AU654009B2 - Phosphate-containing powder automatic dishwashing composition with enzymes - Google Patents

Description

e a i, n, ;r- S654 9

AUSTRALIA

Patents Act 1990 COLGATE-PALMOLIVE COMPANY

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Ii 4 r44 Invention Title: PHOSPHATE-CONTAINING POWDER AUTOMATIC DISHWASHING COMPOSITION WITH ENZYMES The following statement is a full description of this invention including the best method of performing it known to us Fi 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 '2°b 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 o.2° storage. Activity is the property of maintaining enzyme 0 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 Ic;1 of the components of the composition should be as low a level as possible, and this low water content must be maintained during storage, since water in the alkaline product will deactivate the enzymes. This deactivation will cause a decrease in the initial activity of the detergent composition.

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 o5 detergent composition. This will usually accelerate the -0 ~decrease in the activity of the detergent composition. The 0 4 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 ,02,0 or have a low water affinity which will minimize any losses in activity as the detergent is being stored or used.

Powdered detergent compositions which contain enzymes can be made more stable and to have a high activity, if the j i initial free water content of the detergent composition is 25 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 2 more preferably less than 10.6, and most preferably less than 10.3. This low alkalinity of the dishwashing detergent should maintain the stability of the detergent composition which contains a mixture of enzymes, thereby providing a higher initial activity of the mixture of the enzymes and the maintenance of this initial high activity.

A major concern in the use of automatic dishwashing compositions is the formulation of automatic dishwashing compositions which have a low alkalinity and can operate at a high temperature while maintaining superior cleaning performance and dish care. The present invention teaches the preparation and use of powdered automatic dishwashing compositions which are phosphate containing and have superior cleaning performance and dish care and are used at operating Sooi temperatures of 100 0 F to 140 0

F.

a o.

SUMMARY OF THE INVENTION ,r This invention is directed to producing powdered phosphate ,2 ~enzyme-containing automatic dishwashing detergent compositions that have an increased chemical stability and essentially a high activity at wash operating temperatures of 40 0 C to 65 0

C

(104 0 F to 150 0 wherein the composition also can be used as a j 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. r The preferred builder system of the instant compositions 3 i 1 h k- 0E 00 0

O

OG

(OOGQ

comprises at least one phosphate builder salt which can be used in conjunction with a polymeric builder salts and nonphosphate containing builder salts.

It is to be uncderstood that the term powder in this invention includeS within its definition tablets, soluble capsules and soluble sachet. It is also possible to use the instant composition- 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 .i 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 ,20 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 215 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 n e

II

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Eb Al i; e deposition of trou lesome 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 detergebn compositions for automatic dishwashing machines, containing particular low foaming nonionics, builders, filler maferials and enzymes. USoPatent 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. 2,102,851 to Colgate-Palmolive, pertains to rinsing and washing compositions for use in automatic dishwashers. The compositions disclosed have a pH of 6 to 7 and contain an amylolytic and, if desired, a proteolytic o0°°1'5 enzyme, which have been prepared in a special manner from animal pancreas and which exhibit a desirable activity at a pH 4 1 **Qa 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 40420 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.

j 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 iishwashing detergent which uses a IN 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 3 927,938, to Aunstrup et al., discloses specific proteolytic enzymes which exhibit high enzymatic activities in highly alkaline systems. Similar disclosures are found in Britis 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 S bleach-free powdered automatic dishwashing compositions capable of providing superior performance during conventional 4 *4 4 4P 4 t* 4 1 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 cishwashing detergent which is phosphatecontaining and contains a mixture of enzymes as well as 6 i Ir '.2J optionally, a peronygen 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 0 C to 65 0 C (100°F to 150 0 It is an object of this invention.to incorporate a novel enzyme mixture in a phosphate-containing, powdered automatic dishwasher detergent composition for use in automatic dishwashing operations capable of providing at least equal or better performance 0o conventional automatic dishwashing compositions at operating temperatures of 40 0 C to 65 0

C.

