EP0516555A2 - Pulverförmige phosphatenthaltende Zusammensetzung mit Enzymen für Geschirrspülmaschinen - Google Patents

Pulverförmige phosphatenthaltende Zusammensetzung mit Enzymen für Geschirrspülmaschinen Download PDF

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Publication number
EP0516555A2
EP0516555A2 EP92401477A EP92401477A EP0516555A2 EP 0516555 A2 EP0516555 A2 EP 0516555A2 EP 92401477 A EP92401477 A EP 92401477A EP 92401477 A EP92401477 A EP 92401477A EP 0516555 A2 EP0516555 A2 EP 0516555A2
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EP
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Prior art keywords
enzyme
dishwashing composition
percent
detergent
weight
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EP92401477A
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English (en)
French (fr)
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EP0516555A3 (en
Inventor
Fahim U. Ahmed
Julien Drapier
Patrick Durbut
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Colgate Palmolive Co
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Colgate Palmolive Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609Protease or amylase in solid compositions only

Definitions

  • the enzymes in the detergent are maintained in a minimum exposure to moisture and water, the enzymes will suffer a degradation during storage which will result in a product that will have a decreased activity.
  • the initial water content of the components of the composition should be as low a level as possible, and this low water content must be maintained during storage, since water in the alkaline product will deactivate the enzymes. This deactivation will cause a decrease in the initial activity of the detergent composition.
  • the detergent After the detergent container is opened, the detergent will be exposed to the environment which contains moisture. During each instance that the detergent is exposed to the environment it could possibly absorb some moisture. This absorption occurs by components of the detergent composition absorbing moisture, when in contact with the atmosphere. This effect is increased as the container is emptied, since there will be a greater volume of air in contact with the detergent, and thus more available moisture to be absorbed by the detergent composition. This will usually accelerate the decrease in the activity of the detergent composition.
  • the most efficient way to keep a high activity is to start with an initial high activity of enzyme and to use components in the dishwashing composition which do not interact with the enzyme or have a low water affinity which will minimize any losses in activity as the detergent is being stored or used.
  • Powdered detergent compositions which contain enzymes can be made more stable and to have a high activity, if the initial free water content of the detergent composition is less than 10 percent by weight, more preferably less than 9 percent by weight and most preferably less than 8 percent by weight. Furthermore, the pH of a 1.0 wt% aqueous solution of the powdered detergent composition should be less than 11.0 more preferably less than 10.6, and most preferably less than 10.3. This low alkalinity of the dishwashing detergent should maintain the stability of the detergent composition which contains a mixture of enzymes, thereby providing a higher initial activity of the mixture of the enzymes and the maintenance of this initial high activity.
  • a major concern in the use of automatic dishwashing compositions is the formulation of automatic dishwashing compositions which have a low alkalinity and can operate at a high temperature while maintaining superior cleaning performance and dish care.
  • the present invention teaches the preparation and use of powdered automatic dishwashing compositions which are phosphate containing and have superior cleaning performance and dish care and are used at operating temperatures of 100°F to 140°F.
  • This invention is directed to producing powdered phosphate enzyme-containing automatic dishwashing detergent compositions that have an increased chemical stability and essentially a high activity at wash operating temperatures of 40°C to 65°C (104°F to 150°F), wherein the composition also can be used as a laundry presoaking agent. This is accomplished by controlling the alkalinity of the detergent composition and using a unique mixture of enzymes.
  • An alkali metal silicate is used in the powdered dishwashing detergent compositions.
  • the preferred builder system of the instant compositions comprises at least one phosphate builder salt which can be used in conjunction with a polymeric builder salts and nonphosphate containing builder salts.
  • powder in this invention includes within its definition tablets, soluble capsules and soluble sachet. It is also possible to use the instant compositions as a laundry presoaking powder.
  • French Patent No. 2,102,851 to Colgate-Palmolive pertains to rinsing and washing compositions for use in automatic dishwashers.
  • the compositions disclosed have a pH of 6 to 7 and contain an amylolytic and, if desired, a proteolytic enzyme, which have been prepared in a special manner from animal pancreas and which exhibit a desirable activity at a pH in the range of 6 to 7.
  • German Patent No. 2,038,103 to Henkel & Co. relates to aqueous liquid or pasty cleaning compositions containing phosphate salts, enzymes and an enzyme stabilizing compound.
