Detergent composition comprising lime soap dispersant and lipase enzymes

A method of cleaning soiled dishes comprising contacting said dishes with a composition comprising a lipased derived from pseudomonas pseudolacaligenes, a lime soap dispersant having an lime soapdispersing power of no more than eight, and a suds suppressing agent which contains either a silicone suds suppressing agent or a 2-alkyl alcanol suds suppressing agent.

This invention relates to a machine dishwashing and rinsing detergent 
compositions containing lipolytic enzyme obtained from a lipase producing 
strain of pseudomonas pseudoalcaligenes, a lime soap dispersant, and 
preferably water-soluble detergent builder compound. 
The overall performance of a machine dishwashing detergent product is 
judged by not only its ability to remove soils, particularly greasy soils, 
but also by its ability to prevent the redeposition of the soils, or the 
breakdown products of the soils or of any insoluble salts, on the articles 
being washed. The insoluble salts may be the calcium, magnesium or heavy 
metal ion--containing salts of the soils, or the breakdown products of the 
soils, or they may be purely inorganic in nature. Redeposition effects 
results in the articles being coated in an unseemly film, appearing 
streaked or being covered in visible spots which remain intact at the end 
of the wash process. Spotting, filming and streaking effects are visually 
most noticeable on glassware and on plastic articles. 
The performance of a rinsing (or rinse aid) product is judged largely on 
its ability to prevent the, spotting, filming and streaking of the 
articles being rinsed. The ability to prevent the redeposition of soils 
which may have been carried over from the main wash step to the rinse step 
of the machine dishwashing process is therefore a key measure of the 
effectiveness of a rinse aid product. 
Builder compounds are conventionally used in machine dishwashing and 
rinsing detergent products. Their principal action is to chelate magnesium 
and calcium ions. The magnesium and calcium ions may, in the absence of 
builder compounds or in underbuilt conditions, form insoluble salts which 
deposit as visible spots on the surfaces of the articles being washed. It 
is desirable that the builder compounds used in machine dishwashing 
detergent products are water-soluble since water insoluble builders 
compounds may also deposit on the articles being washed, remaining as 
visible spots at the end of the wash process. 
For reasons of environmental compatibility it is desirable that machine 
dishwashing or rinsing detergent products are free from chlorine bleaches 
or phosphate builder compounds. However, spotting and filming effects are 
known to be a particular problem for machine dishwashing and rinsing 
products containing no chlorine bleach and/or no phosphate builder 
compound. 
Lipolytic enzymes (lipases) are known to assist in the breakdown of 
triglyceride and fatty ester soils, and are therefore recognized as being 
of value as components of detergent compositions. Laundry detergent 
products containing lipase are commercialy available in Europe. Machine 
dishwashing and rinsing detergent compositions containing lipolytic enzyme 
have been disclosed, for example, in EP-B-0271555 and EP-A-0346136. 
The disclosure of EP-B-0271155 teaches that the addition of lipases to a 
dishwashing or rinsing composition reduces significantly the formation of 
film or spots on the articles cleaned with such a composition. The 
disclosure of EP-A-0346136 teaches similar spotting and filming reductions 
for the inclusion of special lipases produced by cloning rDNA technologies 
into a machine dishwashing detergent composition. 
The Applicants have however, now found that the inclusion of lipase enzyme 
into machine dishwashing or rinsing detergent compositions whilst 
providing a greasy stain removal benefit does not always provide spotting 
and filming prevention benefits. Indeed, it has unexpectedly been found 
that the inclusion of lipases into such compositions can in fact lead to 
enhanced spotting and filming, and in particular to significantly enhanced 
film formation on plastic articles. 
The Applicants have also established that adverse spotting and filming 
effects may be significantly reduced by the inclusion, in addition to the 
lipolytic enzyme, of a lime soap dispersant into a machine dishwashing or 
rinsing composition. In particular, the aforementioned specific problem of 
film formation on plasticware is ameliorated by the inclusion of the lime 
soap dispersant. 
The inclusion of a lime soap dispersant in the machine dishwashing or 
rinsing compositions moreover, does not appear to lead to any significant 
reduction in the greasy soil removal performance of the lipolytic 
enzyme-containing machine dishwashing or rinsing composition. 
A lime soap dispersant is a material that prevents the precipitation of 
alkali metal, ammonium or amine salts of fatty acids by calcium or 
magnesium ions. Some, but not all, lime soap dispersants also demonstrate 
surfactant capability. Conversely, not all surfactants may act as 
effective lime soap dispersants. It is, however, desirable in the 
detergent compositions of the invention that the lime soap dispersant also 
has surface active (surfactant) capability. 
It is an object of the present invention to provide detergent compositions 
containing a specific lipolytic enzyme, obtained from a lipase producing 
strain of pseudomonas pseudoalcaligenes, which include a compound which 
demonstrates good lime soap dispersant capability wherein the compositions 
provide the mitigation of spotting and filming effects, particularly on 
glassware and plasticware, when used in machine dishwashing or rinsing 
processes. 
The machine dishwashing or rinsing detergent compositions of the present 
invention are of particular value when formulated as compositions 
containing no chlorine bleach and no phosphate builder compound since they 
provide the abovementioned mitigation of spotting and filming effects for 
these formulations where spotting and filming is known to be a particular 
problem. 
According to the present invention there is provided a detergent 
composition suitable for use in a machine dishwashing or rinsing process 
containing 
a) from 0.1% to 40% by weight of a lime soap dispersant compound having a 
lime soap dispersant power of no more than 8; and 
(b) from 0.001% to 2% by weight of active lipolytic enzyme, obtained from a 
lipase producing strain of pseudomonas pseudoalcaligenes. 
Preferably, the composition contains water-soluble detergent builder 
compound. 
Preferably, the detergent builder compound is a non-phosphate detergent 
builder compound. Preferably, the composition is free from chlorine 
bleach. 
According to another aspect of the present invention there is also provided 
a machine dishwashing or rinsing process comprising treating soiled 
articles selected from crockery, glassware,hollowware and cutlery and 
mixtures thereof, with an aqueous liquid having dissolved or dispensed 
therein an effective amount of the machine dishwashing or rinsing 
composition as described hereinabove. By an effective amount of the 
machine dishwashing composition it is meant from 8 g to 60 g of product, 
and by an effective amount of the rinsing composition it is meant from 0.5 
g to 15 g of product, dissolved or dispersed in a wash solution of volume 
from 3 to 10 liters, as are typical product dosages and wash solution 
volumes commonly employed in conventional machine dishwashing or rinsing 
processes. 
The machine dishwashing or rinsing detergent compositions of the present 
invention preferably contain detergent builder compound present at a level 
of from 1% to 80% by weight, preferably from 10% to 70% by weight, most 
preferably from 20% to 60% weight of the composition. The detergent 
builder compound is most preferably water-soluble. 
Suitable water-soluble detergent builder compounds include, but are not 
restricted to monomeric polycarboxylates, of their acid forms homo or 
copolymeric polycarboxylic acids or their salts in which the 
polycarboxylic acid comprises at least two carboxylic radicals separated 
from each other by not more that two carbon atoms, carbonates, 
bicarbonates, borates, phosphates, silicates and mixtures of any of the 
foregoing. 
Suitable water-soluble monomeric or oligomeric carboxylate builders can be 
selected from a wide range of compounds but such compounds preferably have 
a first carboxyl logarithmic acidity/constant (pK.sub.1) of less than 9, 
preferably of between 2 and 8.5, more preferably of between 4 and 7.5. The 
logarithmic acidity constant is defined by reference to the equilibrium 
H.sup.+ +A.sup.- .fwdarw..rarw.HA 
where A is the fully ionized carboxylate anion of the builder salt. 
The equilibrium constant for dilute solutions is therefore given by the 
expression 
##EQU1## 
and pK.sub.1 =log.sub.10 K. 
For the purposes of this specification, acidity constants are defined at 
25.degree. C. and at zero ionic strength. Literature values are taken 
where possible (see Stability Constants of Metal-Ion Complexes, Special 
Publication No. 25, The Chemical Society, London): where doubt arises they 
are determined by potentiometric titration using a glass electrode. 
The carboxylate or polycarboxylate builder can be momomeric or oligomeric 
in type although monomeric polycarboxylates are generally preferred for 
reasons of cost and performance. 
Monomeric and oligomeric builders can be selected from acyclic, alicyclic, 
heterocyclic and aromatic carboxylates having the general formulae 
##STR1## 
wherein R.sub.1 represents H, C.sub.1-30 alkyl or alkenyl optionally 
substituted by hydroxy, carboxy, sulfo or phosphono groups or attached to 
a polyethylenoxy moiety containing up to 20 ethyleneoxy groups; R.sub.2 
represents H, C.sub.1-4 alkyl, alkenyl or hydroxy alkyl, or alkaryl, 
sulfo, or phosphono groups; 
X represents a single bond; O; S; SO; SO.sub.2 ; or NR.sub.1 ; 
Y represents H; carboxy;hydroxy; carboxymethyloxy; or C.sub.1-30 alkyl or 
alkenyl optionally substituted by hydroxy or carboxy groups; 
Z represents H; or carboxy; 
m is an integer from 1 to 10; 
n is an integer from 3 to 6; 
p, q are integers from 0 to 6, p+q being from 1 to 6; and 
wherein, X, Y, and Z each have the same or different representations when 
repeated in a given molecular formula, and wherein at least one Y or Z in 
a molecule contain a carboxyl group. 
Suitable carboxylates containing one carboxy group include the water 
soluble salts of lactic acid, glycolic acid and ether derivatives thereof 
as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. 
Polycarboxylates containing two carboxy groups include the water-soluble 
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, 
maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric 
acid, as well as the ether carboxylates described in German 
Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Pat. No. 3,935,257 and 
the sulfinyl carboxylates described in Belgian Patent No. 840,623. 
Polycarboxylates containing three carboxy groups include, in particular, 
water-soluble citrates, aconitrates and citraconates as well as succinate 
derivatives such as the carboxymethyloxysuccinates described in British 
No. 1,379,241, lactoxysuccinates described in British Patent No. 
