Note: Descriptions are shown in the official language in which they were submitted.
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DISHWASHING COMPOSITIONS COMPRISING
A PHOSPHOLIPASE AND AN AMYLASE
Technical Field
The present invention relates to a dishwashing composition comprising a
phospholipase enzyme and an amylase enzyme.
Background of the Invention
Performance of a detergent product is judged by a number of factors,
including the ability to remove soils, and the ability to prevent the
redeposition of
the soilsLor the breakdown products of the soils on the dishware in the wash.
In
particular, food soils are often difficult to remove effectively from a soiled
item.
Food soils such as greasy/oily soils and stains represent a well-known
cleaning challenge often met by the inclusion of a lipolytic enzyme in the
detergent compositions. Lipolytic enzymes for enhanced removal of
triglycerides
containing soils and stains are indeed well-known in the art. Some examples
are
W095/04808, W093/21229 and W094/25556. In addition to the lipolytic
enzyme, a lime soap dispersant is generally also included in dishwashing
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compositions to provide the mitigation of spotting and filming effects,
particularly
_on glassware and plastic ware, such as described in W095/04806, W094/07985
and W094/07984.
Processed or cooked food soils and stains often contain materials used for the
processing, cooking and flavouring of the food : butter, milk, eggs, oils such
as
soya or olive oil, thickeners, sweeteners such as sugar. These materials are
often based on proteins, fats and/or starches. in addition, such soils and
stains
are generally accompanied by amylose, sugars and their derivatives.
Highly coloured or 'dried-on' soils derived for example, from fruit and/or
vegetables are also particularly challenging soils to remove. These coloured
stains contain highly coloured compounds based on carotenoids compounds
such as a-,~i- and y-carotene and lycopene and xanthophyls (zeaxanthin or
capsanthin), or porphyrins such as chlorophyll and flavonoid pigments and dye
components. This latter group of natural flavonoid based dye components
comprises the highly coloured anthocyanins dyes and pigments based on
peiargonidin, cyanidin, delphidin and their methyl esters and the
antoxanthins.
These compounds are the origin of most of the orange, red, violet and blue
colours occurring in fruits and are abundant in all berries, cherry, red and
black
currents, grapefruits, passion fruit, ~ oranges, lemons, apples, pears,
pomegranate, red cabbage, red beets and also flowers. Carotenoids soils are
derived from carrots and tomatoes and in any processed products containing
these components as well as certain tropical fruits and saffron.
Furthermore these coloured food soils may be removed from soiled articles
into the wash solution, and then may be redeposited from the wash solution
onto
other articles in the wash or onto the interior of the dishwashing machine.
The
problem is particularly noticeable when the wash load includes articles soiled
by
foods naturally containing significant levels of coloured dyestuff molecules,
including for example tomato sauce and curry.
The Applicant has found that plastic articles in the wash, and especially
areas
of the interior of the dishwashing machine which are made of plastic material,
are
particularly susceptible to the staining/discolouration of the dishware by
coloured
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food soils. Said soils can interact with the surface of such plastic
substrates
producing staining which can be very difficult to remove.
A number of the Applicant's copending European Patent Applications have
proposed solutions to solve the problem of coloured food dyestuff deposition
in a
machine dishwashing method. For example, EP 692 947 provides an efficient
dye transfer inhibiting composition for use in a machine dishwashing method.
The composition comprises an enzymatic system capable of generating
hydrogen peroxide in combination with certain metallo catalysts. EP 740 521
describes the use of diacyl and tetraacyi peroxide bleaching species for
inhibiting
the transfer of bleachable food soils and enhancing their removal from plastic
substrates.
Therefore, it is an object of the present invention to formulate dishwashing
compositions providing effective stain removal, especially on greasyloily,
starchy
andlor highly coloured stains and soils. It is a further object of the present
invention to formulate dishwashing compositions preventing the staining
discolouration of the dishware by highly coloured components while avoiding
lime
soap deposits on the dishware.
The above objectives have been met by formulating dishwashing compositions
comprising a phospholipase and an amylase.
Phospholipase enzymes are described in the art : J07177884 describes a
preparation of enzymes comprising a phospholipase for cleaners and leather
processing. GB 2 247 025 discloses an enzymatic dishwashing or rinsing
composition comprising a phospholipase. In combination with proteolytic
enzymes,.said composition is said to be effective in removing egg yolk soil
and
consequently reducing spotting on glassware.
Amylases are commonly used ingredients of dishwashing compositions and
are extensively described in the art.
However, the combined use of phosphoiipase and amylase for effective stains
removal, especially greasy/oily, starchy and highly coloured stains and sails,
for
the prevention of the staining / discoiouration of the dishware by highly
coloured
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components and avoidance of the formation of lime soap deposits on the
.dishware, has never been previously recognised.
Summary of the invention
The present invention relates to dishwashing compositions comprising a
phospholipase and an amylase for effective stain removal, especially
greasy/oily,
starchy and highly coloured stains and soils. The dishwashing compositions of
the present invention also provide the prevention of the staining /
discolouration
of the dishware and plastic components of the dishwasher by highly coloured
components and the avoidance of the formation of lime soap deposits on the
dishware.
Detailed Descriution of the Invention
Phospholipase and amylase enzymes
An essential element of the dishwashing compositions of the present
invention is a phospholipase. It has been surprisingly found that the combined
use of phospholipase and amylase improves tough food cleaning, especially of
fat based, starch based and highly coloured soils and stains, reduces the
level
of staining of dishware, especially plastic dishware or internal machine part,
by
highly coloured components - carotenoids in particular - and prevents lime
soap
deposits on the dishware.
Without wishing to be bound by theory, it is believed that the combined action
of the amylase enzyme for the removal of starch-based components present in
the stains and soils and the enzymatic action of the phospholipase on specific
fat
components, provides substantive stain removal, especially on greasy/oily,
starchy and highly coloured stains and soils.
Without wishing to be bound by theory, it is indeed believed that the
greasy/oily stains/soils carry coloured compounds and are able to absorb onto
dishware, especially plastic material and cause staining. It is thought that
the
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phospholipase enzyme cleaves the insoluble phospholipids into free fatty acids
and soluble lysophospholipids which do not carry the coloured compounds and
therefore prevents the staining / discolouration of the dishware and plastic
components of the dishwasher and achieves significant though food cleaning.
Lipolytic enzymes can be included into dishwashing compositions. However,
these enzymes while providing a greasy stains removal benefit, do not always
provide spotting and filming prevention benefits due to the precipitation of
alkali
metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. It
has been surprisingly found that the addition of a combination of a
phospholipase
with an amylase does provide effective prevention of the staining /
discolouration
of dishware, in particular plastic items, by highly coloured components
without
causing lime soap deposits on the dishware. It is indeed believed that the
phospholipase enzyme is more selective than any other known lipase and
produces significantly less fatty acids, resulting in substantively less lime
soap
deposits.
Substrate material which is most prone to receipt of the transfer of
bleachable food soils is plastic material, such as polypropylene,
polyethylene,
polystyrene (including alkyl butyl styrene) or PVC, being dishware or any
internal
machine part. Such plastic substrate material may interact with any highly
coloured food soils on the substrate surface to produce persistent staining I
discolouration of the substrate. This staining is particularly visible on
translucent
plastic material, as is commonly employed for food storage boxes and tubs.
Suitable phospholipases for the present invention are
EC 3.1.1.32 Phospholipase A1
EC 3.1.1 _4 Phospholipase A2
EC 3.1.1.5 Lysophospholipase
EC 3.1.4.3 Phospholipase C
EC 3.1.4.4 Phospholipase D
Preferred phospholipases for the detergent compositions of the present
invention
are the EC 3.1.1.4 Phospholipase A2 and EC 3.1.1.5 Lysophospholipase.
Commercially available phospholipases are Lecitase~ from Novo Nordisk A/S
and Phospholipase A2 from Sigma.
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The phospholipase are generally included in the compositions of the present
invention at a level of from 0.0001 % to 2%, preferably 0.01 % to 1 % pure
enzyme
by weight of total composition.
Preferred phospholipases for specific applications are of the alkaline type,
i.e. enzymes having an enzymatic activity of at least 10%, preferably at feast
25%, more preferably at least 40% of its maximum activity at a pH ranging from
7
to 12. More preferred phospholipases are enzymes having their maximum
activity at a pH ranging from 7 to 12.
The second essential element of the dishwashing composition of the present
invention is an amylase enzyme.
