WO2009122125A1

WO2009122125A1 - Laundry treatment compositions

Info

Publication number: WO2009122125A1
Application number: PCT/GB2009/000629
Authority: WO
Inventors: Nikolaos Chalkias
Original assignee: Reckitt Benckiser Inc.; Reckitt Benckiser (Uk) Limited
Priority date: 2008-04-01
Filing date: 2009-03-09
Publication date: 2009-10-08
Also published as: GB0805908D0

Abstract

Improved treatment composition which is advantageously used as a laundry additive constituent was useful in providing an effective disinfecting or sanitizing benefits to substrates, including hard and soft substrates, and in particular to fabrics, materials, and garments or textiles being treated being treated in an automatic laundry washing machine. The treatment compositions necessarily include an acid constituent, a peroxygen bleach compound and a bleach activator which are present in respective weight ratios of between 3 and 24, preferably of between 3 and 12. The treatment compositions are demonstrated to be effective against pathogens, such as A.niger, and particularly P.verrusocum.

Description

LAUNDRY TREATMENT COMPOSITIONS

The present invention is generally directed to treatment compositions which are particularly useful in providing a sanitizing benefit to garments, textiles, and the like. More particularly, the present invention is directed to treatment compositions which are useful as additive constituents, or alternately are useful in forming treatment compositions therefrom, which are useful in the treatment of both soft surfaces such as garments, textiles and the like, but which may also be used in the treatment of hard surfaces in order to provide a sanitizing or disinfecting benefits of thereto. As of well understood, garments, textiles, and the like typically require periodic cleaning, namely laundering, in order to both clean any soils are stains which may have been adhered upon, or absorbed into the actual garment or textile, as well as to restore a degree of freshness to the garment or textile and this for the story to a satisfactory condition whereby it can be reused. Advantageously, such garments or textiles are treated utilizing an automatic washing machine, such as may be generally found in developed countries purity of these may be in the form of apparatus adapted for domestic use in a home, as well as apparatus which typically large capacities and are intended for industrial or institutional applications. The results are typically obtained one of the wash cycle of such automatic washing machines provide a sufficient duration of contact between garments or textiles being treated in such a machine with an aqueous laundry liquor such that the treated materials are cleaned and refreshed. Advantageously, the best results were obtained wherein the aqueous laundry liquor also imparts a degree of sanitization or disinfection to the materials being treated. Such sanitization or disinfection may be useful in the eradication of odor causing pathogens, and/or eradication of pathogens such as fungi which may impart to a dirty or undesired appearance to parts of the treated materials. While in the past, chlorine bleach is have been typically used to provide such a dual benefit, unhelpfully chlorine bleach is known to undesirably bleach out colors from such fabrics, materials, and garments or textiles being treated in such a manner. Alternately, or in addition thereto, the use of elevated temperatures of aqueous laundry liquors has also been known in practice, but typically such are energy intensive and require that elevated temperatures, usually in the order of 60°C or higher be established and maintained for a reasonably long time interval, generally 30 minutes or more in order to provide an appreciable sanitizing or disinfecting benefit. Even so, such treatment compositions or treatment protocols have not been successful in eradicating more durable, that is to say more difficult to eradicate pathogens. More recently, the art has provided various commercial compositions including for example, those available in Europe on to the trade names OMINIO

BIANCO (ex. Bolton Manitoba S.p.a., Italy) , and LYSOFORM (ex. Unilever) which are marketed and described to be laundry additive compositions intended to provide a sanitizing benefit as well as whitening benefit to garments, fabrics, textiles or other articles being treated during an automatic laundry washing process which are cited to be useful at lower temperatures, that is to say between about 20°Celsius and 40°C however, even these products have not proven to be effective against certain particularly pernicious pathogens, such as A.niger, but particularly P.verrusocum.

Such shortcomings in the art underscore the need in the art for still further improved treatment compositions which may be used to provide an effective disinfecting or sanitizing benefits to substrates, including hard and soft substrates, and in particular to fabrics, materials, and garments or textiles being treated being treated in an automatic laundry washing machine. It is to these and other objects that the present invention is directed.

In accordance with the first aspect of the invention, there is provided an improved treatment composition which is advantageously used as a laundry additive constituent useful in providing an effective disinfecting or sanitizing benefits to substrates, including hard and soft substrates, and in particular to fabrics, materials, and garments or textiles being treated in an automatic laundry washing machine. The treatment compositions may also provide a whitening and/or bleaching benefit as well to treated substrates. In accordance with the second aspect of the invention there is provided an improved treatment composition according to the first aspect recited above, wherein the treatment composition is effective in providing eradication of certain undesired pathogens, and particularly pernicious pathogens, such as A.niger, but particularly P.verrusocum.

In accordance with a third aspect of the invention, there is provided a hard surface treatment composition which is effective in providing eradication of certain undesired pathogens and in particular certain pernicious pathogens, such as A.niger, but particularly P.verrusocum. In accordance with a fourth aspect of the invention there is provided a method for producing a treatment composition according to any of the foregoing aspects of the invention.

In accordance with the fifth aspect of the invention there is provided a method for treating a hard or soft surface utilizing an aqueous dispersion or solution of the treatment composition according to any of the first through third aspects of the invention.

These and further aspects of the invention, as well as further objects of the invention, will become more apparent from the following specification.

The treatment compositions according to the present invention comprise a source of hydrogen peroxide. A source of hydrogen peroxide herein is any convenient compound or mixture which under appropriate conditions provides an effective amount of hydrogen peroxide in an aqueous liquor, and indeed may be hydrogen peroxide itself. Such are referred to herein as peroxygen bleach compound, viz, one or more compounds, compositions or materials which are capable of providing hydrogen peroxide in an aqueous liquor. Such compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.

Preferred as the peroxygen bleach compounds are one or more peroxygen bleaching compounds including sodium perborate, commercially available in the form of mono-, tri-, and tetra-hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, and sodium peroxide. Particularly preferred are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Percarbonates, and especially sodium percarbonates are especially preferred because as being very stable during storage and yet still dissolves very quickly in the bleaching liquor. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, higher levels and/or faster provision of hydrogen peroxide when added to water.

Such percarbonates may be provided in any form but are conveniently and advantageously provided as particulates or powders which may be provided in an uncoated or in a coated form. The average particle size of uncoated percarbonate ranges from about 400 to about 4000 microns, but more preferably are provided as particles having an average particle size of about 400 to about 1200 microns. If a coated percarbonate is used, the preferred coating materials include mixtures of carbonate and sulphate, silicate, borosilicate, or fatty carboxylic acids.

In the treatment compositions of the invention, the peroxygen bleach compound will comprise at least about 0.1%, preferably from about l%wt. to about 75%wt, more preferably from about 0.5%wt. to about 40%wt., most preferably from about 5%wt. to about 25%wt., still more preferably from about 15%wt. to about 25%wt. based on the total weight of the treatment composition of which it forms a part.