  • US Patent No. 3,799,879 to Francke et al teaches a detergent composition for cleaning dishes, with a pH of from 7 to 9 containing an amylolytic enzyme, and in addition, optionally a proteolytic enzyme.
  • US Patent No 3,827,938, to Aunstrup et al. discloses specific proteolytic enzymes which exhibit high enzymatic activities in highly alkaline systems. Similar disclosures are found in British Patent Specification No. 1,361,386, to Novo Terapeutisk Laboratorium A/S. British Patent Specification No. 1,296,839, to Novo Terapeutisk Laboratorium A/S, discloses specific amylolytic enzymes which exhibit a high degree of enzymatic activity in alkaline systems.
  • the aforementioned prior art fails to provide a stable powdered automatic dishwashing detergent which is phosphate-containing and contains a mixture of enzymes as well as optionally, a peroxygen compound with an activatorfor the simultaneous degradation of both proteins and starches, wherein the combination of anylase and protease enzymes have a maximum activity at a pH of less than 11.0 and the powdered automatic dishwashing detergent has high cleaning performance in a temperature range of 40°C to 65°C (100°F to 150°F).
  • the present invention relates to a powdered automatic dishwashing detergent compositions which comprise non ionic surfactant, alkali metal silicate, a phosphate-containing builder system, optionally, a peroxygen compound with an activator as a bleaching agent,and a mixture of an amylase enzyme and a protease enzyme, wherein said dishwashing composition comprises in percent by weight : wherein said protease enzyme is Maxacal protease enzyme and said amylase enzyme is Maxamyl amylase enzyme, a weight ratio of said protease enzyme to said amylase enzyme being 5:1 to about 1.1:1, wherein said detergent dishwashing composition has a pH of less than 10.5, at a concentration of 10 grams/liter, and the powdered dishwashing detergent composition exhibits high cleaning efficiency for both proteins and starches at a wash temperature of 40°C to 65°C (about 100°F to about 150°F).
  • nonionic surfactants that can be used in the present powdered automatic dishwasher detergent compositions are well known. A wide variety of these surfactants can be used.
  • the nonionic synthetic organic detergents are generally described as ethoxylated propoxylated fatty alcohols which are low-foaming surfactants and may be possibly capped, characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide and/or propyleneoxide (hydrophilic in nature).
  • any hydrophobic compound having a carboxy, hydroxy, amide or amino group with a free hydrogen attached to the oxygen or the nitrogen can be condensed with ethylene oxide or propylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent.
  • the length of the hydrophilic or polyoxyethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.
  • Typical suitable nonionic surfactants are those disclosed in US Patent Nos. 4,316,812 and 3,630,929.
  • the nonionic detergents that are used are the low-foaming polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety.
  • a preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 15.
  • the higher alkanol is a high fatty alcohol of 9 to 11 or 12 to 15 carbon atom and which contain from 5 to 15 or 5 to 16 lower alkoxy groups per mole.
  • the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, usually being major (more than 50%) portion.
  • the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole.
  • Useful nonionics are represented by the low foam Plurafac series from BASF Chemical Company which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Product A(a C 13 -C l5 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide). Product B (a C 13 -C 15 fatty alcohol condensed with 7 mole propylene oxide and 4 mole ethylene oxide), and Product C (a C 13 -C 15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide). Another group of liquid nonionics are available from Shell Chemical Company, Inc.
  • Dobanol 91-5 is a low foam ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 -C 15 fatty alcohol with an average of 7 moles ethylene oxide.
  • Another liquid nonionic surfactant that can be used is sold under the tradename Lutensol SC 9713.
  • Synperonic nonionic surfactants from ICI such as Synperonic LF/D25 LF/RA30 are especially preferred nonionic surfactants that can be used in the powdered automatic dishwasher detergent compositions of the instant invention.
  • Poly-Tergent nonionic surfactants from Olin Organic Chemicals such as Poly-Tergent SLF-18, a biodegradable, low-foaming surfactant is specially preferred for the powdered automatic dishwasher detergent compositions of this instant invention.
  • Poly-Tergent SLF-18 which is water dispersible and has a low cloud point and lower surface tension and lower foaming is very suitable for automatic dishwasher detergent.