Amylases (a and/or (3) can be included for removal of carbohydrate-based
stains. W094/02597, Novo Nordisk A/S published February 03, 1994, describes
cleaning compositions which incorporate mutant amylases. See also
W095/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases
known for use in cleaning compositions include both a- and ~i-amylases. a-
Amylases are known in the art and include those disclosed in US Pat. no.
5,003,257; EP 252,666; WO/91 /00353; FR 2,676,456; EP 285,123; EP 525,610;
EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other
suitable
amylases are stability-enhanced amylases described in W094118314, published
August 18, 1994 and W096/05295, Genencor, published February 22, 1996 and
amylase variants having additional modification in the immediate parent
available
from Novo Nordisk AIS, disclosed in WO 95/10603, published April 95. Also
suitable are amylases described in EP 277 216, W095/26397 and W096123873
(all by Novo Nordisk).
Examples of commercial a-amylases products are Purafect Ox Amy from
Genencor and Termamyl~, Ban~ ,Fungamyl~ and Duramyl~, all available from
Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases : a-
amylases characterised by having a specific activity at least 25% higher than
the
specific activity of Termamyl~ at a temperature range of 25°C to
55°C and at a
pH value in the range of 8 to 10, measured by the Phadebas~ a-amylase activity
assay. Suitable ace variants of the above enzymes, described in W096123873
(Novo Nordisk). Other amylolytic enzymes with improved properties with respect
r
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to the activity level and the combination of thermostability and a higher
activity
level are described in W095/35382.
Preferred amylase enzymes for the dishwashing compositions of the present
invention are selected from
(a) an a-amylase derived from B. licheniformis known as Termamyl~;
(b) an a-amylase variant comprising a C-terminal part of an a-amylase derived
from B. licheniformis and a N-terminal part of an a-amylase derived from B.
amyloliquefaciens or from 8. stearothermophilus, wherein the Met amino acid
residue at position 197 has been substituted preferably by a Leu, Thr, Ala,
Gly,
Ser, Ile or Asp amino acid residue, known as Duramyl~ ; and/or
(c) a variant of an a-amylase described in W095/10603 having a specific
activity
higher than the specific activity of Termamyl~ at a temperature range of
25°C to
55°C and at a pH value in the range of 8 to 10, measured by the
Phadebas ~ a-
amylase activity assay, especially a variant with improved thermal properties,
as
described in W096123873.
Also suitable are the isoamylase enzymes (EC 3.2.1.68). These
debranching enzymes hydrolyse 1,6-a-D-glucosidic branch linkages in glycogen,
amyiopectin and their (i-limit dextrins.
The amylolytic enzymes are generally incorporated in the detergent
compositions of the present invention a level of from 0.0001 % to 2%,
preferably
from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure
enzyme by weight of the composition.
Preferred amylases for specific applications are of the alkaline type, ie
enzymes_having an enzymatic activity of at least 10%, preferably at least 25%,
more preferably at least 40% of its maximum activity at a pH ranging from 7 to
12. More preferred amylases are enzymes having their maximum activity at a pH
ranging from 7 to 12.
The phospholipase and amylase enzymes will preferably be incorporated into
the dishwashing compositions of the present invention at a pure enzyme weight
ratio between 4500:1 and 1:5, more preferably between 50:1 and 1:1.
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They may be of any suitable origin, such as vegetable, animal, bacterial,
fungal and yeast origin. Origin can further be mesophilic or extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic, alkaiophilic,
acidophilic,
halophilic, etc.). Purified or non-purified forms of these enzymes may be
used.
Nowadays, it is common practice to modify wild-type enzymes via protein
genetic engineering techniques in order to optimise their performance
efficiency
in the cleaning compositions of the invention. For example, the variants may
be
designed such that the compatibility of the enzyme to commonly encountered
ingredients of such compositions is increased. Alternatively, the variant may
be
designed such that the optimal pH, bleach stability, catalytic activity and
the like,
of the enzyme variant is tailored to suit the particular cleaning application.
In particular, attention should be focused on amino acids sensitive to
oxidation in the case of bleach stability and on surface charges for the
surfactant
compatibility. The isoeiectric point of such enzymes may be modified by the
substitution of some charged amino acids, e.g. an increase in isoelectric
point
may help to improve compatibility with anionic surfactants. The stability of
the
enzymes may be further enhanced by the creation of e.g. additional salt
bridges
and enforcing calcium binding sites to increase chelant stability.
Dishwashing Deter ent Coma~ositions
The dishwashing detergent composition may also contain various other
components including surfactants, detergent builders, alkalinity sources,
other
bleaching agents, lime soap dispersants, organic polymeric compounds including
polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy
metal ion
sequestrants, enzymes and enzyme stabilisers, corrosion inhibitors, suds
suppressors, solvents, and hydrotropes.
Surfactant slrstem
A highly preferred component of the compositions herein is a surfactant
system comprising surfactant selected from anionic, cationic, nonionic
ampholytic
and zwitterionic surfactants and mixtures thereof. The surfactant system is
typically present at a level of from 0.5% to 40% by weight, more preferably 1
% to
30% by weight, most preferably from 1.5% to 20% by weight of the compositions.
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In one preferred execution the surfactant system consists of low foaming
nonionic surfactant, preferably selected from ethoxylated and/or propoxyiated
nonionic surfactants, more preferably selected from nonionic
ethoxylated/propoxylated fatty alcohol surfactants.
In an alternative preferred execution the surfactant system comprises high
foaming anionic surfactant, particularly alkyl ethoxysuifate surfactant, in
combination with a suds suppressing system.
Anionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in the compositions. These can include salts (including, for example,
sodium, potassium, ammonium, and substituted ammonium salts such as mono-,
di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate
and
sarcosinate surfactants.
Other anionic surfactants include the 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~2-C~$ monoesters) diesters of sulfosuccinate (especially
saturated and unsaturated C6-C~4 diesters), N-acyl sarcosinates. 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
tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol
sulfates,
alkyl phenol ethylene oxide ether sulfates, the C5-C~7 acyl-N-(C~-C4 alkyl)
and -
N-(C~-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkyfpolysaccharides
such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
being described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C6-Ctg alkyl sulfates which have been ethoxylated with from
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about 0.5 to about 20 moles of ethylene oxide per molecule. More preferably,
the
alkyl ethoxysulfate surfactant is a Cg-C1g 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.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of
C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cs-C22 primary
or
secondary afkane sulfonates, Cg-C24 olefin sulfonates, sulfonated
polycarboxylic
acids, alkyl gfyceroi sulfonates, fatty acyi glycerol sulfonates, fatty oleyl
glycerol
sulfonates, and any mixtures thereof.
Anionic carboxvlate surfactant
Anionic carboxylate surfactants suitable for use herein include the alkyl
ethoxy carboxylates, the alkyl polyethoxy poiycarboxylate surfactants and the
soaps ('alkyl carboxyls'), especially certain secondary soaps as described
herein.
Preferred alkyl ethoxy carboxylates for use herein include those with the
formula RO(CH2CH20)x CH2C00-M+ wherein R is a Cg to C1g alkyl group, x
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 %, and the
amount of material where x is greater than 7, is less than about 25 %, the
average x is from about 2 to 4 when the average R is C13 or less, and the
average x is from about 3 to 10 when the average R is greater than C 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 c~rboxylates are those where R is a C12 to C1g alkyl group.
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein
include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a Cg to
C1g alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic
acid radical, and mixtures thereof, wherein at least one R1 or R2 is a
succinic
acid radical or hydroxysuccinic acid radical, and R3 is selected from the
group
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consisting of hydrogen, substituted or unsubstituted hydrocarbon having
between
1 and 8 carbon atoms, and mixtures thereof.
Preferred soap surfactants are secondary soap surfactants which contain
a carboxyl unit connected to a secondary carbon. The secondary carbon can be
in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-
substituted
cyclohexyl carboxylates. The secondary soap surfactants should preferably
contain no ether linkages, no ester linkages and no hydroxyl groups. There
should preferably be no nitrogen atoms in the head-group (amphiphilic
portion).
The secondary soap surfactants usually contain 11-13 total carbon atoms,
although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic
acid.
The following general structures further illustrate some of the preferred
secondary soap surfactants:
A. A highly preferred class of secondary soaps comprises the secondary
carboxyl materials of the formula R3 CH(R4)COOM, wherein R3 is CH3(CH2)x
and R4 is CH3(CH2)y, wherein y can be O or an integer from 1 to 4, x is an
integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most
preferably 8.
