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WO2001025388A1 - Procede favorisant l'aseptisation d'articles en phase apres-lavage de machine a laver la vaisselle automatique - Google Patents

Procede favorisant l'aseptisation d'articles en phase apres-lavage de machine a laver la vaisselle automatique Download PDF

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Publication number
WO2001025388A1
WO2001025388A1 PCT/US1999/022533 US9922533W WO0125388A1 WO 2001025388 A1 WO2001025388 A1 WO 2001025388A1 US 9922533 W US9922533 W US 9922533W WO 0125388 A1 WO0125388 A1 WO 0125388A1
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WO
WIPO (PCT)
Prior art keywords
residue
acid
enzyme
automatic dishwashing
amount
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Application number
PCT/US1999/022533
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English (en)
Inventor
Peter Robert Foley
Lucio Pieroni
William Michael Scheper
Christiaan Arthur Jacques Kamiel Thoen
Ann Margaret Wolff
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU62739/99A priority Critical patent/AU6273999A/en
Priority to PCT/US1999/022533 priority patent/WO2001025388A1/fr
Publication of WO2001025388A1 publication Critical patent/WO2001025388A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to an automatic dishwashing detergent process delivering sanitization benefits. More particularly, the invention relates to a process for controlling post- wash bacte ⁇ cidal contamination by providing an automatic dishwashing detergent process that delivers sanitization benefits du ⁇ ng the post-wash stage of automatic dishwashing by reduction of residual soil deposition on the surface of dishwasher as well as washed and sanitized dishware substrates. Such a process provides enhanced cleaning coupled with sanitization benefits due to significant prevention of bacte ⁇ al action on the dishware and other surfaces.
  • European Patent No. W09423575A1 issued on October 27, 1994 to Applicant Ecolab, Inc. describes a peoxyacid antimicrobial concentrate and use composition, which provides a potent biocide, useful for sanitizing substantially fixed, "m-place" processing lmes in dairies, breweries, and other food processing operations.
  • the invention meets the needs above by providing a method of promoting sanitization of substrates exposed to a post-wash stage after having been washed and sanitized by a wash solution during an automatic dishwashing process.
  • the process includes the step of limiting residue deposition on the substrates washed and sanitized by the automatic dishwashing process to an amount no greater than about 10 mg of residue per 1 m 2 meter of substrate surface. Accordingly, the present invention solves the long-standing need for an inexpensive dishware cleaning system which performs efficiently and effectively in promoting sanitization and preventing further microbial action on washed and sanitized substrates du ⁇ ng the post-wash conditions.
  • a method of using the limitation of residue deposition on substrates exposed to an automatic dishwashing process, for the purpose of promoting sanitization of the substrates which are already washed and sanitized by a wash solution during an automatic dishwashing process is disclosed.
  • the method includes limiting residue deposition on the substrates washed and sanitized by the automatic dishwashing process to an amount no greater than about 10 mg of residue per 1 m 2 meter of substrate surface DETAILED DESCRIPTION OF THE INVENTION
  • substrates which can be sanitized by this composition and method include ceramic, porcelain, plastic, dish cloths, cutting boards, surgical/medical equipment, baby bottles, dishware, dentifrice/dentures, wood, food preparation surfaces, sponges, glass, rubber, metal, coated metal (e.g., Teflon®-coated pans), fabric items and mixtures thereof.
  • the process herein can be employed to at least maintain the level of sanitization attained by killing or reducing the level of viable microbes which may include any various microorganisms, such as bacteria (Gram + or -), viruses (enveloped or unenveloped), parasites, fungi/spores, and other typical household germs commonly found on dishware, tableware and other items commonly washed in a dishwasher.
  • bacteria Gram + or -
  • viruses enveloped or unenveloped
  • parasites fungi/spores
  • fungi/spores and other typical household germs commonly found on dishware, tableware and other items commonly washed in a dishwasher.
  • the present detergent compositions comprise an "effective amount” or a "sanitizing amount” of a particularly defined antimicrobial agent which is preferably a bacte ⁇ cide
  • An "effective amount” or “sanitizing amount” of an antimicrobial agent is any amount capable of measurably sanitizing the substrate, i.e., soiled dishware, when it is washed by the consumer. In general, this amount may vary quite widely.
  • the terms “disinfecting”, “disinfection”, “bactericidal”, “germ kill”, and “sanitization” are intended to mean killing microbes commonly found on dishware, tableware, china and other similar substrates. Examples of various microbes include: germs, bacteria, viruses, parasites, and fungi/spores
  • the detergent compositions used herein contact the substrate for a sufficient time to significantly reduce the amount of microbes on the substrate.
  • significant reduction it is meant that at least about 95% of the microbes on the substrate are killed or otherwise rendered inactive, preferably the amount of microbes on the substrate is reduced by at least about 99%, and most preferably the amount of microbes on the substrate is reduced by at least about 99.9%.
  • post-wash stage it is meant that a stage during automatic dishwashing that normally occurs at the end of the dishwashing cycle, where the washed substrates are left m the dishwasher, either m a heated environment or a non-heated environment. Additionally, this term is used expansively to encompass such conditions where a consumer may leave washed and sanitized dishes m a dishwasher for hours, days or even weeks after the dishwashing has been done. Such a post-wash condition, without having the advantages of the present invention, would normally represent conditions suitable for re-growth of bacteria and microbial action Limiting Residue Deposition on Substrates
  • the process for promoting sanitization of washed and sanitized substrates m post-wash conditions includes the step of limiting residue deposition on the substrates exposed to the automatic dishwashing process to an amount desirably no greater than about 10 mg of residue per 1 m 2 meter of substrate surface, preferably no greater than about 5 mg of residue per 1 m 2 meter of substrate surface, more preferably no greater than about 1 mg of residue per 1 m 2 meter of substrate surface, and most preferably no greater than about 0.1 mg of residue per 1 m 2 meter of substrate surface.
  • the step of limiting residue deposition desirably includes limiting residue that consists essentially of protem, carbohydrate and grease, and mixtures thereof.
  • limiting residue that consists essentially of protem, carbohydrate and grease, and mixtures thereof.
  • PCG protem, carbohydrate and grease
  • At least about 50% of the substrate surface has PCG residue deposition thereon m an amount no greater than about 10 mg of residue per 1 m 2 meter of substrate surface, and preferably, at least about 80% of the substrate surface has PCG residue deposition thereon in an amount no greater than about 10 mg of residue per 1 m 2 meter of substrate surface.
  • the process is earned out by providing a dishwashing detergent composition formulated to provide a wash solution adapted for controllably limiting residue deposition on substrates exposed to the automatic dishwashing process.
  • the detergent composition is a bacte ⁇ cidal automatic dishwashing detergent composition, which includes a builder, a surfactant, a detersive enzyme, adjunct mate ⁇ als, and a bacte ⁇ cide.
  • the bacte ⁇ cide is present m an amount in a range of from about 0.005% to about 15% by weight of the composition.
  • the bacte ⁇ cide is essentially an antimicrobial compound.
  • antimicrobial compounds examples include t ⁇ closan, t ⁇ clocarbon, hydrogen peroxide, other oxygen bleaches, para-chloro-meta-xylenol, lodme/iodophors, selected alcohols, chlorhexidine, phenols, phospho pids, thymol, eugemol, geramol, oil of lemon grass, and hmonene Certain quaternary surfactants may also show antimicrobial action and may be included as a secondary germ kill agent.
  • the preferred detergent compositions formulated to provide a wash solution adapted for controllably limiting residue deposition on substrates exposed to the automatic dishwashing process include a bleaching compound that generates one or more of oxychlo ⁇ ne and other oxygen based bleaching species. Such compositions also preferably contain bleach catalysts, preferably based on Co, Mn or Fe, and most preferably, cobalt based catalysts.
  • bleach solution is defined herein to mean an aqueous solution of the product dissolved at 1,000-6,000 ppm, preferably at 2,500-4,500 ppm, in an automatic dishwasher.
  • the detergent composition contains one of a hydrophilic or hydrophobic bleach activator, preferably, tetraacetylethylenediamme (TAED) and cationic bleach activators, e.g., 6-t ⁇ methylammon ⁇ ocaproyl caprolactum, tosylate.
  • TAED tetraacetylethylenediamme
  • cationic bleach activators e.g., 6-t ⁇ methylammon ⁇ ocaproyl caprolactum
  • the automatic dishwashing detergent (ADD) compositions also contain other bleach species, such as diacyl peroxide bleaching species. Diacyl Peroxide Bleaching Species
  • the ADD composition of the present invention contain from about 0.01% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.2% to about 2% water- msoluble diacyl peroxide of the general formula:
  • R and R! can be the same or different, preferably no more than one is a hydrocarbyl chain of longer than ten carbon atoms, more preferably at least one has an aromatic nucleus.
