents, and mixtures thereof; at least one dispersant constituent; optionally, at least one enzyme constituent; an associative thickener; and water.

The compositions may optionally, but in some cases desirably contain one or more further constituents including buffers, colorants, dyes, fragrances, opacifiers, optical brighteners, enzyme stabilizers, preservatives, and builder constituents.

The present invention also provides an aqueous cleaning composition, which may or not be thickened, which is particularly useful in the spot cleaning of stains and soils on garments and textiles. The composition comprises:

at least one detersive surfactant selected from nonionic, cationic, amphoteric, zwitterionic, and mixtures thereof; at least one organic solvent selected from alcohols, diols, glycols, glycol ethers, 1-methyl-2-pyrrolidone, C₆-Cι₈ methyl esters, aliphatic solvents, and mixtures thereof; at least one polymeric dispersant constituent; at least one enzyme constituent; an associative thickener; and water.

Preferably, the detersive surfactant is a mixture of nonionic and cationic surfactants, where the nonionic surfactant is one or more linear alcohol ethoxylates and the cationic surfactant is one or more ethoxylated amines. Additionally, the organic solvent is selected from diols, glycols, 1-methyl-2-pyrrolidone, C₆-C₁₈ methyl esters, aliphatic solvents, and mixtures thereof.

The compositions of the present invention desirably exhibit a relatively low viscosity under high shear conditions and, conversely, exhibit relatively high viscosity under low shear conditions. Such behavior ensures that the formulations of the present invention can be used in both hand pumpable trigger spray dispensers and in nozzled dispensers. The advantageous viscosity characteristics permit the use of the same formulation in both of these types of dispensers. The compositions also exhibit good soil anti-redeposition properties.

A further aspect of the present invention provides a process for the localized "spot cleaning" of a soiled or stained garment or textile which process contemplates the application to the soil or stained area of an effective cleaning amount of the compositions described herein. Desirably, such spot cleaning is carried out just prior to a subsequent laundering step.

The inventive compositions include one or more detersive surfactants selected from anionic, nonionic, cationic, amphoteric, zwitterionic, and mixtures thereof. Useful anionic surfactants include, but are not limited to, carboxylates (also known as soaps), sulfates, and sulfonates. Examples of the carboxylates are generally the water soluble salts of saturated higher fatty acids of 8 to 18 carbon atoms each, and mixtures thereof. Examples of the sulfates and sulfonates include those having from 8 to 26 carbon atoms and preferably having from 10 to 22 carbon atoms to the molecule, and sulfonated alkyl aryl compounds (e.g., alkylbenzenesulfona.es). Such materials can be ethoxylated. Examples useful anionic surfactants include sodium lauryl sulfate and sodium dodecyl benzene sulfonate. Additional anionic surfactants include the Standapol® and Sulfotex® series from Henkel.

Other examples include polyalkoxycarboxyla.es available under the tradenames

Neodox (alkyl is 12 to 13 carbon atoms); and Sandopan (having tridecyl [branched] and cetyl alkyl chains).

Further examples of detersive surfactants include amine oxides, particularly those where the alkyl chain has from about 8 to 20 carbon atoms, and preferably from 12 to 16 carbon atoms. The carbon chain can be straight, branched, saturated or unsaturated. Examples include lauryl dimethyl amine oxide, myristyl dimethyl amine, and those where the alkyl chain is a mixture of different amine oxides, for example, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide. Other amine oxides of interest include AO-14-2 (bis-(2-hydroxyethyl)isodecyloxypropyl amine oxide) and AO-10-2 (an experimental proprietary amine oxide), both from Tomah Products, Inc. (Milton, Wl).

Examples of nonionic surfactants include alkylphenoxypolyethoxyethanols having alkyl groups of about 7 to 18 carbon atoms and about 9 to 40 or more oxyethylene units such as octylphenoxypolyethoxyethanols, dodecylphenoxypolyethoxyethanols; ethylene oxide derivatives of long-chain carboxylic acids, such as lauric, myristic, palmitic, oleic; ethylene oxide condensates of long-chain alcohols such as lauryl or cetyl alcohol, and the like. A single nonionic surfactant having an appropriate HLB can be utilized or mixtures of nonionic surfactants such that the HLB of the resulting mixture of nonionic surfactants is within the appropriate range. It has generally been found that the nonionic surfactant or mixture of nonionic surfactants should have an HLB within the range of from 8 to 13 for optimum efficiency. Useful nonionic surfactants are the alcohol ethoxylates such as those in the Genapol® series (26-L) from Clariant where C₁₂-Cι₆ linear alcohols are condensed with varying amounts of ethylene oxide.

