IE921750A1 - Improved phosphate-containing powder automatic dishwashing¹composition with enzymes - Google Patents

Abstract

A powdered protease enzyme dishwashing composition containing a mixture of and anamylase enzymes have been found to be very useful in the cleaning of dishware. The compositions contain nonionic surfactants, at least one builder salt, and an alkali metal silicate and optionally a bleaching agent

Description

IMPROVED PHOSPHATE-CONTAINING POWDER AUTOMATIC DISHWASHING COMPOSITION WITH ENZYMES COLGATE-PALMOLIVE COMPANY, a corporation organised and existing under the laws of the State of Delaware, United States of America, of 300 Park Avenue, New York, New York, 10022, United States of America 5015 tS2l75θ· IR 46000 IMPROVED PHOSPHATE-CONTAINING POWDER AUTOMATIC DISHWASHING COMPOSITION WITH ENZYMES BACKGROUND OF THE INVENTION It has been found to be very useful to have enzymes in dishwashing detergent compositions because enzymes are very effective in removing food soils from the surface of glasses, dishes, pots, pans and eating utensils. The enzymes attack these 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 and 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 of the components of the composition should be as low a level Μ 1 7 5 o as possible, and this low water content must be maintained during storage, since water will in the alkaline product deactivate the enzymes. This deactivation will cause a decrease in the initial activity of the detergent composition.

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 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 11.0 more preferably less than 10.6, and most preferably less than 10.3. This low alkalinity of the dishwashing detergent should J 75o . 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 phosphatecontaining and have superior cleaning performance and dish care, and are used at operating temperatures of 100°F to 14O°F.

SUMMARY OF THE INVENTION 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 about 150°F) , 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 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 polymeric builder salts and non-phosphate containing builder salts.

It is to be understood that the term powder in this invention includes within its definition tablets, soluble * 8 2 ϊ / a ο , capsules and soluble sachet. It is also possible to use the instant compositions as a laundry presoaking powder.

Conventional powdered automatic dishwashing compositions usually contain a low foaming surface-active agent, a chlorine bleach, alkaline builder materials, and usually minor ingredients and additives. The incorporation of chlorine bleaches 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 machines, containing particular low foaming nonionics, oo ^9 21 j builders, filler materials and enzymes. US Patent 3,472,783 to Smille recognized that degradation of the enzyme can occur, when an enzyme is added to a highly alkaline automatic dishwashing detergent.

French Patent No. 2,102,351 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 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 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.

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 art 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 895,459; French Patents 2,544,393 and 1,600,256; European Patents 256,679; 266,904; 271,155; 139,329; and 135,226; and Great Britain Patent 2,186,884.

The aforementioned prior art fails to provide a stable powdered automatic dishwashing detergent which is phosphatecontaining and contains a mixture of enzymes as well as optionally, a peroxygen compound with an activator for 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 (104°F to 150°F) . It is an object of this invention to incorporate a novel enzyme mixture in a phosphate-containing, powdered automatic LS2j?50. dishwasher detergent composition for use in automatic dishwashing operations capable of providing at least equal or better performance to conventional automatic dishwashing compositions at operating temperatures of l00°F to 150°F.

DETAILED DESCRIPTION The present invention relates to a powdered automatic dishwashing detergent compositions which comprise a nonionic 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 the powdered automatic dishwashing detergent composition has a pH of less than 11.0 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 (100°F to 150°F) .

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 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). Practically 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 β 7 j □ β fe / 1 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 5 groups. Typical suitable nonionic surfactants are those disclosed in US 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 a 10 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.

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 C13-C,3 fatty alcohol condensed 2 1 7 5 0 · with 6 moles ethylene oxide and 3 moles propylene oxide). Product B (a C13-C!5 fatty alcohol condensed with 7 mole propylene oxide and 4 mole ethylene oxide), and Product C (a C13-C,j 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. under the Dobanol trademark: Dobanol 91-5 is a low foam ethoxylated C9C,j fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 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.