The treatment compositions of the invention also necessarily include a bleach activator, non-limiting examples of which include tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulfonates (e.g. nonanoyloxybenzenesulfonate (NOBS), benzoyloxybenzenesulfonate (BOBS)), acylated sugars (e.g. pentaacetylglucose (PAG)). Further exemplary suitable bleach activators include N-acylated amines, amides, lactams, activated carboxylic esters, carboxylic anhydrides, lactones, acylals, carboxamides, acyllactams, acylated ureas and oxamides, and furthermore, especially nitriles, which in addition to the nitrile group may also contain a quaternized ammonium group. Other known-art bleach activators may also be used as well. The bleach activator may be a single compound or material, or may be a mixture of two or more compounds or materials.

In the treatment compositions of the invention, the bleach activator is necessarily present in an amount of at least 0.1 %wt., but preferably is present in an amount of at least 1 %wt., yet more preferably in an amount of at least about 2%wt. based on the total weight of the treatment composition of which it forms a part. Concurrently, preferably the bleach activator is present in the treatment compositions in amounts not in excess of about 14%wt, preferably not in excess of about 10%wt, and still more preferably are not in excess of about 8%wt. According to the invention the respective weight ratio of peroxygen bleach compound to the bleach activator is necessarily in the ratio of between 3 and 24, preferably of between 3 and 12. Particularly preferred ranges are disclosed with reference to one or more of the examples, described below.

The compositions of the invention necessarily comprise an acid constituent, which includes one or more acids which are present in a sufficient amount in order to impart an acidic pH to aqueous solutions or aqueous dispersions of the treatment compositions. The acids useful in the acid constituent may be one or more water soluble inorganic acids, mineral acids, or water soluble organic acids, with virtually all such known materials contemplated as being useful in the present inventive compositions. Exemplary inorganic acids include, e.g., phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite (sodium metabisulfite), potassium pyrosulfite (potassium metabisulfite), acid sodium hexametaphosphate, acid potassium hexametaphosphate, acid sodium pyrophosphate, acid potassium pyrophosphate and sulfamic acid. Alkyl sulfonic acids, e.g., methane sulfonic acid may also be used as a co-acid component of the acid system. Strong inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid may also be used, however are less preferred due to their strong acidic character; if present are present in only minor amounts. However, the use of water soluble acids as are preferred, including water soluble salts of organic acids. Exemplary organic acids are those which generally include at least one carbon atom, and include at least one carboxyl group (— COOH) in its structure. Exemplary and referred examples of the organic acid to be used in the present invention include linear aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid and valeric acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fUmaric acid and maleic acid; acidic amino acids such as glutamic acid and aspartic acid; and hydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid, alpha-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid and citric acid, as well as acid salts of these organic acids. Preferred useful organic acids include citric acid, cresylic acid, dodecylbenzene sulfonic acid, phosphoric acid, salicylic acid, sorbic acid, sulfamic acid, acetic acid, benzoic acid, boric acid, capric acid, caproic acid, cyanuric acid, dihydroacetic acid, dimethylsulfamic acid, polyacrylic acid, 2-ethyl-hexanoic acid, fumaric acid, I-glutamic acid, isopropyl sulfamic acid, naphthenic acid, oxalic acid, phosphorous acid, valeric acid, maleic acid, acetic acid, adipic acid, formic acid, lactic acid, butyric acid, gluconic acid, malic acid, tartaric acid, as well as glycolic acid. The use of water soluble acids are preferred, including water soluble salts of organic acids, especially citric acid.

The acid constituent is present in a sufficient amount in order to impart an acidic pH to aqueous solutions or aqueous dispersions of the treatment compositions, preferably to establish a pH of 7 - 10, preferably 8 - 10, more preferably 8.5 - 9.5 when the treatment composition is diluted or dispersed in water, preferably at a %wt.:%wt. ratio of treatment composition:water of 1 : 15 - 150, preferably 1 :25 - 100, yet more preferably 1 :50 - 85, and especially preferably at a ratio of 1 :71. Alternately stated, when the treatment compositions of the invention are diluted in water at %wt.:%wt. ratio of treatment composition:water of 1 :15 - 150, to form a an aqueous treatment composition therefrom the bleach activator is present in an amount of between 0.00067%wt. - l%wt, the peroxygen bleach compound is present in an amount of between 0.00067%wt. - 5.35%wt., based on the total weight of the aqueous treatment composition of which it forms a part. When the treatment compositions of the invention are diluted in water at %wt.:%wt. ratio of treatment composition:water of 1:25 - 100, to form a an aqueous treatment composition therefrom the bleach activator is present in an amount of between 0.001%wt. - 0.58%wt., the peroxygen bleach compound is present in an amount of between 0.01%wt. - 3%wt., based on the total weight of the aqueous treatment composition of which it forms a part. When the treatment compositions of the invention are diluted in water at %wt.:%wt. ratio of treatment composition:water of 1 :50 - 85, to form a an aqueous treatment composition therefrom the bleach activator is present in an amount of between 0.0012%wt. - 0.285%wt., the peroxygen bleach compound is present in an amount of between 0.0012%wt. - 1.53%wt., based on the total weight of the aqueous treatment composition of which it forms a part. Finally, when the treatment compositions of the invention are diluted in water at %wt.:%wt. ratio of treatment composition:water of 1 :71, to form a an aqueous treatment composition therefrom the bleach activator is present in an amount of between 0.0014%wt. - 0.2%wt., the peroxygen bleach compound is present in an amount of between 0.0014%wt. - 1.07%wt., based on the total weight of the aqueous treatment composition of which it forms a part. In the foregoing aqueous treatment compositions, the amount of the acid constituent does in some degree depend upon the particular acid or acids selected for use, but advantageously in the non-aqueous form of the treatment composition the acid constituent advantageously comprises between 0.1%wt.- 30%wt, preferably comprises between l%wt- 18%wt. based on the total weight of the non-aqueous form of the treatment composition of which it forms a part, while in aqueous treatment compositions, acid constituent advantageously comprises between 0.00067%wt.- 2.4%wt, preferably comprises between 0.0067%wt.- 1.28%wt. based on the total weight of the aqueous form of the treatment composition of which it forms a part.