1,389,732, and aminosuccinates described in Netherlands Application 
7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane 
tricarboxylates described in British Patent No. 1,387,447. 
Polycarboxylates containing four carboxy groups include oxydisuccinates 
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane 
tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane 
tetracarboxylates. Polycarboxylates containing sulfo substituents include 
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 
and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed 
citrates described in British Patent No. 1,439,000. 
Alicyclic and heterocyclic polycarboxylates include 
cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide 
pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, 
cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 
2,2,5,5-tetrahydrofuran-tetracarboxylates, 
1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of 
polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic 
polycarboxylates include mellitic acid, pyromellitic acid and the phthalic 
acid derivatives disclosed in British Patent No. 1,425,343. 
Of the above, the preferred polycarboxylates are hydroxycarboxylates 
containing up to three carboxy groups per molecule, more particularly 
citrates. 
The parent acids of the monomeric or oligomeric polycarboxylate chelating 
agents or mixtures thereof with their salts, e.g. citric acid or 
citrate/citric acid mixtures are also contemplated as components of 
builder systems of detergent compositions in accordance with the present 
invention. 
Other suitable water soluble organic salts are the homo- or co-polymeric 
polycarboxylic acids or their salts in which the polycarboxylic acid 
comprises at least two carboxyl radicals separated from each other by not 
more than two carbon atoms. Polymers of the latter type are disclosed in 
GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 2000-5000 
and their copolymers with maleic anhydride, such copolymers having a 
molecular weight of from 20,000 to 70,000, especially about 40,000. These 
materials are normally used at levels of from 0.5% to 10% by weight more 
preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of 
the composition. 
Water-soluble detergent builders include, but are not limited to, the 
alkali metal, ammonium and alkanolammonium salts of polyphosphates 
(exemplified by the tripolyphosphates, pyrophosphates, and glassy 
polymeric meta-phosphates), phytic acid, silicates, carbonates (including 
bicarbonates and sesquicarbonates), and sulfates. Borate builders, as well 
as builders containing borate-forming materials that can produce borate 
under detergent storage or wash conditions can also be used but are not 
preferred at wash conditions less that about 50.degree. C., especially 
less than about 40.degree. C. 
Examples of carbonate builders are the alkaline earth and alkali metal 
carbonates, including sodium carbonate and sesqui-carbonate and mixtures 
thereof with ultra-fine calcium carbonate as disclosed in German Patent 
Application No. 2,321,001 published on Nov. 15, 1973. 
Specific examples of phosphate builders are the alkali metal 
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium 
and potassium and ammonium pyrophosphate, sodium and potassium 
orthophosphate, sodium polymeta/phosphate in which the degree of 
polymerization ranges from about 6 to 21, and salts of phytic acid. 
Suitable silicates include the water soluble sodium silicates with an 
SiO.sub.2 : Na.sub.2 O ratio of from 1.0 to 2.8, with ratios of from 1.6 
to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates 
may be in the form of either the anhydrous salt or a hydrated salt. Sodium 
silicate with an SiO.sub.2 : Na.sub.2 O ratio of 2.0 is the most preferred 
silicate. 
Silicates are preferably present in the machine dishwashing detergent 
compositions at the invention at a level of from 5% to 50% by weight of 
the composition, more preferably from 10% to 40% by weight. 
Whilst water-soluble detergent builders are preferred components of the 
detergent compositions of the invention the compositions may also include 
less water soluble builders although preferably their levels of 
incorporation are minimized. Examples of such less water soluble builders 
include the crystalline layered silicates and the largely water insoluble 
sodium aluminosilicates. 
Crystalline layered sodium silicates have the general formula 
EQU NaMSi.sub.x O.sub.x+1.y H.sub.2 O 
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 has a value of 2, 3 or 4 and is 
preferably 2. More preferably M is sodium and y is 0 and preferred 
examples of this formula comprise the .alpha.-, .beta.-, .gamma.- and 
.delta.- forms of Na.sub.2 Si.sub.2 O.sub.5. These materials are available 
from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and 
NaSKS-6. The most preferred material is --Na.sub.2 Si.sub.2 O.sub.5, 
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. The primary requirement is that the 
material should contain at least on functional acidic group of which the 
pKa should be less than 9, providing a capability for at least partial 
neutralisation of the hydroxyl ions released by the crystalline layered 
silicate. 
The incorporation in the particulate of other ingredients additional to the 
crystalline layered silicate and ionisable water soluble compound can be 
advantageous particularly in the processing of the particulate and also in 
enhancing the stability of detergent compositions in which the 
particulates are included. In particular, certain types of agglomerates 
may require the addition of one or more binder agents in order to assist 
in binding the silicate and ionisable water soluble material so as to 
produce particulates with acceptable physical characteristics. 
The crystalline layered sodium silicate containing particulates can take a 
variety of physical forms such as extrudates, marumes, agglomerates, 
flakes or compacted granules. A preferred process for preparing compacted 
granules comprising crystalline layered silicate and a solid, 
water-soluble ionisable material has been disclosed in the commonly 
assigned British Application No. 9108639.7 filed on 23 Apr. 1991 
(Attorney's Docket No CM369F). 
Suitable aluminosilicate zeolites have the unit cell formula Na.sub.z 
(AlO.sub.2).sub.z (SiO.sub.2).sub.y !. XH.sub.2 O wherein z and y are at 
least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, 
preferably from 7.5 to 276, more preferably from 10 to 264. The 
aluminosilicate material are in hydrated form and are preferably 
crystalline, containing from 10% to 28%, more preferably from 18% to 22% 
water in bound form. 
The above aluminosilicate ion exchange materials are further characterised 
by a particle size diameter of from 0.1 to 10 micrometers, preferably from 
0.2 to 4 micrometers. The term "particle size diameter" herein represents 
the average particle size diameter of a given ion exchange material as 
determined by conventional analytical techniques such as, for example, 
microscopic determination utilizing a scanning electron microscope or by 
means of a laser granulometer. The aluminosilicate ion exchange materials 
are further characterised by their calcium ion exchange capacity, which is 
at least 200 mg equivalent of CaCO.sub.3 water hardness/g of 
aluminosilicate, calculated on an anhydrous basis, and which generally is 
in the range of from 300 mg eq./g to 352 mg eq./g. The aluminosilicate ion 
exchange materials herein are still further characterised by their calcium 
ion exchange rate which is at least 130 mg equivalent of CaCO.sub.3 
/liter/minute/(g/liter) 2 grains Ca.sup.++ /gallon/minute/gram/gallon)! 
of aluminosilicate (anhydrous basis), and which generally lies within the 
range of from 130 mg equivalent of CaCO.sub.3 /liter/minute/(gram/liter) 
2 grains/gallon/minute/(gram/gallon)! to 390 mg equivalent of CaCO.sub.3 
/liter/minute/(gram/litre 4 grains/gallon/minute/(gram/gallon)!, based on 
calcium ion hardness. 
Optimum aluminosilicates for builder purpose exhibit a calcium ion exchange 
rate of at least 260 mg equivalent of CaCO.sub.3 
/liter/minute/(gram/liter) 4 grains/gallon/minute/(gram/gallon)!. 
The aluminosilicate ion exchange materials can be naturally occurring 
materials, but are preferably synthetically derived. A method for 
producing aluminosilicate ion exchange materials is discussed in U.S. Pat. 
No. 3,985,669. Synthetic crystalline aluminosilicate ion exchange 
materials are available under the designations Zeolite A, Zeolite B, 
Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the 
formula 
EQU Na.sub.12 AlO.sub.2).sub.12 (SiO.sub.2).sub.12 !.multidot.xH.sub.2 O 
wherein x is from 20 to 30, especially 27. Zeolite X has the formula 
Na.sub.86 (AlO.sub.2).sub.86 (SiO.sub.2).sub.106 !. 276 H.sub.2 O has the 
formula Na.sub.6 (AlO.sub.2).sub.6 (SiO.sub.2).sub.6 !7.5 H.sub.2 O). 
The first essential component of the machine dishwashing or rinsing 
compositions of the invention is a lime soap dispersant compound, which 
has a lime soap dispersing power (LSDP), as defined hereinafter of no more 
than 8, preferably no more than 7, most preferably no more than 6. The 
lime soap dispersant compound is present at a level of from 0.1% to 40% by 
weight, more preferably 1% to 20% by weight, most preferably from 2% to 
10% by weight of the compositions. 
A lime soap dispersant is a material that prevents the precipitation of 
alkali metal, ammonium or amine salts of fatty acids by calcium or 
magnesium ions. A numerical measure of the effectiveness of a lime soap 
dispersant is given by the lime soap dispersing power (LSDP) which is 
determined using the lime soap dispersion test as described in an article 
by H. C. Borghetty and C. A. Bergman, J. Am. Oil. Chem. Soc., volume 27, 
pages 88-90, (1950). This lime soap dispersion test method is widely used 
by practitioners in this art field being referred to , for example, in the 
following review articles; W. N. Linfield, Surfactant Science Series, 
Volume 7, p3; W. N. Linfield, Tenside Surf. Det. , Volume 27, pages 
159-161, (1990); and M. K. Nagarajan, W. F. Masler, Cosmetics and 
Toiletries, Volume 104, pages 71-73, (1989). The LSDP is the % weight 
ratio of dispersing agent to sodium oleate required to disperse the lime 
soap deposits formed by 0.025 g of sodium oleate in 30 ml of water of 
333ppm CaCO.sub.3 (Ca:Mg=3:2) equivalent hardness. 
In the Borghetty/Bergman lime soap dispersion test 5 ml of a 0.5% by weight 
solution of sodium oleate is added to a test tube, followed by loml of a 
hard water solution containing 600 ppm Ca.sup.2+ and 400 ppm Mg.sup.2+ 
(1000 ppm as CaCO.sub.3 equivalent, 700 .degree. Clark Hardness) which 
will cause formation of a lime soap deposit (or curd). An arbitrary amount 
(less than 15 ml) of dispersing agent as a 0.25% by weight solution is 
then added to the test tube. The total volume of solution in the test tube 
is then made up to 30 ml and the test tube is stoppered, inverted 20 times 
and then allowed to stand for 30 seconds. The contents of the test tube 
are then visually inspected to check if the lime soap deposits are still 
intact or whether they have been dispersed into the solution. The test 
procedure is repeated using different amounts of dispersing agent solution 
until the minimum amount of dispersing agent solution which will cause 
dispersion of the lime soap deposits is obtained. 