Poly-Tergent nonionic surfactants from Olin Organic Chemicals such as Poly-Tergent SLF-18, a biodegradable, lowfoaming surfactant is specially preferred for the powdered automatic dishwasher detergent compositions of this instant invention. Poly-Tergent SLF-18, a water dispersible having a low cloud point, has lower surface tension and lower foaming is very suitable for automatic dishwasher detergent.

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 PolyTergent SLF-18, a biodegradable, low-foaming surfactant is specially preferred for the powdered automatic dishwasher detergent compositions of this instant invention. PolyTergent SLF 18, a water dispersible, having a low cloud point 21 7 5 Ο » has lower surface tension and lower foaming is very snitaftlp for automatic dishwasher detergent Other useful surfactants are Neodol 25-7 and Neodol 236.5, 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 secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.

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 similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being 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 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 10, preferably from 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 alkyl polysaccharide surfactant formula. For a particular alkyl polysaccharide molecule x can only assume integral values. In any physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or 4- positions 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 1position, 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. - 921750Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 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 about 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: R2O (CnH2nO) r (Z) x 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 10, preferable 0; and x is from 1.5 to 8, preferably from 1.5 to 4,^m6st ' preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkyl polvglucosides 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 the alkyl polyglucosides can be prepared by a two step procedure in which a short chain alcohol is reacted with glucose or a polyglucoside (x=2 to 4) to yield a short chain alkyl glucoside (x=l to 4) which can in turn be reacted with a longer chain alcohol (R2OH) to displace the short chain alcohol and obtain the desired alkyl polyglucoside. If this two step procedure is used, 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 about 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 polyglucoside 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 nonicnic alkyl polyglycoside characterized by the formula: CnH2n+1O (C6H,0O5) xH wherein n=10(2%); n=12(65%); n=14(21-28%); n=16(4-8%) and n=18(0.5%) and x(degree of polymerization) = 1.6. 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.

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 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. 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 about one H2O per pentasodium tripolyphosphate molecule. Such 921750’ 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 sire of the Thermphos NW TPP, as supplied, usually averages about 200 microns with largest particles being about 400 microns. 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.

Specific examples of such builders are sodium carbonate, potassium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, sodium hexametaphosphae, 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. Pat Nos. 4,144,226, 4,135,092 and 4,146,495, all of which are herein incorporated by reference.

Other phosphate-free builder salts which can be mixed with the phosphate containing builder salts are gluconates, 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 about 2,000 to about 80,000. A preferred low molecular weight polyacrylate is SokalantmCP45 or Sokalan^CPS manufactured by BASF and having a molecular weight of 70,000. Another preferred low molecular weight polyacrylate is AcrysollmLMW45ND manufactured by Rohm and Haas and having a molecular weight of 4,500. Norasol™WL2 comprises 26% LMW45ND sprayed on 74% soda ash.

SokalantmCP45 or CP5 is a copolymer of an acrylic acid and maleic acid anhydride. Such a material should have a water absorption at 38°C and 78 percent relative humidity of less than about 40 percent and preferably less than 30 percent.

The builder is commercially available under the tradename of Sokalan“CP45. This is a partially neutralized copolymer of acrylic acid and maleic anhydride sodium salt. Sokalan“CP5 is classified as a suspending and anti-deposition agent. This suspending agent has a low hygroscopicity. Another builder salt is Sokalan™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. Acusolan64ND provided by Rohm Haas is another useful suspending 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. 4,409,136 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 -9 2 1 7 3 0 * (M2O)x(Al2O3)y(SiO2)x wH2O 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 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 milliequivalents per gram or greater, e.g. 400 meq/g.

The alkali metal silicates are useful anti - corrosion 10 agents which function to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts. Sodium silicates of Na2O:SiO2 ratios of from 1:1 to 1:2.4.

Potassium silicates of the same ratios can also be used. The preferred silicates are sodium disilicate and sodium metasilicate.

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, trimethysilanated silica and triethylsilanated silica. A suitable anti-foaming agent is Silicone TP-201 from Union Carbide. Other suitable antifoaming 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.

Essentially, 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 perborates, 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 thereof at a concentration level of 1 to about 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. Polyacetylated compounds are preferred activators. Suitable preferred activators are tetraacetyl ethylene diamine (TAED), pentaacetyl glucose and ethylidenebenzoate acitate.

The activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water. 2 1 7 5 0-( 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 he 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 the form of a prill having an activity of about ,000 TAU/g. One of the preferred protease enzyme is available under the name Maxapem 15, 20, 30 or Maxapem 42 which is a high alkaline mutant proteolytic enzyme derived from Bacillus acalophylus, and is available from GistBrocades, of the Netherlands in a prill form (activity of about 15, 20, 30 or 40 MPU/g). Preferred enzyme activates per wash are Maxapem 10-100 MPU/g per wash and Maxamyl 625 to 4,000 TAU/g 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 R-60, and is available from Gist-Brocades, of the Netherlands in prill form (activity of about 440 KDU/g). Preferred enzyme activates per wash are Maxatase 200-700 KDU/g per wash.

« I 5 7 5 Ο 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 antifoaming 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 about 4 to about 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 weight percent, more preferably 15 to 65% by weight, and most preferably 15 to 62% by weight percent.

The builder system can also 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 14 weight percent.

The alkali silicate, which is a corrosion inhibitor, wherein sodium disilicate is preferred, will be present in an 921750’ 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 5 percent by weight, more preferably about 0.1 to 7 percent by weight and most preferably 0.4 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 about 18.0 percent by weight. The protease enzyme prills in the automatic dishwashing composition will about 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.

Other components such as perfumes will comprise about 0.1 to about 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 -. S 2 1 ~ 5 υ 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 0.9 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.

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 1/3 less than the bulk density of the bulk density of the standard powders which have a bulk density of 1.0 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 90cc 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.

In accordance with the present invention only about 56cc or about 50 grams of the standard powdered detergent 2 1 7 5 0 ·· composition is needed whereas the dose of concentrated detergent is 33 g weight. 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 about 4 to 7.5 liters of water for the wash cycle and about 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 hard water in the rinse cycle.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 Standard Density Powder Auto-Dish Detergent Composition 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 HRS3342). High a i. 17 5 s soluble sodium silicate (PQ Corporation HS 240), granular sodium sulfate (Kerr-McGee Corporation Trona), granular sodium carbonate (Allied Chemical dense soda ash) were also necessary to give necessary flow property and high solubility of the detergent. Product was made by dry blending all the ingredients.

Table I Ingredients Amount Concentration Sodium Tripolyphosphate (Oxychem HRS3342) 144g 36% Anhydrous Sodium Sulfate-Trona Gran. 104 26 Anhydrous Sodium Carbonate-Allied Dense 88 22 Hydrated Sodium Silicate - PQ HS 240 48 12 Nonionic Surfactant - Tergitol MDS-42 Λ 16 Maxapem CX 30 MPU- Gist-Brocades n 0 Maxamyl P 5000 - Gist-Brocades 0 0_ 400g 100% Amount of Maxapem 30 and Maxamyl enzymes were incorporated in the powder ADD general formula as exemplified in Table I by replacing equivalent amount of sodium sulfate in the product. Rest of the ingredients and the amount remained same in the product.

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 CaCl2 solution) along with baked-on oatmeal soiled substrates against non-enzyme powder ADD, bleachcontaining powder ADD prototype and CASCADE, a commercial powder ADD with 50g dose and PALMOLIVE AUTOMATIC, a commercial -9217 5 0* Liquid ADD with 80g dose. The cleaning performance tests were run at 120°F wash cycle temperatures using tap water (ca. 115 ppm water hardness).