Additional suitable nonionic surfactants include the ethoxylated nonylphenols (especially those having a degree of ethyloxylation of from 3 to 10 moles of ethylene oxide) such as the Surfonic N series available from Texaco Chemicals; and the ethoxylated octylphenols (especially those having from 3 to 10 moles of ethylene oxide) including the Triton X series available from Union Carbide; the ethoxylated secondary fatty alcohols (especially those having from 3 to 10 moles of ethylene oxide) such as the Tergitol series available from Union Carbide; the ethoxylated primary fatty alcohols such as the Neodols available from Shell Chemicals; the ethoxylated sorbitan fatty acid esters such as the Tweens from Uniqema, a division of ICI and the sorbitan fatty acid esters such as the Spans from Uniqema, a division of ICI. Additionally, nonionics such as alkyl polyglycosides are also desirable where the carbon chain length is from about 8 to 16 are available from Henkel Corporation under the Glucopon® trademark.

Examples of cationic surfactants include both short chain alkyl, and long chain alkyl quaternary ammonium compounds, such as for example, lauryl pyridinium chloride, octylbenzyltrimethylammonium chloride, dodecyltrimethylammonium chloride, condensates of primary fatty amines and ethylene oxide, and the like. Additional examples of cationic surfactants also include ethoxylated amines such as those available from Tomah Products, Inc. (Milton, Wl). The alkyl groups range from 10 to 18 carbon atoms and with 2 to 15 moles of ethylene oxide. Examples include E- 14-2 (bis-(2-hydroxyethyl) isodecyloxypropyl amine), E-14-5 (poly (5) oxyethylene isodecyloxypropyl amine), E-17-2 (bis-(2-hydroxyethyl) isotridecyloxypropyl amine), E- 17-5 (poly (5) oxyethylene isotrdecyloxypropyl amine), E-19-2 (bis-(2-hydroxylethyl) C₁₂/Ci₅ alkyloxypropyl amine), E-S-2 (bis-(2-hydroxyethyl) soya amine), E-18-2 (bis-(2- hydroxyethyl) octadecylamine), E-18-5 (poly (5) oxyethylene octadecylamine), E-18-8 (poly (8) oxyethylene octadecyl amine), E-22-2 (bis-(2-hydroxyethyl) octadecyloxypropyl amine), E-T-2 (bis-(2-hydroxyethyl) tallow amine), E-T-5 (poly (5) oxyethylene tallow amine), E-DT-3 (poly (3) oxyethylene 1 ,3 diaminopropane), and E-C-2 (bis-(2- hydroxyethyl) coco amine). Another useful ethoxylated amine is also available from Stepan Chemical under the tradename Biosoft TA-2 (bis-(2-hydroxyethyl) tallow amine).

Amphoteric surfactants include salts of higher alkyl beta-amino propionic acids, for example, sodium N-lauryl beta-alanine, high alkyl substituted betaines, such as lauryl dimethyl ammonium acetic acid, imidazoline type of amphoteric detergents, and quaternary amine derivatives of fatty acids, such as the "Miranol" (trademark) surfactants. Additionally amphoteric surfactants include tallow amidopropyl hydroxylsulfobetaine available under the tradename Crosultaine T-30 from Croda, Inc., glycinates and diglycinates such as tallow diglycinate, available from Witco Corp. under the trade name Sherex EPSC-191.

Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The foregoing and other useful anionic, cationic, nonionic, amphoteric, and zwitterionic surfactants are described in the literature, such as "McCutcheon's Detergents & Emulsifiers 1998 Annual, North America Edition," MC Publishing Co., Glen Rock, N.J. 07452 U.S.A. and in Kirk-Othmer Encyclopedia of Chemical Technology, 4^th Ed., vol. 23, pp. 478-541 (1997).