DETAILED DESCRIPTION The present invention relates to a powdered automatic dishwashing detergent compositions which comprise a nonionic 9 surfactant, alkali metal silicate, a phosphate-containing I 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 0 C to 65 0 C (about 100°F to about 150 0

F).

are The nonionic surfactants thatA.an bo 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 ethoxyiated propoxylated fatty alcohols which are 77 I N ZO~f: L low-foaming surfactans 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 compounu 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 polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those *5 disclosed in US Patent Nos. 4,316,812 and 3,630,929.

o 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 hydrophilic poly-lower alkoxy group to a lipophilic moiety. A o0 preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is S 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 "a f 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 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 8 s 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 C 13

-C,

5 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide).

Product B (a C 13 -C15 fatty alcohol condensed with 7 mole propylene oxide and 4 mole ethylene oxide), and Product C (a

C

13

-C

15 fatty alcohol condensed with 5 moles propylene oxide and o 10 moles ethylene oxide). Another group of liquid nonionics S are available from Shell Chemical Company, Inc. under the.

44 Dobanol trademark: Dobanol 91-5 is a low foam ethoxylated C 9 C, fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C 2

-C,

1 fatty alcohol with an average of 7 moles ethylene oxide. Another liquid nonionic surfactant that can be used is sold under the tradename S. Lutensol SC 9713.

Synperonic nonionic surfactants from ICI such as Synperonic LF/D25 LF/RA30 are especially preferred nonionic surfactants that can be used in the powdered automatic dishwasher detergent compositions of the instant invention.

Poly-Tergent nonionic surfactants from Olin Organic Chemicals such as Poly-Tergent SLF-18, a biodegradable, lowa, rn iFiti~ o t,

I

til Itr foaming surfactant s specially preferred for the powdered automatic dishwasher detergent compositions of this instant invention. Poly-Tergent SLF-18 which is water dispersible and has a low cloud povilt and lower surface tension and lower foaming is very suitable for automatic dishwasher detergent.

Other useful surfactants are Neodol 25-7 and Neodol 23which 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 "20 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 25 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 I i L. I I_ 1 i j Registered Patent Attodney

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1 i 1 itiV,.i i c; Ie $4 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 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 preferably froMi about 1.5 to 4, and most preferably from 1.6 to 2.7 saccharide units galactoside, glucoside, fructoside, glucosyl, fructosyl, and/or galactosyl units).

Mixtures of saccharide moieties may be used in the alkyl 4t .15 polysaccharide surfactants. The number x indicates the number of saccharide units shown later in a particular alkylpolysaccharide surfactant formula. For a particular alkylpolysaccharide molecule x can only assume integral values. In any physical sample can be characterized by the ,20 average value of x and this average value can assume nonintegral 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 or 4- positions rather than at S the 1-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside). However, attachment through the 1-position, glucosides, galactosides, fructosides, etc., is preferred. In the preferred product the additional saccharide units are predominately attached to the 4

I

4,- 444 C 4 F.B. RICE CO. PATENT ATTORNEYS previous saccharid, unit's 2-position. Attachment through the and 6-positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety 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 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 preferably less than 10, alkoxide moieties.

S.Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, i5 tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.

4 1 The alkyl monosaccharides are relatively less soluble in water than the higher alkyl polysaccharides. When used in 20 admixture with alkyl polysaccharides, the alkyl |441 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: 12 Sii 1

R

2 0 (CH 2 r(Z) wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from about 10 to about 18, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to about 10, preferable 0; and x is from 1.5 to about 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R 2 OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired gl:coside. Alternatively the alkyl polyglucosides can be prepared by a two step procedure in oO., which a short chain alcohol (R,OH) an be reacted with glucose, o 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 (R 2 OH) to 20 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 more preferably less than most preferably 0% of the alkyl S 25 polyglucoside.

i The amount of unreacted content) in the desired alk preferably less than mo I alcohol (the free fatty alcohol yl polysaccharide surfactant is re preferably less than 0.5% by 13 _711 r ar nso 81()1 weight of the total of the alkyl polysaccharide. For some uses it is desirable to have the alkyl monosaccharide content less than 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 nonionic alkyl polyglycoside S characterized by the formula: CnH 2 n+ 1 O (C 6 Ho 0 0 5 xH wherein 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 S has: a pH of 6-8(10% of APG 625 in distilled water); a specific gravity at 25 0 F of 1.1 grams/ml; a density at 25 0 F of 20 9.1 kgs/gallons; a calculated HLB of 12.1 and a Brookfield viscosity at 350C, 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.