B. Another preferred class of secondary soaps comprises those carboxyl
compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit,
i.e.,
secondary soaps of the formula R5-R6-COOM, wherein R6 is C7-C10, preferably
C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene,
cyclopentane and cyclohexane. (Note: R6 can be in the ortho, meta or para
position relative to the carboxyl on the ring.)C. Still
another preferred class of secondary soaps comprises secondary carboxyl
compounds of the formula
CHg(CHR)k-(CH2)m-(CHR)n-CH(COOM)(CHR)o-(CH2)p-(CHR)q-CHg, wherein
each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8,
provided that the total number of carbon atoms (including the carboxylate) is
in
the range of 10 to 18. In each of the above formulas A, B and C, the species M
can be any suitable, especially water-solubilizing, counterion.
Especially preferred secondary soap surfactants for use herein are water-
soluble members selected from the group consisting of the water-soluble salts
of
2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid,
2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Alkali metal sarcosinate surfactant
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Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl
or alkenyl group, R1 is a C1-C4 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.
Nonionic surfactant
Essentially any anionic surfactants useful for detersive purposes can be
included in the compositions. Exemplary, non-limiting 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 R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more
preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is
a C5-
C31 hydrocarbyl, preferably straight-chain C5-C1g alkyl or alkenyl, more
preferably straight-chain Cg-C17 alkyl or atkenyl, most preferably straight-
chain
C11-C17 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 glycityt.
Nonionic condensates of atkyl 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 atkyfene oxide.
Nonionic ethoxytated alcohol surfactant
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The alkyl ethoxylate condensation products of aliphatic alcohofs 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.
Nonionic ethoxylatedlaropoxylated fatty alcohol surfactant
The ethoxylated Cg-C1g fatty alcohols and Cg-C1g mixed
ethoxylated/propoxylated fatty alcohols are preferred surfactants for use
herein,
particularly where water soluble. Preferably the ethoxylated fatty alcohols
are the
C10-C1g ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to
50,
most preferably these are the C12-C1g ethoxylated fatty aicohols with a degree
of ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxyiated
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 proipylene 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. Examples of compounds of this type include certain of the
commercially-available PluronicTM surfactants, marketed by BASF.
Nonionic EO condensation i~aroducts with propylene oxidelethylene 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. Examples of this type of
nonionic surfactant include certain of the commercially available TetronicTM
compounds, marketed by BASF.
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Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647, Llenado, issued January 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 poiyglycoside, 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.
The preferred alkyfpolyglycosides have the formula
R20{CnH2n0)t(glycosyl)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.
Nonionic fatty acid amide surfactant
Fatty acid amide surfactants suitable for use herein are those having the
formula:
O
R6 C N(R7)2
wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17
carbon atoms and each R7 is selected from the group consisting of hydrogen,
C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of
from 1 to 3.
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Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the alkyl amphocarboxylic acids.
A suitable example of an alkyl aphodicarboxylic acid for use herein is
Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine Oxide surfactant
Amine oxides useful in the present invention include those compounds
having the formula
O
I
R8(OR4)xN(R5)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms,
preferably 8 to 18 carbon atoms; R4 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 R5 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 R5 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 C10-C1 g alkyl
dimethyl amine oxides and Cg-C1 g 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 C10-C1g alkyl dimethylamine oxide,
and C10_1g acylamido alkyl dimethylamine oxide.
Zwitterionic surfactant
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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 suffonium compounds. Betaine and sultaine surfactants
are exemplary zwitterionic surfactants for use herein.
Betaine surfactant
The betaines useful herein are those compounds having the formula
R(R')2N+R2C00- wherein R is a Cg-C1g hydrocarbyl group, preferably a C10-
C16 alkyl group or C10-16 acylamido alkyl group, each R1 is typically C1-C3
alkyl, preferably methyl,m and R2 is a C1-C6 hydrocarbyl group, preferably a
C1-
C3 alkylene group, more preferably a C1-C2 alkylene group. Examples of
suitable betaines include coconut acyfamidopropyldimethyl betaine; hexadecyl
dimethyl betaine; C12-14 acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl
betaine; 4[C14-16 acylmethylamidodiethylammonio]-1-carboxybutane; C16-18
acylamidodimethylbetaine; C12_1g acylamidopentanediethyl-betaine; [C12-16
acylmethylamidodimethylbetaine. Preferred betaines are C12-18 dimethyl-
ammonio hexanoate and the C10-18 acylamidopropane (or ethane) dimethyl (or
diethyl) betaines. Complex betaine surfactants are also suitable for use
herein.
Sultaine surfactant
The sultaines useful herein are those compounds having the formula
(R(R1)2N+R2S03- wherein R is a Cg-C1g hydrocarbyl group, preferably a C10-
C16 alkyl group, more preferably a C12-C13 alkyl group, each R1 is typically
C1-
C3 alkyl, preferably methyl, and RZ is a C1-Cg hydrocarbyl group, preferably a
C1-C3 alkylene or, preferably, hydroxyalkylene group.
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.
Cationic surfactants
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Cationic surfactants can also be used in the detergent compositions
herein. Suitable cationic surfactants include the quaternary ammonium
surfactants selected from mono Cg-Clg, preferably Cg-C10 N-alkyl or alkenyl
ammonium surfactants wherein the remaining N positions are substituted by
methyl, hydroxyethyl or hydroxypropyl groups.
Detergent Builder System
A highly preferred component of the compositions herein is a detergent
builder system wherein said detergent builder system is preferably present at
a
level of from 0.5% to 80% by weight, more preferably from 1 % to 60% by
weight,
most preferably from 2% to 40% weight of the compositions.
The detergent builder system is preferably water-soluble, and can, for
example, contain builder compound selected from monomeric polycarboxylates
or 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, the alkali metal,
ammonium or alkanonammonium salts of bicarbonates, borates, phosphates,
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 (pK1 ) of less than 9,
preferably of
between 2 and 8.5, more preferably of between 4 and 7.5.
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.
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. 831,3fi8, 821,369 and 821,370. Polycarboxylates
containing two carboxy groups include the water-soluble salts of succinic
acid,
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malonic acid, (ethylenedioxy) diacetic acid, maieic 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. Patent 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 Patent 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 suifosuccinate
derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in
U.S.
Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in
British
Patent No. 1,439,000.
Alicyclic and heterocyclic poiycarboxylates 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 afcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromeliitic 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 the
detergent compositions.
T
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Specific examples of carbonate builder compound include the alkali metal
carbonates, bicarbonates and sesquicarbonates.
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.
Preferably, no
phosphate builder compound is present.
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 aiuminosilicates.
Alkalini
An alkalinity source is a preferred component of the compositions herein. A
useful alkalinity source is provided by silicates which also provide china
care
properties to the detergent formulation. Suitable silicates include the water
soluble sodium silicates with an Si02: Na20 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 Si02: Na20 ratio of 2.0 and metasificate are the most
preferred
silicates.
Silicates are preferably incorporated in the compositions of the invention at
a
level of from 1 % to 50%, preferably from 5% to 40%, most preferably from 5%
to
30% by weight.
Bleaching agents
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The detergent compositions herein may include bleaching agents selected
-from chlorine bleaches, inorganic perhydrate salts, peroxyacid bleach
precursors,
organic peryoxacids and/or metal containing bleach catalyst.
There may be provided a means of delaying the release of oxygen bleach,
which could include any diacyl and/or tetraacyl bleaching species, into the
wash
solution. Said means may be provided, for example by coating a granular bleach
component with a hydrophobic coating, or by choice of physical form of the
bleach which has a slow rate of dissolution by virtue, for example of its
density or
particle size.
Delayed release of the oxygen bleach into the wash solution can be
advantageous in the prevention of tarnishing of silverware in washload,
particularly when a component designed to protectively coat the silver in the
wash is also included in the formulation. Such silver tarnish prevention
technologies are disclosed in the Applicant's co-pending European Applications
Nos. 9370004.4, 93870090.3, 93201918.5 and 93202095.1.
Chlorine bleaching agents
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.
Inorganic perhydrate bleaching agents
The dishwashing compositions herein preferably include an inorganic
perhydrate salt, normally in the form of the sodium salt preferably 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 compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persiiicate 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
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form of the material which provides better storage stability for the
perhydrate salt
in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal
formula NaB02H202 or the tetrahydrate NaB02H202.3H20.