According to especially preferred embodiments of the invention, the treatment composition comprises both a bleach activator and a percarbonate as a peroxygen bleach compound wherein the weight ratio of the percarbonate to the activator is between 3 and 12; and further wherein there is present sufficient acid such that when the treatment compositions are diluted or dispersed in water at a respective weight ratio of 1 :71 to form an aqueous treatment liquor, the resultant pH of the aqueous treatment liquor is between 8 and 10, preferably between 8.5 and 10, preferably is between 8.5 and 9.5, and especially preferably is about 9. The present inventor has surprisingly found that aqueous compositions comprising respective weight ratios of peroxygen bleach compound to the bleach activator both present in respective weight ratios of between 3 and 24, especially preferably in ratios of between 3 and 12, present in an aqueous liquor having a pH of between 8.5 and 10 wherein the peroxygen bleach compound, preferably sodium percarbonate, is present in an amount of at least 0.28%wt. in the aqueous composition and the bleach activator, preferably TAED, is present in an amount of at least 0.028%wt. in the aqueous composition, and wherein the said aqueous composition at a temperature of between 20⁰C and 40⁰C may cause at least a 3 logio, and in some cases preferably at least a 4 logio level of reduction of certain pathogens, including A.niger, but particularly P.verrusocum at contact times of 15 - 60 minutes, especially at 20⁰C and 15 minute contact time, according to the quantitative suspension test according to European Standard EN 1650.

The compositions of the present invention can also optionally comprise one or more further constituents which are directed to improving the aesthetic or functional features of the inventive compositions. Such conventional additives known to the art include but not expressly enumerated here may also be included in the compositions according to the invention. By way of non-limiting example these may include: buffers, pH adjusting agents, whiteners, enzymes, sequestering agents, fillers, flow promoting agents, one or more further surfactants, fabric softeners, antistatic agents, organic solvents, colorants, color stabilizers, fragrances, as well as other optional constituents generally known to view art, particularly as generally known to be useful in laundry, fabric or textile treatment compositions. These may present an effective amounts, or, they may be omitted. By way of non-limiting example pH adjusting agents include phosphorus containing compounds, monovalent and polyvalent salts such as of silicates, carbonates, and borates, certain acids and bases, tartrates and certain acetates. By way of further non-limiting example pH buffering compositions include the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same. Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers. Particularly preferred as buffers are carbonates and bicarbonate salts, especially sodium bicarbonate and the sodium carbonate. It may also be suitable to use as buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, and their alkali metal salts. When present, the pH adjusting agent, especially the pH buffers are present in an amount effective in order to maintain the pH of the inventive composition within a target pH range. While one or more of the foregoing buffers may be omitted, advantageously, the compositions of the invention necessarily include one or more of the foregoing buffers, and preferably wherein a carbonate salt is present, especially wherein sodium carbonate is present in an amount of from l%wt. - 60%wt., and preferably between 5%wt. - 55%wt, and concurrently, were in a bicarbonate salt is present, preferably sodium a bicarbonate is present in an amount of from l%wt. - 70%wt, and preferably between 40% - 65%wt., based on the total weight of the treatment composition of which the buffers form a part. It has been found that to the foregoing inclusion of a buffer provides not only a useful pH buffering effect, but also that the preferred carbonates and bicarbonates which are typically powdered materials also provide a useful support structure or matrix upon which liquid constituents of the treatment compositions of the invention can be absorbed or absorbent, and thus such powdered materials provide a dual functionality of a pH buffering as well as a carrier matrix for such liquid constituents.

The compositions of the invention optionally but in certain cases desirably include a fragrance constituent. Fragrance raw materials may be divided into three main groups: (1) the essential oils and products isolated from these oils; (2) products of animal origin; and (3) synthetic chemicals. The essential oils consist of complex mixtures of volatile liquid and solid chemicals found in various parts of plants. Mention may be made of oils found in flowers, e.g., jasmine, rose, mimosa, and orange blossom; flowers and leaves, e.g., lavender and rosemary; leaves and stems, e.g., geranium, patchouli, and petitgrain; barks, e.g., cinnamon; woods, e.g., sandalwood and rosewood; roots, e.g., angelica; rhizomes, e.g., ginger; fruits, e.g., orange, lemon, and bergamot; seeds, e.g., aniseed and nutmeg; and resinous exudations, e.g., myrrh. These essential oils consist of a complex mixture of chemicals, the major portion thereof being terpenes, including hydrocarbons of the formula (C₅Hs)_n and their oxygenated derivatives. Hydrocarbons such as these give rise to a large number of oxygenated derivatives, e.g., alcohols and their esters, aldehydes and ketones. Some of the more important of these are geraniol, citronellol and terpineol, citral and citronellal, and camphor. Other constituents include aliphatic aldehydes and also aromatic compounds including phenols such as eugenol. In some instances, specific compounds may be isolated from the essential oils, usually by distillation in a commercially pure state, for example, geraniol and citronellal from citronella oil; citral from lemon-grass oil; eugenol from clove oil; linalool from rosewood oil; and safrole from sassafras oil. The natural isolates may also be chemically modified as in the case of citronellal to hydroxy citronellal, citral to ionone, eugenol to vanillin, linalool to linalyl acetate, and safrol to heliotropin.

Animal products used in perfumes include musk, ambergris, civet and castoreum, and are generally provided as alcoholic tinctures.

The synthetic chemicals include not only the synthetically made, also naturally occurring isolates mentioned above, but also include their derivatives and compounds unknown in nature, e.g., isoamylsalicylate, amylcinnamic aldehyde, cyclamen aldehyde, heliotropin, ionone, phenylethyl alcohol, terpineol, undecalactone, and gamma nonyl lactone.

Fragrance compositions as received from a supplier may be provided as an aqueous or organically solvated composition, and may include as a surface-active agent, typically a surfactant, in minor amount. Such fragrance compositions are quite usually proprietary blends of many different specific fragrance compounds. However, one of ordinary skill in the art, by routine experimentation, may easily determine whether such a proprietary fragrance composition is compatible in the compositions of the present invention. hi certain embodiments of the invention, particularly where a fragrance composition is included as part of a treatment composition of the invention, it is often advantageous to include an organic solvent which may be help fill in solubilizing or dispersing the fragrance composition. Non-limiting examples of such solvents include liquid n-paraffins, liquid iso-parafϊϊns, cycloalkanes, aromatic solvents, silicone solvents or oils, as well as organic solvents which are at least partially water-miscible such as monohydric (straight chained or branched) primary, secondary or tertiary lower aliphatic alcohols, especially Ci-C₆ aliphatic primary and secondary alcohols, water-miscible ethers including those having the general structure R'-O-R"-OH, wherein R' is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and R" is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units. When present, such one or more organic solvents may be present in any effective amount, which may be as little as 0.001%wt. to greater amounts, generally up to about 5%wt. a such amounts are typically sufficient in order to provide good solubilization or dispersion of the fragrance composition when present.

One or more coloring agents may also be used in the inventive compositions in order to impart a desired colored appearance or colored tint to the compositions. Known art water soluble or water dispersible pigments and dyes may be advantageously included in certain embodiments and may be added in effective amounts.