25 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

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6r a,

CC

14

K

composition, it nas oeen rouna cna zne mnir;a. wae u=L rsr 04 00 polyacrylate, organl.c and/or inorganic detergent builders as well as phosphate free builder salts such as an alkali carbonate such as sodium carbonate or sodium citrate or a mixture of sodium carbonate and sodium citrate. The nonaqueous liquid nonionic surfactant has dispersed therein fine particles or organic and/or inorganic detergent builders.

A preferred solid builder salt is an alkali.metal polyphosphate such as sodium tripolyphosphate The TPP is a blend of anhydrous TPP and a small amount of TPP hexahydrate such that the chemically bound water content is which corresponds to one H 2 0 per pentasodium tripolyphosphate molecule. Such TPP may be produced by treating anhydrous TPP with a limited amount of water. The presence of the hexahydrate slows down the rapid rate of solution of the TPP in the wash bath and inhibits caking. One suitable TPP is sold under the name Thermphos NW. The particles size of the Thermphos NW TPP, as supplied usually averages about 200 microns with the largest particles being 400 microns. In place of all or part of the alkali metal '20 polyphobphate one or more other detergent builder salts can be used. Suitable other builder salts are alkali metal carbonates, borates, phosphates, bicarbonates, silicates, S lower polycarboxylic acid salts, and polyacrylates, polymaleic anhydrides and copolymers of polyacrylates and polymaleic 25 anhydrides and polyacetal carboxylates.

Specific examples of such builders are sodium carbonate, potassium carbonate, sodium tetraborate, sodium pyrophosphate, sodiumi tripolyphosphate, potassium tripolyphosphate, potassium 000 0* 00 1 1 2 li pyrophosphate, sod um bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate. The builder salts can be used alone with the nonionic surfactant or in an admixture with other builders. Typical builders also include those disclosed in U.S. Pat Nos. 4,316,812, 4,264,466, and 3,630,929 and those disclosed in U.S. ratent Nos. 4,144,226, 4,135,092 and 4,146,495.

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 2,000 to 80,000. A preferred low molecular 15 weight polyacrylate is SokalanCP45 or manufactured by BASF and having a molecular weight of 70,000.

Another preferred low molecular weight polyacrylate is r' Acrysol"LMW45ND manufactured by Rohm and Haas and having a molecular weight of 4,500. Norosol™WL2 comprises 26% LMV sprayed on 74% sodawash.

or CP5 is a copolymer of an acrylic acid and Sa maleic acid anhydride. Such a material should have a water absorption at 38 0 C and 78 percent relative humidity of less Sthan 40 percent and preferably less than 30 percent. The builder is commercially available under the tradename of This is a partially neutralized copolymer of acrylic acid and maleic anhydride sodium salt. Sokalan m is classified as a suspending and anti-deposition agent. This 1 i. ic s~\ :1.

7 suspending agent hr3 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. Acusol"64ND 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 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 i5 formula St ta

(M

2 0),(Al20 3 (SiO0), wH 2

O

wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A 20 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 agents which function to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts.

Sodium silicates of Na 2 O:SiO ratios of from 1:1 to 1:2.4.

Potassium silicates of the same ratios can also be used. The i- ':j g i i i r I 4 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 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 Ott, 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 S remaining components of the detergent formulation can be used.

*q1 A useful and preferred opacifier is titanium dioxide at a O 2O0 concentration level of 0 to 1.0 weight percent.