The lime soap dispersing power is then obtained as: 
##EQU2## 
Thus in accord with the test method described above a material with a lower 
LSDP is a more effective lime soap dispersant than one with a higher LSDP. 
A listing of suitable lime soap dispersants for use in accord with the 
invention is given in the above mentioned review by M. Linfield to be 
found in Tenside. Sust. Det., Volume 27, pages 159-161 (1990). 
Polymeric lime soap dispersants suitable for use herein are described in 
the above mentioned article by M. K. Nagarajan and W. F. Masler, to be 
found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). 
Examples of such polymeric lime soap dispersants include certain 
water-soluble salts of copolymers of acrylic acid, methacrylic acid or 
mixtures thereof, and an acrylamide or substituted acrylamide, where such 
polymers typically have a molecular weight of from 5,000 to 20,000. 
Surfactants having good lime soap dispersant capability will include 
certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and 
ethoxylated alcohols. 
Exemplary surfactants having a LSDP of no more than 8 for use in accord 
with the invention include C.sub.16 -C.sub.18 dimethyl amine oxide, 
C.sub.12 -C.sub.18 alkyl ethoxysulfates with an average degree of 
ethoxylation of from 1-5, particularly C.sub.12 -C.sub.15 alkyl 
ethoxysulfate surfactant with a degree of ethoxylation of about 3 
(LSDP=4), and the C.sub.13 -C.sub.15 ethoxylated alcohols with an average 
degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the trade 
names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH. 
The second essential component of the machine dishwashing or rinsing 
detergent compositions in accord with the invention is lipolytic enzyme, 
obtained from a lipase producing strain of Pseudomonas pseudoalcaligenes 
present at levels of active lipolytic enzyme of from 0.001% to 2% by 
weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 
0.5% by weight of the compositions. 
The lipase is bacterial in origin being obtained from a lipase producing 
strain of Pseudomonas pseudoalcaliaenes. 
The lipase is derived from Pseudomonas pseudoalcaligenes, which is 
described in Granted European Patent, EP-B-0218272. 
The lipolytic enzyme herein has acceptable compatibility with surfactants 
and has high activity at alkaline pH. The cleaning performance of the 
composition is enhanced by the addition of the lipolytic enzyme. 
A lipase unit (LU) is defined as the amound of lipase which produces 1 umol 
of titratable butyric acid per minute in a pH stat, where pH is 7.0, 
temperature is 30.degree. C., and substrate is an emulsion of ributyrin 
and gum arabic in the presence of Ca.sup.++ and NaCl in phosphate buffer. 
A highly preferred component of the machine dishwashing or rinsing 
compositions of the invention is a surfactant system comprising surfactant 
selected from anionic, cationic, nonionic ampholytic, amphoteric and 
zwitterionic surfactants and mixtures thereof. The surfactant system is 
present at a level of from 0.1% to 50% by weight, more preferably 1% to 
25% by weight, most preferably from 2% to 20% by weight of the 
compositions. 
The surfactant system is preferably formulated to be compatible with enzyme 
components present in the composition. In liquid or gel compositions the 
surfactant system is most preferably formulated such that it promotes, or 
at least does not degrade, the stability of enzyme in these compositions. 
A typical listing of anionic, nonionic, ampholytic, and zwitterionic 
classes, and species of these surfactants, is given in U.S. Pat. No. 
3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. A list of 
suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 issued 
to Murphy on Mar. 31, 1981. 
Anionic Surfactant 
The anionic surfactant may be essentially any anionic surfactant, including 
anionic sulfate, sulfonate or carboxylate surfactant. 
Highly preferred anionic surfactants herein are sodium or potassium 
salt-forms for which the corresponding calcium salt form has a low Krafft 
temperature of for example 30 deg. C. or below, or, even better, 20 deg. 
C. or lower. Without being limited by theory, including anionic 
surfacants, the calcium salts of which have low Krafft temperatures, into 
the surfactant systems in accord with the present invention tends to 
minimize film formation on hard surfaces. Thus such anionic surfactants 
may act such as to complement the spotting/filming preventative action of 
the lime soap dispersant components of the compositions in accord with the 
present invention. Examples of such highly preferred anionic surfactants 
are the alkyl(polyethoxy)sulfates. 
Anionic Sulfate Surfactant 
The anionic sulfate surfactant may be any organic sulfate surfactant. It is 
preferably selected from the group consisting of C.sub.6 -C.sub.18 alkyl 
sulfate which has been ethoxylated with from about 0.5 to about 20 moles 
of ethylene oxide per molecule, C.sub.9 -C.sub.17 acyl--N--(C.sub.1 
-C.sub.4 alkyl) glucamine sulfated, --N--(C.sub.2 -C.sub.4 hydroxyalkyl) 
glucamine sulfate, and mixtures thereof. More preferably, the anionic 
sulfate surfactant is a C.sub.6 -C.sub.18 alkyl sulfate which has been 
ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to 
about 5, moles of ethylene oxide per molecule. 
Preferred alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy 
sulfate derived from the condensation product of a C.sub.6 -C.sub.18 
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.sub.6 -C.sub.18 alcohol 
itself is preferable commercially available. C.sub.12 -C.sub.15 alkyl 
sulfate which has been ethoxylated with from about 1 to about 5 moles of 
ethylene oxide per molecule is preferred. 
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 degrees of ethoxylation and/or 
different ethoxylate distributions arising from the specific ethoxylation 
techniques employed and subsequent processing steps such as distillation. 
Anionic sulfate surfactants include the C.sub.5 -C.sub.17 acyl--N--(C.sub.1 
-C.sub.4 alkyl) and --N--(C.sub.1 -C.sub.2 hydroxyalkyl) glucamine 
sulfates, preferably those in which the C.sub.5 -C.sub.17 acyl group is 
derived from coconut or palm kernel oil. These materials can be prepared 
by the method disclosed in U.S. Pat. No. 2,717,894, Schwartz, issued Sep. 
13, 1955. 
The counterion for the anionic sulfate surfactant component is preferably 
selected from calcium, sodium, potassium, magnesium, ammonium, or 
alkanol-ammonium, and mixtures thereof. 
Anionic Sulfonate Surfactant 
Anionic sulfonate surfactants suitable for use herein include essentially 
any sulfonate surfactants including, for example, the salts (eg : alkali 
metal salts) of C.sub.5 -C.sub.20 linear alkylbenzene sulfonates, C.sub.6 
-C.sub.22 primary or secondary alkane sulfonates, C.sub.6 -C.sub.24 olefin 
sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, 
fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, paraffin 
sulfonates, and any mixtures thereof. 
Anionic Alkyl Ethoxy Carboxylate Surfactant 
Alkyl ethoxy carboxylates suitable for use herein include those with the 
fomula RO(CH.sub.2 CH.sub.2 O).sub.x CH.sub.2 COO.sup.- M.sup.+ wherein R 
is a C.sub.6 to C.sub.18 alkyl group, x ranges from 0 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 R is C.sub.13 or less, and the average x is from about 
3 to 6 when the average R is greater than C.sub.13, and M is a cation, 
preferably chosen from alkali metal, alkaline earth metal, ammonium, 
mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, 
potassium, ammonium and mixtures thereof with magnesium ions. The 
preferred alkyl ethoxy carboxylates are those where R is a C.sub.12 to 
C.sub.18 alkyl group. 
Anionic Alkyl Polvethoxy Polycarboxylate Surfactant 
Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include 
those having the formula: 
##STR2## 
wherein R is a C.sub.6 to C.sub.18 alkyl group, x is from 1 to 25, 
R.sub.1, and R.sub.2 are selected from the group consisting of hydrogen, 
methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, 
and mixtures thereof, wherein at least one R.sub.1, or R.sub.2 is a 
succinic acid radical or hydroxysuccinic acid radical, and R.sub.3 is 
selected from the group consisting of hydrogen, substituted or 
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and 
mixtures thereof. 
Alkali Metal Sarcosinate Surfactant 
Other anionic surfactants suitable for the purposes of the invention are 
the alkali metal sarcosinates of formula R--CON(R.sup.1)CH.sub.2 COOM 
wherein R is a C.sub.5 -C.sub.17 linear or branched alkyl or alkenyl group, 
R.sup.1 is a C.sub.1 -C.sub.4 alkyl group and M is an alkali metal ion. 
Preferred examples are the myristyl and oleyl methyl sarcosinates in the 
form of their sodium salts. 
Alkyl Ester Sulphonate Surfactants 
Another class of anionic surfactants useful herein are the alkyl ester 
sulfonate surfactants which include linear esters of C.sub.8 -C.sub.20 
carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03 
according to "The Journal of the American Oil Chemists Society," 52 
(1975), pp. 323-329. Suitable starting materials would include natural 
fatty substances as derived from tallow, palm oil, etc. 
The preferred alkyl ester sulfonate surfactants have the structural 
formula: 
##STR3## 
wherein R.sup.3 is a C.sub.8 -C.sub.20 hydrocarbyl, preferably an alkyl, 
or combination thereof, R.sup.4 is a C.sub.1 -C.sub.6 hydrocarbyl, 
preferably an alkyl, or combination thereof, and M is a cation which forms 
a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming 
cations include metals such as sodium, potassium, and lithium, and 
substituted or unsubstituted ammonium cations, such as monoethanolamine, 
diethanolamine, and triethanolamine. Preferably, R.sup.3 is C.sub.10 
-C.sub.18 alkyl, and R.sup.4 is methyl, ethyl or isopropyl. Especially 
preferred are the methyl ester sulfonates wherein R.sup.3 is C.sub.10 
-C.sub.18 alkyl. 