  • suitable diacyl peroxides are selected from the group consisting of dibenzoyl peroxide, benzoyl glutaryl peroxide, benzoyl succmyl peroxide, d ⁇ -(2-methybenzoyl) peroxide, diphthaloyl peroxide and mixtures thereof, more preferably dibenzoyl peroxide, diphthaloyl peroxides and mixtures thereof.
  • the preferred diacyl peroxide is dibenzoyl peroxide.
  • Particle size can also play an important role in the performance of the diacyl peroxide in an ADD product.
  • the mean particle size as measured by a laser particle size analyzer (e.g. Malvern) on an agitated mixture with water of the diacyl peroxide is preferably less than about 300 ⁇ m, more preferably less than about 150 ⁇ m.
  • water insolubility is an essential characte ⁇ stic of the diacyl peroxide of the present invention, the particle size is important for controlling residue formation m wash.
  • stabilizing additive is defined herein to mean a compound or compounds that prevents the diacyl peroxide from decomposing with other ingredients, especially components m which the diacyl peroxide is soluble in and with which the diacyl peroxide will react while stored in the product.
  • water-insoluble is defined herein to mean limited water solubility, i.e. less than 1%, preferably less than 0.5%, dissolves in water To provide the necessary storage stability it is essential to incorporate the diacyl peroxides in a particle compatible with an ADD formulation. The particle formed protects the diacyl peroxide from interacting with other ingredients and decomposing m the composition over time.
  • This particle is formed by combining the diacyl peroxide with a "stabilizing additive" preferably selected from the group consisting of inorganic salts, antioxidants, chelants, binding agents, coating agents and mixtures thereof.
  • the stabilizing additive should not dissolve the diacyl peroxide.
  • the stabilizing additive in the particle is by weight of the particle from about 0.1 % to about 95%, preferably from about 10% to about 95%, more preferably from about 40% to about 95%o stabilizing additive
  • the stabilizing additive is not miscible with other components of the composition at temperatures at or below 100°F, preferably 120°F.
  • the stabilizing agent would be soluble m the wash solution.
  • the inorganic salt, useful as a stabilizing additive include but are not limited to alkali metal sulfates, citric acid, and boric acid, and their salts, alkali metal carbonates, bicarbonates and silicates and mixtures thereof.
  • Preferred inorganic salts are sodium sulfate and citric acid, which, because they are non-alkalme, prevent alkaline hydrolysis in product.
  • Binding agents and coating agents include but are not limited to certain water soluble polymers in which the diacyl peroxide does not dissolve, ethoxylated C16-C20 alcohols with sufficient ethoxylate groups to prevent dissolution of the diacyl peroxide, aliphatic fatty acids, aliphatic fatty alcohols, maltodextrms, dextrin, starch, gelatin, polyethylene glycols with melting points above 100°F, polyvmyl alcohol, and sorbitol.
  • the polymers include polyacrylates with an average molecular weight of from about 1,000 to about 10,000, and acrylate/maleate or acrylate/ fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 1:2.
  • Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed European Patent Application No. 66,915, published December 15, 1982, incorporated herein by reference.
  • Other suitable copolymers are modified polyacrylate copolymers as disclosed in U.S. Patents 4,530,766, and 5,084,535, both incorporated herein by reference.
  • Transition metal chelants which can be employed are selected from the group consisting of polyacetate and polycarboxylate builders such as the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, ethylenediamme disuccmic acid (especially the S,S- form), nit ⁇ lot ⁇ acetic acid, tartrate monosuccmic acid, tartrate disuccmic acid, oxydisuccmic acid, carboxymethyloxysuccmic acid, melhtic acid, sodium benzene polycarboxylate salts; n ⁇ t ⁇ lot ⁇ s(methylenephosphon ⁇ c acid) d ⁇ ethylenet ⁇ n ⁇ t ⁇ lopentak ⁇ s(methylenephosphon ⁇ c acid), 1 -hydroxyethylidene- 1 , 1 -diphosphonic acid, other phosphonates chelants (e.g. Dequest lme of products from Monsanto), ethylene-N,N'- b ⁇ s(o-hydroxyphenylglycme
  • Antioxidants can also be suitable stabilizing additives. These compounds slow down or stop a reaction even though present in small amounts. In the present invention it is believed the antioxidant would trap or scavenge the radical formed due to thermal decomposition of the peroxide bond. This would prevent the radical from further reacting or propagating the formation of another radical (self-accelerated decomposition) Since this mate ⁇ al would be used in small amounts in the particle, it most likely would not hurt overall performance of the ADD.
  • Suitable antioxidants include but are not limited to citric acid, phosphoric acid, BHT, BHA, ⁇ -tocopherol, Irganox se ⁇ es C (Ciba Giegy), Tenox series (Kodax) and mixtures thereof..
  • agglomerated forms of the present invention may employ aqueous solutions of the polyacrylates discussed herein above as liquid binders for making the agglomerate.
  • the diacyl peroxide particles formed preferably have a mean particle size from about 400 ⁇ m to about lOOO ⁇ m, more preferably from about 600 ⁇ m to about 800 ⁇ m with less than 1% of the diacyl peroxide particle population being greater than 1180 ⁇ m (Tyler 14 mesh) and less than 1% less than or equal to 212 ⁇ m (Tyler 65 mesh).
  • the compositions of the present invention comprise by weight of the composition from about 0.1% to about 30%, preferably from about 1% to about 15%, more preferably from about 1.5% to about 10% of diacyl peroxide particle. pH-Adiustmg Control/Detergency Builder Components
  • compositions herein have a pH of at least 7; therefore the compositions can comprise a pH-adjustmg detergency builder component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
  • a pH-adjusting component which delivers a wash solution pH of from 7 to about 13, preferably from about 8 to about 12, more preferably from about 8 to about 11.0.
  • the pH-adjusting component are selected so that when the ADD is dissolved in water at a concentration of 2000 - 6000 ppm, the pH remains m the ranges discussed above.
  • the preferred non phosphate pH- adjustmg component embodiments of the invention is selected from the group consisting of
  • pH-adjusting component systems are binary mixtures of granular sodium citrate dihydrate with anhydrous sodium carbonate, and three-component mixtures of granular sodium citrate dihydrate, sodium carbonate and sodium disihcate.
  • the amount of the pH adjusting component in the instant ADD compositions is generally from about 0.9% to about 99%, preferably from about 5% to about 70%, more preferably from about 20% to about 60% by weight of the composition.
  • the essential pH-adjusting system can be complemented (i.e. for improved sequestration m hard water) by other optional detergency builder salts selected from phosphate or nonphosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequeste ⁇ ng properties.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamme tetraacetic acid, ethylenediamme disuccmic acid (especially the S,S- form); mt ⁇ lot ⁇ acetic acid, tartrate monosuccmic acid, tartrate disuccmic acid, oxydiacetic acid, oxydisuccimc acid, carboxymethyloxysuccmic acid, melhtic acid, and sodium benzene polycarboxylate salts.
  • Builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamme tetraacetic acid, ethylenediamme disuccmic acid (especially the S,S- form); mt ⁇ lot ⁇ acetic acid, tartrate monosuccmic acid, tartrate disuccmic acid, oxydiacetic acid, oxydisuccimc acid, carboxymethyloxysuccmic acid, melhtic acid, and sodium benzene
  • the detergency builders used to form the base granules can be any of the detergency builders known in the art, which include the va ⁇ ous water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxysulfonates, polyacetates, carboxylates (e.g. citrates), alummosihcates and polycarboxylates.
  • inorganic phosphate builders are sodium and potassium t ⁇ polyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polyme ⁇ zation of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1 -hydroxy- 1, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2- tnphosphomc acid.
  • Other phosphorus builder compounds are disclosed in U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137, 3,400,176 and 3,400,148, incorporated herein by reference.
  • Non-phosphate detergency builders include but are not limited to the va ⁇ ous water- soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such mate ⁇ als. Alternate water-soluble, non-phosphorus organic builders can be used for their sequeste ⁇ ng properties.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamme tetraacetic acid, ethylenediamme disuccmic acid (especially the S,S- form); mt ⁇ lot ⁇ acetic acid, tartrate monosuccmic acid, tartrate disuccmic acid, oxydisuccmic acid, carboxymethyloxysuccimc acid, melhtic acid, and sodium benzene polycarboxylate salts.
  • pH values of the instant compositions can vary du ⁇ ng the course of the wash as a result of the water and soil present.
  • the best procedure for determining whether a given composition has the herein-indicated pH values is as follows: prepare an aqueous solution or dispersion of all the ingredients of the composition by mixing them in finely divided form with the required amount of water to have a 3000 ppm total concentration. Do not have any coatings on the particles capable of inhibiting dissolution. (In the case of the second pH adjusting component it should be omitted from the formula when determining the formula's initial pH value). Measure the pH using a conventional glass electrode at ambient temperature, within about 2 minutes of forming the solution or dispersion.
  • the ADD compositions of the present invention can additionally and preferably do contain an additional amount other bleaching sources.
