CA2145104A1 - Automatic dishwashing composition containing bleach activators - Google Patents

Abstract

An automatic dishwasher detergent is described which contains: (a) from about 0.01% to about 8%, available oxygen (AvO) added as a peroxygen bleach selected from the group consisting of percarbonate, perborate, monopersulfate and mixtures thereof; (b) from about 0.01% to about 10%, of bleach activator selected from the group consisting of benzoylcaprolactam, 4-nitrobenzoylcaprolactam, 3-chlorbenzoyl-caprolactam,nonanoyloxybenzenesulphonate,decanoyloxybenzenesulphonate,benzoyl-valerolactam, octanoyloxybenzenesulphonate, phenylbenzoate, derivatives and mixtures thereof; and (c) from about 0.1% to about 50%, of pH adjusting component, said component providing a wash solution pH from about 8 to about 13. The molar ratioof AvO to bleach activator in the composition is at least 1:1.

Description

2I~5I 04 -AUTOMATIC DISHWASHING COMPOSITION
CONTA~NING BLEACH ACTIVATORS

TECHNICAL FELD
The present invention is in the field of automatic dishwashing detergents.
More specifically, the invention relates to granular automatic dishwashing detergents which provide enhanced cleaning and other benefits, e.g. glass care benefits. The automatic dishwashing compositions comprise a peroxygen bleach component and a oxybenzene sulfonate, valerolactam, and/or caprolactam, particularly valerolactam or caprolactam, type bleach activator at a wash solution pH of at least 8.

BACKGROUND OF THE INVENT~ON
s Automatic dishwashing detergents (hereinafter ADDs) used for washing tableware in the home or institutionally in machines especi~lly designed for thepurpose have long been known. Dishwashing in the seventies is reviewed by Mizunoin Vol. 5, Part III of the Surfactant Science Series, Ed. W.G. Cutler and R.C. Davis, Marcel Dekker, N.Y., 1973, incorporated by rererence. The particular requirements of cle~ncing tableware and leaving it in a sanitary, essenti~lly spotless, residue-free state has indeed resulted in so many particular ADD compositions that the body of art pe,laining thereto is now recognized as quite distinct from other cleansing product arts.
In light of legicl~tiQn and current env.lol".,en~al trends, modern ADD products desirably contain low levels or are sub~an~ially free of inorganic phosphate builder salts and/or are conce.,lra~ed formulations (i.e. 1/2 cup vs. full cup usage).
Unfortunately, nonphosphated ADD products in technical ter ns may sacrifice efficacy, especi~lly owing to the deletion of phosl~h~e and, in some inct~ncec, chlorine .. ~ r cleansing ingredients. Concen~,ated or compact compositions 30 similarly e~hibit formulation problems.
Users of ADDs have come to expect tableware will be rendered e~sPnti~lly spotless and film-free in addition to cleaning In practice, this means avoiding film-forming components. The formulator must employ ingredients which are sufficiently soluble that residues or build-up do not occur. Again, while some ingredients may be 35 adequate on grounds of cleaning, spotting and filming, solubility considerations may diminish their llsefi11ness Solubility considerations are even more acute with the -newer "low usage", "concentrated", ADD compositions whose overall solubility canbe less than that of conventional ("full cup") products.
It has generally been believed by the forrnulator of ADDs that inexpensive cleaning can be achieved via high alkalinity and/or high silicate levels (for example as s provided by forrnulations comprising high percentages by weight of sodium hydroxide or metasilicate). It has been discovered that severe penalties result in these compositions in terms of product corrosiveness to dishwashers and tableware, especially china and glassware and incompatibility with other detergent ingredients.
It is therefore highly desirable, at least in some phosphate-free compact ADDs, to 10 achieve good cleaning end-results without resorting to the use of high alkalinityAligh - silicate.
Peroxygen bleaches are effective for stain and/or soil removal, but such bleaches are te...?elal-Jre and/or pH dependent. As a consequence, there has been a substantial amount of research to develop bleaching systems which contain an activator that renders peroxygen bleaches effective in various wash liquor conditions.
A widely-used bleach activator in ADDs is tetraacetyl ethylene ~i~mine (TAED). TAED provides some hydrophilic cle~ning especi~lly food and beverage stains, but there are problems associated with its use, i.e. slow to release andinefficient dissolution. It has now unexpectedly been discovered that automatic dishwashing detergents, preîe.~bly granular or powder-form, can be provided withimproved cleaning and glasscare benefits by forrnulAting sPlected peroxygen bleach compounds, preferably inorganic salts delivering hydrogen peroxide when dissolved in water, with oxyl,e~zene sulfonate, valerolactam and/or caprolactam activatorspreferably valerolactarn or caprolactam activators1 into the ADDs. These ADD
2s formulations have particularly defined pH ranges and bleach (AvO) to bleach activator ratios. The composition when dissolved at from about 2000 to about 6000 ppm (parts per million) preferably from about 2500 to about 4500 ppm in an automatic dishwasher affords a pH in the range from about 8 to about 13, more preferably from about 9 to about 12, even more pl~Çe~bly from about 9.5 to about11.5. The.molar ratio of bleach (AvO) to bleach activator is at least 1:1, preferably from about 20:1 to about 1:1, more preferably from about 10:1 to about 3:1.
In addition it has been determined that some bleaçhin~ systems, particularly those co-." -;s;ng certain bleach activators and a source of hydrogen peroxide, the bleach activator undergoes perhydrolysis to form a peroxyacid bleaching agent. A3s by-product of the perhydrolysis reaction between such bleach activators and hydrogen peroxide is a diacylperoxide (DAP) species. It has now further been discovered that the DAP's derived from these activators tend to be insoluble, poorly dispersible, oily materials which form a residue which can deposit on the natural rubber machine parts that are exposed to the wash liquor. The oily DAP residue can form a film on the natural rubber parts and promote free radical and peroxide damage to the rubber, which eventually leads to failure of the part. This is particularly true of s rubber parts which have prolonged exposure to the wash liquor.
By the present invention, it has now been discovered that the class of bleach activators especially those derived from caprolactams and valerolactams form peroxyacids upon perhydrolysis without the production of oily, harmful DAP's.
Without intending to be bound by theory, it is believed that these bleach activators 0 provide good cleaning performance with safety to natural rubber, since they do not expose the natural rubber machine parts or articles to DAP oxidation. Whatever the reason, natural rubber parts and articles remain substantially un~ ged by the bleaching systems of the present invention.
Although all the bleach activators disclosed perform efflciently at a pH range 5 from about 8 to about 13. It has been surprisingly found that ox~l,el~cne sulphonate or valerolactam bleach activators are especially effi~ient in ADD formulations at pH
wash solution ranges from about 8 to about 9.5.

The novel ADDs have the property of removing stains, especially tea stains, and tough food objected to by the consumer from dishware, even in a low, i.e. mildly 20 alkaline, pH. The compositions have other cleaning and spotlessness advantages such as enh~nced glass care (i.e. reduction of cloudiness and iridescence negatives) and reduction of silicate/carbonate deposition filming negatives. ADD embo~iments including phosphate free compositions and enzyme-cG."ah-ing co...posilions are provided for powerful cle~ning of wide-ranging 50ils while ,el~ining the advantages 2s of a generally mild and noncorrosive product matrix.

