NZ242826A

NZ242826A - Powdered dishwashing detergent containing protease and amylase enzymes

Info

Publication number: NZ242826A
Application number: NZ24282692A
Authority: NZ
Inventors: Julien Drapier; Patrick Durbut; U Ahmed Fahim
Original assignee: Colgate Palmolive Co
Priority date: 1991-05-31
Filing date: 1992-05-20
Publication date: 1995-04-27
Also published as: CA2069854A1; NO922048L; NO922048D0; FI922489A0; GR920100242A; PT100539A; FI922489A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £42826 2 4 2 b ^ Cuiiipte'.a Cro.".ificat zn Class: Jl.itvOXlffi,. f.'/tf ;/ly* Publication Da: j: . ? ?. A^?-!??? P.O Joj'P-:. W NO nr Patents Form No. 5 PATENTS ACT 1953 Number Dated 20 MAY \192n COMPLETE SPECIFICATION 1 f\ v?<" <s /•' POWDERED AUTOMATIC DISHWASHING COMPOSITION CONTAINING ENZYMES We, COLGATE-PALMOLIVE COMPANY, of 300 Park Avenue, New York 10022, United States of America, a corporation organized under the laws of the State of Delaware, United States of America do hereby declare the invention for which I/we pray that a Patent may be granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 - (Followed by page la) It has been found co be very useful to have enzymes in •dishwashing detergent compositions because enzymes are very •rft-rctive in removing food soils from the surface of glasses, dishes, pots, pans and eating utensils. The enzymes attack those materials while other components of the detergent will •effect other aspects of the cleaning action. However, in order for the enzymes to be highly effective, the composition must be chemically stable, and it must maintain an effective activity at the operating temperature of the automatic dishwasher. Chemical stability, such as to bleach agents, is the property whereby the detergent composition containing enzymes does not undergo any significant degradation during storage. Activity is the property of maintaining enzyme activity during usage. From the time that a detergent is packaged until it is used by the customer, it must remain stable. Furthermore, during customer usage of the dishwashing detergent, it must retain its activity. Unless the enzymes in the detergent are maintained in a minimum exposure to moisture or water, the enzymes will suffer a degradation during storage which will result in a product that will have a decreased activity. When enzymes are a part of the detergent composition, it has been found that the initial water content -.a r:ss;cle, and this lew water concent must be maintained during storage, since water will deactivate the enzymes. This deactivation will cause a decrease in the initial activity of *r.e detergent coniposition. After the detergent container is opened, the detergent will be exposed to the environment which contains moisture, luring 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 which 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 about 2 242 8. 6 : . 5 . This lew alkalinity cr the dishwashing detergent, maintain the stahility cf the detergent composition rcr.tams a mixture of enzymes, thereby providing a :-.:gr.er initial activity of the mixture cf the er.zyrr.es and the r.amtenance cf this initial high activity. A rr.a: cr concern in the use of automatic dishwashing ccrr.pcsiticr.s is the formulation of phosphate-free compositions which are safe to the environment while maintaining superior cleaning performance and dish care. The present invention teaches the preparation and use of powdered automatic dishwashing compositions which are phosphate-free and have superior cleaning performance and dish care. 15 SUMMARY OF THE INVENTION This invention is directed to producing powdered phosphate-free enzyme-containing automatic dishwashing detergent compositions that have an increased chemical - q -tvi'ji 1 it\ jnri t-ssent la I 1> high arti\it\ at wash operating taiperatures of 40 °C to 65 °C, wherein the composition also can be used as a ^ laundry pre-soaking agent. This is accomplished by controlling the alkalinity of the detergent composition and using a unique mixture of enzymes. An alkali metal silicate 2 5 i!«.i> be u-ed in the powdered dishwashing detergent corposi t ions. The preferred builder system of the instant compositions comprises a mixture of sodium carbonate and/or sodium citrate and a low molecular weight polyacrylic polymer. It is to be understood that the term powder in this -30 invention includes within its definition tablets, soluble 3 L. . £ • ^ - rarsul^s a:i;i soluble sachet. It is also possible tic use the :r.s:3::t compositions as a laundry presoaking powder. ror.ver.ticr.al powdered automatic dishwashing compositions usually ccr.tair. a low foaming surface-active agent, a chlorine c, leach, alkaline builder materials, and usually minor ingredients and additives. The incorporation of chlorine cleach requires special processing and storage precautions to protect composition components which are subject to deterioration upon direct contact with the active chlorine. The stability of the chlorine bleach is also critical and raises additional processing and storage difficulties. In addition, it is known that automatic dishwasher detergent compositions may tarnish silverware and damage metal trim on china as a result of the presence of a chlorine-containing bleach therein. Accordingly, there is a standing desire to formulate detergent compositions for use in automatic dishwashing operations which are free of active chlorine and which are capable of providing overall hard surface cleaning and appearance benefits comparable to or better than active chlorine-containing detergent compositions. This reformulation is particularly delicate in the context of automatic dishwashing operations, since during those operations, the active chlorine prevents the formation and/or deposition of troublesome protein and protein-grease complexes on the hard dish