  • Neodol 25-7 and Neodol 23-6.5 are made by Shell Chemical Company, Inc.
  • the former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 13 carbon atoms and the number of ethylene oxide groups present averages 6.5.
  • the higher alcohols are primary alkanols.
  • Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9 (registered trademarks), both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp.
  • the former is mixed ethoxylation product of 11 to 15 carbon atom linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.
  • nonionic detergent also useful in the present compositions as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similarethylene oxide condensation products of higherfatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atom and the number of ethylene oxide groups per mote being 11.
  • higher molecular weight nonionics such as Neodol 45-11, which are similarethylene oxide condensation products of higherfatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atom and the number of ethylene oxide groups per mote being 11.
  • Neodol 45-11 are similarethylene oxide condensation products of higherfatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atom and the number of ethylene oxide groups per mote being 11.
  • Such products are also made by Shell Chemical Company.
  • the number of lower alkoxies wilt usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol.
  • the alkyl polysaccharides are surfactants which are also useful alone or in conjunction with the aforementioned surfactants and those having a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from 1.5 to about 10, preferably from about 1.5 to 4, and most preferably from 1.6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl, and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkyl polysaccharide surfactants.
  • the number x indicates the number of saccharide units shown later in a particular alkylpolysaccharide surfactant formula.
  • x can only assume integral values.
  • any physical sample can be characterized by the average value of and this average value can assume non-integral values.
  • the values of are to be understood to be average values.
  • the hydrophobic group (R) can be attached at the 2-, 3-, or4- positions rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside).
  • attachment through the 1-position i.e., glucosides, galactosides, fructosides, etc.
  • additional saccharide units are predominately attached to the previous saccharide unit's 2-position.
  • Attachment through the 3-, 4-, and 6-positions can also occur.
  • the preferred alkoxide moiety is ethoxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 20, preferably from 10 to 16 carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to 30, preferably less than 10, alkoxide moieties.
  • Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.
  • the alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in admixture with alkyl polysaccharides, the alkyl monosaccharides are solubilized to some extent.
  • the use of alkyl monosaccharides in admixture with alkyl polysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkyl polysaccharides are alkyl polyglucosides having the formula: wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to about 10, preferable 0; and x is from 1.5 to about 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7.
  • R 2 0H a long chain alcohol
  • the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol (R 1 0H) an be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.
  • the short chain alkylglucoside content of the final alkyl polyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkyl polyglucoside.
  • the amount of unreacted alcohol (the free fatty alcohol content) in the desired alkyl polysaccharide surfactant is preferably less than 2%, more preferably less than 0.5% by weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than 10%.
  • alkyl polysaccharide surfactant is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants.
  • alkyl polyglucoside is used to include alkyl polyglycosides because the stereo chemistry of the saccharide moiety is changed during the preparation reaction.
  • APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA.
  • APG 625 has: a pH of 6-8(10% of APG 625 in distilled water); a specific gravity at 25°F of 1.1 grams/ml; a density at 25°F of 9.1 kgs/gallons; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
  • the liquid nonaqueous nonionic surfactant is absorbed on a builder system which comprises a phosphate-containing particles which is a builder salt and optionally a low molecular weight polyacrylate type polymer such as a polyacrylate, organic and/or inorganic detergent builders as well as phosphate free builder salts such as an alkali carbonate such as sodium carbonate or sodium citrate or a mixture of sodium carbonate and sodium citrate.
  • the nonaqueous liquid nonionic surfactant has dispersed therein fine particles or organic and/or inorganic detergent builders.
  • a preferred solid builder salt is an alkali metal polyphosphate such as sodium tripolyphosphate ("TPP").
  • the TPP is a blend of anhydrous TPP and a small amount of TPP hexahydrate such that the chemically bound water content is 1 %, which corresponds to one H 2 0 per pentasodium tripolyphosphate molecule.
  • Such TPP may be produced by treating anhydrous TPP with a limited amount of water. The presence of the hexahydrate slows down the rapid rate of solution of the TPP in the wash bath and inhibits caking.
  • One suitable TPP is sold under the name Thermphos NW.
  • the particles size of the Thermphos NW TPP, as supplied usually averages about 200 microns with the largest particles being 400 microns.
  • alkali metal polyphosphate In place of all or part of the alkali metal polyphosphate one or more other detergent builder salts can be used.