Sodium percarbonate, which is a preferred perhydrate for inclusion in
detergent compositions in accordance with the invention, is an addition
compound having a formula corresponding to 2Na2C03.3H202, 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 March 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 Na2S04.n.Na2C03 wherein n is form 0.1 to 3, preferably n
is from 0.15 to 1.0 and most preferably n is from 0.2 to 0.5.
Another suitabie coating material is sodium silicate of Si02 : Na20 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
usefulness in the detergent compositions.
Peroxyacid bleach precursors
The dishwashing compositions herein also preferably include a peroxyacid
bleach precursor (bleach activator), usually in combination with an inorganic
perhydrate salt. 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.
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The peroxyacid bleach precursors typically 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
imidazoies 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 bleach precursor compounds are the N,N,N1,N1
tetra acetylated compounds of formula
(CH3C0)2-(CH2)x-(CH3C0)2 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 described in EP-A-0170386.
Other peroxyacid bleach precursor compounds include sodium trimethyl
hexanoyloxy benzene sulfonate and sodium acetoxy benzene sulfonate.
Organic peroxvacids
The dishwashing 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.
Useful organic peroxyacids include the amide substituted peroxyacids
described in EP-A-0170386.
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.
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Diacyl and tetraacyf peroxide bleaching species
The diacyi peroxide bleaching species is preferably selected from diacyl
peroxides of the general formula:
O O
R 1-C-O O-C-R2
in which R1 represents an aromatic group or a Cg-C1 g alkyl, preferably Cg-C12
alkyl group containing a linear chain of at least 5 carbon atoms and
optionally
containing one or more substituents (e.g. -N+ (CH3)3,-COOH or -CN) andlor one
or more interrupting moieties
(e.g. -CONH- or -CH=CH-) interpolated between adjacent carbon atoms of the
alkyl radical, and R2 represents an aliphatic or aromatic group compatible
with a
peroxide moiety, such that R1 and R2 together contain a total of 8 to 30
carbon
atoms. Preferably R1 and R2 are linear unsubstituted Cg-C12 alkyl chains.
Most preferably R1 and R2 are identical.
The tetraacyl peroxide bleaching species is preferably selected from tetraacyl
peroxides of the general formula:
O O O O
R3-C-00-C-(CH2)n-C-00-C-R3
in which R3 represents a C1-Cg alkyl, preferably C3 - C~, group and n
represents an integer from 2 to 12, preferably 4 to 10 inclusive
Metal containing bleach catalyst
The compositions described herein may additionally contain as a preferred
component, a metal containing bleach catalyst. Preferably the metal containing
bleach catalyst is a transition metal containing bleach catalyst, more
preferably a
manganese or cobalt-containing bleach catalyst.
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A suitable type of bleach catalyst is a catalyst comprising a heavy metal
_ cation of defined bleach catalytic activity, such as copper, iron cations,
an
auxiliary metal cation having little or no bleach catalytic activity, such as
zinc or
aluminum cations, and a sequestrant having defined stability constants for the
catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic
acid,
ethylenediaminetetra(methyienephosphonic acid) and water-soluble salts
thereof.
Such catalysts are disclosed in U.S. Pat. 4,430,243.
Preferred examples include cobalt (Ill) catalysts having the formula:
Co[(NH3)nM'mB'bT'tQqPp] YY
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5
(preferably
4 or 5; most preferably 5); M' represents a monodentate ligand; m is an
integer
from 0 to 5 (preferably 1 or 2; most preferably 1 ); B' represents a bidentate
ligand; b is an integer from 0 to 2; T' represents a tridentate ligand; t is 0
or 1; Q
is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or
1; and n
+ m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected
counteranions present in a number y, where y is an integer from 1 to 3
(preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain
a
charge-balanced salt, preferred Y are selected from the group consisting of
chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and
combinations
thereof; and wherein further at least one of the coordination sites attached
to the
cobalt is labile under automatic dishwashing use conditions and the remaining
coordination sites stabilize the cobalt under automatic dishwashing conditions
such that the reduction potential for cobalt (III) to cobalt (II) under
alkaline
conditions is less than about 0.4 volts (preferably less than about 0.2 volts)
versus a normal hydrogen electrode.
Preferred cobalt catalysts of this type have the formula:
[Co(NH3)n(M')ml YY
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M'
is a
labile coordinating moiety, preferably selected from the group consisting of
chlorine, bromine, hydroxide, water, and (when m is greater than 1 )
combinations
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thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1 );
m+n =
.6; and Y is an appropriately selected counteranion present in a number y,
which
is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1
charged anion), to obtain a charge-balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride salts having the formula [Co(NH3)5C1] Yy, and especially
[Co(NH3)5C1]C12.
More preferred are the present invention compositions which utilize cobalt
(III)
bleach catalysts having the formula:
[Co(NH3)n(M)m(B)b] TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or
more ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably
1 ); B
is a ligand coordinated to the cobalt by two sites; b is 0 or 1 (preferably
0), and
when b=0, then m+n = 6, and when b=1, then m=0 and n=4; and T is one or
more appropriately selected counteranions present in a number y, where y is an
integer to obtain a charge-balanced salt (preferably y is 1 to 3; most
preferably 2
when T is a -1 charged anion); and wherein further said catalyst has a base
hydrolysis rate constant of less than 0.23 M-1 s-1 (25°C).
Preferred T are selected from the group consisting of chloride, iodide, 13-,
formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate,
bromide, PFg-,
BF4-, B(Ph)4-, phosphate, phosphite, silicate, tosylate, methanesuifonate, and
combinations thereof. Optionally, T can be protonated if more than one anionic
group exists in T, e.g., HP042-, HC03-, H2P04-, etc. Further, T may be
selected from the group consisting of non-traditional inorganic anions such as
anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl
sulfates
(AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g.,
polyacrylates, polymethacrylates, etc.).
The M moieties include, but are not limited to, for example, F-, S04-2, NCS-,
SCN-, S2O3-2, NH3, P043-, and carboxylates (which preferably are mono-
carboxylates, but more than one carboxylate may be present in the moiety as
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long as the binding to the cobalt is by only one carboxylate per moiety, in
which
_case the other carboxylate in the M moiety may be protonated or in its salt
form).
Optionally, M can be protonated if more than one anionic group exists in M
(e.g.,
HP042-, HC03-, H2P04-, HOC(O)CH2C(O)O-, etc.) Preferred M moieties are
substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C1-
C30 (preferably C1-C1g) unsubstituted and substituted alkyl, Cg-C30
(Preferably
C6-C1g) unsubstituted and substituted aryl, and C3-C30 (preferably C5-C1g)
unsubstituted and substituted heteroaryl, wherein substituents are selected
from
the group consisting of -NR'3, -NR'4+, -C(O)OR', -OR', -C(O)NR'2, wherein R'
is
selected from the group consisting of hydrogen and C1-C6 moieties. Such
substituted R therefore include the moieties -(CH2)nOH and -(CH2)nNR'4+,
wherein n is an integer from 1 to about 16, preferably from about 2 to about
10,
and most preferably from about 2 to about 5.
Most preferred M are carboxylic acids having the formula above wherein R is
selected from the group consisting of hydrogen, methyl, ethyl, propyl,
straight or
branched C4-C12 alkyl, and benzyl. Most preferred R is methyl. Preferred
carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic,
decanoic,
dodecanoic, malonic, malefic, succinic, adipic, phthalic, 2-ethylhexanoic,
naphthenoic, oleic, paimitic, triflate, tartrate, stearic, butyric, citric,
acrylic,
aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic
acid.
The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate,
malonate. malic, succinate, maleate), picolinic acid, and alpha and beta amino
acids (e.g., glycine, alanine, beta-alanine, phenylalanine).
Cobalt bleach catalysts useful herein are known, being described for example
along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of
Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-
94.
for example, Table 1 at page 17, provides the base hydrolysis rates
(designated
therein as kOH) for cobalt pentaamine catalysts complexed with oxalate (kOH=
2.5 x 10~ M-1 s-1 (25°C)), NCS- (kOH= 5.0 x 10~ M-1 s-1 {25°C)),
formate
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(kOH= 5.8 x 10-'~ M-1 s-1 (25°C)), and acetate (kOH= 9.6 x 10-'t M-1 s-
1 (25°C)).