SUMMARY OF THE INVENTION
The present invention enco~.,p~sses automatic dishwashing detergent compositions, espec~ y granular or powder-form automatic dishwashing detergent compositions, co,.",. ;sing by weight (a) from about 0.01% to about 8%, prere-ably 0.1 to about 5%, more preferably from about 0.3% to about 4%, most p,e~-ably from about 0.8% to about 3% (as AvO) of peroxygen bleach selected from the group consisting of percarbonate, perborate, monope.~ul&te and mixtures thereof;
(b) from about 0.01% to about 15%, preferably from about 1% to about 3s 10%, more preferably from about 0.1% to about 8%, of bleach activator selected ` - - 214S104 -from the group comprising benzoyloxybenzenesulphonate (BOBS), benzoylcaprolactam (BZC~), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), nonanoyloxybenzenesulphonate (NOBS), phenylbenzoate (PhBz), decanolyoxybenzenesulphonate (Clo-OBS) derivatives; and s mixtures thereof; and (c) from about 0.1% to about 50%, preferably from about 5% to about 30%, of pH adjusting components, said component providing a wash solution pH
from about 8 to about 13, preferably from about 9 to about 12;
wherein a molar ration of component (a) to component (b) is from about 20:1 to 0 about 1:1, preferably from about 10:1 to about 3:1.
While peroxygen bleach compounds, activator and suitable pH agents are the essenti~l ingredients to the present invention, there are also provided embodiments wherein additional components, especially silicate, enzymes, bleach catalyst and/or nonionic surfactant are desirably present. Highly p-tfelled embodirnen~s of the invention are substantially free from phosphate salts and have low (e.g., < 15% SiO ) total silicate content. Additional components include but are not limited to su3s suppressors, other detergent surf~ct~nt~ and mixtures thereo The present invention also encompasses a method for cleaning soiled tableware comprising contacting said tableware with an aqueous medium having a pH in the range from about 8 to about 13, more preferably from about 9 to about 12, and comprising at least from about 0.01% to about 8% (as AvO) of a peroxygen bleach selected from the group consisting of percarbonate, p~,.bo~te, persulfate and mixtures thereof; and from about 0.01% to about 15% bleach activator selected from the group consisting of benzoyloxybel~el1es.llphonate (BOBS), benzoylcaprolactarn (BZCL), benzoylvalerolact~m (BZVL) octanoyloxybefi~nesnlphonate (Cg-OBS), nonanoyloxyb~ Pn~,..lphonate (NOBS), phenylbenzoate (PhBz), decanoyloxybellzene~ lphonate (Clo-OBS)t derivatives; and mixtures thereof. The es~ peroxygen bleach component, activator and pH adjusting agents are added in a solid form to an automatic dishwashing rn~ ine DETAILED DESCRIPTION OF THE rNVENTION
An automatic dishwashing detergent composition comprising by weight:
a) from about 0.01% to about 8% (as AvO) of a peroxygen bleach selected from the group consisting of percarbonate, perborate, monopersulfate and mixtures thereof;
b) from about 0.01% to about 15% of a peroxygen bleach activator selected from the group consisting of benzoylcaprolactam (BzCL), 4-214510~
s -nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (~rOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulphonate (Clo-OBS), benzolyvalerolactam (BZVL), . octanoyloxybenzenesulphonate(Cg-OBS), s pernydrolyzable esters and mixtures thereof, preferably benzoyloxybenzenesulphonate (BOBS), benzoylcaprolactam(BZCL), benzoylvalerolactam (BZVL) octanoyloxybenzenesulphonate(Cg-OBS), nonanoyloxybenzenesulphonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulphonate (CloOBS), derivatives; and mixtures thereof;
0 most preferably benzoylvalerolactam, and benzoylcaprolactam and mixtures thereof; and c) from about 0.1% to about 50% of a pH adjusting component to provide a wash solution pH of from about 8 to about 13;
wherein said composition comprises an AvO to bleach activator ratio of at least 1:1.
A particularly p~e~ed embodiment is phosphate free and further comprises from about 0.5% to about 12%, active detersive enzyme and bleach catalyst.
The term "substantially free" herein refers to subslances that are not intentionally added to the ADD but could be present as impurities in commercial grade raw materials or feedstocks. For example, the present invention encompasses substantially phosphate-free embodiments. Such embodiments generally comprise less than 0.5% of phosphate as P2Os.
The term "wash solution" is defined herein to mean an aqueous solution of the product dissolved at 2,000-6,000 ppm, prefe, ably at 2,500-4,500 ppm, in an automatic dishwasher.
2s Peroxygen Bleach The ADD co-,-pos;lions of the present invention contain an amount of oxygen bleach sl~fficient to provide from 0.01% to about 8%, preferably from about 0.1% to about 5.0/O, more p~ere~ably from about 0.3% to about 4.0%, most preferably from about 0.8% to about 3% of available oxygen (AvO) by weight of the ADD.
Avai!able oxygen of an ADD or a bleach component is the equivalent bleaching oxygen content thereof e,~l)resse~ as %O. For example, co~llne.~;ially availablesodium perborate monohydrate typically has an available oxygen content for bleaching purposes of about 15% (theory predicts a maximum of about 16%).
Methods for determining available oxygen of a formula after m~nuf~cture share similar chemical principles but depend on whether the oxygen bleach incorporatedtherein is a simple hydrogen peroxide source such as sodium perborate or percarbonate, is an activated type (e.g., perborate with tetra-acetyl ethylenediamine) or comprises a preformed peracid such as monoperphthalic acid. Analysis of peroxygen compounds is well-known in the ar~ see, for example, the publications of Swern, such as "Organic Peroxides", Vol. I, D.H. Swern, Editor; Wiley, New York,1970, LC # 72-84965, incorporated by reference. See for example the calculation of s "percent active oxygen" at page 499. This term is equivalent to the terms "available oxygen" or "percent available oxygen" as used herein.
The peroxygen bleaching systems useful herein are those capable of yielding hydrogen peroxide in an aqueous liquor. These compounds include but are not limited to the alkali metal peroxides, organic peroxide bleaching compounds such as 0 urea peroxide and inorganic persalt bleaching compounds such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used.
Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono-, tri-, and tetra-hydrate, sodium 5 pyrophosphate peroxyhydrate,, urea peroxyhydrate, sodium percarbonate, and sodium peroxide. Particularly prefer.ed are sodium p~,.borate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Pc;lca~bolldte is especially prefe, . ed because of envi~on~e~ issues associated with boron. Many geographiesare forcing legislation to eliminate ele.lie..ls such as boron from formulations.
Suitable oxygen-type bl~ ~ches are further described in U. S. Patent No.
4,412,934 (Chung et al), issued November 1, 1983, and peroxyacid bleaches described in European Patent Application 033,259. Sagel et al, published September 13, 1989, both inco~,orated herein by refe.ence, can be used.
Highly p~efe~lc~ percarbonate can be in uncoated or coated form. The average 2s particle size of llncs~ted p~,;cd-l,onate ranges from about 400 to about 1200 microns, most prefe~dbly from about 400 to about 600 microns. If coated pe.-,a.l,onate isused, the p~ ,d coating materials include cd bonate, sulphate, silicate, borosilic~tç~ fatty carboxylic acids, and mixtures thereof.
Activator For ~he excellent bleaching results of the present invention the peroxygen bleach component is form~ ted with an activator (peracid precursor). The activator is present at levels of from about 0.01% to about 15%, preferably from about 1% to about 10%, more preferably from about 1% to about 8%, by weight of the composition. P~ . . . d activators are selected from the group consisting of 3s benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chloroben_oylcaprolactam, benzoylox~l,en~Pne j~llphonate (BOBS), nonanoyloxyben7enesulphonate (NOBS), phenylbenzoate (PhBz), 214~104 decanoyloxybenzenesulphonate (C I o-OBS), benzolyvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzolyvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those s selected having an OBS or VL leaving group.
Preferred caprolactam derived activators are of the formula:
o ll I CH
R'--C N
\ CH2 CH2 wherein Rl is a hydrocarbyl subsituent which contains at least 6 carbon atoms.
Other plefe--ed caprolactams have the formula:
o R1 o C C H2--C H2 \

R3~R5 \ CH2 CH2 /

wherein Rl, R2,R3,R4 and Rs contain from 1 to 12 carbon atoms, preferably from 1to 6 carbon atoms and are .ne",be,s selected from the group consisting of H, halogen, alkyl, alkoxy, alkoxyaryl, arlaryl, alkaryloxy, and substitllentc having the - 15 stmcture:
o O O O
X C ~ C N--R7 ~ and C N
\ /

wherein R6 is selected from the group consisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, and aminoalkyl. X is 0, NH or NR7, wherein R7 is H or a C I -C4 alkyl group; and R8 is an alkyl, cycloalkyl, or aryl group containing from 3 to 11 20 carbon atoms; provided that at least one R substituent is not H.
P~ere~d valerolactam activators are selected from the group consisting of:

214S10~

O ~, C H2 C H2 Il I
R' C N
\ CH2--CH2 wherein R is a substituted or unsubstituted, including saturated or unsaturated alkyl, or alkoxy group containing from about 1 to about 18 carbon atoms, wherein the s longest linear alkyl or alkoxy chain extending from and including the carbonyl carbon containing from about 2 to about 12 carbon atoms.
ii) o R, ~ C H2 C H2 R~R5 \ CH2 CH2 wherein Rl, R2, R3j R4, and Rs may be the same or di~rênt substituents selected from the group consisting of H, halogen, alkyl, alkoxy, alkoxyaryl, alkaryl, andalkaryloxy moieties having from about I to about 12 carbon atoms, preferably from about 3 to about 12 carbon atoms, and sustituents hav`ing the structure:
O O O O
-X-C-R7, -C-N-R9, and -C-N-C

wherein R7 is selected from the group consisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, and aminoalkyl, X is O, NE~ of NR9, wherein R9 is H or aCl-C4 alkyl group; R8 is an alkyl, cycloalkyl, or aryl group containing from 3 to 11 carbon atoms.
The prefe"ed phenylbenzoate activators have the general forrnula:
R, ~0 C $~ R2 wherein Rl, R2, R3, E~4, and Rs may be the same or dif~erent substituents selected from the group consisting of H, halogen, alkyl, alkoxy, alkoxyaryl, alkaryl, andalkaryloxy moieties having from about I to about 12 carbon atoms, preferably from about 3 to about 12 carbon atoms.
Other bleach activators which may be used in the present invention, include the amido-derived bleach activators of the general forrnula:
O C O
R~l~--Nl--R2 1 L, Rl--N ~ _R2 _~ ~

or mixtures thereof, wherein Rl is a alkyl, aryl, or alkaryl group cont~ining from about I to about 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group0 containing from about I to about 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from about I to about 10 carbon atoms, and L is a leaving group.
Also, the benzoxazin-type bleach activators of the formula may be used:

R~ n, wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and Rsmay be the same or di~.enl substiuents selected from H, halogen, alkyl, alkenyl,aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein R6 is H or an alkyl group and carbonyl functions.
Plefelled bleach activators are those described in U.S. Patent 5,130,045, Mitchell et al, and 4,412,934, Chung et al, and copending patent applications U. S.
Serial Nos. 08/064,624, 08/064,623, 08/064,621, 08/064,562, 08/064,564, 08/082,270 and copending application to M. Burns, A.D. Willey, R.T. Hartshorn, C.K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and having U.S. Serial No. (P&G Case 4890R), 2s all of which are incorporated herein by reference.
The mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1: 1, preferably from about 20: 1 toabout l:l,morepreferablyfromabout 10:1 toabout3:1.

pH-Adjusting Control Components The compositions herein comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
It has been discovered that to secure the benefits of the invention, the peroxygen s bleaching component must at least be combined with a pH-adjusting component which delivers a wash solution pH of from 8 to about 13, preferably from about 9 to about 12, more preferably from about 9.5 to about 11Ø The pH-adjusting component are selected so that when the ADD is dissolved in water at a concentration of 2000 - 6000 ppm, the pH remains in the ranges discussed above.
o The preferred non phosphate pH-adjusting component embodiments of the invention is selected from the group consisting of (i) sodium carbonate or sesquicarbonate (ii) sodium silicate, preferably hydrous sodium silicate having SiO2:Na2O ratio of from about 1.:1 to about 2:1;
5 (iii) sodium citrate (iv) citric acid (v) sodium bic&ll,ona~e (vi) sodium borate, preferably borax (vii) sodium hydroxide; and 20 (viii) mixtures of (i)-(vii).
Plefelled embodiments contain low levels of silicate (i.e. Iess than 10% SiO2).
Illustrative of highly p.ere.red pH-adjusting component systems are binary mixtures of granular sodium citrate with anhydrous sodium carl.onate, and three-component mixtures of granular sodium citrate trihydrate, citric acid monohydrate 2s and anhydrous sodium bicarbonate.
The amount of the pH adjusting component in the instant ADD compositions is generally from about 0.9% to about 99%, p~eferably from about 1% to about 50%, by weight of the composition. ~n a prefelled embodiment, the pH-adjusting component is present in the ADD composition in an amount from about 5% to about 30 40%, prefe~bly from about 10% to about 30%, by weight.
For compositions herein having a pH between about 9.5 and about 10.5 (i.e.
the initial wash solution) particularly p(efe..ed ADD embodinlerlts comprise, byweight of ADD, from about 5% to about 40%, preferably from about 10% to about 30%, most pre~ably from about 15% to about 20%, of sodium citrate with from 3s about 5% to about 30%, preferably from about 7% to 25%, most preferably from about 8% to about 20% sodium carbonate.