surfaces and no surfactant system currently known is capable of adequately performing that function. Various attempts have been made to formulate bleach-free low foaming detergent compositions for automatic dishwashing 4 ^ ? .1 b L Q •• ; . • .r.tair.i:: j particular 1 -w reading nomcnics, filler materials and enzymes. US Patent: 3,472,783 - .Srr.ille reccgmzea that degradation of the enzyme can occur, an enzyme is added to a highly alkaline automatic * • ^ »-3 r-> nvrranh j _» O »•" vi O * i ^ W W * *J V •• w • French Patent No. 2,102,851 to Colgate-Palmolive, pertains rinsing and washing compositions for use in automatic iishvashers. The compositions disclosed have a pH of 6 to 7 ir.i contain an amylolytic and, if desired, a proteolytic enzyme, which have been prepared in a special manner from "-inirvil pancreas and which exhibit a desirable activity at a pH :r. the range of 6 to 7. German Patent No. 2,038,103 to Henkel i 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 4,101,457, to Place et al., teaches the use of a proteolytic enzyme having a maximum activity at a pH of 12 in an automatic dishwashing detergent. US Patent 4,162,987, to Maguire et al., teaches a granular or liquid automatic dishwashing detergent which uses a proteolytic enzyme having a maximum activity at a pH of 12 as well as an amylolytic enzyme having a maximum activity at a pH Of 8. US Patent No 3,827,938, to Aunstrup et al., discloses specific proteolytic enzymes which exhibit high enzymatic 5 24 f •. r .•.. a 1 i ?yst-.rr.8. Sirr.ilar disclosures j;---- round -r. British Patent Specif icat ion N'o. 1,351,386, to Novo Terapeutisk Labcracoriur. A/S. British Patent Specification No. 1,296,839, to Novo Terapeutisk Laboratorium A/£, discloses specific amylolytic pnzymes which exhibit a r.igh degree of enzymatic activity in alkaline systems. Thus, while the prior art clearly recognizes the disadvantages of using aggressive chlorine bleaches in automatic dishwashing operations and also suggests bleach-free compositions made by leaving out the bleach component, said irt disclosures are silent about how to formulate an effective bleach-free powdered automatic dishwashing compositions capable of providing superior performance during conventional use. US Patent Nos. 3,821,118 and 3,840,480; 4,568,476, 4,501,681 and 4,692,260 teach the use of enzymes in automatic dishwashing detergents, as well as Belgian Patent 895,4 59; French Patents 2,544,393 and 1,600,256; European Patents 2 56,679; 266,904; 271,155; 139,329; and 135,226; and Great 3ritain Patent 2,186,884. The aforementioned prior art fails to provide a powdered automatic dishwashing detergent which'is phosphate-free and contains a mixture of enzymes for the simultaneous degradation of both proteins and starches, wherein the combination of enzymes have a maximum activity at a pH of less than 11 to 12 as measured by Anson method and the powdered automatic dishwashing detergent has optimized cleaning performance in a temperature range of 40°C to 65°C. 6 / < " > fc. -T 0 £• nxture :r. a pr.csphate-free, powdered automatic dishwasher :e:erger.t composition fcr use m automatic dishwashing p:-rat::r.s capable of providing at least equal or better : errar.ce to conventional automatic dishwashing compositions v„ -renting temperatures cf 43°C to 65°C. rFTAILEr ~£SCRI?T:CN The present invention relates to a powdered automatic iishwashing detergent compositions which comprise a nonionic i * • «. *; > * i» ti.,1 1 1 \ jii .llkali riit.il silifiitf. a phv-'spha ti*-lrt'i' bijilci-r system, a peroxygen compound with activator as a bleaching agent and a mixture of an amylase enzyme and a protease enzyme, wherein the powdered automatic dishwashing detergent composition has a pH of less than 11.5 in the washing liquor at a concentration of 10 grams per liter of water 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. The 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 are 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 7 :.y nature . Practically any hydrophobic ccrr.pcur.d .-.av:::.? a carboxy, hydroxy, amiao or amino group with a free nydrogen attached to the oxygen or the nitrogen can be condensed with ethylene oxide or propylene oxide or with the -1 y • • y a r a 11 on product thereof, polyethylene glycol, to form a r.cncmc detergent. The length of the hydrophilic or polyoxy •ethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those disclosed in "S Patent Nos. 4,316,812 and 3,630,929. Preferably, the nonionic detergents that are used are the low-foaming polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of an 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. Of such materials it is preferred to employ those wherein the higher alkanol is a high fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 15 or 5 to 16 lower alkoxy groups per mole. Preferably, 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. Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole. 8 series :rem 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,j-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide). Product 3 (a C13-Cu fatty alcohol condensed with 7 mole propylene oxide and 4 mole ethylene oxide), and Product C (a C,j•• Cj5 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide). Particularly good surfactants are Plurafac LF132 and LF 231 which are capped nonionic surfactants. Another liquid nonionic surfactant that can be used is sold under the tradename Lutensol SC 9713. Synperonic nonionic surfactant from ICI such as Synperonic LF/D25 are especially preferred nonionic surfactants that can be used in the powdered automatic dishwasher detergent compositions of the instant invention. Other useful surfactants are Neodol 25-7 and Neodol 23-6.5, which products 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 atoms linear 9 Ian tor :s a similar