Other Anionic Surfactants 
Other anionic surfactants useful for detersive purposes can also be 
included in the compositions hereof. These can include salts (including, 
for example, sodium, potassium, ammonium, and substituted ammonium salts 
such as mono-, di- and triethanolamine salts) of fatty oleyl glycerol 
sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, 
isethionates such as the acyl isethionates, N-acyl taurates, fatty acid 
amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters 
of sulfosuccinate (especially saturated and unsaturated C.sub.12 -C.sub.18 
monoesters) diesters of sulfosuccinate (especially saturated and 
unsaturated C.sub.6 -C.sub.14 diesters), N-acyl sarcosinates, sulfates of 
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the 
nonionic nonsulfated compounds being described herein), branched primary 
alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula 
RO(CH.sub.2 CH.sub.2 O).sub.k CH.sub.2 COO--M.sup.+ wherein R is a 
C.sub.8 -C.sub.22 alkyl-, k is an integer from 0 to 10, and M is a soluble 
salt-forming cation, and fatty acids esterified with isethionic acid and 
neutralized with sodium hydroxide. Resin acids and hydrogenated resin 
acids are also suitable, such as rosin, hydrogenated rosin, and resin 
acids and hydrogenated resin acids present in or derived from tall oil. 
Further examples are given in "Surface Active Agents and Detergents" (Vol. 
I and II by Schwartz, Perry and Berch). A variety of such surfactants are 
also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 
to Laughlin, et al. at Column 23, line 58 through Column 29, line 23. 
Nonionic Surfactant 
Suitable nonionic detergent surfactants are generally disclosed in U.S. 
Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, 
line 14 through column 16, line 6, incorporated herein by reference. 
Exemplary, nonlimiting classes of useful nonionic surfactants are listed 
below. 
Nonionic Polyhydroxy Fatty Acid Amide Surfactant 
Polyhydroxy fatty acid amides suitable for use herein are those having the 
structural formula: 
##STR4## 
wherein: R1 is H, C.sub.1 -C.sub.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy 
propyl, or a mixture thereof, preferable C.sub.1 -C.sub.4 alkyl, more 
preferably C.sub.1 or C.sub.2 alkyl, most preferably C.sub.1 alkyl (i.e., 
methyl); and R.sub.2 is a C.sub.5 -C.sub.31 hydrocarbyl, preferably 
straight-chain C.sub.5 -C.sub.9 alkyl or alkenyl, more preferably 
straight-chain C.sub.9 -C.sub.17 alkyl or alkenyl, most preferably 
straight-chain C.sub.11 -Cl.sub.17 alkyl or alkenyl, or mixture thereof; 
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with 
at least 3 hydroxyls directly connected to the chain, or an alkoxylated 
derivative (preferably ethoxylated or propoxylated) thereof. Z preferably 
will be derived from a reducing sugar in a reductive amination reaction; 
more preferably Z is a glycityl. Suitable reducing sugars include glucose, 
fructose, maltose, lactose, galactose, mannose, and xylose. As raw 
materials, high dextrose corn syrup, high fructose corn syrup, and high 
maltose corn syrup can be utilized as well as the individual sugars listed 
above. These corn syrups may yield a mix of sugar components for Z. It 
should be understood that it is by no means intended to exclude other 
suitable raw materials. Z preferably will be selected from the group 
consisting of --CH.sub.2 --(CHOH).sub.n --CH2--OH.sub.2, --CH(CH.sub.2 
OH)--(CHOH).sub.n --, 13 CH.sub.2 OH, --CH.sub.2 --(CHOH).sub.2 
(CHOR')(CHOH)--CH.sub.2 OH, where n is an integer from 3 to 5, inclusive, 
and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylate 
derivative thereof. Most preferred are glycityls wherein n is 4, 
particularly --CH.sub.2 --(CHOH).sub.4 --CH.sub.2 OH. 
In Formula (I), R.sup.1 can be, for example, N-methyl, N-ethyl, N-propyl, 
N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. R2--CO--N&lt; 
can be, for example, cocamide, stearamide, oleamide, lauramide, 
myristamide, capricamide, palmitamide, tallowamide, etc. 
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 
1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 
1-deoxymaltotriotityl, etc. 
The most preferred polyhydroxy fatty acid amide has the general formula: 
##STR5## 
wherein R.sup.2 is a straight chain C.sub.11 -C.sub.17 alkyl or alkenyl 
group. 
Nonionic Condensates of Alkyl Phenols 
The polyethylene, polypropylene, and polybutylene oxide condensates of 
alkyl phenols are suitable for use herein. In general, the polyethylene 
oxide condensates are preferred. These compounds include the condensation 
products of alkyl phenols having an alkyl group containing from about 6 to 
about 18 carbon atoms in either a straight chain or branched chain 
configuration with the alkylene oxide. In a preferred embodiment, the 
ethylene oxide is present in an amount equal to from about 5 to about 25 
moles of ethylene oxide per mole of alkyl phenol. Commercially available 
nonionic surfactants of this type include Igepal.TM. CO-630, marketed by 
the GAF Corporation; and Triton.TM. X-45, X-114, X-100, and X-102, all 
marketed by the Rohm & Haas Company. 
Nonionic Ethoxylated Alcohol Surfactant 
The alkyl ethoxylate condensation products of aliphatic alcohols with from 
about 1 to about 25 moles of ethylene oxide are suitable for use herein. 
The alkyl chain of the aliphatic alcohol can either be straight or 
branched, primary or secondary, and generally contains from 6 to 22 carbon 
atoms. Particularly preferred are the condensation products of alcohols 
having an alkyl group containing from 8 to 20 carbon atoms with from about 
2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred 
are the condensation products of alcohols having an alkyl group containing 
from 12 to 18 carbon atoms with from about 6 to about 10 moles of ethylene 
oxide per mole of alcohol. Examples of commercially available nonionic 
surfactants of this type include Tergitol.TM. 15-S-9 (the condensation 
product of C.sub.11 -C.sub.15 linear alcohol with 9 moles ethylene oxide), 
Tergitol.TM. 24-L-6 NMW (the condensation product of C.sub.12 -C.sub.14 
primary alcohol with 6 moles ethylene oxide with a narrow molecular weight 
distribution), both marketed by Union Carbide Corporation; Neodol.TM. 45-9 
(the condensation product of C.sub.14 -C.sub.15 linear alcohol with 9 
moles of ethylene oxide), Neodol.TM. 23-6.5 (the condensation product of 
C.sub.12 -C.sub.13 linear alcohol with 6.54 moles of ethylene oxide), 
Neodol.TM. 45-7 (the condensation product of C.sub.14 -C.sub.15 linear 
alcohol with 7 moles of ethylene oxide), Neodol.TM. 45-4 (the condensation 
product of C.sub.14 -C.sub.15 linear alcohol with 4 moles of ethylene 
oxide), marketed by Shell Chemical Company, and Kyro.TM. EOBN (the 
condensation product of C.sub.13 -C.sub.5 alcohol with 9 moles ethylene 
oxide), marketed by The Procter & Gamble Company. 
Nonionic Ethoxylated/propoxylated Fatty Alcohol Surfactant 
The ethoxylated C.sub.6 -C.sub.18 fatty alcohols and C.sub.6 -C.sub.18 
mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for 
use herein, particularly where water soluble. Preferably the ethoxylated 
fatty alcohols are the C.sub.10 -C.sub.18 ethoxylated fatty alcohols with 
a degree of ethoxylation of from 3 to 50, most preferably these are the 
C.sub.12 -C.sub.18 ethoxylated fatty alcohols with a degree of 
ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated 
fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a 
degree of ethoxylation of from 3 to 30 and a degree of propoxylation of 
from 1 to 10. 
Nonionic EO/PO Condensates with Propylene Glycol 
The condensation products of ethylene oxide with a hydrophobic base formed 
by the condensation of propylene oxide with propylene glycol are suitable 
for use herein. The hydrophobic portion of these compounds preferably has 
a molecular weight of from about 1500 to about 1800 and exhibits water 
insolubility. The addition of polyoxyethylene moieties of this hydrophobic 
portion tends to increase the water solubility of the molecule as a whole, 
and the liquid character of the product is retained up to the point where 
the polyoxyethylene content is about 50% of the total weight of the 
condensation product, which corresponds to condensation with up to about 
40 moles of ethylene oxide. Examples of compounds of this type include 
certain of the commercially-available Pluronic.TM. surfactants, marketed 
by BASF. 
Nonionic EO Condensation Products with Propylene Oxide/ethylene diamine 
Adducts 
The condensation products of ethylene oxide with the product resulting from 
the reaction of propylene oxide and ethylenediamine are suitable for use 
herein. The hydrophobic moiety of these products consists of the reaction 
product of ethylenediamine and excess propylene oxide, and generally has a 
molecular weight of from about 2500 to about 3000. This hydrophobic moiety 
is condensed with ethylene oxide to the extent that the condensation 
product contains from about 40% to about 80% by weight of polyoxyethylene 
and has a molecular weight of from about 5,000 to about 11,000. Examples 
of this type of nonionic surfactant include certain of the commercially 
available Tetronic.TM. compounds, marketed by BASF. 
Nonionic Alkylpolysaccharide Surfactant 
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 
4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group 
containing from about 6 to about 30 carbon atoms, preferably from about 10 
to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, 
hydrophilic group containing from about 1.3 to about 10, preferably from 
about 1.3 to about 3, most preferably from about 1.3 to about 2.7 
saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms 
can be used, e.g., glucose, galactose and galactosyl moieties can be 
substituted for the glucosyl moieties. (Optionally the hydrophobic group 
is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or 
galactose as opposed to a glucoside or galactoside.) The intersaccharide 
bonds can be, e.g., between the one position of the additional saccharide 
units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide 
units. 
Optionally, and less desirably, there can be a polyalkyleneoxide chain 
joining the hydrophobic moiety and the polysaccharide moiety. The 
preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups 
include alkyl groups, either saturated or unsaturated, branched or 
unbranched containing from 8 to 18, preferably from 10 to 16, carbon 
atoms. Preferably, the alkyl group is a straight-chain saturated alkyl 
group. The alkyl group can contain up to about 3 hydroxyl groups and/or 
the polyalkyleneoxide chain can contain up to about 10, preferably less 
than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, 
nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 
heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, 
galatoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and 
pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides. 