Il -The essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from nonphosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, o ethylenediamine disucçinic acid (especially the S,S- form); nitrilotriacetic acid, tartrate monosuccinic acid, tartrate ~i~uccirlic acid, oxydi~lccinic acid, carboxymethyloxysuccinic acid, mellitic acid, and sodium benzene polycarboxylatesalts.
Bleachable stain benefits can be achieved by deployment of an activator containing oxygen bleach system tliscussed herein above in a controlled pH system.
The pH control system delivers a pH "jump/drop" profile wherein the pH rises quickly (i.e. within 1 minute) in the wash to an initial pH of from about 9.S to about 13, preferably from about 9.8 to about 12, more preferably from about 9.9 to about 11. This initial pH is rn~int~ined for a sufficient period of time, preferably from about 10 seconds to about 10 minlltes~ more preferably from about 0.5 minutes to about 3 minutes. The initial high pH allows sufficient peracid formation via perhydrolysis of the activator(s). The initial pH is then reduced to a pH of less than about 9.S. The pH jump/drop profile ~ inlizes bleach pe, fo""ance and enhances glass care protection when low levels of silicate llisa~s~ed herein are present.
Co~-lpoa;lions of the present invention having a wash solution pH from about 8 to about 9.5 co."~" ise a bleach activator sele~led from the group having an oxyl~,nzene sulphonate or valerolactam leaving groups.
In general, pH values of the instant compositions can vary during the course of the wash as a result of the water and soil present. The best procedure for dete"~ining whether a given composition has the herein-indic~ted pH values is asfollows: prepare an aqueous solution or dispersion of all the ingredients of thecomposition by mixing them in finely divided form with the required amount of water to have a 3000 ppm total concentration. Do not have any coatings on the particles capable of inhibiting dissolution. (In the case of the second pH adjusting component it should be omitted from the forrnula when determining the formula's initial pHvalue). Measure the pH using a conventional glass electrode at ambient temperature, within about 2 minutes of forming the solution or dispersion. To be clear, this 21~S10~

procedure relates to pH measurement and is not intended to be construed as limiting of the ADD compositions in any way; for example, it is clearly envisaged that fully-forrnulated embodiments of the instant ADD compositions may comprise a variety of ingredients applied as coatings to other ingredients, particularly the second pHs adjusting component.
Bleach Catalyst The bleach catalyst material which can is an optional but preferable ingredient, can comprise the free acid forrn, the salts, and the like.
One type of bleach catalyst is a catalyst system comprising a heavy metal 0 cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability con~lants for the catalytic and auxiliary metal cations, particularly ethylenedi-arninetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereo Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the m~ng~nese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Plefe~led examples of theses catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O) I (u-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(C1O4)2, MnIV4(u-o)6( l ,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-o) 1 (u-OAc)2(1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof.
Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododeç~ne, 2-methyl- I ,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful in machine dishwashing compositions and col-c~ .ated powder dete,~,e.~l compositions may also be selected as appropl;ate for the present invention. For examples of suitable bleach catalysts see U.S. Pat.
4,246,612 and U.S. Pat. 5,227,084.
See also U.S. Pat. 5,194,416 which teaches mononuclear m~ng~nese (IV) complexes such as Mn(1,4,7-trimethyl- 1,4,7-triazacyclononane(OCH3)3 (PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is awater-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH
3s groups. Plefelred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
Said ligands are of the formula:

I I
R I -N=C-B-C=N-R4 wherein Rl, R2, R3, and R4 can each be selected from ~I, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted B is a bridging group selected from O, S.
0 CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Plefe,led ligands includepyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with substit1lerlts such as alkyl, aryl, alkoxy, halide, and nitro. Particularly pr~r~"ed is the ligand 2,2'-bispyridylamine. Plefelled s bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmeth~ne and -bispyridylamine complexes. Highly prefel, ed catalysts include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2O2ClO4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)sCI, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-0)2MnIVN4)+and [Bipy2MnIII(u-0)2MnIVbipy2]-(C104)3.
The bleach catalysts of the present invention may also be prtpared by combining a water-soluble ligand with a water-soluble n~ng~rlese salt in aqueous2s media and conce~tlating the resulting mixture by evaporation. Any convenient water-soluble salt of m~ng~nese can be used herein. M~ng~nese (II), (III), (IV) and/or (V) is readily available on a commercial scale. In some instances, sufficient n~np~rlese may be present in the wash liquor, but, in general, it is plefe--ed to add ~ cations in the compositions to ensure its presence in catalytically-effective amounts. Thus, the sodium salt of the ligand and a mc~nber selected from the group consisting of MnSO4, Mn(ClO4)2 or MnC12 (least p(efe.red) are dissolved in waterat molar ratios of ligand:Mn salt in the range of about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-oxygen~ted by boiling and cooled by spraying with nitrogen. The resulting solution is evaporated (under N2, if desired) and the 3s resulting solids are used in the bleaching and detergent compositions herein without further purification.

- `~ 14 21~5104 In an alternate mode, the water-soluble manganese source, such as MnSO4, is added to the bleach/cleaning composition or to the aqueous bleaching/cleaning bath which comprises the ligand. Some type of complex is apparently formed in situ, and improved bleach performance is secured. In such an in situ process, it is convenient s to use a considerable molar excess of the ligand over the manganese, and mole ratios of ligand:Mn typically are 3:1 to 15:1. The additional ligand also ser~es to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from decomposition. One possible such system is described in European patent application, publication no. 549,271.
o While the structures of the bleach-catalyzing manganese-complexes of the present invention have not been elucidated, it may be spec~ ted that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the m~n~nese cation.
Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state.
Due to the ligands' possible six points of ~tt~cllment to the manganese cation, it may be reasonably specul~ted that multi-nuclear species and/or "cage" structures mayexist in the aqueous bleaching media. Whatever the form of the active Mn-ligand species which actually exists, it functions in an apparently catalytic maMer to provide improved bleaching performances on stubborn stains such as tea, ketchup, coffee,wine, juice, and the like.
Other bleach catalysts are descl ibed, for example, in European patent application, publication no. 408,131 (cobalt co".~ Y catalysts), European patentapplications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), 2s U.S. 4,728,455 (.l~np~nese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absol l.ed manganese on minosilic~te catalyst), U.S. 4,601,845 (aluminosilicate support with m~n~nese and zinc or m~gnesium salt), U.S. 4,626,373 (m~ng~nes~ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobaltchelant catalyst) Can~di~n 866,191 (transition metal-co~ ining salts), U.S.
4,430,243 (chelants with manganese cations and non-catalytic metal cations), andU.S. 4,~28,455 (manganese gluconate casalysts).
Silicates The compositions of the type described herein optionally, but preferably 3s comprise alkali metal silicates. The alkali metal silic~tes hereinafter described provide pH adjusting- capability, protection against corrosion of metals and against attack on dishware, inhibition of corrosion to glasswares and chinawares. The SiO2 214510~
~s level is from about 0.5% to about 20 %, preferably from about 1% to about 15%, more preferably from about 2% to about 12%, most preferably from about 3% to about 1 1%, based on the weight of the ADD.
It has been found that at wash solutions of greater than pH 9.5 the presence of s silicate (as SiO2), especially at levels of greater than 11%, may negatively impact glasscare (i.e. glass corrosion). Therefore for overall enhanced performance, sodium silicate levels preferably should be kept at low levels and in the presence of low pH, preferably pH from about 7 to about 9.4, more preferably from about 8.5 to about9.3.
0 Glasscare can be enhanced when the wash solution pH comprising a dissolved silicate containing ADD is less than 9.5, preferably from about 6.5 to about 9.5, more preferably from about 7.0 to about 9.3, most preferably from about 8.0 to about 9.2.
Under these conditions the SiO2 level is from about 0.5% to about 12 %, preferably from about 1% to about 11%, more prefe,~bly from about 2% to about 10%, most preferably from about 3% to about 9%, based on the weight of the ADD. The ratio of SiO2 to the alkali metal oxide (M2O, where M=alkali metal) is typically from about I to about 3.2, preferably from about I to about 3, more preferably from about I to about 2.4. Preferably, the alkali metal silicate is hydrous, having from about 15% to about 25% water, more prefelably, from about 17% to about 20%.
Anhydrous forms of the alkali metal silicates with a SiO2:M2O ratio of 2.0 or more are also less pr~Çe~ed because they tend to be significantly less soluble than the hydrous alkali metal silicates having the same ratio.
Sodium and pot~csium, and especially sodium, silicates are prefe.fed. A
particularly p.e~- .ed alkali metal silicate is a granular hydrous sodium silicate having 2s a SiO2:Na2O ratio of from 2.0 to 2.4 available from PQ Corporation, named Britesil H20 and Britesil H24. Most prefelled is a granular hydrous sodium silicate having a SiO2:Na2O ratio of 2Ø While typical forms, i.e. powder and granular, of hydrous silicate particles are suitable, plefelled silicate particles have a mean particle size between about 300 and about 900 microns with less than 40% smaller than 150 microns and less than 5% larger than 1700 microns. Particularly prefelled is a silicate particle with a mean particle size between about 400 and about 700 microns with less than 20% smaller than 150 microns and less than 1% larger than 1700 microns.
Other suitable silicates include the crystalline layered sodium silicates have the 3s general formula:
NaMSix02x+ 1 .yH20 214~104 -wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above s has a value of 2, 3 or 4 and is preferably s. The most preferred material is -Na2Si2Os, available from Hoechst AG as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.
Low-Foaming Nonionic Surfactant ADD compositions of the present invention can comprise low foaming nonionic surfactants (LFNIs). LFNI can be present in amounts from 0 to about 10%by weight, preferably from about 0.25% to about 4%. LFNIs are most typically used s in ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-silicone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
Preferred LFNIs include nonionic allcoxylated surf~ctAntc, especially ethoxylates derived from primary alcohols, and blends thereof with more sophisticated surf~ctAnts, such as the polyoxypropylene/polyoxyethylene/
polyoxypropylene reverse block polymers. The PO/EO/PO polymer-type surfactants are well-known to have foam suppressing or defoal,ung action, especi~lly in relation to common food soil ingredients such as egg.
The invention encompq~sçs preferred embo~iments wherein LFNI is present, and wherein this cGn,pone.,t is solid at about 95F (35C), more preferably solid at about 77F (25C). For ease of m~nuf~cture, a prefe"ed LFNI has a melting point between about 77F (25C) and about 140F (60C), more preferably between about 80F(26.6C) and 110F (43.3C).
In a plefelle~ embodiment, the LFNI is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol col~A;n;ng from about 8 to about 20 carbon atoms, excluding cyclic carbon atoms, with from about 6 to about15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
A particularly p,efe,red LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 6-C20 alcohol), preferably a C alcohol~ condçnsed with an average of from alout 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to 21~I04 1~