product but with nine moles of ethylene :xide being reacted. Also useful in the present compositions as a component of nonionic detergent are higher molecular weight nonionics, such as N'eodol 45-11, which are similar ethylene cxide condensation products of higher fatty alcohols, with the nigher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also made by Shell Chemical Company. In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophilic moieties the number of lower alkoxies will 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 alkylpolysaccharides are surfactants which are also useful alone or in conjunction with the aforementioned surfactants and have 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 10 surfactant. For a particular alkylpolysaccharide molecule x :an cr.ly assume integral values. Ir. any physical sample car. characterized by the average value of x and this average •"•il.:e car. assume r.or. - integral values. In this specification tho values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or 4-r.csitiens rather than at the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside). However, attachment through the 1-position, i.e., glucosides, galactosides, fructosides, etc., is preferred. In the preferred product the 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. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide chain, the preferred alkoxide moiety is ethoxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 20, preferably from 10 to 16 carbon atoms. Preferably, 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, most preferably 0, alkoxide moieties. Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, 11 :ruc:cs:des, fructosyls, lactcsyls, gluccsyis and/or jalactcsyis and mixtures thereof. The alkyl monosaccharides are relatively less soluble m water thar. the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkyl monosaccharides are sclubilized to some extent. The use of alkyl monosaccharides in admixture with alkylpolysaccharides 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: RjOI^OlrlZ), 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 10 to 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 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (RjOH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkylpolyglucosides can be prepared by a two step procedure in which a short chain alcohol (R,OH) an be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively 12 p r-re-dure ir. which a shore chain alcchcl C. is reacted with sluccse :r a poiyglucoside (x=2 to 4, to yield a short chair, alkyl glucoside ;x»l to 4) which can m turn be reacted with a !::^er chair, alcohol (E:OH; to displace the short chain alcohol and obtain the desired alkylpolyglucoside. If this two step procedure is used, the short chain alkylglucoside content of the final alkylpolyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkylpolyglucoside. The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkylpolysaccharide surfactant is preferably less than about 2%, more preferably less than 0.5% by weight of the total of the alkylpolysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than 10%. The used herein, "alkyl polysaccharide surfactant" is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkyl polysaccharide surfactants. Throughout this specification, "alkyl poiyglucoside" is used to include alkyl- polyglycosides because the stereo chemistry of the saccharide moiety is changed during the preparation reaction. An especially preferred APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA. APG 625 is a nonionic alkyl polyglycoside characterized by the formula: C^.CMQH.oCV.H 13 w.-.oreir. r. = 10;2%); r. = 12(65%); r.» 14(21-28%}; n=16(4-8%) and 3.5%) and x (degree of polymerization) = I.e. APG 625 r.as: a cH of 6-8(10% of APG 625 in distilled water); a specific gravity at 25°C of 1.1 grams/ml; a density at 25aC of '.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. Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases advantages can be obtained by the use of such mixtures. The liquid nonaqueous nonionic surfactant is absorbed on a builder system which comprises a mixture of phosphate"free particles which is a builder salt and a low molecular weight polyacrylate type polymer such as a polyacrylate organic and/or inorganic detergent builders. A preferred solid builder salt is an alkali carbonate such as sodium carbonate or an alkali metal citrate such as sodium citrate or a mixture of sodium carbonate and sodium citrate. When a mixture of sodium carbonate and sodium citrate is used, a weight ratio of sodium citrate to sodium carbonate is 9:1 to 1:9, more preferably 3:1 to 1:3. Other builder salts which can be mixed with the sodium carbonate and/or sodium citrate are gluconates phosphonates and nitriloacetic acid salts. In conjunction with the builder salts are optionally used 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 SokalantmCP45 manufactured by BASF and having a molecular weight of 70,000. Another preferred low molecular 14 ir.z Haas and having a molecular weighs c: 4.5C:. Noraso rcmpnses LMW45NT sprayed or. 74% soda ash. 5oicalar--?1CP45 is a copolymer of ar. acrylic acid and an acid anhydride. Such a material should Lave a water absorption at •9 r and 7 5 percent relative humidity cf less than 4 0 percent and preferably less than 3 0 percent. The builder is commercially available under the tradename of SokalanttBCP45. This is a partially neutralized copolymer of metacrylic acid and maleic anhydride sodium salt. SokalanwCP45 is classified as a suspending and anti-deposition agent. This suspending agent has a low hygroscopicity. Another builder salt is SokalanTPS having a molecular weight of 70,000. 