One or more color stabilizers may also be included in the inventive compositions in order to improve the color fastness of treated substrates and to reduce any undesired bleaching of such treated substrates. By way of nonlimiting example, exemplary color stabilizers include those commercially available under the TINOFIX trademark (ex. Ciba).

The treatment compositions of the invention may also include an optical brighteners also frequently referred to in the art and is as a fluorescent white additive. By way of nonlimiting examples, such include those sold under the trade name TINOPAL (ex. Ciba) such and as TINOPAL CBS which is described to be disodium 2,2'-bis- (phenyl-styryl)disulphonate as well as TINOPAL DMS which is described to be disodium 4,4'bis-(2-moφholino-4-anilino-s-triazin-6-ylamino)stilbene disulphonate. Such one included may be included and useliil amounts. Exemplary useful amounts generally fall within the range on from 0.02%wt. to l%wt. The treatment compositions of the invention may also include one or more chelating agents. Exemplary useful chelating agents include those known to the art, including by way of non-limiting example; aminopolycarboxylic acids and salts thereof wherein the amino nitrogen has attached thereto two or more substituent groups. Preferred chelating agents include acids and salts, especially the sodium and potassium salts of ethylenediaminetetraacetic acid, diethyl enetriaminepentaacetic acid, N- hydroxyethylethylenediaminetriacetic acid, and of which the sodium salts of ethylenediaminetetraacetic acid may be particularly advantageously used. While such chelating agents may be omitted, preferably they are present and when present, they may be included in generally minor amounts such as from 0.001 - 2.5 %wt. based on the weight of the chelating agents and/or salt forms thereof. Desirably, such chelating agents are included in the present inventive composition in amounts from 0.01 - 0. l%wt., but are most desirably present in reduced weight percentages from about 0.01 - 0.5%wt.

The treatment compositions of the invention may include one or more surfactants, selected from anionic, nonionic, cationic, amphoteric or zwitterionic surfactants.

Exemplary anionic surfactants alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl ester sulfates, alkyl diphenyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, alkyl ether sulfates, alpha-olefin sulfonates, beta-alkoxy alkane sulfonates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkylaryl sulfates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 moles of ethylene oxide, alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide), sulfosuccinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, fatty acid amide polyoxyethylene sulfates, acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, alkylpolysaccharide sulfates, alkylpolyglucoside sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof. These anionic surfactants may be provided as salts with one or more organic counterions, e.g, ammonium, or inorganic counteraions, especially as salts of one or more alkaline earth or alkaline earth metals, e.g, sodium.

Further examples of anionic surfactants include water soluble salts or acids of the formula (ROSO₃)_XM or (RSO₃)_XM wherein R is preferably a C₆-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cio-C₂o alkyl component, more preferably a Ci₂-Ci₈ alkyl or hydroxyalkyl, and M is H or a mono-, di- or tri-valent cation, e. g., an alkali metal cation (e. g., sodium, potassium, lithium), or ammonium or substituted ammonium (e. g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) and x is an integer, preferably 1 to 3, most preferably 1. Materials sold under the Hostapur and Biosoft trademarks are examples of such anionic surfactants.

Still further examples of anionic surfactants include alkyl-diphenyl- ethersulphonates and alkyl-carboxylates.

Also useful as anionic surfactants are diphenyl disulfonates, and salt forms thereof, such as a sodium salt of diphenyl disulfonate commercially available as Dowfax® 3B2. Such diphenyl disulfonates are included in certain preferred embodiments of the invention in that they provide not only a useful cleaning benefit but concurrently also provide a useful degree of hydro tropic functionality.

Other anionic surfactants can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C₆-C₂₀ linear alkylbenzenesulfonates, C₆-C₂₂ primary or secondary alkanesulfonates, C₆-C₂₄ olefϊnsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, C₆-C₂₄ alkylpolyglycolethersulfates, alkyl ester sulfates such as Ci_4-16 methyl ester sulfates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated Ci₂-C)₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C₆-Ci₄ diestcrs), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂O)_kCH₂COCTM⁺ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Examples of the foregoing anionic surfactants are available under the following tradenames: Rhodapon®, Stepanol®, Hostapur®, Surfine®, Sandopan®, Neodox®, Biosoft®, and Avanel®.

An anionic surfactant compound which may be particularly useful in the inventive compositions when the compositions are at a pH of 2 or less are one or more anionic surfactants based on alphasulphoesters including one or more salts thereof. Such particularly preferred anionic surfactants may be represented by the following general structures:

wherein, in each of the foregoing:

R¹ represents a C₆ - C₂₂ alkyl or alkenyl group; each of R² is either hydrogen, or if not hydrogen is a SO₃ ^" having associated with it a cation, X⁺, which renders the compound water soluble or water dispersible, with X preferably being an alkali metal or alkaline earth metal especially sodium or potassium, especially sodium, with the proviso that at least one R , preferably at least two R is a (SO₃ ^") having an associated cation X⁺, and, R represents a Ci-C₆, preferably Ci-C₄ lower alkyl or alkenyl group, especially methyl. Notwithstanding the above, in certain preferred embodiments optional surfactants based on anionic surfactants are necessarily absent from the compositions.

Notwithstanding the above, in certain preferred embodiments one or more anionic surfactants are necessarily present in the treatment compositions of the invention, particularly wherein such anionic surfactants are one or more alkylaryl sulfates or sulfonates, and particularly one or more alkylbenzene sulfates or sulfonates, which, when present to our advantageously present in amounts of between 0.001%wt. to about 10%wt., and more preferably to about 7%wt. based on the total weight of the treatment composition of which it forms a part. One class of exemplary, albeit optionally, useful nonionic surfactants are polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.

Further optionally useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms). Other examples are those C₆ -Ci i straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide. Their derivation is well known in the art. Examples include Alfonic® 810-4.5 (also available as Teric G9A5), which is described in product literature from Sasol as a C_8-I0 having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfonic® 810-2, which is described in product literature from Sasol as a C₈_io having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12; and Alfonic® 610-3.5, which is described in product literature from Sasol as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt.%), and an HLB of 10. Product literature from Sasol also identifies that the numbers in the alcohol ethoxylate name designate the carbon chain length (numbers before the hyphen) and the average moles of ethylene oxide (numbers after the hyphen) in the product.