Table II il 2 1 7 δ Q Auto-Dish Performance (Enzyme vs. Non-Enzyme vs. Bleach-Based Product) In Tap Water at 120°F Wash Cycle Temperature Auto-Dish Enzvme Cone. % Dose g Performance, Cleaning Products Maxapem 30 Maxamyl Denatured Egg Baked-On 1 0 0 50g 6.5% Porridge 60.0% 2 0 1 50g 30.5 99.5 3 2 0 50g 98.0 60.0 4 2 1.5 50g 99.0 99.5 5 2 0.5 50g 95.0 98.5 6 1.5 0.25 50g 94.0 95.5 7 1 0.5 50g 93.0 100.0 8 1 0.25 50g 94.5 100.0 9 1 0.25 50g 68.5 100.0 PADD 11614 -90B (contain 1. 2% av.ci; 1 50g 91.5 60.0% CASCADE Powder (contain 1% Av.Cl) 50g 63.0 60.0% PALM AUTO Liq (contain 1% Av.Cl) 80g 91.0 60.0% Non -enzyme poser ADD Conrol (1) barely cleaned any egg and starch soil whereas incorporation of Protein Engineered 42 Maxacal and Maxamyl helped complete removal egg and starchy soil respectively. Enzymes (both Maxapem 30 and Maxamyl) containing powders (2-9) outperformed chlorine bleach containing ADDS like PADD 11614-90B, CASCADE, a commercial powder and PALMOLIVE AUTOMATIC, a commercial Liquid in cleaning egg and starchy soil. 921750· Table III Auto-Dish Products ASTM Spotting/Filming Performance Data 00 ppm Water Hardness, 120°F Wash Cycle Temperature Auto-Dish Products Spotting/Filming Data Powder Auto-Dish (3) 1st Cycle A 3 2nd Cycle A 3 3rd Cycle A 3,4 4th Cycle A 2,3 Powder ADD 11614-90B (Chlorine Bleach) 1st Cycle B5 2nd Cycle B5 3rd Cycle B5 4th Cycle B 3,4 CASCADE Powder (Chlorine Bleach) PALMOLIVE AUTOMATIC Liquid 1st Cycle A 5 2nd Cycle A 6 3rd Cycle AB 6 4th Cycle A 3 (Chlorine Bleach) 1st Cycle BC 3,4 2nd Cycle CD 4 3rd Cycle D 4,5 4th Cycle DE 2,3 Spotting Scale: A best- no spots B very few spots C approximately 25% spot coverage D approximately 50% spot coverage E excessive spots Filming Scale: best - no film slight film noticeable film significant film excessive film Example 2 According to the procedure of U.S. Patent 4,931,203 the following concentrated formulation was produced: Table IV Concentration Sodium Tripolyphosphate Base Bead - D CP 151-627 Protein Sodium Carbonate (Allied Chemical Dense Soda Ash) .00 Sodium Metasilicate ( 1 Na20: 1 SiO2, PQ Metsobeads 20486.00 Sodium Silicate (1 Na20: 1 SiO2, PQ Britesil LD24) 12.00 Nonionic Surfactant (Union Carbide Tergitol MDS-42) 6.00 Maxapem CX 30 (Gist-Brocades) 1.50 Maxamyl P 5,000 (Gist-Brocades) The finished product is aged over two days to give a nice dry free-flowing powder.

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 cross-wise 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. Thirtythree grams of the detergent was used as a single dose per wash. All plates were scored by measuring the percent area cleaned. The multi-soil cleaning test results are reported below. The results tabulated in Table V were average of at least 2 runs. Average results reflect the average performance results obtained in three different water conditions. The product was tested with 33g dose using the ASTM Method D355679 spotting and filming test method combined with denatured egg soiled (egg yolk denatured with 2.5 M CaCl2 solution) along with the 50g dose of commercial powder product. Enzyme containing prototype powder ADD completely removed egg soil and major portion of oatmeal, whereas, CASCADE, a commercial powder barely removed any of the egg and oatmeal soil.

Table V Cleaning performance, Enzyme vs. non-Enzyme Based Product Product Oatmeal Cone. ADD Product (Example 2) Dose 33g CASCADE Powder (Commercial Product) 50g frCleaning Denatured Egg Baked-On 100% 100% 40% 50% 2 ι 7 5 tl Example 3 Standard Density Powder Auto-Dish Detergent Composition A free flowing, highly soluble standard density powder autodish detergent was developed by absorbing nonionic surfactant (Union Carbide Tergitol MDS-42) on highly absorptive sodium tripolyphosphate (Oxy Chem HRS3342). High soluble sodium silicate (PQ Corporation HS 240), granular sodium sulfate (KerrMcGee Corporation Trona), granular sodium carbonate (Allied Chemical dense soda ash) were also necessary to give necessary flow property and high solubility of the detergent. Product was made by dry blending all the ingredients.

