CA2718172A1 - Organic catalyst with enhanced enzyme compatibility - Google Patents

Organic catalyst with enhanced enzyme compatibility Download PDF

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Publication number
CA2718172A1
CA2718172A1 CA 2718172 CA2718172A CA2718172A1 CA 2718172 A1 CA2718172 A1 CA 2718172A1 CA 2718172 CA2718172 CA 2718172 CA 2718172 A CA2718172 A CA 2718172A CA 2718172 A1 CA2718172 A1 CA 2718172A1
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Canada
Prior art keywords
methylbenzyl
cleaning composition
enzyme
benzyl
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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CA 2718172
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French (fr)
Inventor
Gregory Scot Miracle
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to CA 2718172 priority Critical patent/CA2718172A1/en
Publication of CA2718172A1 publication Critical patent/CA2718172A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/349Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/3917Nitrogen-containing compounds
    • C11D3/392Heterocyclic compounds, e.g. cyclic imides or lactames
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • C11D3/3917Nitrogen-containing compounds
    • C11D3/3927Quarternary ammonium compounds

Abstract

This invention relates to cleaning compositions comprising organic catalysts having enhanced enzyme compatibility and processes for making and using such cleaning compositions.

Description

ORGANIC CATALYST WITH ENHANCED ENZYME COMPATIBILITY
FIELD OF INVENTION
This invention relates to cleaning compositions comprising organic catalysts and processes for making and using such cleaning products.

BACKGROUND OF THE INVENTION
Oxygen bleaching agents, for example hydrogen peroxide, are typically used to facilitate the removal of stains and soils from clothing and various surfaces.
Unfortunately such agents are extremely temperature rate dependent. As a result, when such agents are employed in colder solutions, the bleaching action of such solutions is markedly decreased.
In an effort to resolve the aforementioned performance problem, the industry developed a class of materials known as "bleach activators". However, as such materials rapidly lose their effectiveness at solution temperatures of less than 40 C, new organic catalysts such as 3,4-dihydro-2-[2-(sulfooxy)decyl]isoquinolimium, inner salt were developed. In general, while such current art catalysts are effective in lower temperature water conditions, they can inactivate certain enzymes. As most laundry and cleaning compositions are formulated with enzymes, formulating cleaning products with such catalysts can be problematic.
Accordingly, there is a need for an inexpensive cleaning composition comprising an organic catalyst that can provide the combined benefits of formulation flexibility, low water temperature bleaching performance and enzyme compatibility.

SUMMARY OF THE INVENTION

The present invention relates to cleaning compositions comprising organic catalysts having enhanced enzyme compatibility, and methods of making and using same.
DETAILED DESCRIPTION OF THE INVENTION
Definitions As used herein, the term "cleaning composition" includes, unless otherwise indicated, granular or powder-form all-purpose or "heavy-duty" washing agents, especially laundry detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, laundry bars, mouthwashes, denture cleaners, car or carpet shampoos, bathroom cleaners; hair shampoos and hair-rinses; shower gels and foam baths and metal cleaners; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types.
As used herein, the phrase "is independently selected from the group consisting of ....."
means that moieties or elements that are selected from the referenced Markush group can be the same, can be different or any mixture of elements.
The test methods disclosed in the Test Methods Section of the present application must be used to determine the respective values of the parameters of Applicants' inventions.
Unless otherwise noted, all component or composition levels are in reference to the active level of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources.
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
The citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.

Cleaning Compositions Comprising Organic Catalyst Applicants have found that judicious selection of the R' and R2 moieties of the organic catalyst of the present invention results in improved enzyme compatibility.
While not being bound by theory, Applicants believe this is due to favorable partitioning of the catalyst in aqueous environments as a result of the aforementioned judicious selection of the said moieties.
In one aspect of Applicants' invention, Applicants' cleaning compositions comprise an organic catalyst having an enzyme compatibility value of 70 or greater, or even 80 or greater.
In one aspect of Applicants' invention, Applicants' cleaning compositions comprise an organic catalyst having Formula 1 or Formula 2 below or mixtures thereof.

R1 NG~G.SO3 Formula I

R1 N(D G-SO3 O
Formula 2 wherein: G is selected from -0-, -CH2O-, -(CH2)2-, and -CH2-. R' is selected from H or C1-C4 alkyl. Suitable C1-C4 alkyl moieties include, but are not limited to methyl, ethyl, iso-propyl, and tert-butyl. Each R2 is independently selected from C4-C8 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 4-ethylbenzyl, 4-iso-propylbenzyl and 4-tert-butylbenzyl.
Suitable C4-C8 alkyl moieties include, but are not limited to n-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, cyclohexylmethyl, n-heptyl and octyl.
In one aspect of the invention G is selected from -0- and -CH2-. R' is selected from H, methyl, ethyl, iso-propyl, and tert-butyl. Each R2 is independently selected from C4-C6 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
In one aspect of the invention G is -CH2-, R1 is H and each R2 is independently selected from n-butyl, n-pentyl, n-hexyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
The balance of any aspects of the aforementioned cleaning compositions is made up of one or more adjunct materials.

Processes of Making Suitable Organic Catalysts Suitable organic catalysts can be produced using a variety of reaction vessels and processes including batch, semi-batch and continuous processes. Suitable iminium containing versions of the catalysts (Formula 1) can be made in accordance with the general protocol described in the examples and references contained therein. The oxaziridinium ring containing version of the aforementioned catalyst may be produced by contacting an iminium containing version of said catalyst with an oxygen transfer agent such as a peroxycarboxylic acid or a peroxymonosulfuric acid. Such species can be formed in situ and used without purification.