Further exemplary useful nonionic surfactants include alcohol ethoxylates which are described as Cg-C₁₁ ethoxylated alcohols and marketed under the Neodol® tradename. The Neodol® 91 series non- ionic surfactants of interest include Neodol 91- 2.5, Neodol 91-6, and Neodol 91-8. Neodol 91-2.5 has been described as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has been described as having about 6 ethoxy groups per molecule; and Neodol 91-8 has been described as having about 8 ethoxy groups per molecule. Still further examples of ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf D A-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf D A-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf DA- 639 is a 90% solution of DA-630. Further examples of useful nonionic surfactants include alcohol ethoxylates including ClO oxo -alcohol ethoxylates available from BASF under the Lutensol ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol ON 30; Lutensol ON 50; Lutensol ON 60; Lutensol ON 65; Lutensol ON 66; Lutensol ON 70; Lutensol ON 80; and Lutensol ON 110). Yet farther examples of ethoxylated alcohols include those from Tomah Products (Milton, Wl) under the Tomadol tradename with the formula RO(CH₂CH₂O)_nH where R is the primary linear alcohol and n is the total number of moles of ethylene oxide. The ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8 - where R is linear C9/C10/C1 1 and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; - where R is linear CI l and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C12/C13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear C12/C13 C14/ C15 and n is 3, 7, 9, or 12; and 45-7; 45-13 - where R is linear C 14/ Cl 5 and n is 7 or 13.

Other examples of potentially useful nonionic surfactants include those having a formula RO(CH₂CH₂O)_nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci₂H₂₅ to Ci₆H₃₃ and n represents the number of repeating units and is a number of from about 1 to about 12. Surfactants of this formula are presently marketed under the Genapol® tradename. available from Clariant, Charlotte, N.C., include the 26-L series of the general formula RO(CH₂CH₂O)_nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C J₂H₂₅ to Ci₆H₃₃ and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-l, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L- 6ON, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% Ci₂ and 45% Ci₄ alcohols, such as 24-L-3, 24-L-45, 24- L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N. From product literature, the single number following the "L" corresponds to the average degree of ethoxylation (numbers between 1 and 5) and the two digit number following the letter "L" corresponds to the cloud point in ⁰C of a 1.0 wt.% solution in water.

A specific class of potentially useful, albeit optional, nonionic surfactants include are monobranched alkoxylated C 10-fatty alcohols and/or CI l -fatty alcohols; these are jointly referred to as C 10/Cl 1 -fatty alcohols. These materials are nonionic surfactants are monobranched and may have various degrees of alkoxylation, and are typically ethoxylated with between about 3 and 14 moles of ethylene oxide, typically 4, 5, 6, 7, 8, 9, 10 or 14 moles ethylene oxide. Such nonionic surfactants are presently commercially available under the Lutensol® (ex. BASF AG) and are available in a variety of grades e.g., Lutensol© XL 40 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 4 moles of ethoxylation, Lutensol® XL 50 recited by its supplier to be a C10-Guerbet alcohol which is approximately 5 moles of ethoxylation, Lutensol® XL 60 recited by its supplier to be a C10-Guerbet alcohol which is approximately 6 moles of ethoxylation, Lutensol® XL 70 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 7 moles of ethoxylation, Lutensol® XL 40 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 4 moles of ethoxylation, Lutensol® XL 79 recited by its supplier to be a C10-Guerbet alcohol which is approximately 7 moles of ethoxylation, Lutensol® XL 80 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 8 moles of ethoxylation, Lutensol® XL 89 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 8 moles of ethoxylation, Lutensol® XL 90 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 9 moles of ethoxylation, Lutensol® XL 99 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 9 moles of ethoxylation, Lutensol® XL 100 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 10 moles of ethoxylation, Lutensol® XL 140 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 14 moles of ethoxylation, all available from BASF AG. Alternately or additionally, nonionic surfactant based on monobranched alkoxylated ClO-fatty alcohols marketed under the Lutensol® XP series of surfactants, also ex. BASF AG, may also be used. While the foregoing materials are ethoxylated, it is to be understood that other alkoxylated, e.g., propoxylated, butoxylated, as well as mixed ethoxylated and propoxylated branched nonionic alkyl polyethylene glycol ether may also be used.

It is contemplated by the inventors that similar nonionic surfactants based on monobranched alkoxylated Cl 1-fatty alcohols maybe used to substitute part of, or all of the nonionic surfactant based on monobranched alkoxylated ClO-fatty alcohols. These include for example, the Genapol® UD series described as tradenames Genapol® UD 030, Cii-oxo-alcohol polyglycol ether with 3 EO; Genapol® UD, 050 Cπ-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD 070, Cπ-oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080, Cn-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088, Cii-oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110, Cπ-oxo-alcohol polyglycol ether with 11 EO (ex. Clan ant).

A further class of nonionic surfactants which are contemplated to be useful include those based on alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers. Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C₂-C₄ alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols.

A further group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A):

HO-(EO)_x(PO)_y(EO)*-H (A)

where EO represents ethylene oxide,

PO represents propylene oxide, y equals at least 15,

(EO)χ+_y equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000. These surfactants are available under the PLURONIC tradename from BASF or Emulgen from Kao.

Another group of nonionic surfactants appropriate for use in the new compositions can be represented by the formula (B):

R-(EO,PO)a(EO,PO)_b-H (B)

wherein R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block.

Further nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.

Still further useful nonionic surfactants containing polymeric butoxy (BO) groups can be represented by formula (C) as follows:

RO-(BO)_n(EO)_x-H (C)

wherein R is an alkyl group containing I to 20 carbon atoms, n is about 5-15 and x is about 5-15.

Also useful as the nonionic block copolymer surfactants, which also include polymeric butoxy groups, are those which may be represented by the following formula (D):

HO-(EO)_x(BO)_n(EO)_y-H (D)

wherein n is about 5-15, preferably about 15, x is about 5-15, preferably about 15, and y is about 5-15, preferably about 15.

Still further useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula:

where (EO) represents ethoxy,

(PO) represents propoxy, the amount of (PO)_x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO)_y is such as to provide about 20% to 90% of the total weight of said compound. Surfactants based on amine oxides are also contemplated to be possibly useful in the present inventive compositions as optional nonionic surfacants. Exemplary amine oxides include: alkyl di(C_t-C₇) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide; alkyl di(hydroxy C₁-C₇) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide; alkylamidopropyl di(Ci-C₇) amine oxides in which the alkyl group has about 10- 20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Notwithstanding the foregoing, in certain preferred embodiments optional surfactants based on nonionic surfactants are necessarily absent from the compositions.