Desirably, at least two different detersive surfactants are present, as mixtures of different surfactants are expected to provide a broader range of detergency. When, for example, the linear alcohol ethoxylates are used, it is preferred that at least two of them are used, each with a different amount of average moles of ethoxylation. In other instances of the present invention, it is advantageous to substitute an amount of one or more ethoxylated amines for an amount of nonionic surfactant. In further instances of the present invention, it is advantageous to use two linear alcohol ethoxylates and an ethoxylated amine as the detersive surfactant mixture.

The amount of detersive surfactants present in the inventive formulations range from about 0.001 to about 25%wt., preferably from about 0.1 to about 16%wt., and more preferably from about 1 to about 12%wt.

Dispersants are also present in the inventive formulations of the present application. These dispersants generally are also effective anti-redeposition agents, preventing soils that are removed from the cleaned garment or textile to be redeposited during the cleaning cycle.

Preferred dispersants are generally polymeric in nature and include for example acrylic homopolymers, acrylic-maleic copolymers, maleic-olefin copolymers, as well as mixtures thereof. Examples of the foregoing include Acusol 410N, Acusol 445N (polyacrylic acid, Na salt); Acusol 450N and Acusol 480N (modified polyacrylic acid, Na salt); Acusol 479N, Acusol 490N, and Acusol 505N (acrylic acid/maleic acid, Na salt); Acusol 460N (maleic acid/olefin, Na salt); Sokolan CP5 and Sokolan CP12S (maleic acid/acrylic acid, Na salt); and Sokolan CP 9 (maleic acid/olefin, Na salt). The Acusol series are available from Rohm & Haas, Philadelphia, PA and the Sokolan series are available from BASF (Germany and New Jersey). These and other dispersants are described in the literature, such as "McCutcheon's Functional Materials 1998 Annual, North America Edition," MC Publishing Co., Glen Rock, N.J. 07452 U.S.A.

The amount of dispersant in the inventive formulations range from about 0.001 to about 10%wt., preferably from about 0.01 to about 5%wt, and more preferably from about 0.04 to about 5%wt. Preferably, the dispersant is Acusol 445N or a mixture of Acusol 445N and Sokolan CP 9, where the Acusol 445N is present in an amount greater than Sokolan CP 9, generally in amounts of about 0.25 to about 3% Acusol 445N and from about 0.05 to about 0.5 % Sokolan CP 9.

Solvents may also be used with the laundry pre-spotters of the present invention to improve stain removal of oil and grease based stains. Suitable solvents include alcohols, diols, glycols, water miscible ethers, water miscible glycol ethers, 1-methyl-2- pyrrolidone, C₆-Cι₈ methyl esters, aliphatic solvents, and mixtures thereof.

Suitable alcohols include those lower alkyl (from about 2 to 10 carbons) alcohols, such as for example, ethanol, propanol, and isopropanol. Diols and glycols include, for example, propylene glycol, hexylene glycol, and the like. Water miscible ethers include, for example, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and propylene glycol dimethyl ether. Water miscible glycol ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and as well as lower esters of monoalkylethers of ethylene glycol or propylene glycol (for example, propylene glycol monomethyl ether acetate and propylene glycol monobutyl ether acetate). These solvents are generally available from, for example, Union Carbide, Dow Chemical or Hoechst.

Other solvents include aliphatic solvents such as, for example, isoparaffins, normal paraffins, mixed aliphatics, monoesters (available from Exxon Corporation under the Isopar, Norpar, Exxsol and Exxate tradenames), deodorized mineral spirits, alpha- olefins such as tetradecene and low molecular weight non-VOC polybutane. Other solvents include, for example, N-(n-octyl)-2-pyrrolidone and N-methyl-2-pyrrolidone. Tetradecene is available under the trade name Neodene 14 from Shell Oil Corp. or the trade name Gulftene 14 from Chevron Oil Corp. The low molecular weight non-VOC polybutene solvent is available under the trademark Indopol L14 from Amoco Chemical Co. N-(n-Octyl)-2-Pyrrolidone is available from ISP Corp. under the trademark Surfadone LP-100 and N-methyl-2-pyrrolidone is available from ISP Corp under the trademark M-Pyrol.