The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts having the formula [Co(NH3)50Acj Ty, wherein OAc represents an acetate
moiety, and especially cobalt pentaamine acetate chloride, [Co(NH3)50Ac]C12;
as well as [Co(NH3)50Acj(OAc)2; [Co(NH3)50Ac](PF6)2; [Co(NH3)50Ac](S04);
[Co(NH3)50Ac](BF4)2; and [Co(NH3)50Ac](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught
for example in the Tobe article hereinbefore and the references cited therein,
in
U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed.
(1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic
Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorq-Chem., 18, 1497-
1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025
(1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry,
56,
22-25 (1952); as well as the synthesis examples provided hereinafter.
These catalysts may be coprocessed with adjunct materials so as to reduce the
color impact if desired for the aesthetics of the product, or to be included
in
enzyme-containing particles as exemplified hereinafter, or the compositions
may
be manufactured to contain catalyst "speckles".
Lime soar dispersant compound
The compositions herein may contain 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 preferably 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 ff.C. Borghetty and C.A.
Bergman, J.
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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, pages159-
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 0.025g of
sodium oieate in 30m1 of water of 333ppm
CaC03 (Ca:Mg=3:2) equivalent hardness.
Polymeric lime soap dispersants suitable for use herein are described in
the 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 C16-C1g dimethyl amine oxide, C12-C1g alkyl
ethoxysulfates with an average degree of ethoxylation of from 1-5,
particularly
C12-C15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of about
3
(LSDP=4), and the C13-C15 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.
Organic polymeric compound
Organic polymeric compounds may be added to the dishwashing
compositions herein. By organic polymeric compounds it is meant essentially
any
polymeric organic compounds commonly used as dispersants, anti-redeposition
and soil suspension agents in detergent compositions.
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WO 99/01531 PCT/US97/11399
29
Organic polymeric compound may be incorporated into the detergent
compositions of the invention at a level of from 0.05% to 30%, preferably from
0.5% to 15%, most preferably from 1 % to 10% by weight of the compositions.
Organic polymers containing acrylic acid or its salts having an average
molecular weight of less than 15,000, hereinafter referred to as low molecular
weight acrylic acid containing polymer, are particularly preferred organic
polymeric compounds herein.
The low molecular weight acrylic acid containing polymers preferably have an
average molecular weight of less than 15,000, preferably from 500 to 12,000,
more preferably from 1,500 to 10,000, most preferably from 2,500 to 9,000.
The low molecular weight acrylic acid containing polymers may be either
homopolymers or copolymers including the essential acrylic acid or acrylic
acid
salt monomer units. Copolymers may include essentially any suitable other
monomer units including modified acrylic, fumaric, malefic, itaconic,
aconitic,
mesaconic, citraconic and methylenemalonic acid or their salts, malefic
anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures
thereof.
Preferred commercially available low molecular weight acrylic acid containing
homopolymers include those sold under the tradename Sokalan PA30, PA20,
PA15 and PA10 by BASF GmbH, and those sold under the tradename Acusol
45N by Rohm and Haas.
Preferred low molecular weight acrylic acid containing copolymers include
those which contain as monomer units: a) from 90% to 10%, preferably from 80%
to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably
from
20% to 80% by weight of a substituted acrylic monomer or its salts having the
general formula -[CR2-CR1 (CO-O-R3)]- wherein at least one of the substituents
R1, R2 or R3, preferably R1 or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl
group,
R1 or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt. Most
preferred is a substituted acrylic monomer wherein R1 is methyl, R2 is
hydrogen
(i.e. a methyl acrylic acid monomer). The most preferred copolymer of this
type
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WO 99/01531 PCT/US97/11399-
has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic
_ acid and 40% to 20% by weight of methyl acrylic acid.
Preferred commercially available low molecular weight acrylic acid
containing copolymers include those sold under the tradename Sokalan CP10 by
BASF GmbH.
Other suitable polyacrylate/modified poiyacrylate copolymers include
those copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S.
Patents No.s 4,530,766, and 5,084,535 which have a molecular weight of less
than 15,000.
Further examples of organic polymeric compounds include the water soluble
organic 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 the copolymers of
polyacrylate with malefic anhydride having a molecular weight of from 20,000
to
70,000, especially about 40,000.
Other suitable organic polymeric compounds include the polymers of
acrylamide and acrylate having a molecular weight of from 16,000 to 100,000,
and the acrylate/fumarate copolymers having a molecular weight of from 16,000
to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-
351629.
Other organic polymeric compounds suitable for incorporation in the
detergent compositions herein include cellulose derivatives such as
methylcellulose, carboxymethyfcellulose and hydroxyethyfcellulose.
Further useful organic polymeric compounds are the polyethylene glycols,
particularly those of molecular weight 1000-10000, more particularly 2000 to
8000 and most preferably about 4000.
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31
Polymeric dye transfer inhibiting agents
The compositions herein may also comprise from 0.01 % to 10 %, preferably
from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.
al PolYamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having
the following structure formula
P
(I) Ax
R
wherein P is a polymerisable unit, whereto the R-N-O group can be attached to,
or wherein the R-N-O group forms part of the polymerisable unit or a
combination
of both.
O O O
A is NC, CO, C, -O-,-S-, -N- ; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any combination
thereof whereto the nitrogen of the N-O group can be
attached or wherein the nitrogen of the N-O group is part
of these groups.
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32
The N-O group can be represented by the following general
structures
O O
(R1)x -N- (R2)y =N- (R1)x
(R3)z
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic
groups or combinations thereof, x orland y or/and z is 0 or 1 and wherein the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O
group forms part of these groups. The N-O group can be part of the
pofymerisable unit (P) or can be attached to the polymeric backbone or a
combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected from
aliphatic, aromatic, aiicyclic or heterocyclic groups. One class of said
polyamine
N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the
N-O group forms part of the R-group. Preferred polyamine N-oxides are those
wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole,
pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-
group.
Other suitable polyamine N-oxides are the polyamine oxides
whereto the N-O group is attached to the polymerisable unit.
Preferred class of these poiyamine N-oxides are the polyamine N-oxides
having the general formula (I) wherein R is an aromatic,heterocyciic or
alicyclic
groups wherein the nitrogen of the N-0 functional group is part of said R
group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
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33
Another preferred class of polyamine N-oxides are the poiyamine oxides
having the general formula (I) wherein R are aromatic, heterocyclic or
alicyclic
groups wherein the nitrogen of the N-0 functional group is attached to said R
groups. Examples of these classes are polyamine oxides wherein R groups can
be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer inhibiting properties.
Examples of suitable polymeric backbones are polyvinyls, polyalkyfenes,
polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures
thereof.
The amine N-oxide polymers of the present invention typically have a ratio
of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-oxidation.
Preferably,
the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably
from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of
the present invention actually encompass random or block copolymers where
one monomer type is an amine N-oxide and the other monomer type is either an
amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa
< 10, preferably PKa < 7, more preferred PKa < 6.
The poiyamine oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
material
has the desired water-solubility and dye-suspending power. Typically, the
average molecular weight is within the range of 500 to 1000,000; preferably
from
1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from
3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Preferred polymers for use herein may comprise a polymer selected from
N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an
average molecular weight range from 5,000 to 50,000 more preferably from
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34
8,000 to 30,000, most preferably from 10,000 to 20,000. The preferred N-
vinylimidazole N-vinylpyrrolidone copolymers have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8
to
0.3, most preferably from 0.6 to 0.4 .
c Polyvin~pyrrolidone
The compositions herein may also utilize polyvinylpyrrolidone ("PVP"
having an average molecular weight of from 2,500 to 400,000, preferably from
5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably
from 5,000 to 15,000. Suitable polyvinylpyrrolidones are commercially vailable
from ISP Corporation, New York, NY and Montreal, Canada under the product
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average
molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000),
and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available
from 1SP Corporation. Other suitable polyvinyfpyrrolidones which are
commercially available from BASF Cooperation include Sokalan HP 165 and
Sokaian HP 12.
Polyvinylpyrrolidone may be incorporated in the compositions herein at a
level of from 0.01% to 5% by weight of the detergent, preferably from 0.05% to
3% by weight, and more preferably from 0.1 % to 2% by weight. The amount of
polyvinylpyrroiidone delivered in the wash solution is preferably from 0.5 ppm
to
250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to
100 ppm.
d) Polyvinyloxazolidone
The compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average molecular weight of from 2,500 to 400,000, preferably from 5,000 to
200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000
to 15,000.