  • oxygen bleach can be employed in an amount sufficient to provide from 0.01%) to about 8%, preferably from about 0.1% to about 5.0%, more preferably from about 0.3% to about 4.0%, most preferably from about 0.8% to about 3% of available oxygen (AvO) by weight of the ADD.
  • AvO available oxygen
  • Available oxygen of an ADD or a bleach component is the equivalent bleaching oxygen content thereof expressed as % oxygen.
  • commercially available sodium perborate monohydrate typically has an available oxygen content for bleaching purposes of about 15% (theory predicts a maximum of about 16%).
  • Methods for determining available oxygen of a formula after manufacture share similar chemical principles but depend on whether the oxygen bleach incorporated therein is a simple hydrogen peroxide source such as sodium perborate or percarbonate, is an activated type (e.g., perborate with tetra-acetyl ethylenediamme) or comp ⁇ ses a performed peracid such as monoperphthahc acid.
  • the peroxygen bleaching systems useful herein are those capable of yielding hydrogen peroxide in an aqueous liquor. These compounds include but are not limited to 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.
  • Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono-, t ⁇ -, 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. Percarbonate is especially preferred because of environmental issues associated with boron. Many geographies are forcing legislation to eliminate elements such as boron from formulations.
  • Suitable oxygen-type bleaches are further desc ⁇ bed in U.S. Patent No. 4,412,934 (Chung et al), issued November 1, 1983, and peroxyacid bleaches desc ⁇ bed m European Patent Application 033,259. Sagel et al, published September 13, 1989, both incorporated herein by reference, can be used.
  • Highly preferred percarbonate can be in uncoated or coated form.
  • the average particle size of uncoated percarbonate ranges from about 400 to about 1200 microns, most preferably from about 400 to about 600 microns.
  • the preferred coating mate ⁇ als include carbonate, sulfate, silicate, borosilicate, fatty carboxylic acids, and mixtures thereof.
  • An inorganic chlorine bleach ingredient such as chlo ⁇ nated t ⁇ sodium phosphate can be utilized, but organic chlorine bleaches such as the chlorocyanurates are preferred.
  • Water-soluble dichlorocyanurates such as sodium or potassium dichloroisocyanurate dihydrate are particularly preferred.
  • Available chlo ⁇ ne of an ADD or a bleach component is the equivalent bleaching chlorine content thereof expressed as % equivalent CI2 by weight.
  • the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01% to about 15%, preferably from about 1% to about 10%, more preferably from about 1% to about 8%, by weight of the composition.
  • Preferred activators are selected from the group consisting of benzoylcaprolactam (BzCL), 4-n ⁇ trobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C ⁇ Q-OBS), benzolyvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzolyvalerolactam.
  • Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
  • Preferred bleach activators are those desc ⁇ bed in U.S. Patent 5,130,045, Mitchell et al, and 4,412,934, Chung et al, and copendmg patent applications U. S. Serial Nos. 08/064,624, 08/064,623, 08/064,621, 08/064,562, 08/064,564, 08/082,270 and copendmg application to M. Burns, A. D. Willey, R. T. Hartshorn, C. K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and having U.S. Serial No. 08/133,691 (P&G Case 4890R), all of which are incorporated herein by reference.
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator m the present invention generally ranges from at least 1 :1, preferably from about 20:1 to about 1:1, more preferably from about 10: 1 to about 3: 1.
  • Quaternary substituted bleach activators may also be included.
  • the present ADD compositions comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA structures are further desc ⁇ bed in copendmg U.S. Se ⁇ al No. 08/298,903, 08/298,650, 08/298,906 and 08/298,904 filed August 31, 1994, incorporated herein by reference.
  • the bleach catalyst material which is an optional but preferable ingredient, can comp ⁇ se the free acid form, the salts, and the like.
  • One type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybenum, 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 ethylenediammetetraacetic acid, ethylened ⁇ am ⁇ netetra(methylenephosphon ⁇ c acid) and water-soluble salts thereof
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium tungsten, molybenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediammetetraacetic acid, ethylene
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of theses catalysts include
  • ligands suitable for use herein include l,5,9-t ⁇ methyl-l,5,9-t ⁇ azacyclododecane, 2-methyl- 1 ,4,7-t ⁇ azacyclononane, 2-methyl-l,4,7-t ⁇ azacyclononane, and mixtures thereof.
  • bleach catalysts useful in machine dishwashing compositions and concentrated powder detergent compositions may also be selected as approp ⁇ ate for the present invention.
  • suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084.
  • Still another type of bleach catalyst is a water-soluble complex of manganese (II), (HI), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, lditol, dulsitol, manmtol, xyhthol, arabitol, adonitol, meso-eryth ⁇ tol, meso- mositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cychc ligand.
  • Said ligands are of the formula: R 2 R 3
  • R", and R' can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups.
  • Preferred ligands include py ⁇ dme, py ⁇ dazine, pyrimidme, pyrazme, imidazole, pyrazole, and t ⁇ azole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-b ⁇ spy ⁇ dylam ⁇ ne.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-b ⁇ spy ⁇ dylmethane and -bispy ⁇ dylamme complexes. Highly preferred catalysts include Co(2,2'-b ⁇ spy ⁇ dylamme)Cl2,
  • Mn complexed with tetra-N-dentate and bi-N-dentate ligands including ⁇ Mn ⁇ u-
  • the bleach catalysts of the present invention may also be prepared by combining a water- soluble ligand with a water-soluble manganese salt in aqueous media and concentrating the resulting mixture by evaporation. Any convenient water-soluble salt of manganese can be used herein. Manganese (II), (HI), (IV) and/or (V) is readily available on a commercial scale. In some instances, sufficient manganese may be present in the wash liquor, but, m general, it is preferred to add Mn cations in the compositions to ensure its presence in catalytically-effective amounts.
  • the sodium salt of the ligand and a member selected from the group consisting of MnS ⁇ 4, Mn(C104)2 or MnCl2 (least preferred) are dissolved m water at molar ratios of l ⁇ gand:Mn salt in the range of about 1 :4 to 4: 1 at neutral or slightly alkaline pH.
  • the water may first be de-oxygenated by boiling and cooled by spraying with nitrogen. The resulting solution is evaporated (under N 2 , if desired) and the resulting solids are used in the bleaching and detergent compositions herein without further pu ⁇ fication.
  • the water-soluble manganese source such as MnS ⁇ 4
  • the bleach/cleanmg composition or to the aqueous bleachmg/cleanmg bath which comprises the hgand is added to the bleach/cleanmg composition or to the aqueous bleachmg/cleanmg bath which comprises the hgand.
  • Some type of complex is apparently formed in situ, and improved bleach performance is secured.
  • mole ratios of hgand:Mn typically are 3: 1 to 15:1
  • the additional ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from decomposition.
  • One possible such system is desc ⁇ bed in European patent application, publication no. 549,271.
  • the bleach-catalyzmg manganese complexes of the present invention have not been elucidated, it may be speculated that they comp ⁇ se chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
  • the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+HI), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn-hgand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stams such as tea, ketchup, coffee, wme, juice, and the like.
  • bleach catalysts are desc ⁇ bed, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphynn catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on alummosihcate catalyst), U.S. 4,601,845 (alummosihcate support with manganese and zinc or magnesium salt), U.S 4,626,373 (manganese/hgand catalyst), U.S. 4,119,557 (feme complex catalyst), German Pat.
  • compositions of the type described herein optionally, but preferably comprise alkali metal silicates and/or metasihcates.
  • the alkali metal silicates hereinafter desc ⁇ bed provide pH adjusting capability (as desc ⁇ bed above), protection against corrosion of metals and against attack on dishware, inhibition of corrosion to glasswares and chmawares.
  • the SiO level is
  • the alkali metal silicate is hydrous, having from about 15% to about 25% water, more preferably, from about 17% to about 20%.
  • Anhydrous forms of the alkali metal silicates with a S ⁇ 2:M2 ⁇ ratio of 2.0 or more are also less preferred because they tend to be significantly less soluble than the hydrous alkali metal silicates having the same ratio
  • a particularly preferred alkali metal silicate is a granular hydrous sodium silicate having a S ⁇ 2:Na2 ⁇ ratio of from 2.0 to 2.4 available from PQ Corporation, named B ⁇ tesil H20 and B ⁇ tesil H24. Most preferred is a granular hydrous sodium silicate having a S ⁇ 2:Na2 ⁇ ratio of 2.0. While typical forms, i.e. powder and granular, of hydrous silicate particles are suitable, preferred silicate particles have a mean particle size between about 300 and about 900 microns with less than 40% smaller than 150 microns and less than 5% larger than 1700 microns. Particularly preferred is a silicate particle with a mean particle size between about 400 and about 700 microns with less than 20% smaller than 150 microns and less than 1% larger than 1700 microns
  • Suitable silicates include the crystalline layered sodium silicates have the general formula:
  • x in the general formula above has a value of 2, 3 or 4 and is preferably s.