Examples of C₆.ι₈ methyl esters include methyl caprylate-caprate, methyl laurate, and methyl oleate available under the Emery and Emerest trademarks from Henkel Corporation.

The amount of solvent that is present in the inventive formulation ranges from about 0.01 to about 15%wt., preferably from about 0.1 to about 10%wt., and more preferably from about 1 to about 10%wt.

Associative thickeners are water-soluble or water swellable polymers that have chemically attached hydrophobic groups that are capable of non-specific hydrophobic associations similar to those of conventional surfactants. They are also known as hydrophobically modified water soluble polymers.

The associative thickeners utilized in the present invention are water soluble and impart pseudo plastic characteristics to the laundry pre-spotter composition after the polymer is neutralized to a pH of 5.5 or more. Such associative thickeners are generally supplied in the form of an acidic aqueous emulsion or dispersion. The polymers thicken aqueous solutions when the carboxyl groups present are neutralized to a point where the pH of the solution is about 5.5 or greater.

The associative thickener is typically an addition polymer of three components: an alpha-beta-monoethylenically unsaturated monocarboxylic acid or dicarboxylic acid of from 3 to 8 carbon atoms such as acrylic acid or methacrylic acid to provide water solubility, a monoethylenically unsaturated copolymerizable monomer lacking surfactant capacity such as methyl acrylate or ethyl acrylate to obtain the desired polymer backbone and body characteristics, and a monomer possessing surfactant capacity which provides the pseudo plastic properties to the polymer and is the reaction product of a monoethylenically unsaturated monomer with a nonionic surfactant compound wherein the monomer is copolymerizable with the foregoing monomers such as the reaction product of methacrylic acid with a monohydric nonionic surfactant to obtain a monomer such as CH₃(CH₂)₁₅-₁₇(OCH₂CH₂)_eOOCC(CH₃)=CH₂ where "e" has an average value of about 10 or 20. Optionally, up to about 2.0% of a polyethylenically unsaturated monomer such as ethylene glycol diacrylate or dimethacrylate or divinylbenzene can be included if a higher molecular weight polymer is desired.

Additional associative thickeners include maleic anhydride copolymers reacted with nonionic surfactants such as ethoxylated Cι₂ -Cι₄ primary alcohol available under the trade name Surfonic L Series from Texaco Chemical Co. and Gantrez AN-119 from ISP.

Preferably, the associative thickeners include C^-^ alkyl groups in an alkali- soluble acrylic emulsion polymer such as those available under the Acusol trademark from Rohm & Haas Co. of Philadelphia, Pa. Preferred associative thickeners include Acusol 820 and Acusol 1206A. Acusol 820 is believed to be a 30.0% active emulsion polymer of 40.0% methacrylic acid, 50% ethyl acrylate and 10.0% stearyl oxypoly ethyl methacrylic emulsion polymer having approximately 20 moles of ethylene oxide. Acusol 1206A is believed to be a 30% active emulsion polymer with 44% methacrylic acid, 50% ethyl acrylate and 6% stearyl methacrylate polymer having about 10 moles of ethylene oxide.

Another associative thickener is Acusol 823, also available from Rohm & Haas, which is a 30.0% active emulsion polymer composed of 44% methacrylic acid, 50% ethyl acrylate and 6% stearyl oxypoly ethyl methacrylate emulsion polymer having approximately 10 moles of ethylene oxide. Other associative thickeners are also described in United States Patent No. 4,351,754. The amount of associative thickener in the inventive formulations ranges from about 0.01 to about 0.2%wt. active, preferably from about 0.05 to about 0.2%wt, and more preferably from about 0.07 to about 0.2%wt.

The compositions optionally can, but preferably include an enzyme constituent which includes one or more enzymes which are effective in the breakdown of certain stains and soils. The enzyme constituent preferably includes a protease but can also include for example, additional enzymes such as lipases, amylases, pectinases, and peroxidases and the like. The proteases are known to be effective in the breakdown of protein based stains such as blood, mucus, grass, egg, and gravy. Protein based stains are known to be particularly difficult to remove, but in the presence of an effective protease, they are hydrolyzed into peptides and may be more readily removed in a subsequent laundering step.