Cleaning Compositions and Cleaning Composition Additives Comprising Applicants' Organic Catalysts The cleaning composition of the present invention may be advantageously employed for example, in laundry applications, hard surface cleaning, automatic dishwashing applications, as well as cosmetic applications such as dentures, teeth, hair and skin. However, due to the unique advantages of both increased effectiveness in lower temperature solutions and the superior enzyme compatiblity, the organic catalysts of the present invention are ideally suited for laundry applications such as the bleaching of fabrics through the use of bleach containing detergents or laundry bleach additives. Furthermore, the organic catalysts of the present invention may be employed in both granular and liquid compositions.
The organic catalysts of the present invention may also be employed in a cleaning additive product. A cleaning additive product including the organic catalysts of the present invention is ideally suited for inclusion in a wash process when additional bleaching effectiveness is desired.
Such instances may include but, are not limited to, low temperature solution cleaning application.
The additive product may be, in its simplest form, Applicants' organic catalyst. Preferably, the additive could be packaged in dosage form for addition to a cleaning process where a source of peroxygen is employed and increased bleaching effectiveness is desired. Such single dosage form may comprise a pill, tablet, gelcap or other single dosage unit such as pre-measured powders or liquids. A filler or carrier material may be included to increase the volume of such composition. Suitable filler or carrier materials include, but are not limited to, various salts of sulfate, carbonate and silicate as well as talc, clay and the like. Filler or carrier materials for liquid compositions may be water or low molecular weight primary and secondary alcohols including polyols and diols. Examples of such alcohols include, but are not limited to, methanol, ethanol, propanol and isopropanol. The compositions may contain from about 5%
to about 90%
of such materials. Acidic fillers can be used to reduce pH. Alternatively, the cleaning additive may include an activated peroxygen source defined below or the adjunct ingredients as fully defined below.
5 Applicants' cleaning compositions and cleaning additives require a catalytically effective amount of Applicants' organic catalyst. The required level of such catalyst may be achieved by the addition of one or more species of Applicants' organic catalyst. As a practical matter, and not by way of limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least 0.00 1 ppm, from about 0.00 1 ppm to about 500 ppm, from about 0.005 ppm to about 150 ppm, or even from about 0.05 ppm to about 50 ppm of Applicants' organic catalyst in the wash liquor. In order to obtain such levels in the wash liquor, typical compositions herein may comprise from about 0.0002% to about 5%, or even from about 0.00 1%
to about 1.5%, of organic catalyst, by weight of the cleaning compositions.
When the Applicants' organic catalyst is employed in a granular composition, it may be desirable for the Applicants' organic catalyst to be in the form of an encapsulated particle to protect the Applicants' organic catalyst from moisture and/or other components of the granular composition during storage. In addition, encapsulation is also a means of controlling the availability of the Applicants' organic catalyst during the cleaning process and may enhance the bleaching performance of the Applicants' organic catalyst. In this regard, the Applicants' organic catalyst can be encapsulated with any encapsulating material known in the art.
The encapsulating material typically encapsulates at least part, preferably all, of the Applicants' organic catalyst. Typically, the encapsulating material is water-soluble and/or water-dispersible. The encapsulating material may have a glass transition temperature (Tg) of 0 C or higher.