  • Suitable other builder salts are alkali metal carbonates, borates, phosphates, bicarbonates, silicates, lower polycarboxylic acid salts, and polyacrylates, polymaleic anhydrides and copolymers of polyacrylates and polymaleic anhydrides and polyacetal carboxylates.
  • Such builders are sodium carbonate, potassium carbonate, sodium tetraborate, sodium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate.
  • the builder salts can be used alone with the nonionic surfactant or in an admixture with other builders.
  • Typical builders also include those disclosed in U.S. Pat Nos. 4,316,812, 4,264,466, and 3,630,929 and those disclosed in U.S. Patent Nos. 4,144,226, 4,135,092 and 4,146,495.
  • phosphate-free builder salts which can be mixed with the phosphate containing builder salts are glu- conates, phosphonates and nitriloacetic acid salts in conjunction with the builder salts are optionally used a low molecular weight polyacrylates having a molecular weight of 1,000 to 100,000, more preferably 2,000 to 80,000.
  • a preferred low molecular weight polyacrylate is Sokalan t mCP45 or Sokalan t mCP5 manufactured by BASF and having a molecular weight of 70,000.
  • Another preferred low molecular weight polyacrylate is Acrysol t mLMW45ND manufactured by Rohm and Haas and having a molecularweight of 4,500.
  • Norosol TMWL2 comprises 26% LMV 45ND sprayed on 74% sodawash.
  • Sokalan t mCP45 or CP5 is a copolymer of an acrylic acid and a maleic acid anhydride. Such a material should have a water absorption at 38°C and 78 percent relative humidity of less than 40 percent and preferably less than 30 percent.
  • the builder is commercially available under the tradename of Sokalan t mCP45. This is a partially neutralized copolymer of acrylic acid and maleic anhydride sodium salt. Sokalan t mCP45 is classified as a suspending and anti-deposition agent. This suspending agent has a low hygroscopicity.
  • Another builder salt is Sokalan TM CP5 having a molecular weight of 70,000 which is a completely neutralized version of CP45.
  • An objective is to use suspending and anti-redeposition agents that have a low hygroscopicity.
  • Copolymerized polyacids have this property, and particularly when partially neutralized.
  • Acusol t m64ND provided by Rohm Haas is another useful suspending agent.
  • aluminosilicates both of the crystalline and amorphous type.
  • Various crystalline zeolites i.e. alumino-silicates
  • alumino-silicates are described in British Patent No. 1,504,168, U.S. Patent No. 4,409,136 and Canadian Patent Nos. 1,072,835 and 1,087,477.
  • An example of amorphous zeolites useful herein can be found in Belgium Patent No. 835,351.
  • the zeolites generally have the formula wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium.
  • a typical zeolite is type A or similar structure, with type 4A particularly preferred.
  • the preferred aluminosilicates have calcium ion exchange capacities of 200 mllliequivalents per gram or greater, e
  • the alkali metal silicates are useful anti-corrosion agents which function to make the composition anticorrosive to eating utensils and to automatic dishwashing machine parts.
  • the preferred silicates are sodium disilicate and sodium metasilicate.
  • any compatible anti-foaming agent can be used.
  • Preferred anti-foaming agents are silicone anti-foaming agents. These are alkylated polysiloxanes and include polydimethyl siloxanes, polydiethyl siloxanes, polydibutyl siloxanes, phenyl methyl siloxanes, trimethysilanated silica and triethylsilanated silica.
  • a suitable anti-foaming agent is Silicone TP-201 from Union Carbide.
  • Suitable anti-foaming agents are Silicone DB700, DB100 used at 0.2 to 1.0 percent by weight, sodium stearate used at a concentration level of 0.5 to 1.0 weight percent and 1.0 weight percent, and LPKn 158 (phosphoric ester) sold by Hoechst used at a concentration level of 0 to 1.5 weight percent, more preferably 0.1 to 1.0 weight percent.
  • the perfumes that can be used include lemon perfume and other natural scents.
  • any opacifier that is compatible with the remaining components of the detergent formulation can be used.
  • a useful and preferred opacifier is titanium dioxide at a concentration level of 0 to 1.0 weight percent.
  • a key aspect is to keep the free water (non-chemically bounded water) in the detergent composition at a minimum. Absorbed and adsorbed water are two types of free water, and comprise the usual free water found in a detergent composition. Free water will have the affect of deactivating the enzymes.