  • the most preferred material is -Na2Si2 ⁇ 5, available from Hoechst AG as NaSKS-6.
  • the crystalline layered sodium silicate material is preferably present m granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble lonisable mate ⁇ al
  • the solid, water-soluble lonisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof. Dispersant polymers
  • a dispersant polymer in the instant ADD compositions is typically in the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 7% by weight of the ADD composition.
  • Dispersant polymers are also useful for improved filming performance of the present ADD compositions, especially m higher pH embodiments, such as those m which wash pH exceeds about 9.5.
  • Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
  • Dispersant polymers suitable for use herein are illustrated by the film-forming polymers desc ⁇ bed in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983, incorporated herein by reference.
  • Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxyhc acids
  • the alkali metal, especially sodium salts are most preferred.
  • the molecular weight of the polymer can vary over a wide range, it preferably is from about 1000 to about 500,000, more preferably is from about 1000 to about 250,000, and most preferably, especially if the ADD is for use in North Ame ⁇ can automatic dishwashing appliances, is from about 1000 to about 5,000.
  • suitable dispersant polymers include those disclosed U.S. Patent No. 3,308,067 issued March 7, 1967, to Diehl, incorporated herein by reference.
  • Unsaturated monome ⁇ c acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhyd ⁇ de), fumaric acid, ltacomc acid, aconitic acid, mesacomc acid, citraconic acid and methylenemalonic acid.
  • monome ⁇ c segments containing no carboxylate radicals such as methyl vmyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50% by weight of the dispersant polymer.
  • Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by weight of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer.
  • Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
  • Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula:
  • R , R or R preferably R or R , is a 1 to 4 1 2 3 carbon alkyl or hydroxyalkyl group, R or R can be a hydrogen and R can be a hydrogen or
  • the low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000.
  • the most preferred polyacrylate copolymer for use herein has a molecular weight of 3500 and is the fully neutralized form of the polymer compnsmg about 70% by weight acrylic acid and about 30% by weight methacrylic acid.
  • Suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed m U.S. Patents 4,530,766, and 5,084,535, both incorporated herein by reference.
  • dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds for example, having a melting point within the range of from about 30° to about 100°C can be obtained at molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are formed by the polyme ⁇ zation of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol.
  • the polyethylene, polypropylene and mixed glycols are referred to using the formula
  • dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • Sodium cellulose sulfate is the most preferred polymer of this group.
  • Suitable dispersant polymers are the carboxylated polysaccha ⁇ des, particularly starches, celluloses and algmates, described in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 27, 1973; the dext ⁇ n esters of polycarboxyhc acids disclosed m U.S. Pat. No. 3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dext ⁇ ns and starch hydrolysates described in U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches desc ⁇ bed in U.S. Pat. No. 3,629,121, Eldib, issued Dec.
  • Preferred cellulose-de ⁇ ved dispersant polymers are the carboxymethyl celluloses.
  • organic dispersant polymers such as polyaspartate.
  • Low-Foaming Nonionic Surfactant is the organic dispersant polymers, such as polyaspartate.
  • ADD compositions of the present invention can comprise low foaming nonionic surfactants (LFNIs).
  • LFNI can be present in amounts from 0 to about 10% by weight, preferably from about 1% to about 8%, more preferably from about 0.25% to about 4%.
  • LFNIs are most typically used m ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-sihcone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
  • Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates de ⁇ ved from p ⁇ mary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxy ethylene/ polyoxypropylene reverse block polymers.
  • the PO/EO/PO polymer-type surfactants are well-known to have foam suppressing or defoarmng action, especially in relation to common food soil ingredients such as egg.
  • the invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at temperatures below about 100°F, more preferably below about 120°F.
  • the LFNI is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, excluding cyclic carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • a particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C -C alcohol), preferably a C alcohol,
  • the ethoxylated nonionic surfactant so de ⁇ ved has a narrow ethoxylate distribution relative to the average.
  • the LFNI can optionally contain propylene oxide in an amount up to about 15% by weight.
  • Other preferred LFNI surfactants can be prepared by the processes desc ⁇ bed in U.S.
  • LFNI ethoxylated monohydroxy alcohol or alkyl phenol and additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI comprising from about 20% to about 80%, preferably from about 30% to about 70%, of the total LFNI.
  • Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described herein before include those based on ethylene glycol, propylene glycol, glycerol, t ⁇ methylolpropane and ethylenediamme as initiator reactive hydrogen compound.
  • Polymeric compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as Cj2-18 aliphatic alcohols do not generally provide satisfactory suds control m the instant ADDs
  • a particularly preferred LFNI contains from about 40%) to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend comprising about 75%), by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%), by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene initiated with t ⁇ methylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of t ⁇ methylolpropane
  • LFNI m Suitable for use as LFNI m the ADD compositions are those LFNI having relatively low cloud points and high hydrophilic- pophilic balance (HLB). Cloud points of 1% solutions in water are typically below about 32°C and preferably lower, e.g., 0°C, for optimum control of sudsmg throughout a full range of water temperatures.
  • HLB hydrophilic- pophilic balance
  • LFNIs which may also be used include a C alcohol polyethoxylate, having a degree of l o ethoxylation of about 8, commercially available SLF18 from Olin Corp. and any biodegradable LFNI having the melting point properties discussed herein above.
  • Anionic Co-surfactant a C alcohol polyethoxylate, having a degree of l o ethoxylation of about 8, commercially available SLF18 from Olin Corp. and any biodegradable LFNI having the melting point properties discussed herein above.
  • the automatic dishwashing detergent compositions herein can additionally contain an anionic co-surfactant.
  • the anionic co-surfactant is typically in an amount from 0 to about 10%), preferably from about 0.1% to about 8%, more preferably from about 0.5% to about 5%, by weight of the ADD composition.
  • Suitable anionic co-surfactants include branched or linear alkyl sulfates and sulfonates. These may contain from about 8 to about 20 carbon atoms.
  • anionic cosurfactants include the alkyl benzene sulfonates containing from about 6 to about 13 carbon atoms in the alkyl group, and mono- and/or dialkyl phenyl oxide mono- and/or di-sulfonates wherein the alkyl groups contain from about 6 to about 16 carbon atoms. All of these anionic co-surfactants are used as stable salts, preferably sodium and/or potassium.
  • Preferred anionic co-surfactants include sulfobetames, betames, alkyl(polyethoxy)sulfates (AES) and alkyl (polyethoxy)carboxylates which are usually high sudsing.
  • Optional anionic cosurfactants are further illustrated m published British Patent Application No. 2,116,199A; U.S. Pat. No. 4,005,027, Hartman; U.S. Pat. No. 4,116,851, Rupe et al; and U.S. Pat. No. 4,116,849, Leikhim, all of which are incorporated herein by reference.
  • Preferred alkyl(polyethoxy)sulfate surfactants comp ⁇ se a p ⁇ mary alkyl ethoxy sulfate de ⁇ ved from the condensation product of a C -C alcohol with an average of from about 0.5 to
  • compositions of the invention are formulated to have a pH of between 6.5 to 9.3, preferably between 8.0 to 9, wherein the pH is defined herein to be the pH of a 1% solution of the composition measured at 20°C, surp ⁇ smgly robust soil removal, particularly proteolytic soil removal, is obtained when C -C alkyl ethoxysulfate surfactant, with an average degree of
  • ethoxylation of from 0.5 to 5 is incorporated into the composition m combination with a proteolytic enzyme, such as neutral or alkaline proteases at a level of active enzyme of from 0.005%) to 2%.
  • a proteolytic enzyme such as neutral or alkaline proteases at a level of active enzyme of from 0.005%) to 2%.
  • Prefe ⁇ ed alkyl(polyethoxy)sulfate surfactants for inclusion in the present invention are the C -C alkyl ethoxysulfate surfactants with an average degree of
  • ethoxylation of from 1 to 5, preferably 2 to 4, most preferably 3.
  • Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate dist ⁇ butions a ⁇ smg from the specific ethoxylation techniques employed and subsequent processing steps such as distillation.
  • Alkyl(polyethoxy)carboxylates suitable for use herein include those with the formula
  • R is a C to C 2 5 alkyl group, x ranges from O to 10, 2 2 2 6 preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and t ⁇ - ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred alkyl(polyethoxy)carboxylates are those where R is a C
  • Highly preferred anionic cosurfactants herein are sodium or potassium salt-forms for which the corresponding calcium salt form has a low Kraft temperature, e.g., 30°C or below, or, even better, 20°C or lower.
  • Examples of such highly preferred amomc cosurfactants are the alkyl(polyethoxy)sulfates.
  • the preferred anionic co-surfactants of the mvention in combination with the other components of the composition provide excellent cleaning and outstanding performance from the standpoints of residual spotting and filming.