The encapsulating material is preferably selected from the group consisting of carbohydrates, natural or synthetic gums, chitin and chitosan, cellulose and cellulose derivatives, silicates, phosphates, borates, polyvinyl alcohol, polyethylene glycol, paraffin waxes and combinations thereof. Preferably the encapsulating material is a carbohydrate, typically selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, and combinations thereof. Most preferably, the encapsulating material is a starch.
Preferred starches are described in EP 0 922 499; US 4,977,252; US 5,354,559 and US 5,935,826.
The encapsulating material may be a microsphere made from plastic such as thermoplastics, acrylonitrile, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and mixtures thereof; commercially available microspheres that can be used are those supplied by Expancel of Stockviksverken, Sweden under the trademark Expancel , and those supplied by PQ
Corp. of Valley Forge, Pennsylvania USA under the trademarks PM 6545, PM 6550, PM 7220, PM 7228, Extendospheres , Luxsil , Q-cel and Sphericel .
The cleaning compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, or even about 7.5 and 10.5. Liquid dishwashing product formulations may have a pH between about 6.8 and about 9Ø Laundry products typically have a pH of from about 9 to about 11.
Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Adiunct Materials While not essential for the purposes of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance cleaning performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the cleaning composition as is the case with perfumes, colorants, dyes or the like. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S.
Patent Nos.
5,576,282, 6,306,812 B 1 and 6,326,348 B 1.
As stated, the adjunct ingredients are not essential to Applicants' compositions. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:
Bleaching Agents - The cleaning compositions of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1 % to about 50% or even from about 0.1 % to about 25% bleaching agent by weight of the subject cleaning composition.
Examples of suitable bleaching agents include:
(1) photobleaches for example sulfonated zinc phthalocyanine;
(2) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxzone , and mixtures thereof. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R-(C=O)O-O-M wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example, sodium, potassium or hydrogen;
(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof. In one aspect of the invention the inorganic perhydrate salts are selected from the group consisting of sodium salts of perborate, percarbonate and mixtures thereof. When employed, inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt%, or 1 to 30 wt% of the overall composition and are typically incorporated into such compositions as a crystalline solid that may be coated. Suitable coatings include, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and (4) bleach activators having R-(C=O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof - especially benzene sulphonate. Suitable bleach activators include dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be employed, in one aspect of the invention the subject cleaning composition may comprise NOBS, TAED or mixtures thereof.
When present, the peracid and/or bleach activator is generally present in the composition in an amount of from about 0.1 to about 60 wt%, from about 0.5 to about 40 wt % or even from about 0.6 to about 10 wt% based on the composition. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracid or precursor thereof.
The amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.
Surfactants - The cleaning compositions according to the present invention may comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof. When present, surfactant is typically present at a level of from about 0.1% to about 60%, from about 1% to about 50% or even from about 5% to about 40% by weight of the subject composition.
Builders - The cleaning compositions of the present invention may comprise one or more detergent builders or builder systems. When a builder is used, the subject composition will typically comprise at least about 1%, from about 5% to about 60% or even from about 10% to about 40% builder by weight of the subject composition.
Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders and polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Chelating Agents - The cleaning compositions herein may contain a chelating agent.
Suitable chelating agents include copper, iron and/or manganese chelating agents and mixtures thereof When a chelating agent is used, the subject composition may comprise from about 0.005% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the subject composition.
Dye Transfer Inhibiting Agents - The cleaning compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in a subject composition, the dye transfer inhibiting agents may be present at levels from about 0.0001% to about 10%, from about 0.01% to about 5% or even from about 0.1% to about 3% by weight of the composition.
Brighteners - The cleaning compositions of the present invention can also contain additional components that may tint articles being cleaned, such as fluorescent brighteners.
Suitable fluorescent brightener levels include lower levels of from about 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.
Dispersants - The compositions of the present invention can also contain dispersants.
Suitable water-soluble organic materials include the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Enzymes - The cleaning compositions can comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, f3-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in a cleaning composition, the aforementioned enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001%
to about 0.5% enzyme protein by weight of the composition.
Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to 5 the enzymes. In case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound, can be added to further improve stability.
Catalytic Metal Complexes - Applicants' cleaning compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, 10 ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243.
If desired, the compositions herein can be catalyzed by means of a manganese compound.
Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,576,282.
Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S.
5,597,936; U.S. 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. 5,597,936, and U.S. 5,595,967.
Compositions herein may also suitably include a transition metal complex of ligands such as bispidones (WO 05/042532 Al) and/or macropolycyclic rigid ligands -abbreviated as "MRLs". As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per hundred million of the active MRL species in the aqueous washing medium, and will typically provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.
Suitable transition-metals in the instant transition-metal bleach catalyst include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane.
Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. 6,225,464.
Solvents - Suitable solvents include water and other solvents such as lipophilic fluids.
Examples of suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof.
Processes of Making Cleaning and/or Treatment Compositions The cleaning compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in Applicants' examples and in U.S. 5,879,584; U.S. 5,691,297; U.S.