about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution relative to the average.
The LFNI can optionally contain propylene oxide in an amount up to about s 15% by weight. Other preferred LFNI surfactants can be prepared by the processes described in U. S . Patent 4,223 ,163, issued September 16, 1980, Builloty, incorporated herein by reference.
Highly preferred ADDs herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally comprise a 0 polyoxyethylene, polyoxypropylene block polymeric compound; the ethoxylated monohydroxy alcohol or alkyl phenol fraction of the LFNI comprising ~om about 20% to about 80%, preferably from about 30% to about 70%, of the total LFNI.
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described herein before include those based on ethylene 5 glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediz~l~ine as initiator reactive hydrogen compound. Polymeric compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom~ such as C12 18 aliphatic alcohols, do not generally provide s~ti~f~ctory suds control in the instant ADDs. Certain of the block polymer 20 surfactant compounds designated PLURONIC~) and TETRONIC~) by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the mventlon.
A particularly p~erelled LFNI contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend 2s comprising about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene conlaining 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene initi~ted with trimethylolpropane and co~llaining 99 moles of propylene oxide and 24 moles of ethylene oxide per mole 30 ofllill.~lll~!olpropane.
Suitable for use as LFN~ in the ADD compositions are those LFNI having relatively low cloud points and high hydrophilic-lipophilic balance (HLB). Cloudpoints of 1% solutions in water are typically below about 32C and preferably lower, e.g., 0C, for optimum control of sudsing throughout a full range of water 3s temperatures.
LFNIs which may also be used include a C 18 alcohol polyethoxylate, having a degree of ethoxylation of about 8, commercially available SLF18 from Olin Corp.

21~5104 and any biodegradable LFNI having the melting point properties discussed herein above.
Anionic Co-surfactant The automatic dishwashing detergent compositions herein can additionally s contain an anionic co-surfactant. When present, the anionic co-surfactant is typically in an amount from 0 to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.5% to about 5%, by weight ofthe ADD composition.
Suitable anionic co-surfAct~nt~ include branched or linear alkyl sulfates and sulfonates. These may contain from about 8 to about 20 carbon atoms. Other 0 anionic cosurfactants include the alkyl benzene sulfonates containing from about 6 to about 13 carbon atoms in the alkyl group, and mono- and/or dialkyl phenyl oxide mono- and/or di-sulfonates wherein the alkyl groups contain from about 6 to about 16 carbon atoms. All of these anionic co-surfactants are used as stable salts, preferably sodium and/or potassium.
Pre~e~ l ed anionic co-surfactants include sulfobetaines, bet~ines~
alkyl(polyethoxy)sulfates (AES) and alkyl (polyethoxy)carboxylates which are usually high sudsing. Optional anionic co-surf~cta~ts are further illustrated inpublished British Patent Application No. 2,116,199A; U.S. Pat. No. 4,005,027, Hartman, U.S. Pat. No. 4,116,851, Rupe et al; and U.S. Pat. No. 4,116,849, Leikhim, all of which are incorporated herein by reference.
Plefel,ed alkyl(polyethoxy)sulfate surf~ct~ntc CO-..~.liSC a primary alkyl ethoxy sulfate derived from the conden.cation product of a C6-C18 alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 5, ethylene oxide groups. The C -C alcohol itself is prefe.able co.."..~,rcially available. Cl -C15 2s alkyl sulfate whlch has been ethoxylated with from about I to about 5 moles of ethylene oxide per molecule is prefe~ led. Where the compositions of the invention are formul~te~ to have a pH of between 6.5 to 9.3, preferably between 8.0 to 9, wherein the pH is defined herein to be the pH of a 1% solution of the composition measured at 20C, surprisingly robust soil removal, particularly proteolytic soil 30 removal, is obtained when C10-C18 alkyl ethoxysul&te surfactant, with an average degree of ethoxylation of from 0.5 to 5 is incorporated into the composition in co,nbination with a proteolytic enzyme, such as neutral or alkaline proteases at a level of active enzyme of from 0.005% to 2%. Plefe..ed alkyl(polyethoxy)sulfate surfactants for inclusion in the present invention are the C12-C15 alkyl ethoxysulfate 3s surfactants with an average degree of ethoxylation of from I to 5, preferably 2 to 4, most preferably 3.

`_ 2145104 -Conventional base-catalyzed ethoxylation processes to produce an average degree of ethoxylation of 12 result in a distribution of individual ethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, so that the desired average can be obtained in a variety of ways. Blends can be made of material having different s degrees of ethoxyiation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distill~tion.
Alkyl(polyethoxy)carboxylates suitable for use herein include those with the formula RO(CH2CH20)x CH2C00-M wherein R is a C6 to Clg alkyl group, x o ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20%, preferably less than about 15%, most preferably less than about 10%, and the amount of material where x is greater than 7, is less than about 25%, preferably less than about 15%, most preferably less than about 10%, the average x is from about 2 to 4 when the average 5 R is C13 or less, and the average x is from about 3 to 6 when the average R isgreater than C13, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-amrnonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred alkyl(polyethoxy)carboxylates are those where R is a C12 to Clg alkyl 20 group.
Highly prefelred anionic cosurf~ct~nts herein are sodium or potassium salt-forms for which the col-esponding calcium salt form has a low Kraft te...i)ela~ure~
e.g., 30C or below, or, even better, 20C or lower. Examples of such highly prefe, . ed anionic cosurfactants are the alkyl(polyethoxy)sulf~tes.
2s The pr~ d anionic co-surf~ct~nts of the invention in combination with the other collrpollents of the composition provide exc~llent cleaning and outstan-ling p~.r~-.nance from the standpoints of residual spotling and filming. However, many of these co-surf~ct~nts may also be high sudsing thereby requiring the addition of LFNI, LFNI in cGIllbination with alternate suds suppresso-~ as further disclosedhereinafterl or alternate suds suppressors without conventional LFNI components.Arnine Oxide The ADD compositions of the present invention can optionally comprise amine oxide in laccordance with the general formula I:
R (EO) (PO) (BO) N(O)(CH2R')2.qH2O (I) 3s Inlgeneral, it can bYe seen that the structure (I) provides one long-chain moiety R (EO) (P0) (BO) and two short chain moieties, CH2R'. R' is preferably selected represents proYpyleneoxy; and BO represents butyleneoxy. Such amine oxides can be -21~5104 prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more s preferably they have melting-points in the range 30C to 90C. Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide m~nllf~cturers Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and 0 ADMOX 18 from Ethyl Corp.
Preferred embodiments include hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate and hexadecyltris(ethyleneoxy)dimethyl-amine oxide.
Whereas in certain of the preferred embodirnents R' = CH3, there is some 5 latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' = CH OH, such as heY~decylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethy~)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
As noted, certain p-efel-ed embodiments of the instant ADD compositions 20 comprise amine oxide dihydrates. Conventional processes can be used to control the water content and crystallize the amine oxide in solid dihydrate form. A new process comprises (a) conventionally making amine oxide as an aqueous solution or aqueous/organic solvent solution by reacting approp~iate parent amine and aqueous hydrogen peroxide (for eY~mrle, 50% H22); (b) drying the product to secure 25 substantially anhydrous amine oxide (with or without an organic solvent beingpresent to keep the viscosity low); (c) adding two mole equivalents of water per mole of amine oxide; and (d) recrystallizing the wet amine oxide from a suitable solvent, such as ethyl acetate.
In form-ll~ting the instant ADD compositions, the amine oxide may be added 30 to an AD~.composition as a powder. This is especi~lly approp. iate in the case of the amine oxide dihydrates, since these are nonhygroscopic solids. When it is desired to use the anhydrous form of the amine oxides, it is preferable to protect the amine oxide from moisture. It is contemplated to achieve this by conventional means, such as by applying a relatively nonhygroscopic coating, e.g., an anhydrous coating 35 polymer, to amine oxide particles. Alternately, and more preferably, the anhydrous amine oxide should be melted with a conventional low-melting, low-foaming waxy nonionic surfactant which is other than an amine oxide material. Such surfactants are `- 21~510~

-commonly used as "sheeting agents" in granular automatic dishwashing compositions and are illustrated more fillly hereinafter (see description herein below of lowfoaming nonionic surfactant or LFNI). A desirable process comprises heating the LFNI to just above its melting-point, then adding the amine oxide steadily to the s heated LFNI, optionally (but preferably) stirring to achieve a homogeneous mixture;
then, optionally (but preferably) chilling the mixture. When the LFNI has a lower melting point than the amine oxide, the amine oxide need not be completely melted at any stage. The above process illustrates a manner in which the time and extent of exposure of amine oxide to heat are minimized. Once co-melted into a suitable o LFNI, the combined LFNVamine oxide may be applied to an inorganic support, e.g., a pH-adjusting component described hereinafter). One suitable approach is to forrn an agglomerate comprising amine oxide, LFNI and water-soluble alkaline inorganicsalt or water-soluble organic or inorganic builder. In another embodiment, the amine oxide in anhydrous form is melted with a solid-form alcohol or, preferably, an 5 ethoxylated alcohol: this may be appropriate if more cleaning action is required and less sheeting action is desired (e.g., in geographies wherein rinse-aid use is common).
Preferred amine oxides herein are subalanlially free of amine and/or nitrosamine ("impurity"). Preferably, the amine oxide comprises less than about 2%
free amine, more preferably about 1% or lower; and less than about 500 parts per20 billion, more plef~, ~bly less than about 50 parts per billion by weight nitrosamine.
The present invention can contain from 0% to about 10%, preferably from about 1% to about 7%, more preferably from about 1.5% to about 1.5% of the long chain amine oxide; levels are generally expressed on an anhydrous basis unless otherwise specifically indicated.
25 Long-Chain Amine Oxide Solubilizing Aids ~ ithough short-chain amine oxides do not provide the cleaning effect of thelong-chain amine oxide component diccussed above, short-chain amine oxides, suchas octyldimethylamine oxide, decyldimethylamine oxide, dodecylamine oxide and tetradecylamine oxide may be added as solubilizing aids to the long-chain amine 30 oxide. This is especially preîel~ed if the composition is for use in cold-fill automatic dishwashing appliances. When present, a short-chain amine oxide solubilizer is preferably at not more than 1/10 of the total mass of the cle~ning amine oxide component. Thus, levels of short-chain amine oxide are typically in the range from about 0 to about 2.0%, preferably about 0.1% to about 1% of the ADD composition.35 Moreover, it has been discovered that a short-chain amine oxide, if used, is preferably uniforrnly dispersed within the long-chain amine oxide rather than being added to the ADD in a separate particle.