The amount of polyvinyloxazolidone incorporated in the compositions may
be from 0.01 % to 5% by weight, preferably from 0.05% to 3% by weight, and
more preferably from 0.1% to 2% by weight. The amount of polyvinyloxazolidone
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WO 99/01531 PCT/US97/11399-
delivered in the wash solution is typically from 0.5 ppm to 250 ppm,
preferably
from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
e~ Polyvinyiimidazole
The compositions herein may also utilize polyvinyiimidazole as polymeric
dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an
average molecular weight of from 2,500 to 400,000, more preferably from 5,000
to 50,000, and most preferably from 5,000 to 15,000.
The amount of polyvinylimidazole incorpoarted in the compositions may
be from 0.01 % to 5% by weight, preferably from 0.05% to 3% by weight, and
more preferably from 0.1 % to 2% by weight. The amount of polyvinylimidazole
delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5
ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
Heavyr metal ion sequestrants
Heavy metal ion sequestrants are useful components herein. By heavy metal
ion sequestrants it is meant components which act to sequester (chelate) heavy
metal ions. These components may also have calcium and magnesium chelation
capacity, but preferentially they bind heavy metal ions such as iron,
manganese
and copper.
Heavy metal ion sequestrants are preferably present at a level of from
0.005% to 20%, more preferably from 0.05% to 10%, most preferably from 0.1
to 5% by weight of the compositions.
Heav~r metal ion sequestrants, which are acidic in nature, having for example
phosphonic acid or carboxylic acid functionalities, may be present either in
their
acid form or as a complex/salt with a suitable counter cation such as an
alkali or
alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures
thereof. Preferably any salts/complexes are water soluble. The molar ratio of
said
counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include the organo
aminophosphonates, such as the amine alkylene poly (aikylene phosphonates)
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36
and nitrilo trimethylene phosphonates. Preferred organo aminophosphonates are
diethylene triamine yenta (methyiene phosphonate) and hexamethylene diamine
tetra (methylene phosphonate).
Other suitable heavy metal ion sequestrants for use herein include
nitrilotriacetic acid and poiyaminocarboxylic acids such as
ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, or
ethyienediamine disuccinic acid. Especially preferred is ethylenediarnine-N,N'-
disuccinic acid (EDDS), most preferably present in the form of its S,S isomer,
which is preferred for its biodegradability profile.
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.
In one preferred aspect of the invention any heavy metal ion sequestrant,
particularly where said sequestrant comprises organo aminophosphonate
components, is sprayed onto powdered sodium sulphate prior to incorporation
into granular compostions in accord with the invention. This step leads to
enhanced sequestrant stability in the granular detergent matrix.
Cr~rstal girowth inhibitor
A preferred component of the dishwashing compositions herein is a crystal
growth inhibitor selected from organo diphosphonic acid or one of its
salts/complexes. The organo diphosphonic acid component is preferably present
at a level of from 0.005% to 20%, more preferably from 0.1 % to 10%, most
preferably from 0.2% to 5% by weight of the compositions.
The organo diphosphonic acid component may be present in its acid form or
in the form of one of its salts or complexes with a suitable counter cation
and
reference hereinafter to the acid implicitly includes reference to said salts
or
complexes. Preferably any saits/complexes are water soluble, with the alkali
metal and alkaline earth metal salts/complexes being especially preferred.
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37
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid,
more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or
most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP).
Enzyme
Another optional ingredient useful in the dishwashing compositions herein
is one or more enzymes. Preferred enzymatic materials include the commercially
available lipases, neutral and alkaline proteases, esterases, cellulases and
peroxidases conventionally incorporated into detergent compositions. Suitable
enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Other preferred enzymes that can be included in the compositions of the
present invention include lipases. Suitable lipase enzymes for detergent usage
include those produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
Suitable lipases include those which show a positive immunological cross-
reaction with the antibody of the lipase, produced by the microorganism
Pseudomonas fluorescent IAM 1057. This lipase is available from Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hereinafter referred to as "Amano-P". Other suitable commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp.,
U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas
gladioli. Especially suitable lipases are lipases such as M1 LipaseR and
LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UItraR(Novo) which have
found to be very effective when used in combination with the compositions of
the
present invention. Also suitables are the lipolytic enzymes described in EP
258
068, WO 92/05249 and WO 95122615 by Novo Nordisk and in WO 94/03578,
WO 95135381 and WO 96/00292 by Uniiever.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of lipase, namely lipases which do not require interfacial activation.
Addition
of cutinases to detergent compositions have been described in e.g. WO-A-
88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963
and WO 94114964 (Unilever).
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WO 99/01531 PCTNS97/11399 -
38
The lipases and/or cutinases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of the
detergent composition.
Suitable proteases are the subtilisins which are obtained from particular
strains of B. subtilis and B. lichenifonnis (subtilisin BPN and BPN'). One
suitable
protease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold as ESPERASE~ by Novo
Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme
and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable
proteases include ALCALASE~, DURAZYM~ and SAVINASE~ from Novo and
MAXATASE~, MAXACAL~, PROPERASE~ and MAXAPEM~ (protein
engineered Maxacal) from Gist-Brocades. 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 199,404, Venegas, published October 29, 1986, which refers to a
modified bacterial serine protealytic enzyme which is called "Protease A"
herein.
Suitable is what is called herein "Protease C", which is a variant of an
alkaline
serine protease from Bacillus in which lysine replaced arginine at position
27,
tyrosine replaced valine at position 104, serine replaced asparagine at
position
123, and alanine replaced threonine at position 274. Protease C is described
in
EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991.
Genetically modified variants, particularly of Protease C, are also included
herein.
A preferred protease referred to as "Protease D" is a carbonyl hydrolase
variant
having an amino acid sequence not found in nature, which is derived from a
precursor carbonyl hydrolase by substituting a different amino acid for a
plurality
of amino acid residues at a position in said carbonyl hydrolase equivalent to
position +76, preferably also in combination with one or more amino acid
residue
positions equivalent to those selected from the group consisting of +99, +101,
+103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195,
+197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274
according to the numbering of Bacillus amyloliquefaciens subtilisin, as
described
in W095/10591 and in the patent application of C. Ghosh, et al, "Bleaching
Compositions Comprising Protease Enzymes" having US Serial No. 08!322,677,
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WO 99/01531 PCTNS97/11399
39
filed October 13, 1994. Variants of this "Protease D" include protease enzymes
which are non-naturally-occurring carbonyl hydrolase variants having a
different
proteolytic activity, stability, substrate specificity, pH profile and/or
performance
characteristic as compared to the precursor carbonyl hydrolase from which the
amino acid sequence of the variant is derived. As stated earlier, the protease
enzymes are designed to have trypsin-like specificity and preferably also be
bleach stable. The precursor carbonyl hydrolase may be a naturally-occurring
carbonyl hydrolase or recombinant hydroiase. Specifically, such carbonyl
hydrolase variants have an amino acid sequence not found in nature, which is
derived by replacement of a plurality of amino acid residues of a precursor
carbonyl hydrolase with different amino acids. The plurality of amino acid
residues of the precursor enzyme correspond to position +210 in combination
with one or more of the following residues: +33, +62, +67, +76, +100, +101,
+103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166,
+167, +170, +209, +215, +217, +218, and +222, where the numbered position
corresponds to naturally-occurring subtilisin from Bacillus amyloliquefaciens
or to
equivalent amino acid residues in other carbonyl hydrolases or subtilisins,
such
as Bacillus lentus subtilisin.
The carbonyl hydrolase variants which are protease enzymes useful in the
present invention compositions comprise replacement of amino acid residue
+210 in combination with one or more additional modifications. While any
combination of the above listed amino acid substitutions may be employed, the
preferred variant protease enzymes useful for the present invention comprise
the
substitution, deletion or insertion of amino acid residues in the following
combinations: 210/156; 210/166; 210176; 2101103; 210/104; 210!217;
210/156/166; 210/1561217; 210/166/217; 210176/156; 210176/166; 2101761217;
210/76/156/166; 21017fi/156/217; 210176/166/217; 210/76/103/156;
210/76/103/166; 210/76/103/217; 210/76/104/156; 210/76/1041166;
210/76/104/217; 210/76/103/104/156; 210/76/1031104/166; 210/76/103/1041217;
210/76/103/104/156/166; 210/76/103/104/156/217; 210/761103/10411661217
and/or 210176/103/104/156/166/217; 210176/103/104/1661222;
210167/76/103/104/1661222; 210/67/76/10311041166/2181222. Most preferably
the variant enzymes useful for the present invention comprise the
substitution,
deletion or insertion of an amino acid residue in the following combination of
residues: 210/156; 210/166; 210/217; 210/156/166; 210/156/217; 210/166!217;
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WO 99/01531 PCT/US97/11399-
210/76/156/166; 210/76/103/156/166 and 210/761103110411561166 of B. lentos
subtilisin with 210176/103/104/156/166 being the most preferred.