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. Acusolln,640ND provided by Rohm Haas is another useful suspending and anti-redepositing agent. Another class of builders useful herein are the aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeolites (i.e. alumino-silicates) are described in British Patent No. 1,504,168, U.S. Patent No. 4,4 09,13 6 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 (M2O),(Al2Oj)y(Si02), wHjO 15 : to «, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, with type 4A :articularly preferred. The preferred aiuminosiiicates have :al?ium lor. exchange capacities of about 200 milliequivalents per grarr. or greater, e.g. 400 mea/g. The alkali metal silicates are useful anti-corrosion ager.ts which function to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts. Sodium silicates of Na:0/Si0: ratios of from 1:1 to 1:3.4, more preferably 1:1 to 1:2.8. Potassium silicates of the same ratios can also be used. The preferred silicates are sodium disilicate (anhydrous), sodium disilicate (hydrated) and sodium metasilicate and mixtures thereof, wherein the preferred silicate is hydrated disilicate. Essentially, 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, dimethyl silinated silica, trimethysilanated silica and triethylsilanated silica. A suitable anti-foaming agent is Silicone TP-201 from Union Carbide. Other suitable anti-foaming agents are Silicone DB700 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 LPKN 158 (phosphoric ester) sold by Hoechst used at a concentration level of 0 to 1.5 weight percent, more 16 r.e .:sed i::clu;:o lemon perfume and ctr.er natural scents. Essentially, any cpacifier that is compatible with the regaining ccrr.pcne-r.ts cf the detergent formulation can be used. A useful and preferred cpacificr is titanium dioxide at a rcr.cer.trat icr. level of 0 to 1.0 weight percent. A key aspect is to keep the free water (non-chemically cor.ded 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- enoym.es. The detergent composition of the present invention includes a peroxygen bleaching agent at a concentration level of about 0 to about 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. The peroxygen bleaching compound is preferably used in admixture with an activator at a concentration level of 1-5 wt. 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. Polyacetylated compounds are preferred activators. Suitable preferred activators are tetraacetyl ethylene diamine ("TAED"), pentaacetyl glucose and ethylidenebenzoate acetate. 17 w a t e r . The ietorger.t iemulation also contains a mixture of a prctc-c.y11c 6r.;',~? ans an arr.yictytic enzyme and, opt.lonaiiy, 61 lipolytic enzyme that serve to attack and remove organic residues cn glasses, plates, pots, pans ana eating utensils. rrteclytic enzymes attack protein residues, lipolytic enzymes :at residues and amylolytic enzymes starches. Proteolytic -r.nyr.es include the protease enzymes subtilism, bromelin, papain, trypsin and pepsin. Amylolytic enzymes include i.r.ylase enzymes. Lipolytic enzymes include the lipase •r.r.ymes. The preferred amylase enzyme is available under the name Maxamyl, derived from Bacillus licheniformis and is available from Gist-brocades of the Netherlands available in the form of a prill having an activity of about 6,000 TAU/g. One of 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 about 329KADU/g.). Preferred enzyme activates per wash are Maxacal - 300-700 KADU per wash and Maxamyl-2,000 to 4,000 TAU per wash. Another preferred protease enzyme is available under the name Maxatase derived from a novel Bacillus strain designated "PB92" wherein a culture of the Bacillus is deposited with the Laboratory for Microbiology of the Technical University of Delft and has a number OR-60, and is supplied by from Gist-Brocades, of the Netherlands in a prill 18 wr.ere ir. scdiur. disilicate is preferred, will be present ir. an a-cunt cf about : tc percent by weight, rr.cre preferably accu: 2 to about 2 3 percent by weight ana most preferably about 4 to about 23 percent by weight. The opacifier will be present in an amount of about 0 to about 1.0 percent by weight, more preferably about 0.1 to about 7 percent by weight and most preferably about 0.4 percent by weight. The enzymes will be present in an amount in a prill form as supplied by Gist-Brocades at a concentration of about 0.6 to 22.0 percent by weight, more preferably about 0.9 to 20.0 percent by weight, and most preferably about 1.0 to about 18.0 percent by weight. The protease enzyme prills in the automatic dishwashing composition will comprise about 0.5 to about 15.00 percent by weight, more preferably about 0.7 to about 13.0 weight percent and most preferably about 0.8 to about 11.0 percent by weight. The amylase enzyme prills will comprise about 0.3 to about 8.0 percent by weight, more preferably about 0.4 percent to about 7.0 weight percent and most preferably about 0.5 to about 6.0 weight percent. The lipase enzyme will comprise about 0.00 to about 8.0 percent by weight of the detergent composition. A typical lipase enzyme is Lipolase 100 T from Novo Corporation. The lipase enzymes are especially beneficial in reducing grease residues and -"Vi NT' related filming problems on glasses and dishware. Anotheri*** ^ n'l 19 * 20 FEB 1995 ""J International Enzyme Co., Inc. Other components such as perfumes will comprise about O.i to about 5.0 percent by weight of the detergent composition. One method of producing the powder detergent formulation having a bulk density of about 0.8 is to spray dry by any conventional means the nonionic surfactant and defoamer onto the perborate bleach compound and the builder salt. This spray dry materials can be used immediately, but it is preferred to age it 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. The weight ratio of the proteolytic enzyme to the amylolytic enzyme in prill form the powdered automatic dishwasher detergent compositions