  • many of these co-surfactants may also be high sudsmg thereby requi ⁇ ng the addition of LFNI, LFNI m combination with alternate suds suppressors as further disclosed hereinafter, or alternate suds suppressors without conventional LFNI components.
  • the enzyme is a detersive enzyme in the form of an enzyme particle.
  • the enzyme particle comprises a composite particle suitable for incorporation in a detergent composition comp ⁇ smg an enzyme-contammg core mate ⁇ al and a bar ⁇ er layer coated on the enzyme-contaming core mate ⁇ al.
  • the enzyme containing core mate ⁇ al includes the enzyme or enzymes which the composite particle of the present invention is to deliver.
  • the enzyme to be delivered by the present invention is a detersive enzyme.
  • "Detersive enzyme”, as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in an automatic dishwashing composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases. Highly preferred for automatic dishwashing are amylases and or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleanmg-effective amount".
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitemng, deodorizing, or freshness improving effect on substrates such as dishware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comp ⁇ se from about 0.001% to about 15%), preferably about 0.01% to about 10%> by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • the enzyme particle of the present invention is formulated to deliver the desired amount of enzyme to the wash environment.
  • proteases withm the scope of the present invention are the subtilisms which are obtained from particular strains of B subtihs and B. hcheniformis.
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Indust ⁇ es A/S of Denmark, hereinafter "Novo".
  • the preparation of this enzyme and analogous enzymes is desc ⁇ bed in GB 1,243,784 to Novo.
  • proteases include ALCALASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCEVIB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comp ⁇ smg protease, one or more other enzymes, and a reversible protease inhibitor are desc ⁇ bed in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombmant trypsm-hke protease for detergents suitable herein is described in WO 9425583 to Novo.
  • an especially preferred protease is a carbonyl hydrolase variant having an ammo acid sequence not found in nature, which is de ⁇ ved from a precursor carbonyl hydrolase by substituting a different ammo acid for a plurality of ammo acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +195, +197, +204, +206, +216, +260, +265, and/or +274 according to the numbering of Bacillus amylohquefaciens subtihsm, with substitution, deletion or insertion of an ammo acid residue in the following combination of residues: 76/99; 76/104; 76/99/104; 76/103/104; 76/104/107;
  • Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes include, for example, ⁇ -amylases desc ⁇ bed in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
  • Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521.
  • Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL® in commercial use m 1993.
  • These preferred amylases herein share the characte ⁇ stic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement m one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenediamme m buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above-identified reference- point amylase.
  • oxidative stability e.g., to hydrogen peroxide/tetraacetylethylenediamme m buffered solution at pH 9-10
  • Stability-enhanced amylases can be obtained from Novo or from Genencor International.
  • One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein.
  • Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position
  • Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as
  • DURAMYL® oxidative stability enhanced amylase
  • Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056.
  • Specific amylase enzymes for use in the detergent compositions of the present invention include ⁇ -amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ - amylase activity assay.
  • ⁇ -amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incorporated into laundry detergent compositions at a level from 0.00018% to 0.060%o pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producmg fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a ma ⁇ ne mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • CAREZYME® and CELLUZYME®(Novo) are especially useful. See also WO 9117243 to Novo
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzen ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.” Other suitable commercial lipases include Amano- CES, lipases ex Chromobacter viscosum, e.g.
  • Chromobacter viscosum var hpolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co , The Netherlands, and lipases ex Pseudomonas gladioli.
  • the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared m an amount ranging from 0.075 to 2.5 mg protein per liter).
  • Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/hter) lipase va ⁇ ant per liter of wash liquor.
  • the present invention provides the benefit of improved whiteness maintenance on fab ⁇ cs using low levels of D96L variant m detergent compositions containing the mid-cham branched surfactant surfactants in the manner disclosed herein, especially when the D96L is used at levels in the range of about 50 LU to about 8500 LU per liter of wash solution.
  • Cutinase enzymes suitable for use herein are described m WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates du ⁇ ng the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, lignmase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-contammg detergent compositions are disclosed m WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed m U.S. 4,101,457, Place et al, July 18, 1978, and in U.S 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981 Enzymes for use m detergents can be stabilized by various techniques.
  • Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also desc ⁇ bed, for example, m U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is desc ⁇ bed in WO 9401532 A to Novo.
  • mixtures of the above desc ⁇ bed enzymes may also be employed.
  • Particularly preferred are mixtures of chymotrypsm-like protease enzymes and trypsm-hke protease enzymes.
  • the chymotrypsm-like enzymes are those which have an activity ratio, as defined below, of greater than about 15. Particularly, preferred for this class of enzyme are those identified as "Protease D" above.
  • Other chymotrypsm-like protease enzymes suitable for use in the present invention include those obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • Other suitable proteases include ALCALASE® from Novo as well as the proteases known as BPN' and Carlsberg.
  • the trypsin-like enzymes are those which have an activity ratio, as defined below, of less than about 10, preferably less than about 8.
  • Particularly suitable protease enzymes meeting the above requirement are microbial alcalme proteinases such as the protease enzyme obtained from Bacillus Lentus subtihsm including those commercially available under the tradenames SAVINASE® from Novo and PURAFECT® from Genencor International.
  • Other particularly prefe ⁇ ed trypsm-like protease enzymes include those which are non-narurally-occur ⁇ ng carbonyl hydrolase variants which are de ⁇ ved by replacement of a plurality of ammo acid residues of a precursor carbonyl hydrolase corresponding to position +210 in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally-occur ⁇ ng subtihsm from Bacillus amylohquefaciens or to equivalent ammo acid residues in other carbonyl hydrolases or subtihsms, such as Bacillus lentus subtihsm with different ammo
  • the preferred variant protease enzymes useful for the present invention comp ⁇ se the substitution, deletion or insertion of ammo acid residues in the following combinations: 210/156; 210/166; 210/76; 210/103; 210/104; 210/217; 210/156/166; 210/156/217; 210/166/217; 210/76/156; 210/76/166; 210/76/217; 210/76/156/217; 210/76/166/217, 210/76/103/156; 210/76/103/166; 210/76/103/217; 210/76/104/156; 210/76/104/166; 210/76/104/217; 210/76/103/104/156; 210/76/103/104/166;
  • variant enzymes useful for the present mvention comp ⁇ se the substitution, deletion or insertion of an ammo acid residue in the following combination of residues: 210/156; 210/166; 210/217; 210/156/166; 210/156/217; 210/166/217; 210/76/156/166; 210/76/103/156/166 and 210/76/103/104/156/166 of B lentus subtihsm with 210/76/103/104/156/166 being the most preferred.
  • the protease enzymes useful herein encompass the substitution of any of the nineteen naturally occurring L-armno acids at the designated ammo acid residue positions. Such substitutions can be made in any precursor subtihsm (procaryotic, eucaryotic, mammalian, etc.). Throughout this application reference is made to va ⁇ ous ammo acids by way of common one- and three-letter codes. Such codes are identified in Dale, M.W. (1989), Molecular Genetics of Bacteria. John Wiley & Sons, Ltd., Appendix B.
  • the substitution to be made at each of the identified ammo acid residue positions include but are not limited to substitutions at position +210 including I, V, L, and A, substitutions at positions +33, +62, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, and +218 of D or E, substitutions at position 76 including D, H, E, G, F, K, P and N; substitutions at position 103 mcludmg Q, T, D, E, Y, K, G, R and S; and substitutions at position 104 including S, Y, I, L, M, A, W, D, T, G and V; and substitutions at position 222 including S, C, A.
  • Substrate specificity is generally illustrated by the action of an enzyme on two synthetic substrates.
  • An enzyme is placed m a solution with one of the two synthetic substrates The capability of the enzyme in question to hydrolyze the synthetic substrate is then measured.
  • the synthetic substrates employed to measure the specificity of the enzymes of the present invention are the synthetic substrate N-Succmyl-alanyl-alanyl-prolyl-phenylalanyl-p-Nitroamhde, hereinafter suc-AAPF- pNA, and the synthetic substrate N-Benzyl-valyl-araganyl-lysyl-p-Nitroamhde, hereinafter bVGA-pNA, both of which are available from SIGMA Chemicals.
  • a protease in the class of enzymes having trypsm-hke specificity preferentially hydrolyze the synthetic substrate bVGR-pNA but hydrolyze the synthetic substrate sucAAPF-pNA to a much lesser extent.
  • chymotrypsm-like protease enzymes preferentially hydrolyze the synthetic substrate bVGR- pNA but hydrolyze suc-AAPF-pNA to a much lesser extent.