Variant DNA sequences encoding such carbonyl hydrolase or subtilisin
variants are derived from a precursor DNA sequence which encodes a naturally-
occurring or recombinant precursor enzyme. The variant DNA sequences are
derived by modifying the precursor DNA sequence to encode the substitution of
one or more specific amino acid residues encoded by the precursor DNA
sequence corresponding to positions +210, +33, +62, +67, +76, +100, +101,
+103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166,
+167, +170, +209, +215, +217, +218, and +222 in Bacillus lentos or any
combination thereof. Although the amino acid residues identified for
modification
herein are identified according to the numbering applicable to B.
amyloliquefaciens (which has become the conventional method for identifying
residue positions in all subtilisins), the preferred precursor DNA sequence
useful
for the present invention is the DNA sequence of Bacillus lentos. These
recombinant DNA sequences encode carbonyl hydrolase variants having a novel
amino acid sequence and, in general, at least one property which is
substantially
different from the same property of the enzyme encoded by the precursor
carbonyl hydrolase DNA sequence. Such properties include proteolytic activity,
substrate specificity, stability, altered pH profile and/or enhanced
performance
characteristics.
The protease enzymes useful herein encompass the substitution of any of
the nineteen naturally occurring L-amino acids at the designated amino acid
residue positions. Such substitutions can be made in any precursor subtilisin
(procaryotic, eucaryotic, mammalian, etc.). Throughout this application
reference
is made to various amino acids by way of common one- and three-letter codes.
Such codes are identified in Dale, M.W. (1989), Molecular Genetics of
Bacteria,
John Wiley 8~ Sons, Ltd., Appendix B.
Preferably, the substitution to be made at each of.the identified amino acid
residue positions include but are not limited to substitutions at position
+210
including I, V, L, and A, substitutions at positions +33, +62, +76, +100,
+101,
+103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166,
+167, +170, +209, +215, +217, and +218 of D or E, substitutions at position 76
including D, H, E, G, F, K, P and N; substitutions at position 103 including
Q, T,
D, E, Y, K, G, R and S; and substitutions at position 104 including S, Y, I,
L, M,
A, W, D, T, G and V; and substitutions at position 222 including S, C, A. The
CA 02294839 1999-12-30
WO 99/01531 PCTNS97/i1399-
41
specifically preferred amino acids) to be substituted at each such position
are
. designated below in Table I. Although specific amino acids are shown in
Table I,
it should be understood that any amino acid may be substituted at the
identified
residues.
Table I
Amino Acid Preferred Amino Acid to
Residue be Substituted/lnserted
+210 I, V, L, A
+33, +62, +100, +101, +107 D,E
+128, +129, +130, +135
+156, +158, +164, +166
+167, +170, +209, +215
+217 and +218
+76 D,H
+103 A,Q,T,D,E,Y,K,G,R
+104 I,Y, S, L,A,T, G
+222 S, C, A
A comparison of the preferred amino acid residues identified herein for
substitution versus the preferred substitution for each such position is
provided in
Table II.
Table II
+210 +156 +166 +217 +76 +103 +104
B. amyloliquefaciens P E G Y N Q Y
(wild-type)
B. lentus (wild-type) P S S L N S V
Most Preferred Substitution I E/D E/D EID D A IIY
Also suitable for the present invention are proteases described in patent
applications EP 251 446 and WO 91/06637, protease BLAP~ described in
W091/02792 and their variants described in WO 95/23221.
See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93118140 A to Novo. Enzymatic detergents comprising protease, one or more
other enzymes, and a reversible protease inhibitor are described in WO
92/03529 A to Novo. When desired, a protease having decreased adsorption
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WO 99/01531 PCTNS97/11399-
42
and increased hydrolysis is available as described in WO 95/07791 to Procter 8
Gamble. A recombinant trypsin-like protease for detergents suitable herein is
described in WO 94/25583 to Novo. Other suitable proteases are described in
EP 516 200 by Unilever.
The proteolytic enzymes are incorporated in the dishwashing
compositions of the present invention a level of from 0.0001 % to 2%,
preferably
from 0.001 % to 0.2%, more preferably from 0.005% to 0.1 % pure enzyme by
weight of the composition.
The cellulases usable in the present invention include both bacterial or
fungal celluiases. Preferably, they will have a pH optimum of between 5 and 12
and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases
are
disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and
W096102653 which discloses fungal cellulase produced respectively from
Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982
describes cellulases isolated from novel Bacillus species. Suitable cellulases
are
also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and
W095/26398.
Examples of such cellulases are cellulases produced by a strain of
Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola
strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens
having
a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing
415
amino acids; and a -43kD endoglucanase derived from Humicola insolens, DSM
1800, exhibiting cellulase activity; a preferred endoglucanase component has
the
amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
Also suitable cellulases are the EGIII cellulases from Trichoderma
longibrachiatum described in W094/21801, Genencor, published September 29,
~h994. Especially suitable cellulases are the cellulases having color care
benefits.
Examples of such cellulases are cellulases described in European patent
application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and
Celluzyme (Novo Nordisk A/S) are especially useful. See also W091117244 and
W091I21801. Other suitable cellulases for fabric care and/or cleaning
properties
are described in W096/34092, W096117994 and W095/24471.
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WO 99/01531 PCTNS97/11399-
43
Said cellulases are normally incorporated in the detergent composition at
levels from 0.0001 % to 2% of pure enzyme by weight of the detergent
composition.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase and haloperoxidase such as chloro- and bromo-
peroxidase. Peroxidase-containing detergent compositions are disclosed, for
example, in PCT International Application WO 891099813, W089/09813 and in
European Patent application EP No. 91202882.6, filed on November 6, 1991 and
EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase
enzyme.
Preferred enhancers are substitued phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine
(described in WO 94/12621 ) and substitued syringates (C3-C5 substitued alkyl
syringates) and phenols. Sodium percarbonate or perborate are preferred
sources of hydrogen peroxide.
Said peroxidases are normally incorporated in the detergent composition
at levels from 0.0001 % to 2% of active enzyme by weight of the detergent
composition.
Enzyme Stabilizing System
Enzyme-containing compositions herein may comprise from 0.001 % to
10%, preferably from 0.005% to 8%,most preferably from 0.01 % to 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. Such stabilizing
systems can also comprise reversible protease inhibitors.
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44
The compositions herein may further comprise from 0% to 10%, preferably
.from 0.01% to 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 0.5 ppm to 1.75 ppm,
the
available chlorine in the total volume of water that comes in contact with the
enzyme during washing is usually large; accordingly, enzyme stability in-use
can
be problematic.
Suitable chlorine scavenger anions are widely available, and are
illustrated by salts containing ammonium cations or sulfite, bisulfate,
thiosulfite,
thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc.,
organic
amines such as ethylenediarninetetracetic 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.
Corrosion inhibitor
The compositions may also contain corrosion inhibitor which is preferably
incorporated at a level of from 0.05% to 10%, preferably from 0.1 % to 5% by
weight of the 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 C25-
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
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thioanthranoi. Also suitable are the C12-C20 fatty acids, or their salts,
especially
aluminium 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.
Suds sup~~~essing syrstem
The compositions herein may comprise a suds suppressing system
preferably present at a level of from 0.01 % to 15%, more preferably from
0.05%
to 10%, most preferably from 0.1 % to 5% by weight of the composition. A suds
suppressing system is a highly preferred component of the compositions when
the surfactant system comprises high foaming surfactant.
Suitable suds suppressing systems for use herein may comprise
essentially any known antifoarn 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.
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 siioxane units and hydrocarbyl group of various types.
Other suitable antifoam compounds include the monocarboxylic fatty acids
and soluble salts thereof. These materials are described in US Patent
2,954,347, issued September 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
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46
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 C1g-C40 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°C and
about 5°C,
and a minimum boiling point not less than 110°C (atmospheric pressure).