5,574,005;
U.S. 5,569,645; U.S. 5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S.
5,486,303.
Method of Use The present invention includes a method for cleaning a situs inter alia a surface or fabric.
Such method includes the steps of contacting an embodiment of Applicants' cleaning composition, in neat form or diluted in a wash liquor, with at least a portion of a surface or fabric then optionally rinsing and optionally drying such surface or fabric. The surface or fabric may be subjected to a washing step prior to the aforementioned rinsing step. For purposes of the present invention, washing includes but is not limited to, scrubbing, and mechanical agitation. Drying of such surfaces or fabrics may be accomplished by any one of the common means employed either in domestic or industrial settings. Such means include but are not limited to forced air or still air drying at ambient or elevated temperatures at pressures between 5 and 0.01 atmospheres in the presence or absence of electromagnetic radiation, including sunlight, infrared, ultraviolet and microwave irradiation. In one aspect, said drying may be accomplished at temperatures above ambient by employing an iron wherein, for example, said fabric may be in direct contact with said iron for relatively short or even extended periods of time and wherein pressure may be exerted beyond that otherwise normally present due to gravitational force. In another aspect, said drying may be accomplished at temperatures above ambient by employing a dryer.
Apparatus for drying fabric is well known and it is frequently referred to as a clothes dryer. In addition to clothes such appliances are used to dry many other items including towels, sheets, pillowcases, diapers and so forth and such equipment has been accepted as a standard convenience in many nations of the world substantially replacing the use of clothes lines for drying of fabric.
Most dryers in use today use heated air which is passed over and or through the fabric as it is tumbled within the dryer.
The air may be heated, for example, either electronically, via gas flame, or even with microwave radiation. Such air may be heated from about 15 C to about 400 C, from about 25 C to about 200 C, from about 35 C to about 100 C, or even from about 40 C to about 85 C
and used in the dryer to dry a surface and/or a fabric. Without being bound by theory, it is believed that additional bleaching may be obtained from organic catalyst remaining on the surface or fabric during and/or after drying thus it may be advantageous to dry said surface or fabric. As will be appreciated by one skilled in the art, the cleaning compositions of the present invention are ideally suited for use in laundry applications. Accordingly, the present invention includes a method for laundering a fabric. The method comprises the steps of contacting a fabric to be laundered with a said cleaning laundry solution comprising at least one embodiment of Applicants' cleaning composition, cleaning additive or mixture thereof. The fabric may comprise most any fabric capable of being laundered in normal consumer use conditions. The solution preferably has a pH
of from about 8 to about 10.5. The compositions may be employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. The water temperatures typically range from about 5 C to about 90 C. The water to fabric ratio is typically from about 1:1 to about 30:1.
Organic Catal s~t/Enzyme Compatibility Test The test described below uses an alpha amylase activity assay to measure the impact of organic catalysts on the enzyme.
Equipment. UVNis spectrophotometer capable of measuring @ 415 nm, heated magnetic stirrer capable of 40 C, 5 mL Luer lock syringe and filters (Acrodisc 0.45 m), pH
meter, and balance (4-place analytical).
Reagents. MerckTM Amylase Kit (Merck Eurolab, Cat. No. 1.19718.0001); Trizma Base (Sigma Cat # T-1503, or equivalent); Calcium Chloride Dihydrate (Sigma Cat # C-5080, or equivalent); Sodium Thiosulfate Pentahydrate (Sigma Cat # S-6672 or equivalent); Hydrochloric Acid (VWR Cat # JT9535-0, or equivalent); Hardness solution (CTC Group, 3.00 gr/cc or equivalent); Sodium Percarbonate; Peracetic Acid (Aldrich, Cat.# 26933-6 or equivalent);
Amylase enzymes: TermamylTM, NatalaseTM, and DuramylTM (Novozymes, Denmark);
Granular detergent matrix containing no enzyme, organic catalyst or bleaching agents.
1.) Solution Preparation: prepare the following:
a.) TRIS Assay Buffer. Prepare 1 liter of O.IM TRIS buffer, 0.5% sodium thiosulphate (WN), 0.11% calcium chloride (w/v) at pH 8.3.
b.) Blank Detergent Solution. Prepare one liter of 0.5% enzyme and bleach free granular detergent product in deionized water (WN) that is 250 ppm H202 (0.77 gm percarbonate) and 10 gpg hardness (880 UI of hardness).
c.) Termamyl, Duramyl and Natalase Stock. Make 100 mL solutions each of a 0.1633 mg active Termamyl per mL TRIS Buffer, a 0.1159 mg active Natalase per mL TRIS
Buffer, and a 0.1596 mg active Duramyl per mL TRIS Buffer.
d.) Organic catalyst stocks. Make a 500 ppm in methanol solution of m.
e.) Peracetic acid stock. Make a 3955 ppm peracetic acid solution in deionized water.
f.) Amylase reagent. Follow Merck kit instructions for preparing flacons (containers) 1 and 2 using flacon 3 and subsequent mixing of flacons 1 and 2 to produce the final reagent used in the amylase activity analysis.
2.) Sample Analysis a.) Analysis of sample with enzyme only: Add 100 mL of blank detergent solution to a 150 mL beaker. Place beaker on heated stir plate and bring temperature to 40 C
with stirring. Add Y ^ L of enzyme stock to the beaker where Y= 612 ^ L for Duramyl, 306 ^L for Termamyl, or 918 ^L for Natalase. Spike only enzyme of interest.
Stir sample for 1 minute. Start timer. At 7 minutes 45 seconds, pull a sample and filter it using a 0.45 m syringe filter (5 mL syringe). Mix 6 ^L of filtered sample with 250 ^L of amylase reagent in a cuvette and place the cuvette in a UVNIS
spectrophotometer and monitor change in absorbance at 415 nm. Determine length of time (tE) to the nearest second required to obtain an absorbance reading of 1.0 for each enzyme. Use each enzyme's tE in Steps 2.)b.) and 2.)c.) below.
b.) Analysis of sample with enzyme and peracetic acid only. Follow Step 2.)a.) except after enzyme addition, allow solution to stir for 1 minute then add 127 ^ L of peracetic acid stock and start timer. Pull sample at 7 minutes 45 seconds as in Step 2.)a.).
Once sample and reagent are mixed, record the absorbance at tE for the respective enzyme. Designate such absorbance Ab.
c.) Analysis of sample with enzyme, peracetic acid, and organic catalyst.
Follow Step 2.)a.) except after enzyme addition, allow solution to stir for 1 minute then add 127 ^L of peracetic acid stock and 100 ^L of organic catalyst stock and start timer. Pull sample at 7 minutes 45 seconds as in Step 2.)a.). Once sample and reagent are mixed, record the absorbance at tE for the respective enzyme. Designate such absorbance Ac.
3.) Calculate Enzyme Compatibility Value (ECV) a.) Calculate the ECV for each specific enzyme: Termamyl (ECVier), Duramyl (ECVdõ i) and Natalase (ECVnat). The ECV for any specific enzyme is (AJAb) x 100 where Ab and A, are the values determined in Steps 2.)b.) and 2.)c.), respectively, for that enzyme.
b.) The ECV for a given organic catalyst is the average of the individual ECV
values for the three enzymes. Thus, ECV = (ECVter + ECVdur + ECVnat)/3.