The preferred alkylpolyglycosides have the formula 
EQU R.sup.2 O(C.sub.n H.sub.2n O)t(glycosyl).sub.x 
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, 
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl 
groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 
2 or 3, preferably from about 1.3 to about 3, most preferably from about 
1.3 to about 2.7. The glycosyl is preferably derived from glucose. To 
prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed 
first and then reacted with glucose, or a source of glucose, to form the 
glucoside (attachment at the 1-position). The additional glycosyl units 
can then be attached between their 1-position and the preceding glycosyl 
units 2-,3-, 4- and/or 6-position, preferably predominantly the 
2-position. 
Nonionic Fatty Acid Amide Surfactant 
Fatty acid amide surfactants suitable for use herein are those having the 
formula: 
##STR6## 
wherein R.sup.6 is an alkyl group containing from 7 to 21, preferably from 
9 to 17 carbon atoms and each R.sup.7 is selected from the group 
consisting of hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 
hydroxyalkyl, and --(C.sub.2 H.sub.4 O).sub.x H, where x is in the range 
of from 1 to 3. 
Ampholytic Surfactant 
Ampholytic surfactants can be incorporated into the detergent compositions 
herein. These surfactants can be broadly described as aliphatic 
derivatives of secondary or tertiary amines, or aliphatic derivatives of 
heterocyclic secondary and tertiary amines in which the aliphatic radical 
can be straight chain or branched. One of the aliphatic substituents 
contains at least about 8 carbon atoms, typically from about 8 to about 18 
carbon atoms, and at least one contains an anionic water-solubilizing 
group, e.g., carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to 
Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35 for 
examples of ampholytic surfactants. 
Amphoteric Surfactant 
Alkyl Amphocarboxylic Acid Amphoteric Surfactant 
Suitable amphoteric surfactants for use herein include the alkyl 
amphocarboxylic acids of the formula 
##STR7## 
wherein R is a C.sub.8 -C.sub.18 alkyl group, and R.sub.i is of the 
general formula 
##STR8## 
wherein R.sup.1 is a (CH.sub.2).sub.x COOM or CH.sub.2 CH.sub.2 OH, and x 
is 1 or 2 and M is preferably chosen from alkali metal, alkaline earth 
metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from 
sodium, potassium, ammonium and mixtures thereof with magnesium ions. The 
preferred R alkyl chain length is a C.sub.10 to C.sub.14 alkyl group. A 
preferred amphocarboxylic acid is produced from fatty imidazolines wherein 
the dicarboxylic acid functionality of the amphodicarboxylic acid is 
diacetic acid and/or dipropionic acid. A suitable example of an alkyl 
aphodicarboxylic acid for use herein in the amphoteric surfactant 
Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, N.J. 
Amine Oxide surfactant 
Amine oxides useful in the present invention include those compounds having 
the formula: 
##STR9## 
wherein R.sup.3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl 
and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 
carbon atoms, preferably 8 to 16 carbon atoms; R.sup.4 is an alkylene or 
hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 
carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 
3; and each R.sup.5 is an alkyl or hydyroxyalkyl group containing from 1 
to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group 
containing from 1 to 3, preferable 1, ethylene oxide groups. The R.sup.5 
groups can be attached to each other, e.g., through an oxygen or nitrogen 
atom, to form a ring structure. 
These amine oxide surfactants in particular include C.sub.10 -C.sub.18 
alkyl dimethyl amine oxides and C.sub.8 -C.sub.18 alkoxy ethyl 
dihydroxyethyl amine oxides. Examples of such materials include 
dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) 
dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine 
oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine 
oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow 
dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred 
are C.sub.10 -C.sub.18 alkyl dimethylamine oxide, and C.sub.10-18 
acylamido alkyl dimethylamine oxide. 
Zwitterionic Surfactant 
Zwitterionic surfactants can also be incorporated into the detergent 
compositions hereof. These surfactants can be broadly described as 
derivatives of secondary and tertiary amines, derivatives of heterocyclic 
secondary and tertiary amines, or derivatives of quaternary ammonium, 
quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 
3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 
through column 22, line 48 (herein incorporated by reference) for examples 
of zwitterionic surfactants. 
Betaine Surfactant 
The betaines useful herein are those compounds having the formula 
R(R').sub.2 N.sup.+ R.sup.2 COO.sup.- wherein R is a C.sub.6 -C.sub.18 
hydrocarbyl group, preferably a C.sub.10 -C.sub.16 alkyl group or 
C.sub.10-16 acylamido alkyl group, each R.sup.1 is typically C.sub.1 
-C.sub.3 alkyl, preferably methyl,m and R.sup.2 is a C.sub.1 -C.sub.5 
hydrocarbyl group, preferably a C.sub.l -C.sub.3 alkylene group, more 
preferably a C.sub.1 -C.sub.2 alkylene group. Examples of suitable 
betaines include coconut acylamidopropyldimethyl betaine; hexadecyl 
dimethyl betaine; C.sub.12-14 acylamidopropylbetaine; C.sub.8-14 
acylamidohexyldiethyl betaine; 4C.sub.14-16 
acylmethylamidodiethylammonio!-1-carboxybutane; C.sub.16-18 
acylamidodimethylbetaine; C.sub.12-16 acylamidopentanediethyl-betaine; 
C.sub.12-16 acylmethylamidodimethylbetaine. Preferred betaines are 
C.sub.12-18 dimethyl-ammonio hexanoate and the C.sub.10-18 
acylamidopropane (or ethane) dimethyl (or diethyl) betaines. 
Sultaine Surfactant 
The sultaines useful herein are those compounds having the formula 
(R(R.sup.1).sub.2 N.sup.+ R.sup.2 SO.sub.3.sup.- wherein R is a C.sub.6 
-C.sub.18 hydrocarbyl group, preferably a C.sub.10 -C.sub.16 alkyl group, 
more preferably a C.sub.12 -C.sub.13 alkyl group, each R.sup.1 is 
typically C.sub.1 -C.sub.3 alkyl, preferably methyl, and R.sup.2 is a 
C.sub.1 -C.sub.6 hydrocarbyl group, preferably a C.sub.1 -C.sub.3 alkylene 
or, preferably, hydroxyalkylene group. Examples of suitable sultaines 
include C.sub.12 -C.sub.14 dimethylammonio-2-hydroxypropyl sulfonate, 
C.sub.12-14 amido propyl ammonio-2-hydroxypropyl sultaine, C.sub.12-14 
dihydroxyethylammonio propane sulfonate, and C.sub.16-18 dimethylammonio 
hexane sulfonate, with C.sub.12-14 amido propyl ammonio-2-hydroxypropyl 
sultaine being preferred. 
Complex Betaine Surfactant 
The complex betaines for use herein have the formula 
##STR10## 
wherein R is a hydrocarbon group having from 7 to 22 carbon atoms, A is 
the group (C(O)), n is 0 or 1, R.sub.1 is hydrogen or a lower alkyl group, 
x is 2 or 3, y is an integer of 0 to 4, Q is the group -R.sub.2 COOM 
wherein R.sub.2 is an alkylene group having from 1 to 6 carbon atoms and M 
is hydrogen or an ion from the groups alkali metals, alkaline earth 
metals, ammonium and substituted ammonium and B is hydrogen or a group Q 
as defined. 
An example in this category is tallowamphopolycarboxy glycinate, of the 
formula: 
##STR11## 
Preferred amides are C.sub.8 -C.sub.20 alkyl mono- or di-C.sub.2 -C.sub.3 
alkanolamides, especially monoethanolamides, diethanolamides, and 
isopropanolamides. 
Ampholytic, amphoteric and zwitteronic surfactants are generally used in 
combination with one or more anionic and/or nonionic surfactants. 
Cationic Surfactants 
Cationic surfactants can also be used in the detergent compositions herein 
and suitable quaternary ammonium surfactants are selected from mono 
C.sub.6 -C.sub.16, preferably C.sub.6 -C.sub.10 N-alkyl or alkenyl 
ammonium surfactants wherein remaining N positions are substituted by 
methyl, hydroxyethyl or hydroxypropyl groups. 
Hydrotropes 
A hydrotrope is typically added to the compositions of the present 
invention, and may be present at levels of from 0.5% to 25%, preferably 
from 1% to 15%, by weight. Useful hydrotropes include sodium, potassium, 
and ammonium xylene sulfonates, sodium, potassium, and ammonium toluene 
sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures 
thereof. 
Other compounds useful as hydrotropes herein include polycarboxylates. Some 
polycarboxylates have calcium chelating properties as well as hydrotropic 
properties. Particularly useful hydrotropes are alkylpolyethoxy 
polycarboxylate surfactants of the type as previously described herein. 
An example of a commercially available alkylpolyethoxy polycarboxylate 
which can be employed herein is POLY-TERGENT C, Olin Corporation, 
Cheshire, Conn. 
Another compound useful as a hydrotrope is alkyl amphodicarboxylic acid of 
the generic formula: 
##STR12## 
wherein R is a C.sub.8 to C.sub.18 alkyl group, x is from 1 to 2, M is 
preferably chosen from alkali metal, alkaline earth metal, ammonium, 
mono-, di-, and tri-ethanolammonium, most preferably from sodium, 
potassium, ammonium, and mixtures thereof with magnesium ions. The 
preferred alkyl chain length (R) is a C.sub.10 to C.sub.14 alkyl group and 
the dicarboxylic acid functionally is diacetic acid and/or dipropionic 
acid. 
A suitable example of an alkyl amphodicarboxylic acid is the amphoteric 
surfactant Miranol R 2CM Conc.manufactured by Miranol, Inc., Dayton, N.J. 
Suds Suppressing System 
The machine dishwashing or rinsing detergent compositions of the invention 
preferably comprise a suds suppressing system present at a level of from 
0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 
5% by weight of the composition. 
Suitable suds suppressing systems for use herein may comprise essentially 
any known antifoam compound, including, for example silicone antifoam 
compounds, 2-alkyl alcanol antifoam compounds, and paraffin antifoam 
compounds. 
By antifoam compound it is meant herein any compound or mixtures of 
compounds which act such as to depress the foaming or sudsing produced by 
a solution of a detergent composition, particularly in the presence of 
agitation of that solution. 