is 6:1 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 about 1 to 12 percent by weight. The anti-foaming agent will be present in an amount of about 0 to about 1.5 percent by weight, more preferably about 0.1 to about 1.2 percent by weight and most preferably about 0.1 to about 1 percent by weight. The builder system, which is preferably sodium carbonate and/or sodium citrate, is present in an amount of 2 to 40 percent by weight, more 20 :::vLe-racly 4 to 4 0 er-er.t weight sr.A r.os t preferably r to 3 0 percent by weight. The builder system also preferably contains the low molecular weight polyacrylate type polymer at a concentration level of about 0 to 20 weight percent, more preferably 1.0 to 17 weight percent and most preferably a to 17 weight percent. The composition also includes the peroxygen bleaching agent at a concentration of about 0 to 20 wt. percent and the activator at a concentration of about 1 to 5 wt. percent. The alkali silicate, which is a corrosion inhibitor, wherein sodium disilicate is preferred, will be present in an amount of 0 to 40 percent by weight, more preferably 3 to 40 percent by weight and most preferably 4 to 40 percent by weight. The opacifier will be present in an amount of 0 to 1.0 percent by weight, more preferably 0.1 to 0.7 percent by weight and most preferably about 0.4 percent by weight. The enzymes will be present in an amount in a prill 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 21 typical lipase er.zyre is Lipolase ZZ27 from Novo Corporation. The lipase enzymes are especially beneficial in reducing grease residues and related filming problems on glasses and cishware. Another useful lipase enzyme is Amano PS lipase provided by Amano International Enzyme Co., Inc. Other components such as perfumes will comprise 0.1 to 5.0 percent by weight of the detergent composition. One method of producing the powder detergent formulation having a bulk density of 0.8 is to spray dry by any conventional means the nonionic surfactant and defoamer onto the perborate bleach compound and the builder salt. This spray dry materials can be used immediately, but it is preferred to age it 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. The instant 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 less than the bulk density of the bulk density of the standard powders which have a bulk density of about 0.8 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 22 powdered detergent are normally used. In. accordance with the present invention only about 19 cc :r abo^L 15 grams of the concentrated powdered detergent rorr.position is needed. The normal operation of an automatic dishwashing machine can involve the following steps or cycles washing, rinse cycles with cold water and rinse cycles with hot water. The entire wash and rinse cycles require about 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 highly 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. DESCRIPTION OF THE PREFERRED EMBODIMENTS Example i 23 I L\ c . The ::r.cer.:rated powdered r.or.icn:: surfactant detergent '-•exposition was formulated from the following ingredients in the amounts specified according to the previously defined and described dry blending process. 24 TABLE I RAH MATERIALS FORMULA COMPOSITIONS (IN PARTS) A B C D E F G H I Anhydrous Sodium Metasi1icate 23 23 23 23 23 2 3 - - - Sodium Disilicate (22% water) - - - - - - 33 33 33 Nonionic coated Maxacal at 330 KADU/g 8.0 16.0 10.9 10.9 " . Nonionic coated Maxamyi at 5800 TAU/g ~ • 6.9 6.9 6.9 • • ' Nonionic coated Maxatase at 440 KDU/g " ' " " PEG coated Maxacal at 350 KADU/g - - - - - - 13 13 13 I 25 PEG coated Maxamyi at 5900 TAU/g - - - - - - 5 5 & PEG coated Maxapem CX30 at 600 KADU/g " ■ SOKALAN CP 45 at 60% water from BASF 10 10 10 10 10 10 10 10 15 SODA ASH 34 .2 34 .2 34 .2 34 .2 34 .2 34 .2 10 10 10 1 Sodium Citrate Dehydrated - - - - - - 11 11 6 1 TAED - - - • - - 3 - 3 Silicone DB100 0 . 5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Synperonic LFD25 4 . 5 4.5 4.5 4.5 4.5 4.5 0.5 0.5 0.5 Sodium Perborate Monohydrated 10 10 10 10 10 10 10 10 10 Caustic Soda - - - - - 9 - - - Lipolase 100T (Novo) - - - - - - - - 26 ?x~ir'..I-- i: Formulas A-i; or Example 1 were tested in a European style Philips 664 Dishwasher working at 55°C with a charge of 15. C grams per wash of the Formulas !A-I} and 3 ml./per wash of commercial Galaxy rinse aid soid by Colgate-Palmolive Co. The lead of items placed in the dishwasher consisted of 6 plates soiled with 3.0 grams of a mixture of 12.0 grams of porridge oats with 188 grams of water and 3 plates soiled with :.4 grams of calcium chloride denaturated egg yolk and three plates soiled with 5 grams of a microwave oven baked mixture of 177 grams of egg yolk with 50 grams of margarine and 3 cups soiled with tea after overglaze removal wherein all the plates and cups were dried prior to being placed in the dishwasher. The pH of the washing bath and the formulation were measured. The hardness of the rinse water was 38 {C,C0,) ppm. Each formulation was evaluated for spotting and filming. The results were evaluated on a scale of 1 to 10 with the higher number being the better result. 27 c #t TABLE II TEST CLEAN ING PER FORMANC 'E EVALt JATIONS (AT 55 °C) 5QIL REMOVAL A B c D E F G H I OATMEAL 7 7.5 8.5 10 10 10 10 10 10 MICROEGGS 5 7.5 9 5 7.S 9 8.8 8.2 9.0 CALCIUM EGGS 2 9 9.5 2 9.3 9 9.7 9.7 10 FILMING - _ . . 7.6 7.5 7.3 7.6 7.5 SPOTTING • - ■ - . 6.0 7.5 6.3 8.2 7*5 GLASS DAYLIGHT - - - - 8.3 9.2 8.7 TEA STAIN . _ . * . . 10 6 10 GREASY BUILD-UP ON STRAINER * — - ~ 9 5 9 7 8 GREASY BUILD-UP SPOTTING _ - ■ - : - - 8.5 7.2 8,2 FILMING .. _ . . 