  • the detergent composition of the present invention can include a peroxygen bleaching agent at a concentration level of 0 to 20 weight percent, more preferably 0.5 to 17 weight percent and most preferably at 1.0 to 14 weight percent.
  • the oxygen bleaching agents that can be used are alkali metal perborate, percarbonate, perphthalic acid, perphosphates, and potassium monopersulfate.
  • a preferred compound is sodium perborate monohydrate and dihydrate.
  • the peroxygen bleaching compound is preferably used in admixture with an activator at a concentration of 1 to 5 weight percent. Suitable activators are those disclosed in U.S. Patent No. 4,264,466 or in column 1 of U.S. Patent No. 4,430,244, both of which are herein incorporated by reference. Polyacetylated compounds are preferred activators. Suitable preferred activators are tetraacetyl ethylene diamine ("TAED”), pentaacetyl glucose and ethylidenebenzoate acitate.
  • TAED
  • the activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water.
  • the detergent formulation also contains a mixture of a protease enzyme and an amylase enzyme and, optionally, a lipase enzyme that serve to attack and remove organic residues on glasses, plates, pots, pans and eating utensils.
  • Lipolytic enzymes can also be used in the powdered automatic dishwasher detergent composition. Proteolytic enzymes attack protein residues, lipolytic enzymes fat residues and amylolytic enzymes starches. Proteolytic enzymes include the protease enzymes subtilisn, bromelin, papain, trypsin and pepsin. Amylolytic enzymes include amylase enzymes. Lipolytic enzymes include the lipase enzymes.
  • the preferred amylase enzyme is available under the name Maxamyl, derived from Bacillus licheniformis and is available from Gist-brocades of the Netherlands in a prill form (activity of about 5,000 TAU/g).
  • the preferred protease enzyme is available under the name Maxacal derived from Bacillus alcalophilus, and is supplied by Gist-Brocades, of the Netherlands in a prill form (activity of about400 KADU/g).
  • Preferred enzyme activates per wash are Maxacal 200 to 700 KADU/g and Maxamyl 625 to 4000 TAU/g per wash.
  • the weight ratio of the proteolytic enzyme to the amylolytic enzyme in the powdered automatic dishwasher detergent compositions is 8:1 to 1:1, and more preferably 4.5:1 to 1.1:1.
  • the detergent composition can have a fairly wide ranging composition.
  • the surfactant can comprise 0 to 15 percent by weight of the composition, more preferably 0.1 to 15 percent by weight, and most preferably 1 to 12 percent by weight.
  • the soil suspending agent which is preferably a copolymerized polyacrylic acid will be present in an amount of 0 to 20 percent by weight, more preferably 3 to 15 percent by weight and most preferably 5 to 15.0 percent by weight.
  • the anti-foaming agent will be present in an amount of 0 to 1.5 percent by weight, more preferably 0.1 to 1.2 percent by weight and most preferably 0.3 to 1 percent by weight.
  • the builder system which is preferably an alkali metal tripolyphosphate and/or an alkali metal pyrophosphate, is present in an amount of 2 to 40 percent by weight, more preferably 4 to 40 percent by weight and most preferably 5 to 35 percent by weight for a standard product, however, for a concentrated formula, the alkali metal tripolyphosphate is present in an amount of 10 to 65 wt. percent, more preferably 15 to 65 percent by weight and most preferably 15 to 62 percent by weight.
  • the builder system also can contain a low molecular weight polyacrylate type polymer at a concentration level of 0 to 20 weight percent, more preferably 1.0 to 17 weight percent and most preferably about 2 to about 14 weight percent.
  • the alkali silicate which is a corrosion inhibitor, wherein sodium disilicate is preferred, will be present in an amount of 0 to 30 percent by weight, more preferably 3 to 30 percent by weight and most preferably 4 to 28 percent by weight.
  • the opacifier will be present in an amount of 0 to 1.0 percent by weight, more preferably 0.1 to 7 percent by weight and most preferably 0.5 percent by weight.
  • the enzymes will be present in a prilled form as supplied by Gist Brocades at a concentration of 0.8 to 22.0 percent by weight, more preferably 0.9 to 20.0 percent by weight, and most preferably 1.0 to 18.0 percent by weight.