Notwithstanding the immediately foregoing, in certain preferred embodiments surfactants based on nonionic surfactants are necessarily present in the treatment compositions of the present invention. Exemplary cationic surfactant compositions include those which provide a germicidal effect to the compositions, and especially preferred are quaternary ammonium compounds and salts thereof, which may be characterized by the general structural formula:

where at least one of Ri, R₂, R₃ and R₄ is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165. The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long- chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents Ri, R₂, R₃ and R₄ may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water solubility of the quaternary ammonium complex. Further exemplary quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Other very effective types of quaternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like. Notwithstanding the foregoing, in certain preferred embodiments optional surfactants based on cationic surfactants are necessarily absent from the compositions. Notwithstanding the immediately foregoing, in certain preferred embodiments one or more surfactants based on cationic surfactants are necessarily present in the D. inventive treatment compositions. Exemplary amphoteric surfactants which are contemplated to be useful in the cosurfactant constituent include one or more water-soluble betaine surfactants which may be represented by the general formula:

wherein Ri is an alkyl group containing from 8 to 18 carbon atoms, or the amido radical which may be represented by the following general formula:

O H Il I R-C-N- (C H₂ )_a- R₂ wherein R is an alkyl group having from 8 to 18 carbon atoms, a is an integer having a value of from 1 to 4 inclusive, and R₂ is a Ci-C₄ alkylene group. Examples of such water-soluble betaine surfactants include dodecyl dimethyl betaine, as well as coco am i dopropylbetaine. Notwithstanding the above, in certain preferred embodiments optional surfactants based on amphoteric surfactants are necessarily absent from the compositions.

Notwithstanding the immediately foregoing, in certain preferred embodiments surfactants based on amphoteric surfactants are necessarily present in the inventive treatment compositions.

Notwithstanding the foregoing, in certain preferred embodiments optional surfactants based on zwitterionic surfactants are necessarily absent from the compositions.

Notwithstanding the immediately foregoing, in certain preferred embodiments surfactants based on zwitterionic surfactants are necessarily present in the inventive treatment compositions.

When present these one or more further optional surfactants based on nonionic, anionic, cationic, amphoteric or zwitterionic surfactants may be present singly or in mixtures. When present they may be included in any amount which is effective to provide a desired benefit, such as a desired to terror sieve benefits. Advantageously, the total amount of such surfactants typically does not exceed about 10% by weight of the total weight of the treatment compositions of which they form a part.

The treatment compositions of the invention may also include one or more fabric softening constituents, such as long chain cationic surfactants such as are known to the detergent art.

The treatment compositions of the invention may also include one or more enzymes, which may provide cleaning performance, fabric care and/or sanitation benefits. By way of nonlimiting example, exemplary enzymes include transferases, hydrolases, lyases, isomerases and ligases. Examples of the hydrolases include but are not limited to: carboxylic ester hydrolase, thiolester hydrolase, phosphoric monoester hydrolase, and phosphoric diester hydrolase which act on the ester bond; glycosidase which acts on O-glycosyl compounds; glycosylase hydrolysing N-glycosyl compounds; thioether hydrolase which acts on the ether bond; and exopeptidases and endopeptidases which act on the peptide bond. Preferable among them are carboxylic ester hydrolase, glycosidase and exo- and endopeptidases. Specific examples of suitable hydrolases include (1) exopeptidases such as aminopeptidase and carboxypeptidase A and B and endopeptidases such as pepsin, pepsin B, chymosin, trypsin, chymotrypsin, elastase, enteropeptidase, cathepsin B, papain, chymopapain, ficain, thrombin, plasmin, renin, subtilisin, aspergillopepsin, collagenase, clostripain, kallikrein, gastricsin, cathepsin D, bromelain, chymotrypsin C, urokinase, cucumisin, oryzin, proteinase K, thermomycolin, thermitase, lactocepin, thermolysin, bacillolysin. Preferred among them is subtilisin; (2) glycosidases such as α-amylase, /3-amylase, glucoamylase, isoamylase, cellulase, endo- l,3(4)-j8-glucanase (β-glucanase), xylanase, dextranase, polygalacturonase (pectinase), lysozyme, invertase, hyaluronidase, pullulanase, neopuUulanase, chitinase, arabinosidase, exocellobiohydrolase, hexosaminidase, mycodextranase, endo-l,4-/3-mannanase

(hemicellulase), xyloglucanase, endo-]δ-galactosidase (keratanase), mannanase and other saccharide gum degrading enzymes as described in WO-A-99/09127. Preferred among them are α-amylase and cellulase; (3) carboxylic ester hydrolase including carboxylesterase, lipase, phospholipase, pectinesterase, cholesterol esterase, chlorophyllase, tannase and wax-ester hydrolase. Preferred is lipase which is known to be particularly effective in removing fatty or oleophilic soils are stains from substrates. Non-limiting examples of transferases and ligases include glutathione S-transferase and acid-thiol ligases. Non-limiting examples of lyases include hyaluronate lyase, pectate lyase, chondroitinase, pectin lyase, alginase II. Non-limiting examples of endopeptidases (proteolytic enzymes or proteases) which may be used in the treatment compositions of the present invention include proteolytic enzymes are the subtilisins, which can be obtained from particular strains of B. subtilis, B. lentus, B. amyloliquefaciens and B. licheniformis, such as the commercially available from a variety of commercial sources including for example, Novo Industri A/S, Copenhagen, Denmark and Genencor International. Non- limiting examples of useful lipases include those of bacterial or fungal origin, as well as chemically or genetically modified variants of these enzymes are included. Non-limiting examples of suitable amylases include those of bacterial or fungal origin, as well as chemically or genetically modified variants of these enzymes. Non-limiting examples of suitable cellulases include those of bacterial or fungal origin, as well as chemically or genetically modified variants thereof. When present such one or more enzymes may be advantageously included in the treatment compositions in amounts of as little as 0.00001%wt. to amounts usually not exceeding 5%wt, and more preferably 0.00 l%wt. to 0.5%wt., which are recited in terms of pure enzyme protein and based on the total weight of the treatment composition of which such enzymes form a part. When present, such enzymes can be added as separate single ingredients (prills, granulates, stabilised liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (e.g. cogranulates) to the treatment composition of which they form a part..

The treatment compositions according to the invention may optionally include one or more builder constituents. Such builder constituents are known from the laundry detergent art, and for example alumino silicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof. Preferred builders include aluminosilicate ion exchange materials and sodium carbonate. The aluminosilicate ion exchange materials are believed to exhibit both a high calcium ion exchange capacity and a high exchange rate. In a preferred form the treatment composition of the invention is provided as a free- flowing powder and it's flow may be improved by the incorporation of a small amount of a powder structurant. Examples of powder structurants, some of which may play also other roles in the formulation, include, by way of nonlimiting example, fatty acids (or fatty acid soaps), sugars, acrylate or acrylate/maleate polymers, (e.g., SOKALAN polymers, ex. BASF) sodium silicate, sodium sulfate, and dicarboxylic acids to name a few. Other powder structurants known from the laundry detergent art, although not specifically elucidated here, are also contemplated to be useful as well. It is contemplated that the powder structurant.may also be useful as a carrier for liquid constituents of the treatment compositions of the invention, as has been generally described above with regard to buffer constituents.