  • the overall specificity of a protease enzyme can then be determined by measuring that enzyme's specificty against each of the synthetic substrates and then taking a ratio of that enzyme's activity on the two synthetic substrates. Accordingly, for the purposes of the present invention, the activity specificty ratio is determined by the formula:
  • An enzyme having a ratio of less than about 10, more preferably less than about 8 and most preferably less than about 7 may then be considered to demonstrate trypsin-hke specificty for the purposes of the present invention while an enzyme having a ratio greater than about 15, preferably greater than about 17.5 and most preferably greater than about 20 may be considered to demonstrate chymotrypsin-hke Specificty for the purposes of the present invention
  • the mixture is allowed to incubate for 15 minutes at 25 °C Upon completion of the incubation pe ⁇ od, an enzyme inhibitor, PMSF, is added to the mixture at a level of 0.5 mg per mL of buffer solution.
  • the absorbency or OD value of the mixture is determined on a Gilford Response UV spectrometer, Model # 1019 read at a visible light 410 nm wavelength. The absorbence then indicates the activity of the enzyme on the synthetic substrate The greater the absorbence, the higher the level of activity against that substrate. Accordingly, absorbence is equal to enzyme activity for purposes of the present invention.
  • the mixed protease enzyme system of the present invention is employed in compositions at higher-end levels of from less than about 10%, more preferably less than about 5% and even more preferably less than about 2% and at lower-end levels of from greater than about 0.0001%, more preferably greater than about 0.1% and even more preferably greater than about 0.5% by weight of the composition.
  • the ratio of chymotrypsm-like protease enzyme to trypsm-hke protease enzyme ranges from about 0.5: 1 to about 10: 1 and more preferably from about 2:1 to about 5:1 and most preferably from about 1 :1 to about 3: 1.
  • the protease enzyme is present in the compositions m an amount sufficient to provide a ratio of mg of active protease per 100 grams of composition to ppm theoretical Available O2 ("Av ⁇ 2") from any peroxyacid m the wash liquor, referred to herein as the Enzyme to Bleach ratio (E/B ratio), ranging from about 1:1 to about 20:1.
  • Av ⁇ 2 ppm theoretical Available O2
  • E/B ratio Enzyme to Bleach ratio
  • the manufacture of the core mate ⁇ al herein comprising the enzyme can be conducted using a va ⁇ ety of methods, according to the desires of the formulator and the available equipment.
  • va ⁇ ety of methods according to the desires of the formulator and the available equipment.
  • the following illustrate va ⁇ ous methods of manufacture, and are included for the convenience of the formulator and not by way of limitation.
  • the particles herein can be formulated as "marumes". Marumes and their manufacture are disclosed in U.S. Patent 4,016,041 and B ⁇ tish 1,361,387. Marumes can be prepared using an apparatus known under the trademark "Marume ⁇ zer” from Fuji Paudal, KK, and is desc ⁇ bed in U.S. 3,277,520 and German 1,294,351. Basically, the formation of marumes involves spheronizmg extrudate noodles comprising the enzyme and a earner.
  • the core layer herein can be manufactured in the form of "p ⁇ lls".
  • a slurry comprising the enzyme and a earner melt is introduced through a spray head into a cooling chamber.
  • the particle size of the resulting p ⁇ lls can be controlled by regulating the size of the spray drops of the slurry. The size of the drops will depend on the viscosity of the slurry, the spray pressure, and the like.
  • the manufacture of p ⁇ lls is more fully disclosed m U.S. 3,749,671.
  • the particles herein are made by a process compnsmg the following basic steps:
  • Preferred methods for manufacturing the particles herein include: buildmg-up of layers of earner in a fluidized bed, Wurster-type coater, drum granulation, pan coaters, and like techniques for building up a granule by adding consecutive layers on top of a core material, all of which are well-known to those skilled in the art of particle manufacture.
  • a typical process suitable for use in the manufacture of the composite particles herein is desc ⁇ bed m detail in U.S. Patent 5,324,649, incorporated herein by reference.
  • the composite particles herein may be manufactured using one or more "carrier" mate ⁇ als as described above which incorporate enzyme in a mat ⁇ x. Since the enzyme is intended for use in an aqueous medium, the earner material should dissolve or readily disperse m water under the intended use conditions in order to release the enzyme to perform its detersive functions. The earner mate ⁇ al should be inert to reaction with the enzyme components of the particle under processing conditions and after granulation. Additionally, the carrier material should preferably be substantially free of moisture present as unbound water, as noted hereinafter.
  • the earner for the soluble or dispersible composite enzyme particles herein can comp ⁇ se a mixture of an inert, water-dispersible or water-soluble, typically inorganic granule material and a binder
  • the binder serves to provide integral particles containing the enzyme and granule material
  • Such particles will typically comp ⁇ se: from about 50% to about 95%, by weight, of the granule mate ⁇ al; from about 5% to about 50%>, by weight, of the binder; and from about 0.01% to about 15%, by weight, of the enzyme.
  • Granule materials useful in such particles include inert, inorganic salts.
  • inert is meant that the salts do not deletenously interact with the enzyme.
  • Non-hmitmg examples include sodium sulfate, sodium carbonate, sodium silicate, and other ammonium and alkali metal sulfates, carbonates and silicates, and the like.
  • suitable organic binders include the water soluble organic homo- or co- polyme ⁇ c polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed m GB-A-1,596,756.
  • Prefe ⁇ ed examples of such compounds are the polymers which contain acrylic acid, that is to say homopolymers of acrylic acid and copolymers with any suitable other monomer units, and which have a average molecular weight of from 2,000 to 100,000.
  • Suitable other monomer units include modified acrylic, fumaric, maleic, ltacomc, acomtic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vmylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhyd ⁇ de having a average molecular weight of from 20,000 to 100,000.
  • Prefe ⁇ ed acrylic acid containing polymers have an average molecular weight of less than 15,000, and include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 445N by Rohm and Haas.
  • Other suitable polymers include Acusol 450N and 410N.
  • acrylic acid containing copolymers include those which contain as monomer units: a) from 90%> to 10%, preferably from 80% to 20% > by weight acrylic acid or its salts and b) from 10% to 90%>, preferably from 20% to 80%> by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CR j (CO-0-R3)]- wherein at least one of the substituents Ri , R2 or R3, preferably R ⁇ or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, Rj or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • Most prefe ⁇ ed is a substituted acrylic monomer wherein Rj is methyl, R2 is hydrogen (i.e. a methacryhc acid monomer).
  • the most prefe ⁇ ed copolymer of this type has a average molecular weight of from 4500 to 3000 and contains 60% to 80% by weight of acrylic acid and 40% to 20%) by weight of methacryhc acid.
  • a suitable example includes Acusol 480N available from Rohm & Haas.
  • polyammo compounds are useful as organic binders herein including those denved from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vmyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic binders suitable herein include essentially any charged and non charged cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxy- propylmethylcellulose, hydroxyethylcellulose, and ethylhydroxyethylcellulose.
  • Suitable binders include the C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 pnmary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include polyvmyl alcohol, polyvmyl acetate, the polyvinylpy ⁇ ohdones with an average molecular weight of from 12,000 to 700,000 and the polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10" preferably 1000 to 400,000 most preferably 1000 to 10,000.
  • Copolymers of maleic anhydride with ethylene, methylvmyl ether or methacryhc acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric matenals useful as binder agents.
  • polymeric matenals may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include the C10-C2O mono- and diglycerol ethers and also the Ci 0-C20 fatty acids.
  • PEG polyethylene glycols
  • fatty acids and or fatty amides preferably having a melting point in the range from about 38°C to about 77°C
  • fatty alcohols preferably having a melting point in the range from about 38°C to about 77°C
  • Paraffin waxes preferably having a melting point in the range from about 38°C to about 77°C, can also be used singly
  • ca ⁇ ier matenals are paraffin waxes which should melt in the range of from about 38°C (100°F) to about 43°C (110°F), C 16 - C 2 o fatty acids and ethoxylated C 16 - C 2 ⁇ alcohols. Mixtures of suitable ca ⁇ ier materials are also envisaged.
  • Va ⁇ ous other materials may be used in the ca ⁇ ier, including finely divided cellulosic fibers (see U.S. 4,106,991) sugars, starches, and the like, according to the desires of the formulator. If used, such other materials will typically compnse from about 2% to about 50%, by weight, of the composite particles herein.
  • the barner layer of the composite particle of the present invention comprises a water soluble carboxylate compound. While other ingredients may be included in the barner layer, the barner layer is predominately water-soluble carboxylate. Typically, the barner layer includes at least about 50% water-soluble carboxylate and more preferably compnses at least 75%) water-soluble carboxylate.
  • the phrase "water soluble carboxylate compound" includes carboxylates, dicarboxylates and polycarboxylate anions.
  • the water soluble carboxylate is a salt of a metal or nitrogen-based cation. Prefe ⁇ ed metals include the alkali metals such as sodium. Preferred nitrogen-based cations include ammonium compounds.
  • Prefe ⁇ ed carboxylate compounds include citrates, succinates and maleates with citrates being the more prefe ⁇ ed and sodium citrate dihydrate the most prefe ⁇ ed. Of course, mixtures of carboxylates may also be employed. While not wishing to be bound by theory, it is believed that the barner compound, and m particular, the sodium citrate forms a tight crystal structure around the particle which then acts as a barner to oxidative degradation. Accordingly, via the use of the barner layer, a supe ⁇ or enzyme particle is provided.