Table VI Ingredients Amount Concentration Sodium Tripolyphosphate (Oxy Chem HRS3342) 144g36% Anhydrous Sodium Sulfate-Trona Gran. 10426 Anhydrous Sodium Carbonate-Allied Dense 8822 Hydrated Sodium Silicate - PQ HS 240 4812 Nonionic Surfactant - Tergitol MDS-42 16 4 Maxatase - Gist Brocades 0 Maxamyl P 5000 - Gist-Brocades 0 400g 100% Amount of Maxatase P440,000 and Maxamyl P5,000 prilled enzymes were incorporated in the powder ADD general formula as exemplified in Table VI by replacing equivalent amount of sodium sulfate in the product. Rest of the ingredients and the amount remained same in the product.

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 921750* with denatured egg soiled (egg yolk denatured with 2.5 M CaCl2 solution) along with baked-on oatmeal soiled substrates against non-enzyme powder ADD, bleachcontaining powder ADD prototype and a commercial (CASCADE) powder ADD with 50g dose and a commercial (PALMOLIVE AUTOMATIC) Liquid ADD with 80g dose. The cleaning performance tests were run at 120°F wash cycle temperatures using tap water (ca. 115 ppm water hardness). δ 2 ί '/ 5 0 * Auto-Dish Performance (Enzyme vs. Non-Enzyme vs. Bleach-Based Product) In Tap Water at 120°F Wash Cycle Temperature Table VII Auto-Dish Enzymes Cone. % Dose g Performance, % Cleaning Products Maxatase Maxamyl Denatured Egg Baked-On Porridge 1 0 0 50g 7.5 60.0% 2 0 1 50g 32.0 99.0 3 2 0 50g 95.0 60.0 4 2 1 ..5 50g 98.5 99.5 5 2 0.5 50g 95.0 98.5 6 1.5 0.25 50g 96.0 96.0 7 1 0.5 50g 96.0 100.0 8 1 0.25 50g 95.0 100.0 9 1 0.25 50g 70.5 100.0 Powder ADD 11614-90B (contain 1.2¾ Av.Cl) 50g 91.5 60.0 Commercial Powder (contain 1% Av.Cl) 50g 63.0 60.0 Commercial Liq (contain : 1% Av.Cl) 80g 91.0 60.0 Non- enzyme poser ADD Conrol (1) barely cleaned any egg and starch soil whereas incorporation of Maxatase and Maxamyl helped complete removal egg and starchy soil respectively.

Enzymes (both Maxatase and Maxamyl) containing powders (2-9) outperformed chlorine bleach containing ADDs like PADD 1161490B, commercial powder and commercial Liquid in cleaning egg and starchy soil.

Auto-Dish Products ASTM Spotting/Filming Performance Data 300 ppm Water Hardness, 12O°F Wash Cycle Temperature Auto-Dish Products Spotting/Filming Data Table VIII Powder Auto-Dish (3) 1st Cycle A 3 2nd Cycle A 3 3rd Cycle A 3,4 4th Cycle A 2,3 Powder ADD 11614-90B (Chlorine Bleach) 1st Cycle B5 2nd Cycle B5 3rd Cycle B5 4th Cycle B 3,4 Commercial Powder (Chlorine Bleach) 1st Cycle A 5 2nd Cycle A 6 3rd Cycle AB 6 4th Cycle A 3 Commercial Liquid (Chlorine Bleach) Spotting Scale: A B C D E Filming Scale: 1st Cycle BC 3,4 2nd Cycle CD 4 3rd Cycle D 4,5 4th Cycle DE 2,3 best, no spots very few spots approx. 25% spot coverage approx. 50% spot coverage excessive coverage spots best, no film slight film noticeable film significant film examine film Example 4 According to the procedure of U.S. Patent 4,931,203 the following concentrated formulation was produced: Table IX Ingredients Concentration Sodium Tripolyphosphate Base Bead - DCP 151-627 61.00% Sodium Carbonate (Allied Chemical Dense Soda Ash) 10.00 Sodium Metasilicate ( 1 Na20: 1 SiO2, PQ Metsobeads 20486.00 Sodium Silicate (1 Na20: 1 SiO2, PQ Britesil LD24) 12.00 Nonionic Surfactant (Union Carbide Tergitol MDS-42) 6.00 Maxatase P 440,000 (Gist Brocades) 3.50 Maxamyl P 5,000 (Gist Brocades) 1.50 The finished product is aged over two days to give a nice dry free-flowing powder.