In accordance with certain particularly preferred embodiments the treatment compositions of the invention are powdered treatment compositions which comprise (in certain embodiments consist essentially of):

20%wt. or more of a percarbonate, preferably sodium percarbonate; at least 2%wt. of a an activator, preferably wherein the activator is TAED; wherein the weight ratio of the percarbonate to the activator is between 3 and 12; sufficient acid such that when the treatment compositions are diluted or dispersed in water at a respective weight ratio of 1 :71 to form an aqueous treatment liquor, the resultant pH of the aqueous treatment liquor is between 8 and 10, preferably between 8.5 and 10, preferably is between 8.5 and 9.5, and especially preferably is about 9; and, wherein when the treatment composition is diluted or dispersed in water at a respective weight ratio of 1 :71 at 20⁰C - 40⁰C to form an aqueous treatment composition, said aqueous treatment composition exhibits a degree of pathogenic efficacy of at least 3 logio, and in some cases preferably at least a 4 log₁₀ level of reduction of certain pathogens, including A.niger, but particularly P.verrusocum at contact times of 15 - 60 minutes, especially at 20⁰C and 15 minute contact time, according to the quantitative suspension test according to European Standard EN 1650; and, optionally but preferably, if a bicarbonate, e.g., sodium bicarbonate is present in an amount in excess of 35%wt., the acid should be present in an amount of less than 5%wt, and further optionally, but preferably, if a carbonate, e.g, sodium carbonate, is present in an amount in excess of 35%wt, the acid should be present in an amount of at least 10%wt., or may be present in greater amounts.

The treatment compositions of the invention may take any physical form but his advantageously provided either as a free-flowing powder which is desirably also preferably anhydrous, or in a unit-dosage form such as in the form of a compacted tablet or cake, as well as in the form of a powder and closed in a water insoluble, or a water- soluble film to form a sachet.. Coming into consideration as water insoluble films include one or more of polyamide, polyolefins while coming into consideration as water soluble films include polyvinyl alcohols and copolymers thereof. The treatment compositions according to the invention are advantageously used as a laundry additive for providing any disinfecting or sanitizing benefits to textile goods, e.g. garments, textiles, fabrics, or other materials which are treated in a largely aqueous laundry liquor. Thus in such an aspect the invention also provides a treatment method for providing such disinfecting or sanitizing benefits to textile goods, e.g. garments, textiles, fabrics, or other materials which are treated in a largely aqueous laundry liquor. While they may be added in any useful amount, advantageously the treatment compositions are added on a weight:weight ratio of treatment cυmposition:water of 1 : 15 - 150, preferably 1 :25 - 100, yet more preferably 1 :50 - 85, and especially preferably at a ratio of 1 :71, the last ratio being approximately equivalent to a "use dilution" of 70 grams of the non- aqueous treatment composition to 5 litres of water. As such a laundry additive, the treatment compositions are conveniently used as an additive in a conventional domestic or commercial washing machine apparatus, which typically operates to provide a wash liquor having a temperature of between about 10°C and about 40⁰C, but advantageously the compositions of the invention are used at wash liquors of between 20° and 40⁰C, preferably between about 30⁰C and 40⁰C. Of course, the treatment compositions of the invention can be used at lower temperatures, namely just above 0⁰C to much higher temperatures, which typically however are not in excess of about 80⁰C, preferably are not in excess of about 60⁰C and get more preferably or not in excess of about 50⁰C. Such elevated temperatures may be established by any washing machine apparatus, and/or alternately may be established by a supply of hot water from a storage tank, boiler, and the like. Further advantageously, in order to provide an effective sanitizing benefit the textile goods are retained in contact in the laundry liquor at time intervals of which may be any time effective in order to provide such as sanitizing benefit, even times as short as 30 seconds, but advantageously such times are least 15 minutes to about 60 minutes, and at temperatures of between about 20⁰C and 40⁰C, with typically better results expected at longer contact times. Advantageously, good results are obtained when the textile goods are retained in contact in the laundry liquor or in the laundry liquor has a temperature of the least 30⁰C, and even more preferably at least 40⁰C. It is to be understood that the formation of peracetic acid occurs at a faster rate it higher temperatures, namely at 30⁰C and especially at 40⁰C although ample purse you to guess it may be formed at lower temperatures such ads at about 20⁰C although longer reaction times, typically on the order of the least 10 minutes at such lower temperatures is required in order to generate in situ a sufficient concentration of peracetic acid.

Alternately the treatment compositions of the invention can be simply added to a volume of water in order to form an equally as treatment composition, or to a volume of water, such as may be present in a container or a tub, in order to form a laundry liquor to which may be supplied textile goods. For example, it may be perceived to be advantageous, or desirable from a consumer standpoint to simply soak such textile goods in a laundry liquor which may be no more than aqueous dispersion of the inventive compositions in a water such as a pre-soak, or even as a post-wash soak. Such a pre-soak or post-wash soak may of course be practiced wholly apart or separate from, or even in the absence of a conventional laundry process, such as via the use of conventional domestic or commercial washing machine apparatus. Alternately, such a pre-soak or post-wash soak may also be practiced as part of a manual laundry washing process. In such an application the treatment compositions may be added to water in the same ratios, and at the same temperatures, and for the same contact times as discussed above with reference to its use in a conventional domestic or commercial washing machine apparatus.

Although primarily discussed herein as a treatment composition which finds use as a laundry additive composition or laundry additive products useful in conjunction with an automatic laundry apparatus, or alternately as an additive to a quantity of water in order to form a pre-wash soak or a post-wash soak composition, it is nevertheless to be appreciated that aqueous treatment compositions formed by dissolving or dispersing a quantity of a non-aqueous form of the treatment composition of the invention, e.g., powdered form, in a suitable quantity of water may be used as a hard surface treatment composition in order to provide a cleaning and/or sanitizing and/or disinfecting benefits to hard surfaces. Advantageously such a dilution or dispersion of the non-aqueous form of the treatment composition to water is formed at a respective ratio of treatment composition :water of 1 :15 - 150, preferably 1 :25 - 100, yet more preferably 1 :50 - 85, and especially preferably at a ratio of 1 :71 in order to form a hard surface treatment composition therefrom. Such a hard surface treatment composition can be those readily formed, and his preferably formed less than one hour prior to its application to a hard surface, preferably less than 30 minutes, more preferably less than 15 minutes prior to the application of the aqueous hard surface treatment composition with us formed to a hard surface in need of a cleaning and/or disinfecting and/or sanitizing benefit. When thus formed, such a hard surface treatment composition can be conveniently dispensed either by direct applications such as by pouring or spraying onto or near the locus of any stain or other area of a hard surface in need of treatment, or alternately can be applied via a disposable or reusable wipe or wiping article such as a sponge to said locus or area on a hard surface.