EXAMPLES
Unless otherwise indicated, materials can be obtained from Aldrich, P.O. Box 2060, Milwaukee, WI 53201, USA.

Example 1: Preparation of 3,4-dihydro-4,4-dibenzyl-2-(3-sulfopropyl isoguinolinium, internal salt CN Base 0FCN
C6HSCHZBr Reduction NHZ
(1) (2) (3) Formic Acid Polyphosphoric Acid Phosphorous Pentoxide N / HN~r H
(5) 0 0S0 (4) QCN
(6) 5 Step 1. Preparation of=,^-dibutyl-benzeneacetonitrile (2): To a flame dried 500 mL three neck round bottomed flask, equipped with a dry argon inlet, magnetic stir bar, and thermometer, is added benzyl cyanide ((1), 5.0 gm.; 0.043 mol) and tetrahydrofuran (100 mL).
To the reaction is slowly added sodium hydride (60% in oil) (7.2 gm, 0.1075 mol) over one hour.
Once addition is complete the reaction is stirred at room temperature for 1 hour. To the reaction is added benzyl 10 bromide (18.4 gm; 0.043 mol) and the reaction is stirred at 50 C for 18 hours. The reaction is evaporated to dryness, residue dissolved in toluene and washed with IN HCI.
Organic phase is dried with Na2SO4, filtered and evaporated to yield ^,L1-dibutyl-benzeneacetonitrile (2), wt= 7.7 gm (65%).
15 Step 2. Preparation of 1-amino-2,2,dibutyl-2-phenylethane (3): 11,11 -Dibutyl-benzeneacetonitrile ((2), 7.0 gm; 0.0237 mol) is dissolved in borane-THF complex (1.1 equiv.) at room temperature for 18 hours. Once reaction is complete, ethanol (50 mL) is added, and the reaction is evaporated to dryness. Once dry, the residue is suspended in 100 mL IM HCI, and the suspension is evaporated to dryness on a rotory evaporator. This procedure is repeated three times. After the final evaporation, the white residue is dissolved in IM NaOH
(100 mL), and extracted with diethyl ether (2 x 150 mL). The extracts are combined, dried with Na2SO4, filtered and evaporated to dryness to yield I-amino-2,2,dibutyl-2-phenylethane (3), wt=
6.4 gm (90%).
Step 3. Preparation of 3,4-dihydro-4,4-dibenzyl-isoquinoline (5): To a flame dried 100 mL three neck round bottomed flask, equipped with an addition funnel, dry argon inlet, magnetic stir bar, thermometer, Dean Stark trap, and heating bath is added I -amino-2,2,dibutyl-2-phenylethane ((3),5.0 gm., 0.0166 mol) and toluene (25 mL). To the addition funnel is added formic acid (5.0 gm). The formic acid is added slowly to the stirring reaction solution over 60 minutes and solids form. Once addition is complete the reaction is brought to reflux and water removed via a Dean Stark trap. Once the reaction is complete, the toluene is removed to yield N-formyl-(3,(3-dibutyl-(3 -phenethylamine (4), wt= 4.9 gm (90%). The formamide (4) is then contacted with polyphosphoric acid (30 gm)/phosphorous pentoxide (6 gm), using standard Bischler/Napieralski conditions, at 170 C for 18 hours. The reaction is then neutralized with aqueous NaOH, keeping the temperature between 60 -80 T. Once neutral, the product is extracted with toluene to yield 3,4-dihydro-4,4-dibenzyl-isoquinoline (5). The product can be further purified on silica gel.
Step 4. Preparation of 3,4-dihydro-4,4-dibutyl-2-(3-sulfopropyl)isoquinolinium, internal salt (6):
To a flame dried 100 mL round bottomed flask is added 3,4-dihydro-4,4-dibenzyl-isoquinoline ((5)3.0 gm; 0.0 10 mol) and acetonitrile (25 mL). The solution is stirred at room temperature under argon and to the solution is added 1,2-oxathiolane-2,2-dioxide (1.34 gm;
0.0 11 mol). The reaction is warmed to 50 C and stirred for 18 hours. The reaction is cooled to room temperature, and allowed to stand at room temperature over night. The formed solids are collected by filtration, and washed with chilled acetonitrile, to yield 3,4-dihydro-4,4-dibenzyl-2-(3-sulfopropyl)isoquinolinium (6).

Example 2: Preparation of 3 ,4-dihydro-4,4-dipentyl-2-(3-sulfopropyl iso uinolinium, internal salt The desired product is prepared according to Example 1, substituting pentyl chloride for benzyl chloride in Step 1.

Example 3: Preparation of 3,4-dihvdro-4,4-dihexyl-2-(3-sulfopropyl)isoguinolinium, internal salt The desired product is prepared according to Example 1, substituting hexyl chloride for benzyl chloride in Step 1.

Example 4: Preparation of 3,4-dihydro-4,4-dibutyl-2-(3-sulfopropyl isoguinolinium, internal salt The desired product is prepared according to Example 1, substituting butyl chloride for benzyl chloride in Step 1.

Example 5: Preparation of 3,4-dihvdro-4,4-di(2-methylphen llmethyl)-2-(3-sulfopropyl)isoquinolinium, internal salt The desired product is prepared according to Example 1, substituting 2-methylbenzyl chloride for benzyl chloride in Step 1.
Example 6: Preparation of 3,4-dihvdro-4,4-di(3-methylphenylmethyl)-2-(3-sulfopropyl)isoguinolinium, internal salt The desired product is prepared according to Example 1, substituting 3-methylbenzyl chloride for benzyl chloride in Step 1.
Example 7: Preparation of 3,4-dihydro-4,4-di(4-methvlphen lymethyl)-2-(3-sulfopropyl)isoguinolinium, internal salt The desired product is prepared according to Example 1, substituting 4-methylbenzyl chloride for benzyl chloride in Step 1.

Example 8: Preparation of 3,4-dihydro-4,4-di(cyclohexylmethyl)-2-(3-sulfopropyl)isoquinolinium, internal salt The desired product is prepared according to Example 1, substituting chloromethyl cyclohexane (prepared from cyclohexanemethanol according to Coe et al., Polyhedron 1992, 11(24), pp. 3123-8) for benzyl chloride in Step 1.

Example 9: Preparation of 3,4-dihydro-4,4-di(phenylmethyl)-2-(3-sulfobutyl)isoguinolinium, internal salt The desired product is prepared according to Example 1, substituting 1,2-oxathiane-2,2-dioxide for 1,2-oxathiolane-2,2-dioxide in Step 4.

Example 10: Preparation of 3 ,4-dihydro-4,4-di(phen ly methyl)-2-[3-(sulfooxy)ethyl]isoquinolinium, internal salt The desired product is prepared according to Example 1, substituting 1,3,2-dioxathiolane-2,2-dioxide for 1,2-oxathiolane-2,2-dioxide in Step 4.

Example 11: Preparation of 3,4-dihydro-4,4-di(phen lymethyl)-2-[3-(sulfooxy)propyllisoquinolinium, internal salt The desired product is prepared according to Example 1, substituting 1,3,2-dioxathiane-2,2-dioxide for 1,2-oxathiolane-2,2-dioxide in Step 4.