7.7 7.5 7.3 GLASS DAYLIGHT ' • - - - - 8.5 8,5 9.8 GREASY BUILD-UP ON STRAINER ■ — ** - • • 9.0 9.0 9.0 The above described examples of illustrative compositions of the invention were evaluated for performance according to the following laboratory test methods. All cleaning performance were carried out under European washing conditions in automatic dishwashers with a built-in heater and water softening ion-exchange resin, at a temperature range of about 50°C to about 65°C with 3ml of a rinse aid (Galaxy Rinse Aid) used in the later stages of the cycle (automatically dispersed by a built-in closing device 28 illustrative ccrr.pcsit ions were used as a simple dose per wash. In the so-called soil cleaning zest, 3 cups and 2 sets of plates were identically soiled with food itea stair., oatmeal seil, hardened egg soil and microwave cven-cooked egg soil). Th-- cup staining was obtained by using 3 cups previously filled with a 5% fluorhydric acid solution during 15 minutes :n :rder to remove the protection. The cups were washed and dried just before staining. The tea stain was prepared by adding 90 ml boiling water to one 2g dose of LIPTON yellow label tea and leaving the system at test for 20 minutes. After emptying, the cups were then allowed to dry for 12 hours. Oatmeal soil was prepared by boiling 24 grams of Quaker oats in 400 ml of tap water for ten minutes and then homogenized with a high shearing device (Ultrawax). Three grams of this mixture was spread as thin film onto 7.5 inch china plates. The plates were aged for 2 hours at 80°C, and then stored overnight at room temperature. Hardened egg soil was prepared by mixing egg yolk with an equal amount of 2.5N calcium chloride solution. 0.4 grams of this mixture was applied as a thin crosswise film to the usable surface of 7.5 inch china plates. Microwave-egg soil was prepared by mixing hot egg yolk and cooked margarine with a homogenizer (Ultraturax device). Five grams of this mixture were spread as thin film onto 7.5 inch china plates, and the soiled plates were baked afterwards for one minute in a microwave oven. The two type of egg soils were stored overnight at room 29 six clear: glasses. The twelve soiled plates, the three soiled :ups, ir.d the six glasses were always placed in the same i~iriti:::s ir. tr.e disr.washer at each run. In each test four iifferer.t compositions were assessed using a series of four iii.-:: was hers. All washed plates were scored each run by determining the percent area cleaned (percentage of soil removal) with the aid cf a reference scale of gradually cleaned plates. Average percentages of soil removal for each type of soil after four runs were converted in a 0 to 10 scale, 0 being for no soil removal and 10 for perfect cleaning. Glasses were rated in a viewing box for filming and spotting and under natural lighting for evaluation. They were rated according to a scale ranging from 0 (bad performance) to 10 (perfectly clean glasses) with the aid of reference glasses. In the multisoil cleaning test different dishware/soil combinations were used. The dishwasher load included each run six plates of oatmeal, three cups soiled with tea, one dish of white sauce, one dish of rice, four glasses soiled with tomato juice, four glasses soiled with cocoa, and four soiled with milk. Pieces of cutlery (forks, knives and spoons, six each) were also included and soiled with porridge soil, rice and rice with cheese soils. Same Latin Square procedure was used as for soil cleaning test. Percentages of soil removal on all the dishware and glasses were converted in 0 to 10 scale, 0 being for no soil 30 evaluation according to a C .bad performance) to 10 'very good perforxar.ee, scale with the aid or reference glasses. A -different, scale was used to distinguish the data from soil removal performance. Results tabulated were average of four runs In the greasy residue build-up test, the dishwasher load included six clean plates in the lower basket and six clean glasses in the upper basket. The soil load was consisting of ICO grams of a greasy soil mixture prepared by mixing mustard 42 weight V) white vinegar (33 wt. V), corn oil (15 wt. %), and lard (10 wt. %) altogether. In each test, four different compositions were assessed according to a Rubin Square procedure by using a series of four dishwashers during at the same time. 50 grains of greasy soil mixture were poured each run in the wash bath together with fifteen grams of the detergent composition used as a single dose per wash. After each run, the upper basket containing the six glasses, the cutlery basket with the plastic tiles as well as the dishwasher filter elements were moved from one dishwasher to the following one, before conducting the next run. Such a procedure was used to assess the performance of compositions on glasses and on plastic dishware surfaces under conditions of repeated washer in the presence of said greasy soil mixture. After each cycle, glasses were scored in a viewing box for filming and spotting and under natural lighting for 966d 31 perfectly clear, glasses) scale as for the so-called soil cleaning test with the aid of reference glasses. The same procedure was repeated three times using the same set cf glasses so as to calculate average performance results for each composition after 4 cycles. The dishwashers filter parts were also inspected after each cycle to evidence greasy deposit build up differences between compositions. The concentrated powdered nonionic surfactant detergent composition was formulated from the following ingredients in the amounts specified according to the previously defined and described dry blending process. 