  • the protease enzyme prills in the automatic dishwashing composition will comprise 0.5 to 15.00 percent by weight, more preferably 0.7 to 13.0 weight percent and most preferably 0.8 to 11.0 percent by weight.
  • the amylase enzyme prills will comprise 0.3 to 8.0 percent by weight, more preferably 0.4 percent to 7.0 weight percent and most preferably 0.5 to 6.0 weight percent.
  • the lipase enzyme prills will comprise 0.00 to 8.0 percent by weight of the detergent composition.
  • a typical lipase enzyme is Lipolas 100 T from Novo Nordisk of Denmark.
  • the lipase enzymes are especially beneficial in reducing grease residues and related filming problems on glasses and dishware.
  • Another useful lipase enzyme is Amaneo PS lipase provided by Amaneo International Enzyme Co., Inc.
  • perfumes will comprise 0.1 to 5.0 percent by weight of the detergent composition.
  • One method of producing the detergent powder formulation consisting first of spraying and absorbing nonionic surfactant into the phosphate and carbonate builder salts and mixed thoroughly in a rotary drum. The absorbed builder salt was then aged overnight to completely absorb the nonionic to form a free flowing powder which was then mixed with sodium sulfate and silicate in a twin-shelled blender. Finally, enzyme prills were added and mixed thoroughly to form a free flowing detergent powder.
  • Another method of producing the powder detergent formulation having a bulk density of 0.90 is to spray dry by any conventional means the nonionic surfactant and defoamer into the perborate bleach compound and the builder salt. This spray dry materials can be used immediately, but it is preferred to age then for 24 hours. The spray dried materials are dry blended in any suitable conventional blender such as a tumble blender at about room temperature with the other ingredients of the composition until a homogenous blend is obtained.
  • compositions also can be produced as low density powders according to the procedure as set forth in U.S. Patent 4,931,203, wherein these powders have a bulk density 1/3 less than the standard powders which have a bulk density of about 1.0 kg/liter.
  • the bulk density of these powders can be less than 0.7 kg/liter.
  • the concentrated powdered nonionic automatic dishwashing detergent compositions of the present invention disperses readily in the water in the dishwashing machine.
  • the presently used home dishwashing machines have a measured capacity for 80cc or 90 grams of detergent. In normal use, for example, for a full load of dirty dishes 60 grams of powdered detergent are normally used.
  • the normal operation of an automatic dishwashing machine can involve the following steps or cycles: washing, rinse cycles with cold/hot water and rinse cycles with hot water.
  • the entire wash and rinse cycles require 60 minutes.
  • the temperature of the wash water is 40°C to 65°C and the temperature of the rinse water is 55°C to 65°C.
  • the wash and rinse cycles use 4 to 7.5 liters of water for the wash cycle and 4 to 7.5 liters of water for the hot rinse cycle.
  • the concentrated powdered automatic dishwashing detergent compositions exhibit excellent cleaning properties and because of the high concentration of the detergent in the composition, the detergent is not totally consumed during the wash cycle or totally eliminated during the rinse cycle such that there is a sufficient amount of detergent remaining during the rinse cycle to substantially improve the rinsing.
  • the washed and dried dishes are free of undesirable traces, deposits or film due to the use of hot water in the rinse cycle.
  • compositions do not contain clays such as bentonites and laponites, the addition of these types of clays to the instant invention would cause an increased spotting of glassware during the washing cycle.
  • a free flowing, highly soluble standard density powder auto-dish detergent was developed by absorbing nonionic surfactant (Union Carbide Tergitol MDS-42) on highly absorptive sodium tripolyphosphate Oxy Chem HRS 3342.
  • High soluble sodium silicate PQ Corporation HS 240
  • granular sodium sulfate Kerr-McGee Corporation Trona
  • granular sodium carbonate Allied Chemical dense soda ash
  • the finished product was aged over a period of two days to give a nice dry free-flowing powder.
  • the product was tested with 50g dose using the ASTM spotting and filming test method combined with denatured egg soiled (egg yolk denatured with 2.5 M CaC1 2 solution) along with baked-on oatmeal soiled substrates against non-enzyme powder ADD, bleach-containing powder ADD prototype and CASCADE powder ADD supplied +P+G with 50g dose and PALMOLIVE AUTOMATIC Liquid ADD supplied by Colgate Palmolive with 80g dose.