Example 12: Preparation of 3,4-dihydro-4,4-di(4-methvlphen lymethyl)-7-methyl-2-(3-sulfopropyl)isoguinolinium, internal salt Step 1: Preparation of4-Methyl-D-(4-methylphenyl)-D-[(4-methylphenyl)methyl]-benzenepropanenitrile.
Part a. Preparation of silica catalys: Silica (MKC-500, specific surface area 497 m2 g'; obtained from Nikki Chemical) is activated by treatment with 6N HCl and dried in a vacuum at 120 C. A
mixture of 7.0 g of activated silica gel and 80 mL of toluene is placed in a flask and stirred for one hour. Then, 25 mL ofN-(2-aminoethyl)-3-aminopropyltrimethoxysilane (SH-6020; obtained from Troy Silicone) is injected by syringe and the resulting mixture refluxed with an oil bath for 8 h. After cooling, the silica gel is filtered and washed with benzene in a soxhlet extractor for 12 h. The purified silica is washed again three times with diethyl ether and allowed to stand overnight in air. One gram of the purified silica is then suspended in 1.5 mL
of dioxane for 8 h, after which 4.3 mL of 1,10-dibromodecane is added and the mixture stirred at 80 C overnight in an oil bath. The silica is then filtered on a glass filter and washed with dioxane, acetone and 1%
NH4OH and subsequently washed with acetone and diethyl ether. The silica so obtained is dried at 50 C under reduced pressure overnight.
Part b. Preparation of 4-Methyl-^-(4-methylphenyl)-^-[(4-methylphenyl)methyl]-benzenepropanenitrile: A flask containing 1.0 g (2 mmol) of sodium cyanide (95%) dissolved in 5 mL of 50% NaOH aqueous solution is charged with 0.3 g silica catalyst, followed by 4-methylbenzyl chloride (6.8 mmol) and I mL toluene. The flask is placed in an oil bath and heated at 40 C with stirring for 48 h, after which 10 mL toluene is added. The organic layer is filtered and the filtrate evaporated to yield 4-methyl-^-(4-methylphenyl)-^-[(4-methylphenyl)methyl]-benzenepropanenitrile.

Step 2. Preparation of 4-methyl-11 -(4-methylphenyl)-^-[(4-methylphenyl)methyl]-benzenepropanamine: The desired product is prepared according to Example 1, Step 2, substituting 4-methyl- ^ -(4-methylphenyl)- ^ -[(4-methylphenyl)methyl]-benzenepropanenitrile for ^, ^-dibutyl-benzeneacetonitrile.

Step 3. Preparation of 3,4-dihydro-4,4-di(4-methylphenylmethyl)-7-methyl-isoquinoline: The desired product is prepared according to Example 1, Step 3, substituting 4-methyl-^-(4-methylphenyl)- ^ -[(4-methylphenyl)methyl]-benzenepropanamine for 1-amino-2,2,dibutyl-2-phenylethane.

Step 4. Preparation of 3,4-dihydro-4,4-di(4-methylphenylmethyl)-7-methyl-2-(3-sulfopropyl)isoquinolinium, internal salt: The desired product is prepared according to Example 1, Step 4, substituting 3,4-dihydro-4,4-di(4-methylphenylmethyl)-7-methyl-isoquinoline for 3,4-dihydro-4,4-dibenzyl-isoquinoline.
Example 13: Preparation of 3,4-dihydro-4,4-di(4-iso-propylphenylmethyl -7-iso-propel-2-(3-sulfopropyl isoguinolinium, internal salt The desired product is prepared according to Example 12, substituting 4-iso-propylbenzyl chloride for 4-methylbenzyl chloride.

Example 14: Simultaneous Preparation of Organic Catalyst Mixture Comprising Catalysts of Formula 3 Wherein R' are Independently H, Methyl, Ethyl and Mixtures Thereof.

,Cl~, kN~S-Formula 3 The desired mixture of products is prepared according to Example 12, substituting a mixture of benzyl chloride (source for R' = H), 4-methylbenzyl chloride (source for R' =
methyl), and 4-ethylbenzyl chloride (Oakwood Products, Inc., West Columbia, SC 29172, USA;
source for R' _ ethyl) for 4-methylbenzyl chloride. This results in a mixture of 18 distinct organic catalyst compounds.

Example 15 Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations.
A B C D E F
Linear alkylbenzenesulfonate 20 22 20 15 20 20 C12 Dimethylhydroxyethyl ammonium chloride 0.7 1 1 0.6 0.0 0.7 AE3S 0.9 0.0 0.9 0.0 0.0 0.9 AE7 0.0 0.5 0.0 1 3 1 sodium tripolyphosphate 23 30 23 17 12 23 Zeolite A 0.0 0.0 0.0 0.0 10 0.0 1.6R Silicate 7 7 7 7 7 7 Sodium Carbonate 15 14 15 18 15 15 Polyacrylate MW 4500 1 0.0 1 1 1.5 1 Carboxy Methyl Cellulose 1 1 1 1 1 1 SavinaseTM 32.89mg/g 0.1 0.07 0.1 0.1 0.1 0.1 Natalase 8.65mg/g 0.1 0.1 0.1 0.0 0.1 0.1 Brightener 15 0.06 0.0 0.06 0.18 0.06 0.06 Brightener 49 0.1 0.06 0.1 0.0 0.1 0.1 Diethylenetriamine pentacetic acid 0.6 0.3 0.6 0.25 0.6 0.6 MgSO4 1 1 1 0.5 1 1 Sodium Percarbonate 0.0 5.2 0.0 0.0 0.0 0.0 Photobleach 0.0030 0.0015 0.0015 0.0020 0.0045 0.0010 Sodium Perborate Monohydrate 4.4 0.0 3.85 2.09 0.78 3.63 NOBS 1.9 1.9 1.66 1.77 0.33 0.75 TAED 0.58 0.58 0.51 0.0 0.015 0.28 Organic Catalyst * 0.0185 0.0185 0.0162 0.0162 0.0111 0.0074 Balance Balance to Balance to Balance Balance Balance Sulfate/Moisture to 100% 100% 100% to 100% to 100% to 100%
5 * Organic catalyst prepared according to Examples 1 through 14, or mixtures thereof.
Any of the above compositions is used to launder fabrics at a concentration of 3500 ppm in water, 25 C, and a 25:1 water:cloth ratio. The typical pH is about 10 but can be can be adjusted by altering the proportion of acid to Na- salt form of alkylbenzenesulfonate.