  • the barner layer is employed at levels of from about 1% to about 50% by weight of the particle, preferably from about 5% to about 40% and most preferably from about 10% to about 30%.
  • An outer overlayer is optionally, but preferably, applied over the barner layer.
  • the overlayer may provide a number of additional benefits to the enzyme particle of the present invention including, but not limited to, an additional level of protection to the enzyme containing core, reduced dusting, enhanced solubility, etc.
  • the overlayer need not provide for stability of the enzyme in the absence of the bamer layer, but it should be sufficiently non- reactive m the presence of the barner layer to active m conjunction with the bamer layer in reducmg oxidative attack.
  • the overlayer is typically present at levels of from about 0.1% to about 60%, and more preferably from about 1% to about 30%.
  • Appropriate matenals include water-soluble polymers, fatty acids, waxes, surfactants/dispersants and alkaline materials, all as hereinbefore descnbed as "ca ⁇ ier" materials.
  • water-soluble polymers include, but is not limited to, polyacrylic acids, polyethlyene glycols, polyvmyl alcohols, polyvmylpy ⁇ ohdone, starches, and most prefe ⁇ ed, celluloses such as hydroxy propyl methyl cellulose.
  • Suitable surfactants include nonionic surfactants and wetting agents such as Neodol® from Shell Oil Co. and Triton® from Rohm and Haas.
  • alkaline matenals include silicates, carbonates and bicarbonates, particularly alkali metals such as sodium silicate and sodium carbonate
  • the outerlayer may comprise va ⁇ ous "free-flow" agents such as clays and zeolites.
  • the outerlayer may include vanous additives, including, but not limited to, whiteners, pigments, fillers such as CaC ⁇ 3 and talc, plasticizers such as PEG and PVP or other coloring agents, such as T ⁇ 0 2 .
  • vanous additives including, but not limited to, whiteners, pigments, fillers such as CaC ⁇ 3 and talc, plasticizers such as PEG and PVP or other coloring agents, such as T ⁇ 0 2 .
  • the composite particles of the present invention may include a stabilizing additive to enhance the stability of the enzyme, i.e reduce oxidation, minimize odor, etc.
  • the stabilizing additive may be added to each or all layers of the composite particle including the enzyme- contammg core, ba ⁇ ier layer and outer overlayer.
  • the stabilizing additive according to the present invention may be present in the particle at levels of from about 0.1% to about 60% by weight of the particle, and more preferably from about 0.1% to about 25% by weight of the particle, and most preferably from about 0.5% to about 10% by weight of the particle.
  • antioxidants include antioxidants, chelants, radical quenchers, alkaline ingredients and reductive agents. These assure good odor and enzyme stability under long term storage conditions for the compositions.
  • antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-l; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroqumone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocoph- erols, Eastman Chemical Products, Inc., as Tenox GT-l/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA.
  • any of the ingredients m these mixtures such as ascorbic acid, ascorbic palmitate, BHT, BHQ and BHA, may be employed individually as well
  • reductive agents include sodium borohyd ⁇ de, hypophosphorous acid, sulfites, thiosulfates and bisulfites particularly the alkali metals such as sodium and mixtures thereof.
  • Suitable radical quenchers for use in the present invention include the Tmuvin series available from Ciba-Geigy.
  • Alkaline materials suitable for use m the present invention include silicates, carbonates and bicarbonates, particularly the alkali metals such as sodium.
  • Chelatmg agents may be selected from the group consisting of ammo carboxylates, ammo phosphonates, polyfunctionally-substituted aromatic chelatmg agents and mixtures therein, all as hereinafter defined.
  • Ammo carboxylates useful as optional chelatmg agents include ethylenediammetetrace- tates, N-hydroxyethylethylenediammetnacetates, mtnlot ⁇ acetates, ethylenediamme tetrapro- pnonates, t ⁇ ethylenetetraammehexacetates, diethylenetnammepentaacetates, and ethanoldi- glycmes, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Ammo phosphonates are also suitable for use as chelatmg agents in the particles of the invention when at least low levels of total phosphorus are permitted m detergent compositions, and include ethylenediammetetrakis (methylenephosphonates) as DEQUEST. Prefe ⁇ ed, these ammo phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelatmg agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Prefe ⁇ ed compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- d ⁇ hydroxy-3 ,5 -disulfobenzene .
  • EDDS ethylenediamme disuccmate
  • the final composite particles should have a low free water content to favor m-product stability and minimize the stickiness of the composite particles.
  • the composite particles should preferably have a free water content of less than about 10%, preferably less than about 6%, more preferably less than about 3%, and most preferably less than 1%. Excess free water can be removed by standard drying processes. Enzvme Stabilizing System
  • Enzyme-containing compositions herein may comprise from about 0.001% to about 10%), preferably from about 0.005%> to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comp ⁇ se calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally more effective than magnesium ions and are prefe ⁇ ed herein if only one type of cation is being used.
  • Typical detergent compositions, especially liquids, will comp ⁇ se from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 milhmoles of calcium ion per liter of finished detergent composition, though va ⁇ ation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated.
  • Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts co ⁇ espondmg to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease- cutting action of certain types of surfactant.
  • Borate stabilizers when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of bone acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use.
  • Substituted boric acids such as phenylboronic acid, butaneboromc acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron m detergent compositions may be possible though the use of such substituted boron de ⁇ vatives.
  • Stabilizing systems of example automatic dishwashing compositions may further compnse from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlo ⁇ ne bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • chlo ⁇ ne levels m water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlonne in the total volume of water that comes in contact with the enzyme, for example du ⁇ ng dishwashing, can be relatively large; accordingly, enzyme stability to chlo ⁇ ne m-use is sometimes problematic Since perborate or percarbonate, which have the ability to react with chlo ⁇ ne bleach, may present in certain of the instant compositions m amounts accounted for separately from the stabilizing system, the use of additional stabilizers against chlorine, may, most generally, not be essential, though improved results may be obtainable from their use.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolam e (MEA), and mixtures thereof can likewise be used Likewise, special enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility.
  • scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, sahcylate, etc., and mixtures thereof can be used if desired.
  • chlo ⁇ ne scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-contammg embodiment of the invention, even then, the scavenger is added only for optimum results Moreover, the formulator will exercise a chemist's normal skill m avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients, if used.
  • such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage Accordingly, such materials, if present, are desirably protected in a particle such as that desc ⁇ bed m US 4,652,392, Bagmski et al. Silicone and Phosphate Ester Suds Suppressors
  • the ADDs of the invention can optionally contain an alkyl phosphate ester suds suppressor, a silicone suds suppressor, or combinations thereof.
  • Levels in general are from 0% to about 10%, preferably, from about 0.001% to about 5% Typical levels tend to be low, e.g , from about 0.01% to about 3% when a silicone suds suppressor is used.
  • Preferred non- phosphate compositions omit the phosphate ester component entirely Sihcone suds suppressor technology and other defoammg agents useful herein are extensively documented m "Defoaming, Theory and Industrial Applications", Ed., P. R.
  • polydimethylsiloxanes having trimethylsilyl or alternate endblock g units may be used as the silicone. These may be compounded with silica and/or with surface-active nonsihcon components, as illustrated by a suds suppressor comprising 12% silicone/ silica, 18% stearyl alcohol and 70% starch in granular form.
  • a suitable commercial source of the silicone active compounds is Dow Corning Corp.
  • Levels of the suds suppressor depend to some extent on the sudsmg tendency of the composition, for example, an ADD for use at 2000 ppm comp ⁇ smg 2% octadecyldimethylamme oxide may not require the presence of a suds suppressor. Indeed, it is an advantage of the present invention to select cleaning-effective amine oxides which are inherently much lower in foam-formmg tendencies than the typical coco amine oxides. In contrast, formulations m which amine oxide is combined with a high-foammg amomc cosurfactant, e.g., alkyl ethoxy sulfate, benefit greatly from the presence of suds suppressors.
  • a high-foammg amomc cosurfactant e.g., alkyl ethoxy sulfate
  • Phosphate esters have also been asserted to provide some protection of silver and silver- plated utensil surfaces, however, the instant compositions can have excellent silvercare without a phosphate ester component. Without being limited by theory, it is believed that lower pH formulations, e.g., those having pH of 9.5 and below, plus the presence of the essential amine oxide, both cont ⁇ bute to improved silver care.
  • Prefe ⁇ ed alkyl phosphate esters contain from 16-20 carbon atoms.
  • Highly prefe ⁇ ed alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
  • compositions may also contain co ⁇ osion inhibitor.
  • co ⁇ osion inhibitors are prefe ⁇ ed components of machine dishwashing compositions in accord with the invention, and are preferably incorporated at a level of from 0.05%> to 10%, preferably from 0.1% to 5% by weight of the total composition.