A key aspect is to keep the free water (non-chemically S. 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 18 of 0 to 20 weight percent, more preferably 0.5 to 17 weight percent and most preferably at 1.0 to 14 weight percent. The oxygen bleaching agents that can be used are alkali metal perborate, percarbonate, perphthalic acid, perphosphates, and potassium monopersulfate. A preferred compound is sodium perborate monohydrate and dihydrate. The peroxygen bleaching compound is preferably used in admixture with an activator at a concentration of 1 to 5 weight percent. Suitable activators are those disclosed in U.S. Patent No. 4,264,466 or in column 1 of U.S. Patent No. 4,430,244, both of which are herein incorporated by reference. Polyacetylated compounds are preferred activators. Suitable preferred activators are i" tetraacetyl ethylene diamine pentaacetyl glucose and ethylidenebenzoate acitate.

The activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water.

I; The detergent formulation also contains a mixture of a protease enzyme and an amylase enzyme and, optionally, a lipase enzyme that serve to attack and remove organic residues on glasses, plates, pots, pans and eating utensils. Lipolytic enzymes can also be used in the powdered automatic dishwasher detergent composition. Proteolytic enzymes attack protein residues, lipolytic enzymes fat residues and amylolytic enzymes starches. Proteolytic enzymes include the protease enzymes subtilisn, bromelin, papain, trypsin and pepsin.

Amylolytic enzymes include amylase enzymes. Lipolytic enzymes include the lipase enzymes. The preferred amylase enzyme is 6

I

available under the name Maxamyl, derived from Bacillus licheniformis and is available from Gist-brocades of the Netherlands in a prill form (activity of about 5,000 TAU/g).

The preferred protease enzyme is available under the name Maxacal derived from Bacillus alcalophilus, and is supplied by Gist-Brocades, of the Netherlands in a prill form (activity of about 400 KADU/g). Preferred enzyme activates per wash are Maxacal 200 to 700 KADU/g and Maxamyl 625 to 4000 TAU/g per wash.

The weight ratio of the proteolytic enzyme to the amylolytic enzyme in the powdered automatic dishwasher detergent compositions is 8:1 to 1:1, and more preferably 4.5:1 to 1.1:1.

e tt The detergent composition can have a fairly wide ranging composition. The surfactant can comprise 0 1- p rnnt by weight of the compoition, morc p.rof-ably 0.1 to 15 percent by weight, and meie preferably 1 to 12 percent by weight. The S soil suspending agent which is preferably a copolymerized 4I polyacrylic acid will be present in an amount of 0 to i, 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 4 to 40 percent by weight and most preferably 5 to 35 percent by weight for a LVI. cA aescrinea as ecnoxy.acea propoxyLcLut-u at-- a 7 7 i standard product, however, for a concentrated formula, the alkali metal tripolyphosphate is present in an amount of 10 to wt. percent, more preferably 15 to 65 percent by weight and most preferably 15 to 62 percent by weight. The builder system also can contain a low molecular weight polyacrylate type polymer at a concentration level of 0 to 20 weight percent, more preferably 1.0 to 17 weight percent and most preferably about 2 to about 14 weight percent.

The alkali silicate, which is a corrosion inhibitor, wherein sodium disilicate is preferred, will be present in an amount of 0 t-Qe prent by weight, me rproa 3 to percent by weight and es preferably 4 to 28 percent by weight.

SThe opacifier will be present in an amount of 0 to percent by weight, more preferably 0.1 to 7 percent by weight and most preferably 0.5 percent by weight.

The enzymes will be present in a prilled form as supplied by Gist Brocades at a concentration of 0.8 to 22.0 percent by weight, more preferably 0.9 to 20.0 percent by weight, and most preferably 1.0 to 18.0 percent by weight. The protease enzyme prills in the automatic dishwashing composition will Scomprise 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 25 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 9T 21 7 .4i O bec 8 L. 1 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 0.1 to percent by weight of the detergent composition.