32 r TA3LS III | RAW MATERIALS l I PARTS ) FORM! TLA CO* IPOSITIC INS (IN 1 1 A B C D E F G Anhydrous Sodium 1 Metasilicate 23 23 23 23 - - - Sodium Disilicate tat 22% water) - - - - 23 23 23 Nonionic coated Maxacal at 3 30 KADU/g - 8.0 16.0 - - - - Nonionic coated Maxamyi at 5800 TAU/g - - - - 6.9 6.9 11 Nonionic coated Maxatase at 440 KDU/g 10.9 10.9 7 PEG coated Maxacal at 350 KADU/g - - - - - ! - r-j :oa:ea Maxamyi at 59 00 TAU/g PEG coated Maxanem CX30 at 600 KADU/g SOKALAN C?45 at 60% water from BASF 10 10 .10 10 10 10 10 SODA ASH 34.2 34.2 34.2 34.2 34.2 29.2 29 Sodium Citrate Dihydrated TAED SILICONE D3100 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SYNPERONIC LFD25 4.5 4.5 4.5 4-5 4.5- 4.5 4.5 SODIUM m*PCRATE MONOHYDRATED 10 10 10 10 10 10 10 CAUSTIC SODA LIPOLASE 100T (NOVO) RAW MATERIALS FORMULA COMPOSITIONS (IN PARTS) H , I J i K ; L j M in : r V.ecasilicar- - - • 1 ! j Disilicate at | 22% water) 2 3 - - ; - - i I 1 "7 4 z, * J Nonionic coated y.axcal at 23C KADU/g - - - - - - Nonionic ccated Maxamyi at EBCO TAU/g 5 5 3 3 3 5 5 Nonionic coatc-d Maxatase ac 44 0 KDU/g * * 13 * — 15 15 13 13 PEG coaced Maxcal at 35 3 KADU/g - - - - - - - PEG coaced Kaxamyl at 59 00 TAU/g - - - - - - - PEG coated Maxapen CX 3 0 at 500 KADU/g - - - - - - SOKALAN CP 4 5 at 60% water from BASF 10 10 10 10 5 10 10 SODA ASH 29 26 28.2 5 22 .7 5 31 26 26 SODIUM CITRATE DIHYDRATED - - - - - - - TAED - 3 3 3 3 3 3 SILICONE DB100 0.5 0.5 0.25 0. 75 0.5 0.5 0.5 SYNPERONIC LFD25 4.5 4.5 2.5 7.5 4.5 4.5 4.5 SODIUM PERBCRATE MONOHYDRATED 10 10 10 10 10 10 10 CAUSTIC SODA 5 5 5 5 5 1.9 1.9 35 'i lifclase :cct i ! |i '.novo) | | 1 36 r ;:o-.ulas AN :: Exarrple III w.;-s:eu a European Philips 664 Dishwasher working at 55"C with a charge of 15.. jrams per wash cf the "orr.ulas iA-.N) and 3 ml./per wash ;™.ercial Galaxy rinse aid sold by Colgate-Palmoiive Co. The Load cf items placed in the dishwasher consisted of 6 places soiled with 3.0 grams cf a mixture of 12.0 grams of porridge oats with 138 grams of water and 3 plates soiled with - .4 ararr.s of calcium chloride denaturated egg yolk and three plates soiled with 5 grams of a microwave oven baked mixture of 177 grams of egg yolk with 50 grams of margarine and 3 cups soiled with tea after overglaze removal wherein all the plates and cups were dried prior to being placed in the dishwasher. The pH of the washing bath and the formulation were measured. The hardness of the rinse water was 38 (C2C03) ppm. Each formulation was evaluated for spotting and filming. The results were evaluated on a scale of l to 10 with the higher number being the better result. 37 £4 2 b TEST CLE ANING PERFORMJ &NCE EVi HLUATI03 IS (AT 55°C) ! "il removal A B C D E F G 'j catmeal 7 7.5 8.5 10 10 10 10 r..-. ~ 5 7.5 9 5 7.0 7.4 7.2 calcium eggs 2 9 9.5 2 8.8 9.1 8.9 filming - - - - 7.5 7.6 7.8 glass daylight - - - - - - tea stain - - . - * - . greasy build-up on strainer - - - - - - - greasy build-up spotting - - > - - - - - FILMING - - - . - - - - GLASS DAYLIGHT - - - - - - - GREASY BUILD-UP ON STRAINER - - - - - - - 38 r t TEST C 55°C) LEANIN* 3 PERFC 5RMAKCI : EVALD NATIONS (AT SOIL REMOVAL H I J K L M N 'OATMEAL 10 10 10 10 10 10 10 MICROEGGS 7.5 7 7.8 7.8 7.8 6.2 6.8 CALCIUM EGGS 10 10 10 10 10 10 9.8 FILMING 7.8 7.7 6.7 7.8 6.5 7.4 8.2 SPOTTING 7.7 7.8 6.3 8.2 7.3 7.8 9.0 GLASS DAYLIGHT m - - • i - 8.8 9.7 TEA STAIN 5 9 - ♦ - - - GREASY fiUILD-UP ON STRAINER - * - - - 9 5 GREASY BUILD-UP SPOTTING * - - - - 7.1 8.3 FILMING - ■ - - - - 7.4 7.7 GLASS DAYLIGHT , - - - ■ - - 8.1 9 «3 GREASY BUILD-UP* ON STRAINER - - - - « 8.0 1,3 The above described examples of illustrative compositions of the invention were evaluated for performance according to the following laboratory test methods. All cleaning performance were carried out under European washing conditions in automatic dishwashers with a built-in heater and water softening ion-exchange resin, at a temperature range of about 50°C to about 65°C with 3ml of a rinse aid (Galaxy Rinse Aid) used in the later stages of the cycle (automatically dispersed by a built-in closing device during the last rinse cycle). Fifteen grams of the illustrative compositions were used as a simple dose per wash. 39 .. 0 '-- ■ so oallea soil *---st. - :;j:. s . .-■•. : : . w-r-:- identically soiled with feed tea stair., oatrr.eal :1, hardened egg soil and microwave oven-cooked egg soil; . :up staining was obtained by using 3 cups previously tilled with a 5% fluorhydric acid solution during 15 minutes ir. :rder to remove the protection. The cups were washed and iri--d just before staining. The tea stain was prepared by aiding 50 ml boiling water to one 2g dose of LIPTON yellow lah-?: tea and leaving the system at test for 20 minutes. After emptying, the cups were then allowed to dry for 12 hours. Catmeal soil was prepared by boiling 24 grams of Quaker oats in 400 ml of tap water for ten minutes and then homogenized with a high shearing device (Ultrawax). Three grams of this mixture was spread as thin film onto 7.5 inch china plates. The plates were aged for 2 hours at 80°C, and then stored overnight at room temperature. Hardened egg soil was prepared by mixing egg yolk with an equal amount of 2.5N calcium chloride solution. 0.4 grams of this mixture was applied as a thin crosswise film to the usable surface of 7.5 inch china plates. Microwave-egg soil was prepared by mixing hot egg yolk and cooked margarine with a homogenizer (Ultraturax device). Five grams of this mixture were spread as thin film onto 7.5 inch china plates, and the soiled plates were baked afterwards for one minute in a microwave oven. The two type of egg soils were stored overnight at room temperature. Six plates of oatmeal, 3 cups soiled with tea, and three plates of each egg were used per wash, together with 40 2 k 't ••: loan glasses. The twelve plates. the three soiled rips, -ind the six glasses were always placed in the same i-:s::::r.s :r. the dishwasher at each rur.. In each test four i::: erc-r.t compositions were assessed using a series of four : s r.wasr.ers. All washed plates were scored each run by determining the p-.