-2~ 219510~

When the granular automatic dishwashing compositions are destined for use in hot-fill automatic dishwashing appliances, e.g., those commonly available in theUnited States, the el sential long-chain amine oxide preferably comprises R =C 8 and is preferred over R =C ~ 6 on grounds of mass efficiency; in this circumstance tLe use s of short-chain amine oxlde solubilizers is typically avoided.
Non-amine oxide solubilizing aids can be substituted, for example, solid-form alcohols or alcohol ethoxylates (the same as may be independently used for sheeting action or protection of the long-chain amine oxide from water discussed herein above).
o Silicone and Phosphate Ester Suds Suppressors The ADDs of the invention can optionally contain an alkyl phosphate ester suds suppressor, à silicone suds suppressor, or combinations thereof. Levels in general are from 0% to about 10%, preferably, from about 0.001% to about 5%.
Typical levels tend to be low, e.g., from about 0.01% to about 3% when a silicone 5 suds suppressor is used. Preferred non-phosphate compositions omit the phosphate ester component entirely.
Silicone suds suppressor technology and other defoaming agents useful herein are extensively documented in "Defoaming, Theory and Industrial Applications", Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herein20 by reference. See especially the chapters entitled "Foam control in DetergentProducts" (Ferch et al) and "Surfactant Antifoams" (Blease et al). See also U.S.Patents 3,933,672 and 4,136,045. Highly preftl,ed silicone suds suppressors are the compounded types known for use in laundry detergents such as heavy-duty granules, although types hitherto used only in heavy-duty liquid detergents may also be 25 incorporated in the instant compositions. For exa~..ple, polydimethylsiloxanes having tli~ th~rlsilyl or alternate endblocking units may be used as the silicone. These may be compounded with silica and/or with surface-active nonsilicon components, as illustrated by a suds suppressor comprising 12% silicone/ silica, 18% stearyl alcohol and 70% starch in granular form. A suitable commercial source of the silicone active 30 compounds is Dow Corning Corp.
~ evels of the suds suppressor depend to some extent on the sudsing tendencyof the composition, for example, an ADD for use at 2000 ppm comprising 2%
octadecyldimethylamine oxide may not require the presence of a suds suppressor.
Indeed, it is an advantage of the present invention to select cleaning-effective amine 35 oxides which are inherently much lower in foam-forming tendencies than the typical coco amine oxides. In contrast, formulations in which amine oxide is combined with 23 21~5104 a high-foaming anionic cosurfactant, e.g., alkyl ethoxy sulfate, benefit greatly from the presence of suds suppressors.
Phosphate esters have also been asserted to provide some protection of silver and silver-plated utensil surfaces, however, the instant compositions can have s excellent silvercare without a phosphate ester component. Without being limited by theory, it is believed that lower pH formulations, e.g., those having pH of 9.5 and below, plus the presence of the essenti~l amine oxide, both contribute to improved sllver care.
If it is desired nonetheless to use a phosphate ester, suitable compounds are lo disclosed in U.S. Patent 3,314,891, issued April 18, 1967, to Schmolka et al, incorporated herein by reference. Preferred alkyl phosphate esters contain from 16-20 carbon atoms. Highly p~efe~ed alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
It has been found preferable to avoid the use of simple calcium-pre~ipitating soaps as antifoams in the present compositions as they tend to deposit on the dishware. Indeed, phosphate esters are not entirely free of such problems and the formulator will generally choose to minimize the content of potentially depositing antifoams in the instant compositions.
Detersive Enzymes (including enzyme adjuncts) The compositions of this invention may optionally, but preferably, contain from 0 to about 8%, preferably from about 0.001% to about 5%, more preferably from about 0.003% to about 4%, most preferably from about 0.005% to about 3%, by weight, of active detersive enzyme. The knowledgeable formulator will appreciate2s that di~-~,n~ enzymes should be selected depending on the pH range of the ADD
co.~.pc3;tion. Thus, Savinase~) may be preferred in the instant compositions when formu1?ted to deliver wash pH of 10, whereas Alcalase@) may be pleft. .ed when the ADDs deliver wash pH of, say, 8 to 9. Moreover, the formulator will generally select enzyme variants u~ith enh~nced bleach compatibility when forTrlul~tin~ oxygen b'eac~l~.s con~ ;ng compositions ofthe present invention.
In general, the ~r~fe.~.,d detersive enzyme herein is selected from the group COha;Slillg of prot~ s, amylases, lipases and mixtures thereof. Most prefelled are proteases or amylases or mixtures thereof.
The proteolytic enzyme can be of animal, vegetable or microorganism (prefe,.ed) origin. More prtfe.red is serine proteolytic enzyme of bacterial origin.
Purified or nonpurified forms of enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified rnutants are included by definition, as are close 214~104 structural enzyme variants. Particularly preferred by way of proteolytic enzyme is bacterial serine proteolytic enzyme obtained from Bacillus, Bacillus subtilis and/or Bacillus licheniformis. Suitable commercial proteolytic enzymes include Alcalase(~, Esperase(~, Durazym(3, Savinase(~), Maxatase(~), Maxacal(~)~ and Maxapem@) 15 s (protein engineered Maxacal); Purafect(~ and subtilisin BPN and BPN' are also comrnercially available. Preferred proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 0 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" herein. Most plcÇe-led iswhat is called herein "Protease C", which is a triple variant of an alkaline serine protease from Bacillus in which tyrosine replaced valine at position 104, serinereplaced asparagine at position 123, and alanine replaced l}ueor~ine at position 274.
Protease C is described in EP 90915958:4, co.~sponding to WO 91/06637, Published May 16, 1991, which is incorporated herein by reference. Genetically modified variants, particularly of Protease C, are also included herein. Some prefe..ed proteolytic enzymes are selected from the group consisting of Savinase(~), Esperase(!9, Maxacal(~), Purafect(Z~, BPN', Protease A and Protease B, and mixtures 20 thereof. Bacterial serine protease enzymes obtained from Bacillus subtilis and/or Bacillus lichen,fo...us are prefelled. An especially prefelled protease herein referred to as NProtease D" is a carbonyl hydrolase variant having an amino acid sequence not found in natur4 which is derived from a precursor carbonyl hydrolase by substituting a di~re.~t arnino acid for a plurality of amino acid residues at a position in said 2s carbonyl hydrolase equivalent to position +76 in combination with one or more amino acid residue position equivalent to those selected from the group consisting of +99, +101, +103, +107 and +123 in Bacillus amyloliquefaciens subtilisin as described in the concurrently filed patent application of A. Baeck, C.K. Ghosh, P.P. Greycar, RR. Bott and L.J. Wilson, entitled "Protease-Con~aining Cleaning Compositions"
and having U.S. Serial No. (P&G Case 5040). This application is incorporated herein by reference.
~lefel,ed lipase-co,ll~;nil~g compositions comprise from about 0.001 to about 0.01% lipase, from about 2% to about 5% amine oxide and from about 1% to about 3% low foaming nonionic surfactant.
3s Suitable lipases for use herein include those of bacterial, animal, and fungal origin, including those from chemically or genetically modified mutants. Suitable bacterial lipases include those produced by Pseudomonas, such as Pseudomonas 2s stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference. Suitable lipases include those which show a positive immunologicalcross-reaction with the antibody of the lipase produced from the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification s have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978, which is incorporated herein by reference. This lipase is available under the trade name Lipase P "Amano," hereina~er referred to as "Amano-P." Such lipases should show a positive imrnunological cross reaction with the Amano-P
antibody, using the standard and well-known immunodiffilsion procedure accordinglo to Oucheterlon (Acta. Med. Scan., 133, pages 76-79 (19S0)). These lipases, and a method for their immunological cross-reaction with Amano-P, are also described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987, incorporated herein by reference. Typical examples thereof are the Arnano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. Iipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum var.lipolyticum NRRlb 3673, and further Chromobacter viscosum lipases, and lipases ex Pseudomonas gladioli. A prefel,ed lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272. Other lipases of interest are Amano AKG and Bacillis Sp lipase (e.g. Solvay enzyrnes). Additional lipases which are of interest where they are co,l,patible with the composition are those described in EP A 0 339 681, published November 28, 1990, EP A 0 385 401, published September 5, 1990, EO A 0 218 272, published April 15, 1987, and PCT/DK
88/00177, published May 18, 1989, all incorporated herein by lel~l~,nce.
Suitable fi~ngal lipases include those produced by Hurnicola lanuginosa and Th~.,.G...~ces lq~nl~inosus. Most prefel,ed is lipase obtained by cloning the gene from ~ mlicolq~ Iq~ll)gnosa and e.~p~es~ing the gene in Aspergillus oryzae as described in European Patent Application 0 258 068, incorporated herein by reference, co.lulle~f ;ally available under the trade name LipolaseR from Novo-Nordisk.
Any amylase suitable for use in a dishwashing detergent composition can be used in these compositions. Arnylases include for example, 2-amylases obtained from a special strain of B. Iicheniforrns, descl,bed in more detail in British PatentSpeçifi~qtionNo. 1,296,839. Amylolytic enzymes include, for example, RapidaserU,MaxamylTU, TermamylT~ and BANT~. In a preft" ed embodiment, from about 3s 0.001% to about 5%, preferably 0.005% to about 3%, by weight of active amylase can be used. Preferably from about 0.005% to about 3% by weight of active protease can be used. Preferably the amylase is MaxamylTU and/or TermamylTU and 214~10~