  • Suitable co ⁇ osion inhibitors include paraffin oil typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50: prefe ⁇ ed paraffin oil selected from predominantly branched C 2 5_45 species with a ratio of cyclic to noncyclic hydrocarbons of about 32:68; a paraffin oil meeting these characteristics is sold by Wmtershall, Salzbergen, Germany, under the trade name WINOG 70.
  • co ⁇ osion inhibitor compounds include benzotnazole and any derivatives thereof, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionahde and thioanthranol.
  • Cj 2 -C 2 o fatty acids, or their salts especially aluminum t ⁇ stearate.
  • the Cj 2 -C 2 o hydroxy fatty acids, or their salts are also suitable.
  • Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
  • BHT betahydroxytoluene
  • filler materials can also be present in the instant ADDs. These include sucrose, sucrose esters, sodium chlo ⁇ de, sodium sulfate, potassium chlonde, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the ADD composition. Prefe ⁇ ed filler is sodium sulfate, especially m good grades having at most low levels of trace impurities.
  • Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates in magnesium-salt form. Note that preferences, in terms of pu ⁇ ty sufficient to avoid decomposing bleach, applies also to builder ingredients.
  • Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc., can be present in minor amounts.
  • Bleach-stable perfumes (stable as to odor); and bleach-stable dyes (such as those disclosed m U.S. Patent 4,714,562, Roselle et al, issued December 22, 1987); can also be added to the present compositions in appropriate amounts Other common detergent ingredients are not excluded.
  • Smce certain ADD compositions herein can contain water-sensitive ingredients, e.g., in embodiments compnsmg anhydrous amme oxides or anhydrous citnc acid, it is desirable to keep the free moisture content of the ADDs at a minimum, e.g., 7% or less, preferably 4% or less of the ADD; and to provide packaging which is substantially impermeable to water and carbon dioxide.
  • Plastic bottles including refillable or recyclable types, as well as conventional ba ⁇ ier cartons or boxes are generally suitable.
  • ingredients are not highly compatible, e.g., mixtures of silicates and citric acid, it may further be desirable to coat at least one such ingredient with a low-foammg nonionic surfactant for protection.
  • a low-foammg nonionic surfactant for protection.
  • waxy mate ⁇ als which can readily be used to form suitable coated particles of any such otherwise incompatible components.
  • the detergent compositions may a contain any known detergent components, particularly those selected from pH-adjusting and detergency builder components, other bleaches, bleach activators, silicates, dispersant polymers, low-foaming nonionic surfactants, anionic co-surfactants, enzyme stabilizers, suds suppressors, co ⁇ osion inhibitors, fillers, hydrotropes and perfumes.
  • the detergent compositions may be in a granular for, a p ⁇ ll, or a tablet form.
  • a prefe ⁇ ed granular or powdered or tableted detergent composition comp ⁇ ses by weight:
  • a pH adjusting component consisting of water-soluble salt, builder or salt/builder mixture selected from STPP, sodium carbonate, sodium sesquicarbonate, sodium citrate, citric acid, sodium bicarbonate, sodium hydroxide, and mixtures thereof;
  • compositions are typically formulated to provide an m-use wash solution pH from about 9.5 to about 11.5.
  • protease D comprising a protease D core material, a sodium citrate dihydrate ba ⁇ ier layer and a HPMC overlayer.
  • the AvO level of the above formula is 2.2%.
  • the perborate is obtained from DeGussa Corp.
  • the bacte ⁇ cide is tnclosan
  • EXAMPLE 2 The following detergent composition was pressed into tablet form, in accordance with another aspect of this invention, each tablet weighing about 25 g, and prepared by compression of the granular dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:
  • the bacte ⁇ cide is T ⁇ closan.
  • a method of using the limitation of residue deposition on substrates exposed to an automatic dishwashing process, for the purpose of promoting sanitization of the substrates which are already washed and sanitized by a wash solution during an automatic dishwashing process includes limiting residue deposition on the substrates washed and sanitized by the automatic dishwashing process to an amount no greater than about 10 mg of residue per 1 m 2 meter of substrate surface.
  • the amount of residue deposition on the subsfrates is limited to an amount no greater than about 5 mg of residue per 1 m 2 meter of substrate surface, more preferably, to an amount no greater than about 1 mg of residue per 1 m 2 meter of substrate surface, and most preferably, to an amount no greater than about 0.1 mg of residue per 1 m 2 meter of substrate surface.
  • the residue that is targeted for limitation in the weight amounts as set forth above, consists essentially of protein, carbohydrate and grease, and mixtures thereof.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé de lavage en machine à laver la vaisselle automatique qui assure avantageusement l'aseptisation en phase après-lavage de machine à laver la vaisselle automatique. On limite le dépôt de résidus sur les substrats nettoyés au cours du lavage automatique pour ne pas dépasser environ 10 mg de résidus par m2 de surface de substrat.
PCT/US1999/022533 1999-09-30 1999-09-30 Procede favorisant l'aseptisation d'articles en phase apres-lavage de machine a laver la vaisselle automatique WO2001025388A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU62739/99A AU6273999A (en) 1999-09-30 1999-09-30 Process for promoting sanitization of articles during post-wash stage of automatic dishwashing
PCT/US1999/022533 WO2001025388A1 (fr) 1999-09-30 1999-09-30 Procede favorisant l'aseptisation d'articles en phase apres-lavage de machine a laver la vaisselle automatique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1999/022533 WO2001025388A1 (fr) 1999-09-30 1999-09-30 Procede favorisant l'aseptisation d'articles en phase apres-lavage de machine a laver la vaisselle automatique

Publications (1)

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WO2001025388A1 true WO2001025388A1 (fr) 2001-04-12

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PCT/US1999/022533 WO2001025388A1 (fr) 1999-09-30 1999-09-30 Procede favorisant l'aseptisation d'articles en phase apres-lavage de machine a laver la vaisselle automatique

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WO (1) WO2001025388A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195619A2 (fr) * 1985-03-15 1986-09-24 Diversey Corporation Procédé de désinfection, de nettoyage et de rinçage et compositions à cet effet
EP0361380A2 (fr) * 1988-09-28 1990-04-04 Jörg-Peter Prof. Schür Procédé pour laver, désinfecter et rincer la vaisselle en machine, et composition utilisée
DE3832989A1 (de) * 1988-09-29 1990-04-05 Dispo Kommerz Ag Huenenberg Fluessiges phosphatfreies reinigungsmittel fuer geschirrspuelmaschinen (geschirrspuelmittel)
JPH0578696A (ja) * 1991-01-08 1993-03-30 Matsushita Electric Ind Co Ltd 食器洗い機用洗剤
FR2754184A1 (fr) * 1996-10-08 1998-04-10 Parizzi Maurice Procede pour la desinfection des tambours et cuves et accessoires de vidange des machines a laver le linge ou la vaisselle
WO1998045392A1 (fr) * 1997-04-04 1998-10-15 Benckiser Consumer Products, Inc. Adjuvant de rinçage antimicrobien a usage sanitaire
JPH10276960A (ja) * 1997-04-02 1998-10-20 Hitachi Ltd 食器洗い乾燥機
WO1999003512A2 (fr) * 1997-07-21 1999-01-28 The Procter & Gamble Company Procede de nettoyage de substrats a l'aide de compositions de detergence

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195619A2 (fr) * 1985-03-15 1986-09-24 Diversey Corporation Procédé de désinfection, de nettoyage et de rinçage et compositions à cet effet
EP0361380A2 (fr) * 1988-09-28 1990-04-04 Jörg-Peter Prof. Schür Procédé pour laver, désinfecter et rincer la vaisselle en machine, et composition utilisée
DE3832989A1 (de) * 1988-09-29 1990-04-05 Dispo Kommerz Ag Huenenberg Fluessiges phosphatfreies reinigungsmittel fuer geschirrspuelmaschinen (geschirrspuelmittel)
JPH0578696A (ja) * 1991-01-08 1993-03-30 Matsushita Electric Ind Co Ltd 食器洗い機用洗剤
FR2754184A1 (fr) * 1996-10-08 1998-04-10 Parizzi Maurice Procede pour la desinfection des tambours et cuves et accessoires de vidange des machines a laver le linge ou la vaisselle
JPH10276960A (ja) * 1997-04-02 1998-10-20 Hitachi Ltd 食器洗い乾燥機
WO1998045392A1 (fr) * 1997-04-04 1998-10-15 Benckiser Consumer Products, Inc. Adjuvant de rinçage antimicrobien a usage sanitaire
WO1999003512A2 (fr) * 1997-07-21 1999-01-28 The Procter & Gamble Company Procede de nettoyage de substrats a l'aide de compositions de detergence

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199317, Derwent World Patents Index; Class D25, AN 1993-140543, XP002139089 *
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 01 29 January 1999 (1999-01-29) *

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