10 Example 16 Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations.
A B C D
Linear alkylbenzenesulfonate 8 7.1 7 6.5 AE3S 0 4.8 0 5.2 Alkylsulfate 1 0 1 0 AE7 2.2 0 3.2 0.1 C10.12 Dimethyl 0.75 0.94 0.98 0.98 hydroxyethylammonium chloride Crystalline layered silicate (6-Na2Si2O5) 4.1 0 4.8 0 Zeolite A 20 0 17 0 Citric Acid 3 5 3 4 Sodium Carbonate 15 20 14 20 Silicate 2R (Si02:Na2O at ratio 2:1) 0.08 0 0.11 0 Soil release agent 0.75 0.72 0.71 0.72 Acrylic Acid/Maleic Acid Copolymer 1.1 3.7 1.0 3.7 Carboxymethylcellulose 0.15 1.4 0.2 1.4 Protease (56.00mg active/g) 0.37 0.4 0.4 0.4 Amylase (21.55mg active/g) 0.3 0.3 0.3 0.3 Lipase (11.00mg active/g) 0 0.7 0 0.7 Tetraacetyl ethylene diamine (TAED) 3.6 4.0 3.6 4.0 Percarbonate 13 13.2 13 13.2 Organic Catalyst* 0.04 0.02 0.01 0.06 Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer (EDDS) 0.2 0.2 0.2 0.2 Hydroxyethane di phosphonate (HEDP) 0.2 0.2 0.2 0.2 MgSO4 0.42 0.42 0.42 0.42 Perfume 0.5 0.6 0.5 0.6 Suds suppressor agglomerate 0.05 0.1 0.05 0.1 Soap 0.45 0.45 0.45 0.45 Sodium sulfate 22 33 24 30 Sulphonated zinc phtalocyanine 0.07 0.12 0.07 0.12 Photobleach 0.0014 0.002 0.0014 0.001 Speckles 0.03 0.05 0.03 0.05 Balance Balance Balance Balance to 100% to 100% to to Water & Miscellaneous 100% 100%
* Organic catalyst prepared according to Examples I through 14, or mixtures thereof.

Any of the above compositions is used to launder fabrics at a concentration of 10,000 ppm in water, 20-90 0C, and a 5:1 water:cloth ratio. The typical pH is about 10 but can be can be adjusted by altering the proportion of acid to Na-salt form of alkylbenzenesulfonate.

Example 17 Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations.
A B C D E F
Linear Alkylbenzenesulfonate 19.0 15.0 20.0 19.0 18.0 17.5 Alkylsulfate 1.1 1.0 0.8 1.0 1.1 1.2 AE3S 0.3 0.2 0.0 0.1 0.3 0.5 Polyacrylic Acid, partially 6.0 5.5 7.5 7.0 5.8 6.0 neutralized Sodium Xylene Sulfonate* 1.5 1.9 2.0 1.7 1.5 1.0 PEG 4000 0.3 0.25 0.35 0.15 0.2 0.10 Brightener 49 0 0 0.32 0.04 0.04 0.16 Brightener 15 0 0 0.68 0.08 0.08 0.32 Moisture 2.50 2.00 2.90 2.20 2.40 1.80 Sodium carbonate 20.0 17.5 21.0 20.2 19.0 18.0 Sodium Sulfate 0.20 0.30 0.50 0.30 0.45 0.10 Sodium Silicate 0.25 0.25 0.55 0.30 0.25 0.10 Crystalline layered silicate of 2.7 3.0 2.2 3.7 1.5 1.0 formula 8-Na2Si2O5 Zeolite A 11.0 11.0 12.5 10.2 9.5 8.0 Protease 0.20 0.50 1.0 0.15 0.40 0.0 Silicone Suds Suppressor 0.40 0.35 1.00 0.60 0.50 0.00 Coarse Sulfate 21.5 23.0 21.0 21.0 20.0 18.5 Amine Reaction Product 0.40 0.25 0.10 0.35 0.60 0.00 comprising ^ -Damascone* * * *
Perfume 0.10 0.30 0.20 0.20 0.40 0.50 Sodium Percarbonate 2.8 4.5 2.00 4.7 7.4 10.0 Conventional Activator (NOBS) 2.10 3.7 1.00 3.0 5.0 10.0 Organic Catalyst** 0.005 0.10 1.00 0.25 0.05 0.05 Bluing agent*** 0.50 0.20 1.00 0.30 0.10 0.00 Balance Balance Balance Balance Balance Balance to to to to to to Filler 100% 100% 100% 100% 100% 100%
* Other hydrotropes, such as sodium toluenesulfonate, may also be used.
** Organic catalyst prepared according to Examples 1 through 14, or mixtures thereof.
*** Such as Ultramarine Blue or Azo-CM-Cellulose (Megazyme, Bray, Co. Wicklow, Ireland) * * * * Prepared according to WO 00/02991.
Any of the above compositions is used to launder fabrics at a concentration of ppm in water, 5-25 C, and a 15:1 - 25:1 water:cloth ratio. The typical pH is about 9.5-10 but can be can be adjusted by altering the proportion of acid to Na- salt form of alkylbenzenesulfonate.