  • the cleaning performance tests were run at 120°F wash cycle temperatures using tap water (ca. 115 ppm water hardness).
  • the finished product is aged over two days to give a nice dry free-flowing powder.
  • Example 2 Laboratory performance of the compositions of Example 2 were carried out using multi-soils. This was done to show differences between the prototype formulations and commercial products.
  • Egg soil was prepared by mixing egg yolk with an equal amount of 2.5 N calcium chloride solution. This mixture was applied as thin crosswise film to the usable surface of 7.5 inch china plates. The plates were aged in 50% relative humidity overnight.
  • Oatmeal soil was prepared by boiling 24 grams of Quaker Oats in 400 ml of tap water for ten minutes. Three grams of this mixture was spread as thin film onto a 7.5 inch china plate. The plates were aged for 2 hours at 80°C. They were then stored overnight at room temperature. Two plates of each egg and oatmeal were used per wash. The plates were placed in the same positions in the dishwasher.

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EP19920401477 1991-05-31 1992-05-29 Phosphate-containing powder automatic dishwashing composition with enzymes Withdrawn EP0516555A3 (en)

Applications Claiming Priority (2)

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US70856891A 1991-05-31 1991-05-31
US708568 1996-09-05

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AU (1) AU654009B2 (de)
CA (1) CA2069849A1 (de)
FI (1) FI922492A (de)
GR (1) GR920100244A (de)
IE (1) IE921743A1 (de)
NO (1) NO922051L (de)
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PT (1) PT100534A (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2283494A (en) * 1993-11-03 1995-05-10 Procter & Gamble Machine dishwashing
WO1996017047A1 (en) * 1994-11-29 1996-06-06 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
EP2428572A2 (de) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alpha-Amylase Varianten der Gattung Bacillus alcalophilus, Zusammensetzungen mit Alpha-Amylase Varianten und Anwendungsverfahren
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
US20140261585A1 (en) * 2013-03-15 2014-09-18 Whirlpool Corporation Dishwasher
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU656375B2 (en) * 1991-05-31 1995-02-02 Colgate-Palmolive Company, The Powdered automatic dishwashing composition containing enzymes
US5173207A (en) * 1991-05-31 1992-12-22 Colgate-Palmolive Company Powered automatic dishwashing composition containing enzymes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0425214A2 (de) * 1989-10-23 1991-05-02 Unilever Plc Enzymhaltige Waschmittelzusammensetzungen und deren Verwendung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8321923D0 (en) * 1983-08-15 1983-09-14 Unilever Plc Machine-dishwashing compositions
GB8328075D0 (en) * 1983-10-20 1983-11-23 Unilever Plc Dishwashing compositions
NZ230842A (en) * 1988-10-21 1992-05-26 Colgate Palmolive Co Nonionic heavy duty particulate detergent containing protease, amylase and cellulase

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0425214A2 (de) * 1989-10-23 1991-05-02 Unilever Plc Enzymhaltige Waschmittelzusammensetzungen und deren Verwendung

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2283494A (en) * 1993-11-03 1995-05-10 Procter & Gamble Machine dishwashing
WO1996017047A1 (en) * 1994-11-29 1996-06-06 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching
US5703027A (en) * 1994-11-29 1997-12-30 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching
EP2428572A2 (de) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alpha-Amylase Varianten der Gattung Bacillus alcalophilus, Zusammensetzungen mit Alpha-Amylase Varianten und Anwendungsverfahren
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
US20140261585A1 (en) * 2013-03-15 2014-09-18 Whirlpool Corporation Dishwasher
US9861258B2 (en) * 2013-03-15 2018-01-09 Whirlpool Corporation Dishwasher
US10561295B2 (en) 2013-03-15 2020-02-18 Whirpool Corporation Dishwasher

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IE921743A1 (en) 1992-12-02
NZ242824A (en) 1995-04-27
AU654009B2 (en) 1994-10-20
AU1620792A (en) 1992-12-03
FI922492A (fi) 1992-12-01
FI922492A0 (fi) 1992-05-29
EP0516555A3 (en) 1994-07-20
PT100534A (pt) 1994-01-31
NO922051L (no) 1992-12-01
NO922051D0 (no) 1992-05-25
GR920100244A (el) 1993-03-31
CA2069849A1 (en) 1992-12-01

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