The suds suppressing system may be incorporated into the detergent 
compositions by essentially any process route. One preferred suds 
suppressing system comprises in combination a spray-on component and a 
particulate component. 
Preferred spray-on components comprise in combination an antifoam compound 
and a carrier fluid and optionally a dispersant compound. The antifoam 
compound is dissolved, dispersed, suspended or emulsified in said carrier 
fluid. The carrier fluid should be inert in nature, that is it should not 
undergo undesirable chemical reaction with the antifoam compound, and also 
preferably be storage stable under normal atmospheric conditions and in 
the environment of a granular detergent matrix. 
Any spray-on component is incorporated into the granular detergent 
compositions of the invention by a spray-on process, that is a process 
whereby the fluid is sprayed on to some or all of the individual granular 
components of the composition. Highly preferably the spray-on process will 
be such as to provide a uniform and sufficient application of the suds 
suppressing component to any granular components of the composition which 
comprise a high sudsing surfactant. 
A preferred composition for a spray-on component comprises 
(a) antifoam compound, preferably silicone antifoam compound, most 
preferably a silicone antifoam compound comprising in combination 
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 
95% by weight of the silicone antifoam compound; and 
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight 
of th e si licone/silica antifoam compound; 
wherein said silica/silicone antifoam compound is incorporated at a level 
of from 5% to 50%, preferably 10% to 40% by weight of the spray-on 
component; 
(b) a dispersant compound, most preferably comprising a silicone glycol 
rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene 
oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 
0.5% to 10%, preferably 1% to 10% by weight of the spray-on component; a 
particularly preferred silicone glycol rake copolymer of this type is 
DCO544, commercially available from DOW Corning; 
(c) an inert carrier fluid compound, most preferably comprising a C.sub.16 
-C.sub.18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 
50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 
70%, by weight of the spray-on component; 
Any spray on component of the suds suppressing system may be incorporated 
as such, or in a preferred execution may be mixed with other components 
such as liquid nonionic surfactants, and perfume, and this mixture sprayed 
on as a whole. 
Particulate components of the suds suppressing system are particulate in 
form and incorporated into the compositions of the invention in this form. 
By particulate form it is meant essentially any of the particulate forms 
which may be typically adapted by a component of a granular detergent 
composition. The particulate component can therefore be, for example, in 
the form of granules, flakes, prills, marumes or noodles. In a preferred 
execution the particulate is granular in nature. Granules themselves may 
be agglomerates formed by pan or drum agglomeration or by an in-line 
mixer, and also may be spray-dried particles produced by atomising an 
aqueous slurry of the ingredients in a hot air stream which removes most 
of the water. The spray dried granules are then subjected to densification 
steps, eg : by high speed cutter mixers and/or compacting mills, to 
increase density before being reagglomerated. 
Any particulate component of the suds suppressing system may comprise in 
combination antifoam compound, and a carrier material which is highly 
preferably water-soluble or water-dispersible in nature. 
A suitable particulate antifoam component useful in the compositions herein 
comprises a mixture of an alkylated siloxane of the type hereinabove 
disclosed and solid silica. 
The solid silica can be a fumed silica, a precipitated silica or a silica, 
made by the gel formation technique. The silica particles suitable have an 
average particle size of from 0.1 to 50 micrometers, preferably from 1 to 
20 micrometers and a surface area of at least 50 m.sup.2 /g. These silica 
particles can be rendered hydrophobic by treating them with dialkylsilyl 
groups and/or trialkylsilyl groups either bonded directly onto the silica 
or by means of a silicone resin. It is preferred to employ a silica the 
particles of which have been rendered hydrophobic with dimethyl and/or 
trimethyl silyl groups. A preferred particulate antifoam compound for 
inclusion in the detergent compositions in accordance with the invention 
suitably contain an amount of silica such that the weight ratio of silica 
to silicone lies in the range from 1:100 to 3:10, p preferably from 1:50 
to 1:7. 
Another suitable particulate antifoam component is represented by a 
hydrophobic silanated (most preferably trimethyl-silanated) silica having 
a particle size in the rang e from 10 nanometers to 20 nanometers and a 
specific surface area above 50 m.sup.2 /g, intimately admixed with 
dimethyl silicone fluid having a molecular weight in the range from about 
500 to about 200,000 at a weight ratio of silicone to silanated silica of 
from about 1:1 to about 1:2. 
Suitable particulate antifoam components are disclosed in Bartollota et al. 
U.S. Pat. No. 3,933,672. 
A highly preferred particulate antifoam component is described in 
EP-A-0210731 and comprises a silicone antifoam compound and an organic 
carrier material having a melting point in the range 50.degree. C. to 
85.degree. C., wherein the organic carrier material comprises a monoester 
of glycerol and a fatty acid having a carbon chain containing from 12 to 
20 carbon atoms. EP-A-0210721 discloses other preferred particulate 
antifoam components wherein the organic carrier material is a fatty acid 
or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or 
a mixture thereof, with a melting point of from 45.degree. C. to 
80.degree. C. 
Other highly preferred particulate antifoam components are described in 
copending European Application 91870007.1 in the name of the Procter and 
Gamble Company which components comprise silicone antifoam compound, a 
carrier material, an organic coating material and glycerol at a weight 
ratio of glycerol:silicone antifoam compound of 1:2 to 3:1. Copending 
European Application 91201342.0 also discloses highly preferred 
particulate antifoam components comprising silicone antifoam compound, a 
carrier material, an organic coating material and crystalline or amorphous 
aluininosilicate at a weight ratio of aluminosilicate:silicone antifoam 
compound of 1:3 to 3:1. The preferred carrier material in both of the 
above described highly preferred granular suds controlling agents is 
starch. 
An exemplary particulate antifoam component for use herein is a particulate 
agglomerate component, made by an agglomeration process, comprising in 
combination 
(i) from 5% to 30%, preferably from 8% to 15% by weight of the component of 
silicone antifoam compound, preferably comprising in combination 
polydimethyl siloxane and silica; 
(ii) from 50% to 90%, preferably from 60% to 80% by weight of the 
component, of carrier material, preferably starch; 
(iii) from 5% to 30%, preferably from 10% to 20% by weight of the component 
of agglomerate binder compound, where herein such compound can be any 
compound, or mixtures thereof typically employed as binders for 
agglomerates, most preferably said agglomerate binder compound comprises a 
C.sub.16 -C.sub.18 ethoxylated alcohol with a degree of ethoxylation of 
from 50 to 100; and 
(iv) from 2% to 15%, preferably from 3% to 10%, by weight of C.sub.12 
-C.sub.22 hydrogenated fatty acid. 
The incorporation of silicon e antifoam compounds as components of seperate 
particulate components also permits the inclusion therein of C.sub.20 
-C.sub.24 fatty acids, microcrystalline waxes and high MWt copolymers of 
ethylene oxide and propylene oxide which would otherwise adversely affect 
the despersibility of the matrix. Techniques for forming such particulates 
are disclosed in U.S. Pat. No. 3,933,672. 
A preferred suds suppressing system has the weight ratio of antifoam 
compound comprised in the spray-on component to antifoam compound 
comprised in the particulate component of from 5:1 to 1:1, most preferably 
from 4:1 to 2:1. 
Particularly preferred antifoam compounds for use herein are silicone 
antifoam compounds defined herein as any antifoam compound including a 
silicone component. Such silicone antifoam compounds also typically 
contain a silica component. The term "silicone" as used herein, and in 
general throughout the industry, encompasses a variety of relatively high 
molecular weight polymers containing siloxane units and hydrocarbyl group 
of various types. 
Preferred silicone antifoam compounds are the siloxanes having the general 
structure: 
##STR13## 
where each R independently can be an alkyl or an aryl radical. Examples of 
such substituents are methyl, ethyl, propyl, isobutyl, and phenyl. 
Preferred polydiorganosiloxanes are polydimethylsiloxanes having 
trimethylsilyl endblocking units and having a viscosity at 25.degree. C. 
of from 5.times.10.sup.-5 m.sup.2 /s to 0.1 m.sup.2 /s i.e. a value on n 
in the range 40 to 1500. These are preferred because of their ready 
availability and their relatively low cost. 
Other suitable antifoam compounds include the monocarboxylic fatty acids 
and soluble salts thereof. These materials are described in U.S. Pat. No. 
2,954,347, issued Sep. 27, 1960 to Wayne St. John. The monocarboxylic 
fatty acids, and salts thereof, for use as suds suppressor typically have 
hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 
carbon atoms. Suitable salts include the alkali metal salts such as 
sodium, potassium, and lithium salts, and ammonium and alkanolammonium 
salts. 
Other suitable antifoam compounds include, for example, high molecular 
weight hydrocarbons such as paraffin, fatty esters (e.g. fatty acid 
triglycerides), fatty acid esters of monovalent alcohols, aliphatic 
C.sub.18 -C.sub.40 ketones (e.g. stearone) N-alkylated amino triazines 
such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine 
chlortriazines formed as products of cyanuric chloride with two or three 
moles of a primary or secondary amine containing 1 to 24 carbon atoms, 
propylene oxide, bis stearic acid amide and monostearyl di-alkali metal 
(e.g. sodium, potassium, lithium) phosphates and phosphate esters. The 
hydrocarbons, such as paraffin and haloparaffin, can be utilized in liquid 
form. The liquid hydrocarbons will be liquid at room temperature and 
atmospheric pressure, and will have a pour point in the range of about 
-40.degree. C. and about 5.degree. C., and a minimum boiling point not 
less than 110.degree. C. (atmospheric pressure). It is also known to 
utilize waxy hydrocarbons, preferably having a melting point below about 
100.degree. C. Hydrocarbon suds suppressors are described, for example, in 
U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al. The 
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and 
heterocyclic saturated or unsaturated hydrocarbons having from about 12 to 
about 70 carbon atoms. The term "paraffin", as used in this suds supressor 
dicussion, is intended to include mixtures of true paraffins and cyclic 
hydrocarbons. 
Copolymers of ethylene oxide and propylene oxide, particularly the mixed 
ethoxylated/propoxylated fatty alcohols with an alkyl chain length of from 
10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a 
degree of propoxylation of from 1 to 10, are also suitable antifoam 
compounds for use herein. 