One method of producing the detergent powder formulation consisting first of spraying and absorbing nonionic surfactant into the phosphate and carbonate builder salts and mixed thoroughly in a rotary drum. The absorbed builder salt was then aged overnight to completely absorb the nonionic to form r 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 L detergent powder. Another method of producing the powder detergent formulation having a bulk density of 0.90 is to spray dry by any conventional means the nonionic surfactant and defoamer into the perborate bleach compound and the :,'120 builder salt. This spray dry materials can be used (I4 0, 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 9 density 1/3 less than the standard powders which have a bulk density of about 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 80cc or 90 grams of detergent. In normal use, for example, for a full load of dirty dishes 6& 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 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 0

C

to 65 0 C and the temperature of the rinse water is 55 0 C to I 9- 0 C. The wash and rinse cycles use 4 to 7.5 liters of water for the wash cycle and 4 to 7.5 liters of water for the hot rinse cycle.

The concentrated powdered automatic dishwashing detergent Scompositions 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 23 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 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 high)y absorptive sodium tripolyphosphate Oxy Chem HRS 3342. High soluble sodium silicate (PQ Corporation HS 240), granular sodium sulfate (Kerr-McGee Corporation Trona), granular sodium carbonate (Allied Chemical dense soda ash) 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 HRS 3342) 144g 36% Anhydrous Sodium Sulfate-Trona Gran.

Anhydrous Sodium Carbonate-Allied Dense Hydrated Sodium Silicate PQ HS 240 Nonionic Surfactant Tergitol MDS-42 Maxacal P 400,000 Gist-Brocades Maxamyl P 5000 Gist-Brocades 104 26 88 22 00 00 400g 100% Amount of Maxacal P 400,000 and Maxamyl P prilled enzymes were incorporated in the powder general formula as 5,000

ADD

0 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 M CaCI 2 solution) along with baked-on oatmeal soiled substrates against non-enzyme powder ADD, bleachcontaining powder ADD prototype and CASCADE powder ADD supplied +P+G with 50g dose and PALMOLIVE AUTOMATIC Liquid ADD supplied by Colgate Palmolive with 80g dose. The cleaning 0o performance tests were run at 120 0 F wash cycle temperatures o using tap water (ca. 115 ppm water hardness).

la A l i t, 4 12 Table II Auto-Dish Performance (Enzyme vs. Non-Enzyme vs. Bleach-Based Product) In Tap Water at 120 0 F Wash Cycle Temperature Auto-Dish Enzymes Conc. Dose g Performance, Cleaning Products Maxacal Maxamyl Denatured Egg Baked-On Porridge 1 0 0 50g 5.5% 2 0 1 50g 30.5 99.5 3 2 0 50g 95.0 4 2 1.5 50g 98.5 99.5 5 2 0.5 50g 95.0 98.5 6 1.5 0.25 50g 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 Powder PADD 11614-90B t (contain 1.2% AV.C1) 50g 91.560 CASCADE Powder (contain 1% Av.Cl) 50g 63.0 25 PALM AUTO Liq (contain 1% Av.Cl) 80g 91.0 Non-enzyme poser ADD Conrol barely cleaned any egg and starch soil whereas incorporation of Maxacal and Maxamyl helped complete removal egg and starchy soil respectively.

Enzymes (both Maxacal and Maxamyl) containing powders (2-9) outperformed chlorine bleach containing ADDs like PADD 11614- CASCADE powder and PALMOLIVE AUTOMATIC Liquid in cleaning egg and starchy soil.

26 26 L- i_ ;li ih sue SUrfactant is x ess than more preferably less than 130.5% by 13 r- I Table III Auto-Dish Products ASTM Spotting/Filming Performance Data 300 ppm Water Hardness, 120°F Wash Cjcle Temperature Auto-Dish Products Powder Auto-Dish (3) Spotting/Filminc Data 1st Cycle A 3 2nd Cycle A 3 3rd Cycle A 3,4 4th Cycle A 2,3 Powder ADD 11614-90B (Chlorine Bleach) 2nd 3rd 4th 1st Cycle Cycle Cycle Cycle B 3,4 CASCADE Powder (Chlorine Bleach) 1st Cycle A 2nd Cycle A 6 3rd Cycle AB 6 4th Cycle A 3 *4 4 u 4"25 srre 0 I4 o 5 r 6 44 I *444 30 4 4

ON.

o 1

I.