The enzyme constituent is optional but when incorporated into the formulation, it is present in an effective amount. It is preferred that the compositions of the present invention contain an enzyme constituent. It will be recognized by one of ordinary skill in the art that the activity of the enzymes in a commercially available preparation may vary and that such activity is very relevant in determining the amount of the commercially available preparations to be used in the formulations of the present invention. Thus, one skilled in the art may determine by means of a few routine experiments what amount of a commercially available enzyme preparation is to be included in the inventive compositions. Examples of a commercially available proteases include ESPERASE and SAVINASE (including, but not limited to, for example Savinase 16.0L and Savinase 10.0 LCC) (available from Novo Nordisk), advantageously present in an amount from about 0.001 to about 5%wt, based on the total weight of the composition. Preferably, amounts of from about 0.001 to about 1%wt are useful.

The compositions of the invention are aqueous in nature. Water is added in order to provide 100% by weight of the compositions of the invention. The water may be tap water, but is preferably distilled or soft water, and is most preferably deionized or soft water. The inventive compositions desirably include at least 70%wt water and more preferably include at least 80%wt water. The formulations of the present invention may also include one or more optional constituents including, but not limited to pH adjusting agents, pH buffering agents, perfumes, dyes, colorants, optical brighteners, hydrotropes, builders, chelating agents, germicides, fungicides, preservative constituents, anti-oxidants, anti-corrosion agents, ironing aids, and antistatic agents.

As enzyme stabilizers, any one of borates, propylene glycol, calcium salts, sodium salts of short chain carboxylic acids, and mixtures thereof, can be added as effective stabilizers.

Borates, such as borax can also be included and function as a pH buffering constituent. Additional pH buffering agents include citrates, citric acid and the like.

In certain preferred embodiments, a minor but effective amount of a biocidal composition, which acts as a preservative, is also included. An example of such a material is Dowicil 75 (available from Dow Chemical Co.). Others can be used so long as they do not deleteriously effect the other constituents, especially the enzyme constituents.

Those of ordinary skill in the art will appreciate that many optional constituents have more than one function and thus their identification as having a particular function should not be deemed a limitation.

The compositions can be prepared in a conventional manner such as simply mixing the constituents in order to form a homogeneous aqueous cleaning composition. For example, one method of preparing the formulations of the present invention is to make a premix which contains the organic solvent and the detersive surfactants. The other materials are mixed together in conventional equipment and then the premix is subsequently blended with the aforesaid mixture to form a homogeneous formulation. If desired, fragrance can be added after the premix addition.

A second method of preparing the formulations of the present invention is to again make a premix as mentioned above. The remaining materials, except for a retained portion of the dispersant constituent, are mixed together. The premix is then subsequently blended with the aforementioned mixture to form a homogeneous mixture. The retained portion of dispersant constituent is then mixed with this mixture to form a homogeneous formulation. If desired, a fragrance can be added with the portion of dispersant. Preferably, the acrylic homopolymer and/or the acrylic-maleic copolymer dispersants are the retained dispersant.

The compositions of the present invention can be packaged in any suitable container, such as an unpressurized bottle or in a pressurized container or in a solid stick. Pressurized containers are made with suitable containers and the addition of a suitable propellant to the composition, such as known hydrocarbon propellants (e.g., propane, butane, isobutane, pentane, isopentane), halogenated hydrocarbon propellants (e.g., chlorodifluoromethane, difluoroethane, dichlorodifluoromethane), as well as pressurized gases such as air, carbon dioxide and nitrogen.

Of course, depending upon the package, the viscosity of the compositions will be formulated accordingly.

The substrates which can be treated with the compositions of the present invention include textile fibers or filaments, and finished or fabricated fibrous articles such as textiles and garments. The textiles include those made of natural fibers, such as cotton and wool, as well as synthetic organic fibers such as nylon, polyolefm, acetate, rayon, acrylic and polyester fibers.

The following examples illustrate the inventive compositions of the present application. The constituents are added as obtained from their respective supplier and the amounts below are on total amount added, not active amounts.

Table 1 sets forth exemplary formulations of the present invention. The availability of the various constituents and how supplied are shown in Table 2.