Suitable 2-alky-alcanols antifoam compounds for use herein have been 
described in DE 40 21 265. The 2-alkyl-alcanols suitable for use herein 
consist of a C.sub.6 to C.sub.16 alkyl chain carrying a terminal hydroxy 
group, and said alkyl chain is substituted in the a position by a C.sub.1 
to C.sub.10 alkyl chain. Preferably, the alkyl chain carrying the hydroxy 
group is a C.sub.8 to C.sub.12 alkyl chain, and the alkyl chain in the a 
position is a C.sub.2 to C.sub.8 alkyl chain, most preferably C.sub.3 to 
C.sub.6. Preferably all alkyl chains herein are straight. It has been 
found that 2-hexyl-decanol and 2-butyl-decanol are particularly suitable 
for use herein. 2-hexyl-decanol and 2-butyl- octanol are commercially 
available fron Condea under the trade names ISOFOL 16 and ISOFOL 12. The 
suds suppressing system for use herein comprises from 0.01% to 15% by 
weight of the total composition of said 2-alkyl-alcanols, preferably from 
0.05% to 10%, most preferably from 0.1% to 5%. Mixtures of 
2-alkyl-alcanols can be used in the compositions according to the present 
invention. Such mixtures are comprised in commercially available 
materials, for instance ISALCHEM 123 R from Enichem. 
The machine dishwashing detergent compositions of the invention will 
preferably included bleaching agent selected from chlorine bleaches, 
inorganic perhydrate salts, peroxyacid bleach precursors and organic 
peryoxacids. 
Chlorine bleaches include the alkali metal hypochlorites and chlorinated 
cyanuric acid salts. The use of chlorine bleaches in the composition of 
the invention is preferably minimized, and more preferably the 
compositions contain no chlorine bleach. 
The machine dishwashing detergent compositions in accord with the invention 
will generally include an inorganic perhydrate salt, normally in the form 
of the sodium salt at a level of from 1% to 40% by weight, more preferably 
from 2% to 30% by weight and most preferably from 5% to 25% by weight of 
the detergent compositions. 
The machine dishwashing detergent compositions of the present invention 
will also generally include peroxyacid bleach precursors (bleach 
activators). The peroxyacid bleach precursors are normally incorporated at 
a level of from 1% to 20% by weight, more preferably from 1% to 10% by 
weight, most preferably from 1% to 7% by weight of the compositions. 
The machine dishwashing detergent compositions may also contain organic 
peroxyacids at a level of from 1% to 15% by weight, more preferably from 
1% to 10% by weight of the composition. 
Examples of inorganic perhydrate salts include perborate, percarbonate, 
perphosphate, persulfate and persilicate salts. The inorganic perhydrate 
salts are normally the alkali metal salts. The inorganic perhydrate salt 
may be included as the crystalline solid without additional protection. 
For certain perhydrate salts however, the preferred executions of such 
granular compositions utilize a coated form of the material which provides 
better storage stability for the perhydrate salt in the granular product. 
Sodium perborate, which is the most preferred perhydrate for inclusion in 
the machine dishwashing detergent compositions in accordance with the 
invention, can be in the form of the monohydrate of nominal formula 
NaBO.sub.2 H.sub.2 O.sub.2 or the tetrahydrate NaBO.sub.2 H.sub.2 O.sub.2 
.multidot.3H.sub.2 O. 
Sodium percarbonate, which is another preferred perhydrate for inclusion in 
detergent compositions in accordance with the invention, is an addition 
compound having a formula corresponding to 2Na.sub.2 CO.sub.3 
.multidot.3H.sub.2 O.sub.2, and is available commercially as a crystalline 
solid. The percarbonate is most preferably incorporated into such 
compositions in coated form. The most preferred coating material comprises 
mixed salt of an alkali metal sulphate and carbonate. Such coatings 
together with coating processes have previously been described in 
GB-1,466,799, granted to Interox on 9th Mar. 1977. The weight ratio of the 
mixed salt coating material to percarbonate lies in the range from 1:200 
to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 
1:19. Preferably, the mixed salt is of sodium sulphate and sodium 
carbonate which has the general formula Na.sub.2 SO.sub.4 
.multidot.n.multidot.Na.sub.2 CO.sub.3 wherein n is form 0.1 to 3, 
preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5. 
Another suitable coating material is sodium silicate of SiO.sub.2 :Na.sub.2 
O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous 
solution to give a level of from 2% to 10%, (normally from 3% to 5%) of 
silicate solids by weight of the percarbonate. Magnesium silicate can also 
be included in the coating. other suitable coating materials include the 
alkali and alkaline earth metal sulphates and carbonates. 
Potassium peroxymonopersulfate is another inorganic perhydrate salt of 
particular usefulness in the machine dishwashing detergent compositions. 
Peroxyacid bleach precursors for inclusion in the machine dishwashing 
detergent compositions in accordance with the invention probably contain 
one or more N- or O- acyl groups, which precursors can be selected from a 
wide range of classes. Suitable classes include anhydrides, esters, imides 
and acylated derivatives of imidazoles and oximes, and examples of useful 
materials within these classes are disclosed in GB-A-1586789. The most 
preferred classes are esters such as are disclosed in GB-A-836988, 864798, 
1147871 and 2143231 and imides such as are disclosed in GB-A-855735 & 
1246338. 
Particularly preferred precursor compounds are the N,N,N.sup.1,N.sup.1 
tetra acetylated compounds of formula 
##STR14## 
wherein x can be O or an integer between 1 & 6. 
Examples include tetra acetyl methylene diamine (TAMD) in which x=1, tetra 
acetyl ethylene diamine (TAED) in which x=2 and tetraacetyl hexylene 
diamine (TAHD) in which x=6. These and analogous compounds are described 
in GB-A-907356. The most preferred peroxyacid bleach precursor is TAED. 
Another preferred class of peroxyacid bleach activator compounds are the 
amide substituted compounds of the following general formulae: 
##STR15## 
wherein R.sup.1 is an aryl or alkaryl group with from about 1 to about 14 
carbon atoms, R.sup.2 is an alkylene, arylene, and alkarylene group 
containing from about 1 to 14 carbon atoms, and R.sup.5 is H or an alkyl, 
aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be 
essentially any leaving group. R.sup.1 preferably contains from about 6 to 
12 carbon atoms. R.sup.2 preferably contains from about 4 to 8 carbon 
atoms. R.sup.1 may be straight chain or branched alkyl, substituted aryl 
or alkylaryl containing branching, substitution, or both and may be 
sourced from either synthetic sources or natural sources including for 
example, tallow fat. Analogous structural variations are permissible for 
R.sup.2. The substitution can include alkyl, aryl, halogen, nitrogen, 
sulphur and other typical substituent groups or organic compounds. R.sup.5 
is preferably H or methyl. R.sup.1 and R.sup.5 should not contain more 
than 18 carbon atoms total. Amide substituted bleach activator compounds 
of this type are described in EP-A-0170386. 
Other peroxyacid bleach precursor compounds include sodium nonanoyloxy 
benzene sulfonate, sodium trimethyl hexanoyloxy benzene sulfonate, sodium 
acetoxy benzene sulfonate and sodium benzoyloxy benzene sulfonate as 
disclosed in, for example, EP-A-0341947. 
The machine dishwashing detergent compositions of the invention may also 
contain organic peroxyacids of which a particularly preferred class are 
the amide substituted peroxyacids of general formulae: 
##STR16## 
where R.sup.1, R.sup.2 and R.sup.5 are as defined previously for the 
corresponding amide substituted peroxyacid bleach activator compounds. 
Other organic peroxyacids include diperoxy dodecanedioc acid, diperoxy 
tetra decanedioc acid, diperoxyhexadecanedioc acid, mono- and diperazelaic 
acid, mono- and diperbrassylic acid, monoperoxy phthalic acid, perbenzoic 
acid, and their salts as disclosed in, for example, EP-A-0341 947. 
Detergent compositions in which solid peroxybleach precursors are protected 
via an acid coating are disclosed in the Applicant's copending British 
Application No. 9102507.2 filed Feb. 6, 1991. 
Anti-redeposition and soil-suspension agents suitable herein include 
cellulose derivatives such as methylcellulose, carboxymethylcellulose and 
hydroxyethylcellulose, homo-or co-polymeric polycarboxylic acids or their 
salts and polyamino compounds. Polymers of this type include the 
polyacrylates and copolymers of maleic anhydride with ethylene, 
methylvinyl ether or methacrylic acid, the maleic anhydride constituting 
at least 20 mole percent of the copolymer disclosed in detail in 
EP-A-137669. Polyamino compounds such as those derived from aspartic acid 
are disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. These materials 
are normally used at levels of from 0.5% to 10% by weight, more 
preferably; from 0.75% to 9%, most preferably from 1% to 8% by weight of 
the composition. 
Other useful polymeric materials are the polyethylene glycols, particularly 
those of molecular weight 1000-10000, more particularly 2000 to 8000 and 
most preferably about 4000. These are used at levels of from 0.2% to 5% by 
weight, more preferably from 0.25% to 2.5% by weight. These polymers and 
the previously mentioned homo- co-polymeric polycarboxylate salts are 
valuable for reducing ash deposition, and improving cleaning performance 
on clay, proteinaceous and oxidizable soils in the presence of transition 
metal impurities. 
Another optional ingredient useful in detergent compositions is one or more 
enzymes. 
Preferred additional enzymatic materials include the commercially available 
amylases, neutral and alkaline proteases, and, esterases conventionally 
incorporated into detergent compositions. Suitable enzymes are discussed 
in U.S. Pat. Nos. 3,519,570 and 3,533,139. 
Preferred commercially available protease enzymes include those sold under 
the tradenames Alcalase and Savinase by Novo Industries A/S (Denmark) and 
Maxatase by International Bio-Synthetics, Inc. (The Netherlands). Protease 
enzyme may be incorporated into the compositions in accordance with the 
invention at a level of from 0.005% to 2% active enzyme by weight of the 
composition. 