the protease is Savinase(~) and/or protease B. As in the case of proteases, the formulator will use ordinary skill in selecting amylases or lipases which ex~ibit good activity within the pH range of the ADD composition.
Enzyme Stabilizing System s Preferred enzyme-cont~ining compositions, especially liquid compositions, herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can o comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
The stabilizing system of the ADDs herein may further comprise from 0 to about 10%, prefelably from about 0.01% to about 6% by weight, of chlorine bleachscavengers, added to prevent chlorine bleach species present in many water supplies from Attnc~ing and inactivating the enzymes, especially under alkaline conditions.
While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
Suitable chlorine scavenger anions are widely available, indeed ubiquitous, and are illustrated by salts co~Aining an~l,onium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylene~;z~ ,etetracetic acid (EDTA) or alkali metal salt thereof, monoeth~lol~mine (~A), and mixtures thereof can likewise be used. Other 2s conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium pell,o.~te tetrahydrate, sodium perborate monohydrate and sodium pe.cal~onale, as well as phosphate, condensed phosphate, acetate, benzoate, cit~ate, fo,l.late, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be performed by several~ofthe ih~,die.lts separately listed under better recognized functions, (e.g., other co"lpone~lts of the invention including oAygen bleaches), there is no requi~,.l,en~ to add a se~lâràle chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment ofthe invention; even then, the scavenger is added only for optimum results. Moreover, 3s the formulator will exercise a chemist's normal skill in avoiding the use of any scavenger which is tAl,~n~ely incompatible with other optional ingredients, if used.
For eY~mple, forrnulation chemi~t~ generally recognize that combinations of reducing 21~51~1g -agents such as thiosulfate with strong oxidizers such as percarbonate are not wisely made unless the reducing agent is protected from the oxidizing agent in the solid-form ADD composition. In relation to the use of ammonium salts, such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or s liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Patent 4,652,392, Baginski et al.
Dispersant Polymer Ple~l.ed compositions herein may additionally contain a dispersant polymer.
When present, a disp~,r~&ll~ polymer in the instant ADD compositions is typically in - the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 7% by weight of the ADD composition.
Dispelsanl polymers are useful for improved filming performance of the present ADD compositions, especially in higher pH embodiments, such as those in which wash pH eYçee~ls about 9.5. Particularly prefelred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
Dis~e.~ant polymers suitable for use herein are illustrated by the film-forming polymers described in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983, incorporated herein by reference.
Suitable polymers are preferably at least partially neutralized or alkali metal,allul~ol~ium or substihlted al,unollium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids. The alkali metal, especially sodium salts are most p, efelred.
While the mol~cul~r weight ofthe polymer can vary over a wide range, it preferably is from about 1000 to about 500,000, more preferably is from about 1000 to about250,000, and most preferably, especially if the ADD is for use in North Americanautom~ti~ d;;.h~..wlfll~g appliances, is from about 1000 to about 5,000.
Other suitable di~ &llt polymers include those disclosed in U.S. Patent No.
3,308,067 issued March 7, 1967, to Diehl, incorporated herein by reference.
Unsaturated monomeric acids that can be pol~n,c~ized to form suitable dispersantpolymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monornPric segments containing no carboxylate radicals such as methyl vinyt ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50% by weight of the dispersallt polymer.
Copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by 214~104 ._ weight of the dispersant polymer can also be used. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer.
Particularly preferred dispersant polymers are low molecular weight modified s polyacrylate copolymers. Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight 2f a slubstituted 3crylic monomer or its salt and have the general forrnula: -[(C(R )C(R )(C(O)OR )]- wherein the incomplete valencies inside o the square b[aces a2re hydrogen and at least one of the substituents R, R 2 or R ~
preferably R or R3, is a 1 to 4 carbon alkyl or hydroxyalkyl group, R or R can be a hydrogen and R can be a hydrogeln or alkali m2etal salt. Most pr3efe,-ed is a substituted acrylic monomer wherein R is methyl, R is hydrogen and R is sodium.
The low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most prere~ably from about 1,000 to about 5,000. The most p.efe~cd polyacrylate copolymer for use herein has a molecular weight of 3500 and is the fully neutralized form of the polymer comprising about 70% by weight acrylic acid and about 30% by weight meth~crylic acid.
Other suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766, and 5,084,535, both incorporated herein by reference.
Agglomerated forms of the present invention may employ aqueous solutions of polymer di~ye~lts as liquid binders for making the agglomerate (particularly when the composition COhS;~l~ of a mixture of sodium citrate and sodium carbonate).
Fspeci~lly pref~ d are polyacrylates with an average molecular weight of from about 1,000 to about 10,000, and acrylate/maleate or acrylate/ fumarate copolymers with an average nlo'ecvlsr weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 1:2. Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate mono,l,~,~ are ~ osed in European Patent Application No. 66,91S, published DecG",~er 15, 1982, incorporated herein by reference.
Other dispe~sant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be oblained from the Dow Chemical Company of Midland, Michigan.
Such compounds for e- ...ple, having a melting point within the range of from about 30O to about 100oC can be obtained at molecular weights of 1450, 3400, 4S00, 6000, 7400, 9500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. The polyethylene, s polypropylene and mixed glycols are referred to using the formula HO(CH2CH O) (CH2CH(CH3)O) (CH(CH3)CH20)OH wherein m, n, and o are integers satis~ying the molecular weight and temperature requirements given above.
Yet other dispe.~alll polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most p-e~l l ed polymer of this group.
Other suitable dispersant polymers are the carboxylated polysaccharides, particularly ~lalches~ celluloses and alginates, described in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starchethers, starch esters, oxidized starches, dextrins and starch hydrolysates desclil)ed in U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated slar~hes described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21, 1971; and the dextrin slarlhes described in U.S. Pat. No. 4,141,841, McDanald, issued Feb. 27, 1979; all incorporated herein by reference. Preferred cellulose-derived dispersant polymers are the carboxymethyl celluloses Yet another group of acceptable dispel sanls are the organic dispersant polymers, such as polyaspartate.
Corrosion Inhibitor The present co"~posilions may also contain corrosion inhibitor. Such corrosion inh;~ ols are p~e~lled components of m~chine dishwashing compositions in accord with the invention, and are preferably incorporated at a level of from 0.05%
to 10%, preferably from 0.1% to 5% by weight of the total composition.
Suitable co~l~s;on inhibitors include paraffin oil typically a predominantly ~ ched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50: prefe.,~d paraffin oil selected from predo",inanlly b.dnched C2s~s species with a ratio of cyclic to noncyclic hydrocarbons of about 32:68; a paraffn oil I;ng these characteristics is sold by Wintershall, Sal~rgen, Germany, under the trade name WINOG 70.
Other suitable corrosion inhibitor compounds include benzotriazole and any derivatives thereof, ~.ercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and .

thioanthranol. Also suitable are the C12-C20 fatty acids, or their salts, especially aluminum tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
s Other Optional Adjuncts Depending on whether a greater or lesser degree of compactness is required, filler materials can also be present in the instant ADDs. These include sucrose,sucrose esters, sodium chloride, sodlum sulfate, potassium chloride, potassium sulfate, etc., in amounts up to about 70%, preferably from 0% to about 40% of the 0 ADD composition. Ple~e,led filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.
Sodium sulfate used herein preferably has a purity sufficient to ensure it is non-reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates in m~n~ium-salt form. Note that prefeteilces, in terms of purity 5 sufficient to avoid decomposing bleach, applies also to builder ingredients.
Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc., can be present in minor amounts.
Bleach-stable perfumes (stable as to odor); and bleach-stable dyes (such as those disclosed in U.S. Patent 4,714,562, Roselle et al, issued December 22, 1987);
20 can also be added to the present compositions in appropriate amounts. Other common detergent ingredieuls are not excluded.
Since certain ADD compositions herein can contain water-sensitive ingredients, e.g., in embodirn~rlts comprising anhydrous amine oxides or anhydrous citric acid, it is desirable to keep the free moisture content of the ADDs at a 2s minimum~ e.g., 7% or less, preferably 4% or less of the ADD; and to provide packaging which is sllbst~nti~lly impermeable to water and carbon dioxide. Plastic bottles, inclu-ling refillable or recyclable types, as well as conventional barrier cartons or boxes are generally suitable. When ingredients are not highly compatible, e.g., ~I~Lllr~s of s;~:c~tçs and citric acid, it may further be desirable to coat at least one 30 such ingredient with a low-fo~min~ nonionic surfactant for protection. There are numerous waxy materials which can readily be used to forrn suitable coated particles of any such otherwise incompatible components.
Method for Cleaning The present invention also encompasses methods for cleaning soiled tableware.
3s A prefe,lcd method comprises contacting the tableware with a pH wash aqueous me~ m of at least 8. The aqueous medi~lm comprising at least about 0.1% available 21451~4 .

oxygen added as peroxygen bleach and at least about 0 01% of bleach activator selected from the group consisting of benzoylvalerolactam or benzoylcap~olactam A prefell~d method for cleaning soiled tableware using the pH jump/drop profile comprises contacting tableware with an aqueous medium having an initial s range pH in a wash solution from about 8 to about 13, more preferably from about 9 to about 12, and comprising at least about 0 1% of a peroxygen bleach system, such as a peroxygen bleach and precursor, and a second coated pH adjusting component to yield a final wash pH between about 6 5 to about 9 5; preferably from about 7 0 to about 9 3 0 The aqueous meclillm is formed by dissolving a solid-form automatic dishwashing detergent cont~ining in an automatic dishwashing machine A
particularly pre~..ed method also includes low levels of silicate, preferably from about 0 5% to about 12% SiO2.
The following examples illustrate the compositions of the present invention 5 These examples are not meant to limit or otherwise define the scope of the invention All parts, pelce..lages and ratios used herein are eApressed as percent weight unless otherwise specified EXA~LE I
Granular automatic dishwashing detergents of the present invention wherein 20 glasscare and stain removal benefits are achieved in a pH jump/drop profile are as follows:
Table 1 % by weight of active material Ing.ed;e~.li A B C
2s Citrate 400 Coated citric acidl 15 00 26 80 21 50 Acusol480N2 6 00 6 00 6 00 So~ carbonate 9 00 --- ---Britesil H20 (as SiO2) 8 50 -- --~e~silicate (as SiO2) -- 8 50 8 50 Alkyl ethoxy(3)sulfate 3 00 --- ---Nonionic surfactant3 ~~~ 3 00 3 00 Termamyl 60T 1 50 1 50 1 50 Plot~ase D (4.6% prill) 1 60 --- ---3s Alcalase2T --- 3 60 3 60 Perca.l,onate(Interox) (asAvO) 1 50 1 50 1 50 Benzoylvalerolactam 3 80 -- --21~5104 3~