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 cross-wise 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. Thirtythree grams of the detergent was used as a single dose per 921750* wash. All plates were scored by measuring the percent area cleaned. The multi-soil cleaning test results are reported below. The results tabulated in Table IX were average of at least 2 runs. Average results reflect the average performance results obtained in three different water conditions.

The product was tested with 3 3g dose using the ASTM method D 3556-79 spotting and filming test method combined with denatured egg soiled (egg yolk denatured with 2.5 M CaCl2 solution) along with the 50g dose. Enzyme containing prototype powder ADD completely removed egg soil and of commercial powder product oatmeal, whereas, commercial Powder barely removed any of the egg and oatmeal soil.

Table X Cleaning performance Enzyme vs. non-Enzyme based product.

Product on Oatmeal Commercial ADD Product (Example 2) 100% CASCADE Powder (Commercial powder) 50% Dose 33g 50g %Cleanincr Denatured Egg - Baked100%

Claims (14)

WHAT IS CLAIMED IS:

1. A powdered detergent containing a mixture of a protease enzyme and an amylase enzyme which comprises 10 to 40 percent by weight of an alkali metal silicate wherein said dishwashing composition has a pH of less than 11.0.

2. The powdered dishwashing composition according to claim 1 wherein said dishwashing composition contains 0.5 to 13.0 percent by weight of said protease enzyme and 0.3 to 8.0 weight percent of said amylase enzyme.

3. The powdered dishwashing composition according to claim 2 wherein said dishwashing composition further contains a lipase enzyme.

4. The concentrated powdered dishwashing composition according to claim 1 wherein said dishwashing composition includes 2.0 to 15.0 percent by weight of said nonionic surfactant.

5. The powdered dishwashing composition according to claim 1 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, opacifiers and perfumes.

6. The powdered dishwashing composition according to claim 1 which includes 0 to 20.0 percent by weight of a copolymerized polyacrylic acid and a copolymer thereof.

7. The concentrated powdered dishwashing composition according to claim 6 which contains an alkali metal perborate.

8. The concentrated powdered dishwashing composition according to claim 7 which contains an alkali metal perborate activator. - e. z. ; 5 y <

9. The concentrated powdered dishwashing composition according to claim 5 which contains a lipase enzyme.

10. The concentrated powdered dishwashing composition according to claim 2 wherein said dishwashing composition comprises in percent by weight: low molecular weight polyacrylate polymer 0 - 20.0% alkali metal silicate 0 - 40.0% liquid nonionic surfactant 0 - 15.0% phosphate-free builder salt 10.0 - 65.0% anti-foaming agent 0 - 1.5% protease enzyme 0.5 - 15.0% amylase enzyme 0.3 - 8.0%

11. The concentrated powdered dishwashing composition according to claim 1 which includes about 0.1 to 1.2 weight percent of an anti-foaming agent.

12. The concentrated powdered dishwashing composition according to claim 1, wherein said protease enzyme is Maxapem 30 and Maxapem 42 proteases enzyme and said amylase enzyme is Maxamyl amylase enzyme, a weight ratio of said protease enzyme to said amylase enzyme being 5:1 to 1.1:1, wherein said detergent dishwashing composition has a pH of less than 10.5.

13. The concentrated powdered dishwashing composition according to claim 1, wherein said proteast enzyme is Maxatase protease enzyme and said amylase enzyme is Maxamyl amylase enzyme, a weight ratio of sait protease enzyme to said amylase enzyme being 5:1 to 1.1:1, wherein said detergent dishwashing composition has a pH of less than 10.5. '' ' 3 b

14. A powdered detergent substantially as described herein with reference to the Examples.