The order of addition of the components which provide the formulations of the present invention can be varied. In one variation, a premix of propylene glycol and the nonionic surfactant(s) (and cationic surfactant if present) is first made. Then, this premix and the remaining components (e.g., associative thickener, dispersants, enzymes, and other optional materials) can be added to water with stirring.

A second variation is to again prepare the premix as mentioned. Then, the associative thickener is added to the water with stirring. Thereafter, the dispersant is added to this associative thickener/water mixture with stirring. Finally, the remaining components are added.

It has been found that formulations made using the second variation provide an initial low viscosity formulation which makes it easier to manufacture. Spot Cleaning Test

The above formulations and controls mentioned below were tested in order to evaluate their spot cleaning performance on stained textile swatches. The evaluation was in accordance with a protocol outlined in ASTM D-4265 (Reapproved 1998), using grass, spinach, dirty motor oil, synthetic sebum, vegetable oil, spaghetti sauce (RAGU, Old World Style Traditional), bandy black clay, french fry grease, and bacon grease. The vegetable, french fry and bacon grease stains were colored with an oil soluble dye (Sudan Red) to track the cleaning efficacy of the various compositions.

In the test, cotton 400 broad cloth swatches (stripped of processing chemicals) were used as the substrate. For each formulation or control tested, each swatch was stained with all nine stains and soils mentioned above in accordance with ASTM D-4265 and then allowed to dry. Three swatches were used for each washer and each formulation was evaluated at two contact times (1 and 5 minutes) and at two rubbing conditions (no rubbing and rubbing). For each formulation or control tested, three separate lots were evaluated. An aliquot of 2ml. of the above formulations to be evaluated was used on each stain, when rubbed, rub three or five times from the reverse side of the swatch to distribute the formulation, and within 1 minute were introduced into a washing machine. The washing bath contained 132.5 grams of a commercially available laundry detergent (Ultra Purex liquid, Dial Corp.) and washed for 12 minutes, in a wash bath of water hardness of 120 ppm and a temperature of 90°F (32.2°C), followed by a cold water rinse, and spun to remove excess water. The washing bath also included four pounds of white cotton towels as ballast to simulate a full load of garments to be washed. In some testing, cotton 400 or cotton tubing was used and the contact time was 5 minutes with rubbing.

The laundered swatches were then removed, tumble dried in a domestic clothes dryer, and then removed from the dryer for evaluation. A Stain Removal Index (SRI) value was measured and evaluated for each stain. The above formulations were compared against commercially available materials (Spray "N" Wash "push/pull" (P/P) formulation; Spray "N" Wash trigger formulation; and New SHOUT formulation; Spray "N" Wash available from Reckitt Benckiser; New SHOUT available from S.C. Johnson & Sons).

Stain removal from the various soils were assessed quantitatively as an SRI value using a Hunter Lab colorimeter, which measured each of the following values at various areas of the swatches subsequently washed: the lightness (L_c) of an unstained and untreated area on subsequently washed swatch; the lightness of the stained and subsequently washed swatch (L_w); redness-greenness of an unstained and untreated area on subsequently washed swatch (a_c); redness-greenness of the stained and subsequently washed swatch (a_w); yellowness-blueness of an unstained and untreated area on subsequently washed swatch (b_c); and yellowness-blueness of the stained and subsequently washed swatch (b_w). Each of these values measured as the amount of the standardized white light reflected from the fabrics. The quantitatively evaluated values were measured for the various tested fabric swatches and the SRI for each stain/swatch was calculated using the following equation:

SRI = 100 - [(L_c- L_w)² + (a_c - a_w)² + (b_c - b_w)²]¹'²

The results of the evaluation are shown in Tables 3a and 3b below. Table 3a shows data where the formulations were just applied to cover the entire stain surface and were not rubbed into the stain. Table 3b shows data where the formulations were applied to cover the entire stain surface and were then rubbed into the stain as mentioned above. The average values of the three stained swatches for each stain per formulation tested are presented. The SRI values range from 0 to 100, with a value of 100 indicating complete soil removal. Columns having an * indicate that statistically significant differences exist between data in the columns. For example, in Table 3a, Example 3 and the Shout control were at parity when evaluating the cleaning efficacy on bandy black clay, Example 3 was had better cleaning efficacy than the Shout control against french fry grease (82.79 vs. 81.70), and the SNW trigger had poorer cleaning efficacy than the Shout control against bacon grease (67.76 vs. 69.96).