Benzoyloxybenzenesulphonate -- 3.80 --Nonanoyloxybenzenesulphonate -- - 3.80 Diethylene triamine penta methylene phosphonic acid 0.13 0.13 0.13 s Polydimethylsiloxane 2.00 -- --Sulfate, water, etc. balancc Initial wash solution pH 10.2 12.00 12.00 Final wash solution pH 9.0 9.0 9.0 1 Citric acid coated with 3.5% of paraffin wax/petrolatum/C16H33(OC2H4)2 oOH
ratio of 96.5:2.5: 1.
2 From Rohm and Haas 3Low cloud point, high hydrophilic-lypophilic balance EXA~LE rI
Granular automatic dishwashing detergent containing lowpH/silicate wherein 5 ~l~ssc~re and stain removal benefits are achieved are as follows:
Table 2 % by weight of active material Ingredients D E F
Citric acid 18.60 18.60 18.60 Acusol 480N1 6.00 6.00 6.00 Sodium carbonate 4.50 4.50 4.50 Britesil H20 (as Si2) 8.50 8.50 8.50 Alkyl ethoxy (3) sulfate 3.00 3.00 3.00 Termamyl 60T 1.50 1.50 1.50 2s Alcalase 2T 3.60 3.60 3.60 Pe~,~l,onate (Interox) (as AvO) 1.50 1.50 1.50 13e.~o.~1~alerolactam 3.80 -- --Benzoyloxybc~ lrhonate - 3.80 --Nonanoylo~y~cn7~ rhonate -- -- 3.80 Diethylene ~ nt penta methylene phosphonic acid 0.13 0.13 Polydil"~ll,ylsiloxane 2.00 2.00 2.00 Sulfate, water etc. balance balance balance pH 8.5 8.5 8.5 3s IDispcrsallt from Rohm and Haas 21451~

EXAMPLE III
Granular automatic dishwashing detergents containing lowpH/silicate wherein glass care and stain removal benefits are achieved are as follows:
Table 3 s % by weight of active material Ingredients G H
Citrate 1.25 10.00 10.00 Citric acid 17.50 11.00 11.00 Acusol 480N1 6.00 6.00 --0 Polyaspartate -- -- 6.00 Sodium carbonate 15.50 -- --Sodium bicarbonate -- 20.00 20.00 Britesil H20(as SiO2)8.50 8.50 8.50 Nonionic surfactant2 2.00 3.00 3.00 Terrnamyl 60T 1.50 1.50 1.50 Alcalase 2T 3.60 3.60 3.60 Pell~olalemonohydrate (asAvO) 1.50 1.50 1.50 Benzoyloxyl,e.)7~ c, ~lphonate 3.80 -- --Benzoylcaprolactam -- 3.80 --Nonanoxyl,e~-7f~.-e~,Jlphonate -- -- 3.80 Diethylene t~ e penta acetic acid 0.13 0.13 0.13 Sulfate, water, etc. balance-pH 9.0 9.0 9.0 2s 1 Dispe. ~an~ from Rohm and Haas 2 Low cloud, high HLB nonionic surfactant EXA~LE IV
Granular alltorn~fic dishwashing detergents wherein stain removal and cleaning benefits are achieved are as follows:
- Table 4 % by weight of active material Ingredients J K L
Citrate 15.00 15.00 20.00 Acusol 480N1 6 00 6 00 6.90 3s Sodiumcarbonate 20 00 20.00 23 00 Britesil H20 (SiO2) Nonionic surfactant2 2.00 2.00 2.00 Savinase 12T 2.00 2.00 2.00 Tennamyl 60T 1.00 1.00 1.00 Percarbonate (as AvO) 1.50 1.50 1.50 Benzoylcaprolactam 2.00 3.80 2.00 s Diethylene triamine penta acetic acid 0.13 0.13 0.13 l,l-hydroxyethane diphosphonic acid 0.50 0.50 0.50 Sulfate, water, etc. balance-pH 10.0 10.0 10.0 I Dispersant from Rohm and Haas 2 Low cloud, high HLB nonionic surfactant Table 5 % by weight of active material Ingredients M N O
Citrate 20.00 20.00 20.00 Acusol 480N1 6.90 6.90 6.90 Sodium carbonate 23.00 23.00 23.00 Britesil H20 (as Si2) 7.50 Nonionic surfactant2 2.00 2.00 2.00 Savinase 12T 2.00 2.00 2.00 Termamyl 60T 1.00 1.00 1.00 Percarbonate (asAvO) 1.00 1.50 1.50 Benzoylcaprolactam 2.00 3.80 3.80 Diethylene triamine penta acetic acid0.13 0.13 --2s S,S-Ethylene ~:~.n;~c dicucc~ te -- -- 0.13 I,l-h~d~A~lhanc diphosphonic acid 0.50 0.50 0.50 Sulate, water, etc. balance-pH 10.0 10.0 10.0 1 Diap~hlt from Rohm and Haas 30 2 Low cl~ud, high HLB nonionic surfactant Table 6 % by weight of active material Ingredients P ~2 R
Citrate 20.00 20.00 20.00 3s Acusol 480N1 6.90 6.90 6.90 Sodium cdllJoAdte 23.00 23.00 23.00 Britesil H20 (as Si2) 214510~

Nonionic surfactant2 2.00 2.00 2.00 Savinase 12T 2.00 2.00 2.00 Termamyl 60T 1.00 1.00 1.00 Percarbonate (as AvO) .1.50 1.00 1.50 s Benzoylvalerolactam 3.80 2.00 --Benzoyloxybenzenesulphonate -- -- 3.80 S,S-ethylene diamine disuccinate 0.13 0.13 0.13 l,l-hydroxyethane diphosphonic acid 0.50 0.50 0.50 Sulfate, water, etc. balance-0 pH 10.0 10.0 10.0 1 Dispersant from Rohm and Haas 2 Low cloud, high HLB nonionic surfactant Table 7 % by weight of active material Ingredients S _ U
Citrate 15.00 20.00 20.00 Acusol 480N1 6.00 6.90 6.90 Sodium carbonate 20.00 23.00 23.00 Britesil H20 (as SiO2) 9.00 7.50 ~.50 Nonionic surfactant2 2.00 2.00 2.00 Savinase 12T 2.00 2.00 2.00 Terrnamyl 60T 1.00 1.00 1.00 Pe.l.ol~temonohydrate (asAvO) 1.50 1.50 --Pe.ca-l,ondle (as AvO) -- -- 1.50 2s Cg - OBS -- -- 1.20 Cg - OBS 2.00 2.00 --Clo - OBS -- -- 0.80 Diethylene ll;~---ne penta acetic acid 0.13 0.13 --S,S-ethylene ~ ne di~uccin~te -- -- 0.13 Sulfate, water, etc. balance-pH 10.0 10.0 10.0 1 Dispe. s&.l from Rohm and Haas 2 Low cloud, high HLB nonionic surfactant Table 8 % by wei~ht of active material Ingredients V W X

Citrate 20.00 20.00 20.00 Acusol 480N1 6.90 6.90 6.90 Sodium carbonate 23.00 23.00 23.00 Britesil H20 (as SiO2) 7 50 7 50 7 50 s Nonionic surfactant2 2.00 2.00 2.00 Savinase 12T 2.00 2.00 2.00 Terrnarnyl 60T 1.00 1.00 1.00 Percarbonate ~as AvO) 1.00 1.50 0.75 C8 - OBS 1.20 2.30 2.30 Clo - OBS 0.80 1.50 1.50 S,S-ethylene ~ mine ~isuccin~te 0.13 0.13 0.13 Sulfate, water, etc. balancc-pH 10.0 10.0 10.0 1 Dispe, ~l from Rohm and Haas 5 2 Low cloud, high HLB nonionic surfactant Table 9 % by weight of active material Ingredients Y Z
Citrate 20.00 20.00 Acusol 480N1 6.90 6.90 Sodium c~l~ondte 23.00 23.00 Britesil H20 (as Si2) Nonionic surfactant2 2.00 2.00 Savinase 12T 2.00 2.00 2s Termamyl 60T 1.00 1.00 Per~l,orl~te (as AvO) 0.75 1.50 C8 - OBS 3.0O ---Clo - OBS 2.00 ---a-e --- 3.80 S,Sethylerle ~i; n~ t~i~ucçin~te 0.13 0.13 Sulfate, water, etc. -- -- -- balance -- -- --pH 10.0 10.0 1 Dispc~ ~ant ~om Rohm and Haas 2 Low cloud, high HLB nonionic surfactant Table 10 % by weight of active material Ingredients AA BB CC

-Citrate 29 00 29 00 29.00 Acusol 480N1 6 00 6.00 6.00 Sodium carbonate Britesil H20 (as SiO2) 17.00 17 00 17.00 s l,l-hydroxyethane diphosphonic acid 0.50 0 50 0.50 Nonionic surfactant2 1.50 1 50 1.50 Savinase 12T 2.00 2.20 2.20 Termamyl 60T 1.50 1.50 1.50 Perboratemonohydrate (asAvO) 0.30 0.30 0.30 0 Pe,l,oldte tetrahydrate (as AvO) 0.90 0.90 0.90 Benzoylcaprolactam 3.80 7.00 --Benzoylvalerolactam -- -- 7.00 Diethylene til~u.une penta methylene phosphonicacid 0.13 0.13 0.13 Paraffin 0.50 0.50 0.50 Benzot,iazole 0.30 0.30 0.30 Sulfate, water, etc. balancc-pH 10.0 10.0 10.0 1 Dispel ~al~l from Rohm and Haas 20 2 Low cloud, high HLB nonionic surfactant Table 1 1 % by wei~ht of active material Ingredients DD EE
Citrate 29 00 29.00 2s Acusol 480N1 6.00 6.00 Sodium ca~bonate 5.00 5.00 So~iun~ ~fet~ c~te 9.80 9.80 1,1 h~ o~lh~ediphosphol~icacid 0.50 0.50 Nonionic surfactant2 1.50 1.50 Savinase 12T 2.00 2.20 Termarnyl 60T 1.50 1.50 Pe~ca,l,onate (as AvO) 1 20 1.20 Benzoylvalerolactam -- 3 . 80 Benzoylcaprol~ct~n~ 3 .80 --3s Diethylene ll;anune penta methyl phosphonic acid 13 13 Paraffin 0.50 0.50 21~510~