Preferred amylases include, for example, &-amylases obtained from a special 
strain of B licheniforms, described in more detail in GB-1,269,839 (Novo). 
Preferred commercially available amylases include for example, Rapidase, 
sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo 
Industries A/S. Amylase enzyme may be incorporated into the composition in 
accordance with the invention at a level of from 0.001% to 2% active 
enzyme by weight of the composition. 
Enzyme Stabilizing System 
Preferred enzyme-containing 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 comprise calcium ion, boric acid, propylene glycol, short 
chain carboxylic acid, boronic acid, and mixtures thereof. 
The compositions herein may further comprise from 0 to about 10%, 
preferably from about 0.01% to about 6% by weight, of chlorine bleach 
scavengers, added to prevent chlorine bleach species present in many water 
supplies from attacking 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 containing ammonium cations or sulfite, 
bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as 
carbamate, ascorbate, etc., organic amines such as 
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, 
monoethanolamine (MEA), and mixtures thereof can likewise be used. Other 
conventional scavengers such as bisulfate, nitrate, chloride, sources of 
hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate 
monohydrate and sodium percarbonate, as well as phosphate, condensed 
phosphate, acetate, benzoate, citrate, formate, 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 of the 
ingredients separately listed under better recognized functions, (e.g., 
other components of the invention including oxygen bleaches), there is no 
requirement to add a separate chlorine scavenger unless a compound 
performing that function to the desired extent is absent from an 
enzyme-containing embodiment of the invention; even then, the scavenger is 
added only for optimum results. Moreover, the formulator will exercise a 
chemist's normal skill in avoiding the use of any scavenger which is 
majorly incompatible with other optional ingredients, if used. For 
example, formulation chemists generally recognize that combinations of 
reducing 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 solid-form 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 liberate ammonia during 
storage. Accordingly, such materials, if present, are desirably protected 
in a particle such as that described in U.S. Pat. No. 4,652,392, Baginski 
et al. 
Corrosion Inhibitor 
The present compositions may also contain corrosion inhibitor, preferably 
incorporated at a level of from 0.05% to 10%, preferably from 0.1% to 5% 
by weight of the total composition. 
Suitable corrosion inhibitors include paraffin oil typically a 
predominantly branched aliphatic hydrocarbon having a number of carbon 
atoms in the range of from 20 to 50; preferred paraffin oil selected from 
predominantly branched C.sub.25-45 species with a ratio of cyclic to 
noncyclic hydrocarbons of about 32:68; a paraffin oil meeting these 
characteristics is sold by Wintershall, Salzbergen, Germany, under the 
trade name WINOG 70. 
Other suitable corrosion inhibitor compounds include benzotriazole and any 
derivatives thereof, mercaptans and diols, especially mercaptans with 4 to 
20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, 
thionalide and thioanthranol. Also suitable are the C.sub.12 -C.sub.20 
fatty acids, or their salts, especially aluminium tristearate. The 
C.sub.12 -C.sub.20 hydroxy fatty acids, or their salts, are also suitable. 
Phosphonated octa-decane and other anti-oxidants such as 
betahydroxytoluene (BHT) are also suitable. 
Heavy Metal Ion Sequestrant 
The detergent compositions of the invention may be formulated to contain as 
a non-essential component heavy metal ion sequestrant, incorporated at a 
level of from 0.005% to 3%, preferably 0.05 to 1%, most preferably 0.07% 
to 0.4%, by weight of the total composition. 
Suitable heavy metal ion sequestrant for use herein include organic 
phosphonates, such as amino alkylene poly (alkylene phosphonate), alkali 
metal ethane 1-hydroxy disphosphonates, nitrilo trimethylene phosphonates. 
Preferred among above species are diethylene triamine penta (methylene 
phosphonate), hexamethylene diamine tetra (methylene phosphonate) and 
hydroxy-ethylene 1,1 diphosphonate. 
The phosphonate compounds may be present either in their acid form or as a 
complex of either an alkali or alkaline metal ion, the molar ratio of said 
metal ion to said phosphonate compound being at least 1:1. Such complexes 
are described in U.S. Pat. No. 4,259,200. Preferably, the organic 
phosphonate compounds are in the form of their magnesium salt. 
Other suitable heavy metal ion sequestrant for use herein include 
nitrilotriacetic acid and polyaminocarboxylic acids such as 
ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, 
ethylenediamine disuccinic acid or the water soluble alkali metal salts 
thereof. Especially preferred is ethylenediamine-N,N'-disuccinic acid 
(EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted 
ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are 
the free acid form and the sodium or magnesium salt or complex thereof. 
Examples of such preferred sodium salts of EDDS include Na.sub.2 EDDS and 
Na.sub.3 EDDS. Examples of such preferred magnesium complexes of EDDS 
include MgEDDS and Mg.sub.2 EDDS. The magnesium complexes are the most 
preferred for inclusion in compositions in accordance with the invention. 
Still other suitable heavy metal ion sequestrants for use herein are 
iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or 
glyceryl imino diacetic acid, described in EPA 317 542 and EPA 399 133. 
The heavy metal ion sequestrant herein can consist of a mixture of the 
above described species. 
Other optional ingredients suitable for inclusion in the compositions of 
the invention include perfumes, colours and filler salts, with sodium 
sulfate being a preferred filler salt. 
The machine dishwashing or rinsing compositions of the invention can be 
formulated in any desirable form such as powders, granulates, pastes, 
liquids, gels and tablets. 
In general, granular machine dishwashing or rinsing detergent compositions 
in accordance with the present invention can be made via a variety of 
methods including dry mixing, spray drying, agglomeration and granulation. 
A preferred method of making the granular machine dishwashing compositions 
involves a combination of dry mixing and agglomeration techniques. 
The bulk density of the granular detergent compositions in accordance with 
the present invention typically have a bulk density of at least 650 
g/liter, more usually at least 700 g/liter and more preferably from 800 
g/liter to 1200 g/liter. 
Bulk density is measured by means of a simple funnel and cup device 
consisting of a conical funnel moulded rigidly on a base and provided with 
a flap valve at its lower extremity to allow the contents of the funnel to 
be emptied into an axially aligned cylindrial cup disposed below the 
funnel. The funnel is 130 mm and 40 mm at its respective upper and lower 
extremities. It is mounted so that the lower extremity is 140 mm above the 
upper surface of the base. The cup has an overall height of 90 mm, an 
internal height of 87 mm and an internal diameter of 84 mm. Its nominal 
volume is 500 ml. 
To carry out a measurement, the funnel is filled with powder by hand 
pouring, the flap valve is opened and powder allowed to overfill the cup. 
The filled cup is removed from the frame and excess powder removed from 
the cup by passing a straight edged implement e.g. a knife, across its 
upper edge. The filled cup is then weighed and the value obtained for the 
weight of powder doubled to provide the bulk density in g/liter. Replicate 
measurements are made as required. 
The particle size of the components of granular compositions in accordance 
with the invention should preferably be such that no more that 5% of 
particles are greater than 1.4 mm in diameter and not more than 5% of 
particles are less than 0.15 mm in diameter. 
Generally, if the machine dishwashing or rinsing detergent compositions are 
in liquid form the liquid should be thixotropic (ie; exhibit high 
viscosity when subjected to low stress and lower viscosity when subjected 
to high stress), or at least have very high viscosity, for example, of 
from 1,000 to 10,000,000 centipoise. In many cases it is desirable to 
include a viscosity control agent or a thixotropic agent to provide a 
suitable liquid product form. Suitable thixotropic or viscosity control 
agents include methyl cellulose, carboxymethylcellulose, starch, 
polyvinyl, pyrrolidone, gelatin, colloidal silica, and natural or 
synthetic clay minerals. 
Pasty compositions in accordance with the invention generally have 
viscosities of about 5,000 centipoise and up to several hundred million 
centipoise. In order to provide satisfaction pasty compositions a small 
amount of a solvent or solubilizing agent or of a gel-forming agent can be 
included. Most commonly, water is used in this context and forms the 
continuous phase of a concentrated dispersion. Certain nonionic 
surfactants at high levels form a gel in the presence of small amount of 
water and other solvents. Such gelled compositions also envisaged in the 
present invention. 
In the detergent compositions, the abbreviated component identifications 
have the following meanings: 
Citrate: Tri-Sodium citrate dihydrate 
Phosphate: Sodium tripolyphosphate 
MA/AA: Copolymers of 1:4 maleic/acrylic acid, average molecular weight 
about 80,000 
Silicate: Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O ratio normally 
follows) 
Carbonate: Anhydrous sodium carbonate 
Protease: Proteolytic enzyme sold under the tradename Savinase by Novo 
Industries A/S 
Amylase: Amylolytic enzyme sold under the tradename Termamyl by Novo 
Industries A/S 
Lipase: Lipolytic enzyme obtained from a lipase producing strain of 
Pseudomonas pseudoalcaligenes 
Nonionic: C.sub.13 -C.sub.15 mixed ethoxylated/propoxylated fatty alcohol 
with an average degree of ethoxylation of 3.8 and an average degree of 
propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh. 
Sulphate: Anhydrous Sodium Sulphate 
Perborate: anhydrous sodium parborate monohydrate bleach, empirical formula 
NaBO.sub.2 .multidot.H.sub.2 O 
TAED: Tetraacetyl ethylene diamine 
SCS: Sodium cumene sulphonate 
Dobanol: A blend of C.sub.12 -C.sub.15 ethoxylated alcohols with an average 
degree of ethoxylation of 9, sold under the tradename Dobanol 25.9 by 
Shell Chemicals (UK) Ltd 
LSD1: A blend of C.sub.13 -C.sub.15 ethoxylated alcohols with an average 
degree of ethoxylation of 30, sold under the tradename Lutensol A030 by 
BASF GmbH. 
LSD2: A blend of C.sub.13 -C.sub.15 ethoxylated alcohols with an average 
degree of ethoxylation of 12, sold under the tradename Lutensol A012 by 
BASF GmbH. 
LSD3: C.sub.13 -C.sub.15 alkyl ethoxysulfate with a degree of ethoxylation 
of 3 
Suds Suppressor: 12% silicone/silica, 18% stearyl alcohol, 70% starch, in 
granular form.