Tables 4a and 4b show cleaning data of other formulations of the present invention. >

(O

10

^M o

¹ bandy black clay

² dirty motor oil

³ Spray "N" Wash available from Reckitt Benckiser available from S.C. Johnson & Sons. Used as control.

10

As can be seen from the SRI data in Tables 3a and 3b, the formulations of the present invention had excellent stain removal performance, particularly with regard to bandy black clay. The data also show improved or comparable performance when compared to commercial products.

Examples 4 to 6 were also evaluated against several stains in the same manner as above. The results are shown in Table 5.

As can be seen from the data in Table 5, the addition of an ethoxylated amine provides a benefit when spot cleaning oily and greasy stains.

Other test data of examples of formulations within the scope of the present invention are shown in Table 6.

t to

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As can be seen from Table 6, other formulations of the present invention show good cleaning against a variety of stains.

Although the invention has been described with reference to the preferred embodiments, it will be apparent to one skilled in the art that variations and modifications are contemplated within the spirit and scope of the invention. The drawings and the description of the preferred embodiments are made by way of example rather than to limit the scope of the invention, and it is intended to cover within the spirit and scope of the invention all such changes and modifications.

Claims

Claims:

1. An aqueous cleaning composition useful in spot cleaning of garments and textiles comprising:

at least one detersive surfactant selected from anionic, nonionic, cationic, amphoteric, zwitterionic, and mixtures thereof; at least one organic solvent selected from alcohols, diols, glycols, glycol ethers,

1-methyl-2-pyrrolidone, C₆-Cι₈ methyl esters, aliphatic solvents, and mixtures thereof; at least one dispersant constituent; optionally, at least one enzyme constituent; an associative thickener; and water.

2. The composition according to claim 1 wherein the dispersant is a polymeric dispersant.

3. The composition according to any preceding claim which contains at least one enzyme constituent.

4. An aqueous cleaning composition useful in spot cleaning of garments and textiles comprising: at least one detersive surfactant selected from nonionic, cationic, amphoteric, zwitterionic, and mixtures thereof; at least one organic solvent selected from alcohols, diols, glycols, glycol ethers, l-methyl-2-pyrrolidone, C₆-Cι₈ methyl esters, aliphatic solvents, and mixtures thereof; at least one polymeric dispersant constituent; at least one enzyme constituent; an associative thickener; and water.

5. The composition according to any preceding claim wherein the detersive surfactant includes at least one nonionic.

6. The composition according to any preceding claim wherein the detersive surfactant includes at least one nonionic and one anionic.

7. The composition according to any preceding claim wherein the detersive surfactant includes at least one nonionic and one cationic.

8. The composition according to any preceding claim wherein at least one of the nonionic surfactants is linear alcohol ethoxylate.

9. The composition according to any preceding claim wherein at least two of the nonionic surfactants are linear alcohol ethoxylates.

10. The compositions according to any preceding claim wherein the cationic surfactant is an ethoxylated amine.

11. The composition according to any preceding claim wherein the organic solvent is selected from propylene glycol and N-methyl-2-pyrrolidone.

12. The composition according to any preceding claim wherein the organic solvent is propylene glycol.

13. The composition according to any preceding claim wherein the dispersant is selected from acrylic acid homopolymers, acrylic acid/maleic acid copolymers, maleic acid/olefin copolymers, and mixtures thereof.

14. The compositions according to any preceding claim wherein the enzyme constituent is selected from a protease, lipase, pectinase, amylase, peroxidase, and mixtures thereof.

15. The composition according to any preceding claim wherein the enzyme constituent is a protease.

16. The composition according to any preceding claim which further comprises one or more constituents selected from buffers, colorants, dyes, fragrances, opacifiers, optical brighteners, enzyme stabilizers, preservatives, and builder constituents.

16. An aqueous cleaning composition which is useful in spot cleaning of stains and soils on garments and textiles substantially as described in the Examples.

17. A process for the localized cleaning of a soiled or stained garment or textile which process comprises the step of:

applying to the soil or stained area of the garment or textile a cleaning effective amount of the compositions according to any preceding claim.