Benzotriazole 0 30 0 30 Sulfate, water, etc balance-pH 100 100 1 Dispersant from Rohm and Haas 5 2 Low cloud, high HLB nonionic surfactant EXAMPLE V
Granular automatic detergent compositions wherein stain removal and silvercare benefits are achieved are as follows:
o Table 12 Builder FF GG
Sodium citrate dihydrate 33.0 Sodium tripolyphosphate - 46.0 Sodium metasilicate 9.9 9.9 Sodiumcarbonate 10.1 10.1 ) 1,1-hydroxyethane diphosphonic acid 0.83 0.83 Polyacrylatel 4.0 4.0 Pell,ota~e monohydrate (as AvO) 1.95 1.95 Pe.l.o.ate tetrahydrate (as AvO) 8.65 8 65 Benzoylox~l,enzene sulfonate 4.78 4.78 Diethylene triamine penta methylene 0.65 0.65 phosphonic acid Savinase 12TlTermamyl 60T 3.7 3.1 3c~h~rdroA~rtoluene 0.3 0.3 Paraffln 0.5 0.5 Nonionic2 1.5 1.5 Sodium Sulphst~., minors balance lPA30 from BASF GmbH
2PIurafiaC LF404 EXAMPLE VI
Tablet cG,l,pos;lions of the present invention are as follows:
Table 13 Builder HH II JJ KK
Citrate 20.9 20.9 16.7 ---Phosphate -- -- -- 25.8 Acrylic acid/Maleic acid -- -- 11.1 --co-polymer Polyacrylatel 2.7 2.7 -- --s Carbonate 14.0 14.0 -- 1.6 Bicarbonate -- -- 48.6 --1,1 -hydroxyethane 0.36 0.36 -- --diphosphonic acid Silicate 2r(SiO2) 12.2 12.2 -- --o Met~cilic~ste (SiO2) -- -- -- 44.8 Paraffin 0.36 0.36 0.2 0.2 Benzotriazole 0.21 0.21 -- --Pell,olate tetrahydrate 0.64 0.64 0.64 --(as AvO) PelbGlate monohydrate ... (as AvO) 0.22 0.22 -- --Percarbonate (as AvO) -- -- -- 1.00 Benzoylcaprolactam 3.2 5.1 5.0 --Phenylbenzoate -- -- -- 5.00 Diethylene triamine penta methylene phosphoric acid 0.09 0.09 -- --Savinase 6T -- -- 1.15 --Savinase 12T 1.58 ` 1.58 -- --Termamyl 60T 1.1 1.1 1.0 --Nonionicsurfactant 1.18 1.18 0.8 --S!llrhste, water, minors balance pH 11.0 11.0 9.5 12.6 lPA30 from BASF GmbH

. EXA~LE VII
Granular f !tom-~ic dishwashing detergents co"Laining l~anganese complexes wherein ~Ycell~nt stain removat and cleaning benefits are achieved are as follows:
Table 14 Ingredients LL MM
Citrate 15.00 20.00 Acusot 480N1 6.00 6.90 Sodium carbonate 20.00 23.00 ._ Britesil H20 (SiO2) Nonionic surfactant2 2.00 2.00 Savinase 12T 2.00 2.00 Termamyl 60T 1.00 1.00 s Percarbonate (as AvO) 1.50 1.50 Benzoylcaprolactam 1.90 1.90 Diethylene triamine penta acetic acid 0.13 0.13 Mn Catalyst3 300 ppm300ppm o l,l-hydroxyethane diphosphonic acid 0.50 0.50 Sulfate, water, etc. balancc-pH 10.0 10.0 1 Dispc,~al.~ from Rohm and Haas 2 Low cloud, high HLB nonionic surfactant 3 1:1 mole ratio of Mn cation and ligand to form Mnlv2 (u-0)3(1,4,7-trimethyl-1,4,7-triacyclononane)2-(PF6)2 in situ or prefo, l"ed.
WHAT IS CLAIMED IS:

Claims (24)

1. An automatic dishwashing detergent composition comprising:
(a) from about 0.01% to about 8%, available oxygen (AvO) added as a peroxygen bleach selected from the group consisting of percarbonate, perborate, monopersulfate and mixtures thereof;
(b) from about 0.01% to about 10%,of bleach activator selected from the group consisting of benzoylcaprolactam, 4-nitrobenzoylcaprolactam, 3-chlorbenzoylcaprolactam, nonanoyloxybenzenesulphonate, decanoyloxybenzenesulphonate, benzoylvalerolactam, octanoyloxybenzenesulphonate, phenylbenzoate derivatives and mixtures thereof; and (c) from about 0.1% to about 50%, of pH adjusting component, said component providing a wash solution pH from about 8 to about 13;

wherein said composition comprises a molar ratio of AvO to bleach activator of at least 1:1.

2. A composition according to Claim 1 wherein said peroxygen bleach activator is selected from the group consisting of benzoyloxybenzenesulphonate, benzoylcaprolactam, benzoylvalerolactam, nonanoyloxybenzenesulphonate, phenylbenzoate; and mixtures thereof.

3. A composition according to Claim 2 further comprising from about 0.1% to about 10% of a low foaming nonionic surfactant.

4. A composition according to Claim 3 wherein said pH adjusting component of (c) is a salt or salt/builder mixture selected from (i) sodium carbonate or sesquicarbonate (ii) sodium citrate (iii) citric acid (iv) sodium bicarbonate (v) sodium borate (vi) sodium hydroxide; and (vii) mixtures thereof.

5. A composition according to Claim 4 further comprising from about 0.001% to about 5% of a detersive enzyme.

6. A composition according to Claim 5 comprising from about 0.5% to about 3%
available oxygen.

7. A composition according to Claim 6 wherein said peroxygen bleach compound is selected from the group consisting of percarbonate salts or perborate salts.

8. A composition according to Claim 2 further comprising a bleach catalyst is selected from the group consisting of MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triacyclononane)2-(PF6)2, MnIII2(u-O)1(u-OAc)2(1,4,7-tri-methyl-1,4,7-triacyclononane)2-(ClO4)2; MnIV4(u-O)6(1,4,7-triacy-clononane)4-(CiO4)2;
MnIIIMnIV4(u-O)1(u-OAc)2 (1,4,7-tri-methyl-1,4,7-triacyclononane)2-(ClO4)3;
Mn(1,4,7-trimethyl-1,4,7-triazacyclononane(OCH3)3-(PF6); Co(2,2'-bispyridyl-amine)Cl2; Di-(isothiocyanato)bispyridylamine-cobalt (II); trisdipyridylamine-cobalt (II) perchlorate; Co(2,2-bispyridylamine)2- O2ClO4; Bis-(2,2'-bispyridylamine) copper(II) per-chlorate; tris(di-2-pyridylamine) iron (II) perchlorate; Mn gluconate;
Mn(CF3SO3)2; Co(NH3)5Cl; binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2]-(ClO4)3 and mixtures thereof.

9. A composition according to Claim 5 further comprising from about 0.5% to about 12% SiO2.

10. A composition according to Claim 9 wherein said ratio of AvO to bleach activator is from about 20:1 to about 1:1.

11. A composition according to Claim 10 further comprising from about 0.01% to about 2% of a short-chain amine oxide

12. A composition according to Claim 11 further comprising from about 0.5% to about 20% of a dispersant polymer selected from the group consisting of polyacrylates and polyacrylate copolymers..

13. A composition according to Claim 12 wherein said wash solution pH is from about 9.0 to about 12Ø

14. A composition according to Claim 13 further comprising from about 0.1% to about 8% of an anionic co-surfactant.

15. A composition according to Claim 14 wherein said low foaming nonionic surfactant is selected from the group consisting of alkoxylated alcohols, glucosamides and mixtures thereof.

16. A composition according to Claim 15 wherein said anionic cosurfactant is selected from alkylethoxysulfates, alklyethoxycarboxylates and mixtures thereof.

17. A composition according to Claim 16 further comprising from about 0.01% to about 6% by weight of an enzyme stabilizing system.

18. A composition according to Claim 19 wherein said detersive enzyme is selected from the group consisting of protease, amylase, lipase and mixtures thereof.

19. A composition according to Claim 7 wherein said peroxygen bleach activator is benzoylcaprolactam, phenylbenbenzoate, benzoylvalerolactam and mixtures thereof.

20. A composition according to Claim 18 comprising from about 0.005 to about 3% by weight protease or amylase.

21. A granular or powdered automatic dishwashing detergent composition which comprises by weight:
(a) from about 0.3% to about 4% of available oxygen added as a peroxygen bleach component selected from the group consisting of percarbonate, perborate and mixtures thereof;
(b) from about 0.8% to about 5% bleach activator selected from the group consisting of benzoylcaprolactam, benzoylvaerolactam, benyoyloxybnezenesulphonate, and mixtures thereof;
(c) from about 0.1% to about 50% of a pH adjusting component consisting of water-soluble salt or salt/builder mixture selected from sodium carbonate, sodium sesquicarbonate, sodium citrate, citric acid, sodium bicarbonate, sodium hydroxide, and mixtures thereof;
(d) from about 1% to about 11% silicate;
(e) from 0 to about 10% of a low-foaming nonionic surfactant other than amine oxide;

(f) from 0 to about 10% of an anionic cosurfactant;
(g) from 0 to about 2% of a short-chain amine oxide;
(h) from 0 to about 10% of a silicone suds suppressor;
(i) from 0.001% to about 5% of an active detersive enzyme;
(j) from 0 to about 25% of a dispersant polymer; and (k) from 0 to about 40% of sodium sulfate, wherein said composition has a molar ratio of AvO to peroxygen bleaching compound of from about 20:1 to about 1:1 and a wash solution pH from about 9.5 to about 11.5.

22. A composition according to Claim 21 further comprising a bleach catalyst- isselected from the group consisting of MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triacyclononane)2-(PF6)2, MnIII2(u-O)1(u-OAc)2(1,4,7-tri-methyl-1,4,7-triacyclononane)2-(ClO4)2; MnIV4(u-O)6(1,4,7-triacy-clononane)4-(ClO4)2;
MnIIIMnIV4(u-O)1(u-OAc)2 (1,4,7-tri-methyl-1,4,7-triacyclononane)2-(ClO4)3;
Mn(1,4,7-trimethyl-1,4,7-triazacyclononane(OCH3)3-(PF6); Co(2,2'-bispyridyl-amine)Cl2; Di-(isothiocyanato)bispyridylamine-cobalt (II); trisdipyridylamine-cobalt (II) perchlorate; Co(2,2-bispyridylamine)2- O2ClO4; Bis-(2,2'-bispyridylamine) copper(II) per-chlorate; tris(di-2-pyridylamine) iron (II) perchlorate; Mn gluconate;
Mn(CF3SO3)2; Co(NH3)5Cl; binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2]-(ClO4)3 and mixtures thereof.

23. A method for cleaning soiled tableware comprising contacting said tableware with a pH wash aqueous medium of at least 8 and comprising at least about 0.1%
available oxygen added as peroxygen bleach and at least about 0.01% of bleach activator selected from the group consisting of benzoylvalerolactam or benzoylcaprolactam.

24. A method according to Claim 23 wherein said aqueous medium is formed by dissolving a solid dishwashing detergent composition in an automatic dishwashing machine.