40 t 9 1 i~ Palmolive Automatic ADD (Chlorine Bleach) 1st 2nd 3rd 4th Cycle BC 3,4 Cycle CD 4 Cycle D Cycle DE 2,3 coverage coverage Spotting Scale: Filming Scale: best; no spots very few spots approx. 25% spot approx. 50% spot excessive spots best slight film noticeable film significant film excessive film

J",

Ii 1 f eL.- I I i I II ui liaim mi-- 28 Example 2 According to the procedure of U.S. Patent 4, 931,203 the following concentrated formulation was produced: TABLE IV INGREDIENTS Concen Sodium Carbonate (Base Bead DCP 151-627) Sodium Carbonate (Allied Chemical Dense Soda Ash) Sodium Metasilicate (1 Na 2 0: 1 Si0 2 PQ Metsobeads 2048) Sodium Silicate (1 Na20: 1 SiO 2 PQ Britesil LD24) Nonionic Surfactant (Union Carbide Tergitol MDS-42) Maxacal P 400,000 (Gist-Brocades) Maxamyl P 5,000 (Gist-Brocades) itration 61.00% 10.00 6.00 12.00 6.00 3.50 1.50 I t i r 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 25 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 a thin film onto a 7.5 inch china plate. The plates were aged for 2 hours at 80 0 C. They were then stored overnight at room temperature. Two

I

I

r

I

I

u plates of each egg and oatmeal were used per wash. The plates were placed in the same positions in the dishwasher. Thirtyfive 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 D3556- 79 spotting and filming test method combined with denatured egg soiled (egg yolk denatured with 2.5 M CaCl 2 solution) along with the 50g dose of commercial powder product. Enzyme Scontaining prototype powder ADD completely removed egg soil and of oatmeal, whereas, commercial Powder barely removed any 5 of the egg and oatmeal soil.

Table V Cleaning Performance Enzyme vs. Non-Enzyme Based Product *4 I "20 Product Dose %Cleaning *o Denatured Egg Baked-On Oatmeal Concentrated .t t ADD Product (Example 2) 33g 100% 100% I I CASCADE Powder (Commercial powder) 50g 40% 29

Claims (12)

1. A powdered automatic dishwashing detergent composition comprising 0.1 to 15 percent by weight of a nonionic surfactant, 3 to 30 percent by weight of an alkali metal silicate, 2 to 40 percent by weight of a phosphate-containing builder system, and a mixture of a Maxacal protease enzyme and an amylase enzyme, wherein said Maxacal protease enzyme is present in an amount of to 15 percent by weight and said amylase enzyme is present in an amount of 0.3 to 0.8 percent by weight, the total concentration of enzyme being 0.8 to 22.0 percent by weight, and wherein said dishwashing composition has a pH of less than 11.0 and operates at a wash temperature of i 40 0 C to 65 0 C.

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

3. The powdered dishwashing composition according to claim 2 wherein said dishwashing composition further r 20 contains a lipase enzyme.

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

5. The powdered dishwashing composition according to 25 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 powdered dishwashing composition according to claim 6 which contains an alkali metal perborate. 11Z &_I 17 i I- 31

8. The powdered dishwashing composition according to claim 6 which contains an alkali metal perborate activator.

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

The powdered dishwashing composition according to claim 2 wherein said dishwashing composition comprises in percent by weight: low molecular weight polyacrylate polymer 0 20.0% anti-foaming agent 0

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

12. The powdered dishwashing composition according to claim 1 wherein said protease enzyme is Maxacal protease enzyme and said amylase enzyme is Maxamyl amylase enzyme, a weight ratio of said protease enzyme to said amylase enzyme being 4.5:1 to about 1.1:1, wherein said detergent S dishwashing composition has a pH of less than 10.5. DATED this 28th day of June 1994 C' 4 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO. r 01' I *1 i' j2l ,-r ,1 m ABSTRACT OF THE DISCLOSURE A powdered dishwashing composition containing a mixture of protease enzyme and ananylase enzymes have been found to be very useful in the cleaning of dishware. The compositions contain a nonionic surfactants, phosphate builder salt, and an alkali metal silicate and optionally a bleaching agent. *00 1 J ~t j