Example 18 The organic catalysts listed below are tested according to Applicants' Organic Catalyst/Enzyme Compatibility Test using [Peracetic Acid] = 5.0 ppm; [organic catalyst] = 0.5 ppm and the following results are obtained.

Enzyme Compatibility Values Entry* ** Catalyst Moieties ECVter ECVdu, ECVnat ECV
R2; G

3 benzyl;-O- 101 100 103 101 4 benzyl; -CH2- 102 99 104 102 5 4-methylbenzyl; - 103 99 99 * Entry 1 and 2 are Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-((1,1-dimethylethoxy)methyl)ethyl] ester, internal salt and Sulfuric acid mono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl] ester, internal salt, respectively, which are not encompassed by Applicants' Formulae 1 and 2.
** R' is H for entries 3-5.

Example 19 A fabric requiring cleaning is contacted at ambient temperature for 12 minutes at a 25:1 water:cloth ratio with an aqueous solution of 500 ppm of bleaching detergent composition formulation E described in Example 17. The fabric is removed from the wash water, rinsed in ambient temperature water, and subsequently tumble dried in a domestic clothes dryer at a temperature between 35 and 100 C. Additional bleaching is obtained during drying and after the fabric has been dried.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (20)

1. A cleaning composition comprising:
a.) an organic catalyst selected from the group consisting of organic catalysts having the following formulae:

(iii) and mixtures thereof;
wherein G is selected from -O-, -CH2O-, -(CH2)2-, and -CH2-; R1 is selected from H or C1-C4 alkyl; each R2 is independently selected from C4-C8 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 4-ethylbenzyl, 4-iso-propylbenzyl and 4-tert-butylbenzyl;
b.) one or more adjunct ingredients.
2. The cleaning composition of Claim 1 wherein G is selected from -O- and -CH2-; R1 is selected from H, methyl, ethyl, iso-propyl, and tert-butyl; and each R2 is independently selected from C4-C6 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
3. The cleaning composition of Claim 2 wherein G is -CH2-; R1 is H; and each R2 is independently selected from n-butyl, n-pentyl, n-hexyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
4. The cleaning composition of Claim 1 comprising an organic catalyst having the following formula:

wherein G is selected from -O-, -CH2O-, -(CH2)2-, and -CH2-; R1 is selected from H or C1-C4 alkyl; each R2 is independently selected from C4-C8 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 4-ethylbenzyl, 4-iso-propylbenzyl and 4-tert-butylbenzyl.
5. The cleaning composition of Claim 4 wherein G is selected from -O- and -CH2-; R1 is selected from H, methyl, ethyl, iso-propyl, and tert-butyl; and each R2 is independently selected from C4-C6 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
6. The cleaning composition of Claim 5 wherein G is -CH2-; R1 is H; and each R2 is independently selected from n-butyl, n-pentyl, n-hexyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
7. The cleaning composition of Claim 1 comprising an organic catalyst having the following formula:

wherein G is selected from -O-, -CH2O-, -(CH2)2-, and -CH2-; R1 is selected from H or C1-C4 alkyl; each R2 is independently selected from C4-C8 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 4-ethylbenzyl, 4-iso-propylbenzyl and 4-tert-butylbenzyl.
8. The cleaning composition of Claim 7 wherein G is selected from -O- and -CH2-; R1 is selected from H, methyl, ethyl, iso-propyl, and tert-butyl; and each R2 is independently selected from C4-C6 alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
9. The cleaning composition of Claim 8 wherein G is -CH2-; R1 is H; and each R2 is independently selected from n-butyl, n-pentyl, n-hexyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.
10. The cleaning composition of Claim 1 wherein at least one of said one or more adjunct ingredients is selected from an activated peroxygen source, an enzyme, a surfactant and mixtures thereof.
11. The cleaning composition of Claim 4 wherein at least one of said one or more adjunct ingredients is selected from an activated peroxygen source, an enzyme, a surfactant and mixtures thereof.
12. The cleaning composition of Claim 7 wherein at least one of said one or more adjunct ingredients is selected from an activated peroxygen source, an enzyme, a surfactant and mixtures thereof.
13. The cleaning composition of Claim 1 comprising the following adjunct ingredients: an activated peroxygen source, an enzyme and a surfactant.
14. The cleaning composition of Claim 4 comprising the following adjunct ingredients: an activated peroxygen source, an enzyme and a surfactant.
15. The cleaning composition of Claim 7 comprising the following adjunct ingredients: an activated peroxygen source, an enzyme and a surfactant.
16. The cleaning composition of Claim 1 wherein G is -CH2-; R1 is H; and each R2 is independently selected from n-butyl, n-pentyl, n-hexyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl, said composition comprising the following adjunct ingredients: an activated peroxygen source, an enzyme and a surfactant.
17. The cleaning composition of Claim 1, wherein said catalyst has an enzyme compatibility value of 70 or greater.
18. The cleaning composition of Claim 17 wherein said catalyst has an enzyme compatibility value of 80 or greater, said composition comprising the following adjunct ingredients: an activated peroxygen source, an enzyme and a surfactant.
19. A process of cleaning a surface or fabric comprising the steps of contacting said surface or fabric with the cleaning composition of Claim 1, then optionally washing and/or rinsing said surface or fabric.
20. A method of bleaching a fabric and/or surface comprising drying a fabric and/or surface comprising an organic catalyst obtained by contacting said fabric and/or surface with an organic catalyst according to Claim 1.
CA 2718172 2010-10-28 2010-10-28 Organic catalyst with enhanced enzyme compatibility Abandoned CA2718172A1 (en)

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