-rcc-r.t area cleaned (percentage of soil removal) with the aid : » reference scale of gradually cleaned plates. Average percentages of soil removal for each type of soil after four runs were converted in a 0 to 10 scale, 0 being for no soil removal and 10 for perfect cleaning. Glasses were rated in a viewing box for filming and spotting and under natural lighting for evaluation. They were rated according to a scale ranging from 0 (bad performance) to 10 (perfectly clean glasses) with the aid of reference glasses. In the multisoil cleaning test different dishware/soil combinations were used. The dishwasher load included each run six plates of oatmeal, three cups soiled with tea, one dish of white sauce, one dish of rice, four glasses soiled with tomato juice, four glasses soiled with cocoa, and four soiled with milk. Pieces of cutlery (forks, knives and spoons, six each) were also included and soiled with porridge soil, rice and rice with cheese soils. Same Latin Square procedure was used as for soil cleaning test. Percentages of soil removal on all the dishware and glasses were converted in 0 to 10 scale, 0 being for no soil removal and 10 for perfect cleaning. Glasses were also scored for filming, spotting redeposition of soils and global 41 O : 1 y t £. J L V. v •. i : *. . i ; Lai ::ert crrr.ance - to 12 very good ;.:-rr: crrr.ar.-e scale with the aid cf reference glasses. A different scale was used to distinguish the data from soil rerr oval r-erfcrrar.ce. Results tabulated were average of four In the greasy residue build-up test, the dishwasher load included six clear, plates in the lower basket and six clean glasses in the upper basket. The soil load was consisting of ICO grams of a greasy soil mixture prepared by mixing mustard '42 weight %) white vinegar (33 wt. %), corn oil (15 wt. V), and lard (10 wt. %) altogether. In each test, four different compositions were assessed according to a Rubin Square procedure by using a series of four dishwashers during at the same time. 50 grains of greasy soil mixture were poured each run in the wash bath together with fifteen grains of the detergent composition used as a single dose per wash. After each run, the upper basket containing the six glasses, the cutlery basket with the plastic tiles as well as the dishwasher filter elements were moved from one dishwasher to the following one, before conducting the next run. Such a procedure was used to assess the performance of compositions on glasses and on plastic dishware surfaces under conditions of repeated washer in the presence of said greasy soil mixture. After each cycle, glasses were scored in a viewing box for filming and spotting and under natural lighting for 966d aspect according to the same 0 (bad performance) to 10 42 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> iz-j-ziy clean glasses; scale as icr me sc-called s::l ar.mg test, with the aid of reference glasses. The sane procedure was repeated three times using the same cf glasses so as to calculate average performance results each composition after 4 cycles.
The dishwashers filter ts were also inspected after each cycle to evidence greasy csit build up differences between compositions. 43 • - . r<. c. >. A.„-.f.ir:0 cc!erpeni ccrrpos ;! ior, cor ' ' - ■- <••..'>*!t* df.t, ^r, j:\iuse ^rwcri coriprjscs > • : c: -n u 1 rsui i :e:a: !•.
J itute, wiierem saia distittisri.rig «i ' :.
H c! 'I,^i: i i .7i, The powdered dishwashing composition according to -in- : wnereir. said dishwashing composition contains 0.5 to percent by weight of said protease enzyme and 0.3 to 8.0 weight percent of said amylase enryrr.e. 3.
The powdered dishwashing composition according to claim 2 wherein said dishwashing composition further contains a lipase enzyme. 4.
The powdered dishwashing composition according to claim l wherein said dishwashing composition includes 2.0 to 15.0 percent by weight of a nonionic surfactant. 5.
The powdered dishwashing composition according to claim l which comprises an effective amount of one or more adjuvants selected from the group consisting of anti-encrustation agents, oxygen bleaching agents, sequestering agents, anti-corrosion agents, anti-foam agents, optical brighteners, opacifiers and perfumes. 6.
The powdered dishwashing composition according to claim l which includes 0 to 20.0 percent by weight of a copolymerized polyacrylic acid. 7.
The powdered dishwashing composition according to claim 6 which contains an alkali metal perborate 44 242826 The powdered dishwashing composition according to claim t> which loi.tains an alkali metal perborate activator. The powdered dishwashing composition according to claim 1 which contains, a lipase en/yme.
10. The powdered dishwashing composition according to claim 1 wherein said dishwashing composition comprises in percent by weight: lew molecular weight polyacrylate polymer alkali metal silicate liquid nonionic surfactant -phosphate-free builder salt -anti- foaming agent protease enzyme amylase enzyme
11. The powdered dishwashing composition according to claim 1 which includes 0.1 to 1.2 weight percent of an anti-foaming agent. 0 - 20.0V 0 - 40.0V 0 - 15.0V .0 - 40.0% 0 - 1.5V 0 _ 5 - 15.0% 0 .3 - 6.0%
12. The powdered dishwashing composition according to claim I, wherein said protease enzyme is Maxacal protease enzyme (as herein defined) and said amylase enzyme is Maxamyi Amylase enzyme (as herein defined), the weight ratio of said protease enzyme to said amylase enzyme being 2:1 to 1.1:1, wherein said detergent dishwashing composition has a pH of less than 10.5.
13. The powdered dishwashing composition according to claim 10, wherein said protease enzyme is Maxatase protease enzyme (as herein defined) and said amylase enzyme is Maxamyi Amylase enzyme (as herein defined), the weight ratio of said protease en/yme to said amylase enzyme being from 2:1 to substantially 1.1:1, wherein said detergent dishwashing composition has a p» ^ {,^'n 9-5-WEST.WALKER, McCABE i. i >>'' i pnr: .rrndhf/c pna thf APPiir.. </div>