The hard surface treatment compositions are readily used in the disinfection and/or sanitizing of hard surfaces by application a cleaning effective amount of a hard surface cleaning composition according to any of the prior recited inventive aspects to a hard surface in need of such treatment, and concurrently or subsequently, wiping the surface with a cloth, wipe or wiping article. The hard surface treatment composition may also provide a cleaning benefit as well to treated hard surfaces as an ancillary primary benefit of providing disinfection and/or sanitization.

According to a further aspect of the invention, there is provided a method for the manufacture of said compositions as described herein. The following examples exhibit exemplary and preferred formulations of the invention. It is to be understood that these examples are provided by way of illustration only and that further useful formulations falling within the scope of the present invention and the claims may be readily produced by one skilled in the art without deviating from the scope and spirit of the invention.

Examples

Compositions according to the examples were produced by mixing measured amounts of the individual recited constituents in a suitable blender, such as a tumble blender in order to produce a non-aqueous, namely an anhydrous form of a treatment composition according to the invention. Constituents which were provided in the form of liquids, such as organic solvents, fragrances were added to the dry constituents and were absorbed or absorbed onto the same. The resultant compositions were diy, free flowing powders which were readily dispersible or dissolvable in water.

The specific formulations of examples according to the invention are described on Table 1 wherein it is to be understood that this compositions falling within the scope of the invention are labeled utilizing the letter "E" followed by an integer digit. Compositions according to a comparative example, and falling outside of the scope of the invention, are identified utilizing the letter "C" followed by an integer digit, or are otherwise clearly identified as being a prior-art composition.

The constituents used to form the examples as well as the comparative examples are identified more folly on the following Table 2.

The pathogenic efficacy of the foregoing treatment compositions according to El to E8 described on foregoing Table 1 were evaluated by forming aqueous treatment compositions of El to E8 at dilutions of either 1 :15 or 1 :71 parts by weight of treatment composition :water at a temperature of between 20⁰C and 40⁰C may cause at least a 3 logio, and in some cases preferably at least a 4 logio level of reduction of certain pathogens, including A.niger, but particularly P.verrusocum at contact times of 15 — 60 minutes, especially at 20⁰C and 15 minute contact time, according to the quantitative suspension test according to European Standard EN 1650. The results of this testing is indicated on the following Table 3. Similar testing on comparative compositions, Cl, C2 and C3 described on Table 1 above, as well as on two commercially available European products which were diluted as indicated on their respective product packaging.

n.t. = sample not tested

As is evident from the test results the compositions according to El to E8 at the indicated temperatures and dilutions exhibited at least a 4 logio reduction at one or more of the test conditions against P. verrucosum, a pathogen which is recognized in the art as being particularly difficult to eradicate under such test conditions. In contrast, all of the comparative compositions tested performed significantly worse than the compositions according to El - E8, even though tested at longer contact times of 30 minutes and 60 minutes.

While described in terms of the presently preferred embodiments, it is to be understood that the present disclosure is to be interpreted as by way of illustration, and not by way of limitation, and that various modifications and alterations apparent to one skilled in the art may be made without departing from the scope and spirit of the present invention.

Claims

Claims:

1. A powdered treatment composition effective disinfecting or sanitizing benefits to substrates which comprises:

20%wt. or more of a percarbonate; at least 2%wt. of a an activator; wherein the weight ratio of the percarbonate to the activator is between 3 and 12; sufficient acid such that when the treatment compositions are diluted or dispersed in water at a respective weight ratio of 1 :71 to form an aqueous treatment liquor, the resultant pH of the aqueous treatment liquor is between 8 and 10; and, wherein when the composition is diluted or dispersed in water at a respective weight ratio of 1 :71 at 20°C - 40°C to form an aqueous treatment composition, said aqueous treatment composition exhibits a degree of pathogenic efficacy of at least 3 log₁₀, level of reduction of certain pathogens, including A.niger, or P.verrusocum at contact times of 15 - 60 minutes; and, optionally but preferably, if a bicarbonate is present in an amount in excess of 35%wt, the acid is present in an amount of less than 5%wt., and further optionally, but preferably, if a carbonate is present in an amount in excess of 35%wt, the acid is in an amount of at least 10%wt.

2. A powdered treatment composition according to claim 1 wherein the percarbonate is sodium percarbonate.

3. A powdered treatment composition according to claim 1 wherein the activator is TAED.

4. A powdered treatment composition according to claim 1, wherein the composition contains sufficient acid such that when the treatment compositions are diluted or dispersed in water at a respective weight ratio of 1 :71 to form an aqueous treatment liquor, the resultant pH of the aqueous treatment liquor is between 8.5 and 10.

5. A powdered treatment composition according to claim 4, wherein the composition contains sufficient acid such that when the treatment compositions are diluted or dispersed in water at a respective weight ratio of 1 :71 to form an aqueous treatment liquor, the resultant pH of the aqueous treatment liquor is between 8.5 and 9.5.

6. A powdered treatment composition according to any preceding claim wherein, when the composition is diluted or dispersed in water at a respective weight ratio of 1 :71 at 20⁰C - 40⁰C to form an aqueous treatment composition, said aqueous treatment composition exhibits a degree of pathogenic efficacy of at least 3 logio, level of reduction of certain pathogens, including A.niger, or P.verrusocum at contact times of 15 - 60 minutes; according to the quantitative suspension test according to European Standard EN 1650.

7. A powdered treatment composition according to any preceding claim wherein when the composition is diluted or dispersed in water at a respective weight ratio of 1 :71 at 20⁰C - 40⁰C to form an aqueous treatment composition, said aqueous treatment composition exhibits a degree of pathogenic efficacy of at least 4 logio, level of reduction of certain pathogens, including A.niger, or P.verrusocum at contact times of 15 - 60 minutes;

8. A laundry additive for providing any disinfecting or sanitizing benefits to textile goods according to any preceding claim.

9. A method for providing a disinfecting or sanitizing benefit to textile goods, which are treated in a largely aqueous laundry liquor which comprises the steps of; providing a powdered treatment composition according to any of claims 1 — 7 to a sufficient amount of water at respective weight:weight ratio of treatment composition :water of 1 :15 — 150 to form a laundry liquor having a temperature of

10⁰C and about 60°C; and, p roviding textile goods in the laundry liquor and contacting the textile goods in the laundry liquor for sufficient time to provide a sanitizing benefit to the textile goods.

10. A method for providing a cleaning and/or sanitizing and/or disinfecting benefit to a hard surface, comprising the steps of: forming a hard surface treatment composition by dissolving or dispersing a quantity of powdered treatment composition according to any of claims 1 - 7 in a suitable quantity of water to form a hard surface treatment composition therefrom; and, applying the hard surface treatment composition to a hard surface in order to provide a a cleaning and/or sanitizing and/or disinfecting benefit thereto.