It is
also known to utilize waxy hydrocarbons, preferably having a melting point
below
about 100°C. Hydrocarbon suds suppressors are described, for example,
in U.S.
Patent 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.
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 C6 to C16 alkyl chain carrying a terminal hydroxy group, and said alkyl
chain
is substituted in the alpha position by a C1 to C10 alkyl chain. Mixtures of 2-
alkyl-
alcanols can be used in the compositions according to the present invention.
Solvent
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47
The compositions herein may contain organic solvents, particularly when
formulated as liquids or gets. The compositions in accord with the invention
preferably contain a solvent system present at levels of from 1 % to 30% by
weight, preferably from 3% to 25% by weight, more preferably form 5% to 20%
by weight of the composition. The solvent system may be a mono, or mixed
solvent system. Preferably, at least the major component of the solvent system
is
of low volatility.
Suitable organic solvent for use herein has the general formula
RO(CH2C(Me)HO)nH, wherein R is an alkyl, alkenyl, or alkyl aryl group having
from 1 to 8 carbon atoms, and n is an integer from 1 to 4. Preferably, R is an
alkyl group containing 1 to 4 carbon atoms, and n is 1 or 2. Especially
preferred
R groups are n-butyl or isobutyl. Preferred solvents of this type are 1-n-
butoxypropane-2-of (n=1 ); and 1 (2-n-butoxy-1-methylethoxy)propane-2-of
(n=2),
and mixtures thereof.
Other solvents useful herein include the water soluble CARBITOL
solvents or water-soluble CELLOSOLVE solvents. Water-soluble CARBITOL
solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the
alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble
carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol. Water-
soluble
CELLOSOLVE solvents are compounds of the 2-alkoxyethoxy ethanol class, with
2-butoxyethoxyethanol being preferred.
Other suitable solvents are benzyl alcohol, and diols such as 2-ethyl-1,3-
hexanediol and 2,2,4-trimethl-1,3-pentanediol.
The low molecular weight, water-soluble, liquid polyethylene glycols are
also suitable solvents for use herein.
The alkane mono and diois, especially the C1-Cg alkane mono and diols
are suitable for use herein. C1-C4 monohydric alcohols (eg: ethanol, propanol,
isopropanol, butanol and mixtures thereof) are preferred, with ethanol
particularly
preferred. The C1-C4 dihydric alcohols, including propylene glycol, are also
preferred.
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Hydrotropes
Hydrotrope may be added to the compositions herein, and is typically
present at levels of from 0.5% to 20%, preferably from 1 % to 10%, 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 optional ingiredients
Other optional ingredients suitable for inclusion in the compositions herein
include perfumes, colours and fillers.
pH of the compositions
The automatic dishwashing compositions preferably have a pH as a 1%
solution in distilled water at 20°C of from 8.5 to 13.0, preferably
from 9.5 to 11.5,
most preferably from 9.8 to 11Ø The manual dishwashing compositions
preferably have a pH as a 1 % solution in distilled water at 20°C of
from 4 to 11.0,
preferably from 5 to 8.
The pH of the compositions may be adjusted by the use of various pH adjusting
agents. Preferred acidification agents include inorganic and organic acids
including, for example, carboxyiate acids, such as citric and succinic acids.
Bicarbonates, particularly sodium bicarbonate, are useful pH adjusting agents
herein. A highly preferred acidification acid is citric acid which has the
advantage
of providing builder capacity to the wash solution.
Form of the compositions
The dishwashing compositions herein can be formulated in any desirable
form such as powders, tablets, granulates, pastes, liquids and gels.
Liquid compositions
The dishwashing compositions herein may be formulated as liquid
compositions which typically comprise from 94% to 35% by weight, preferably
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49
from 90% to 40% by weight, most preferably from 80% to 50% by weight of a
liquid carrier, e.g., water, preferably a mixture of water and organic
solvent.
Gel compositions
Gel compositions are typically formulated with polyakenyl polyether having
a molecular weight of from about 750,000 to about 4,000,000.
Solid compositions
The dishwashing compositions herein may also be in the form of solids,
such as powders, granules and tablets.
The particle size of the components of granular compositions should
preferably be such that no more that 5% of particles are greater than 1.4mm in
diameter and not more than 5% of particles are less than 0.15mm in diameter.
The bulk density of granular detergent compositions is typically at least
450 g/litre, more usually at least 600 g/litre and more preferably from 650
g/litre
to 1100 g/litre.
Dishwashing method
The dishwashing method may be essentially any conventional
dishwashing method.
The dishwashing method is preferably a machine dishwashing method
perfomned using a dishwasher machine, which may be selected from any of
those commonly available on the market. A machine dishwashing method
comprises treating soiled articles with an aqueous liquid having dissolved or
dispensed therein an effective amount of the machine dishwashing or rinsing
composition. By an effective amount of detergent composition it is generally
meant from 5g to 60g of detergent composition per wash, dissolved or dispersed
in an aqueous wash solution volume of from 3 to 10 litres, to provide a wash
solution concentration of the detergent composition of from 0.05% to 2% by
weight. The wash temperature may be in the range 40oC to 65oC as commonly
is employed in such methods. A rinse aid composition rnay also be used, if
desired.
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According to a manual dishwashing method, soiled dishes are contacted
with an effective amount of the dishwashing composition, typically from 0.5-
20g
(per 25 dishes being treated). Preferred manual dishwashing methods include
the application of a concentrated solution to the surfaces of the dishes or
the
soaking in large volume of dilute solution of the detergent composition.
Makinc,~~rocesses - granular compositions
In general, granular detergent compositions can be made via a variety of
methods including dry mixing, spray drying, agglomeration and granulation.
The following examples are meant to exemplify compositions of the
present invention, but are not necessarily meant to limit or otherwise define
the
scope of the invention.
In the detergent compositions, the enzymes levels are expressed by pure
enzyme by weight of the total composition and unless otherwise specified, the
detergent ingredients are expressed by weight of the total compositions. The
abbreviated component identifications therein have the following meanings:
STPP : Sodium tripolyphosphate
Citrate : Tri-sodium citrate dehydrate
Bicarbonate : Sodium hydrogen carbonate
Carbonate : Anhydrous sodium carbonate
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio
= 1.6-3.2)
Metasilicate : Sodium metasilicate (Si02:Na20 ratio = 1.0)
PB1 : Anhydrous sodium perborate monohydrate
PB4 : Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
Percarbonate : Anhydrous sodium percarbonate of nominal
formula
2.Na2C03.3H202
Nonionic : C13-C15 mixed ethoxyfated/propoxylated fatty
alcohol
with an average degree of ethoxylation of
3.8 and an
average degree of propoxylation of 4.5.
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TAED : Tetraacetyl ethylene diamine
HEDP : Ethane 1-hydroxy-1,1-diphosphonic acid
DETPMP : Diethyltriamine yenta (methylene) phosphonate,
marketed by monsanto under the tradename
bequest
2060
MnTACN : Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane.
PAAC : Pentaamine acetate cobalt (III) salt
BzP : Benzoyl Peroxide
Paraffin : Paraffin oii sold under the tradename Winog
70 by
Wintershall.
Protease : Proteolytic enzyme sold under the tradename
Savinase,
Alcalase, Durazym by Novo Nordisk AIS, Maxacal,
Maxapem sold by Gist-Brocades and proteases
described in patents W091/06637 andlor W095/10591
and/or EP 251 446.
Amylase : Amylolytic enzyme sold under the tradename
Purafact
Ox AmR described in WO 94/18314, WO96/05295
sold
by Genencor; Termamyl~, Fungamyl~ and Duramyl~,
all available from Novo Nordisk A/S and
those
described in W095/26397.
Lipase : Lipolytic enzyme sold under the tradename
Lipolase,
Lipolase Ultra by Novo Nordisk A/S and Lipomax
by
Gist-Brocades.
Phospholipase : Phoshoiipase enzyme sold under the tradename
Lecitase~ by Novo Nordisk A/S andlor Phospholipase
A2 by Sigma.
BTA : Benzotriazole
PA30 : Polyacrylic acid of average molecular
weight
approximately 4,500
MA/AA : Randon copolymer of 4:1 acrylate/maieate,
average
molecular weight about 70,000
480N : Random copolymer of 7:3 acrylatelmethacrylate,
average molecular weight about 3,500
PolygeIICarbopol: High molecular weight crosslinked polyacrylates.
Sulphate : Anhydrous sodium sulphate.
NaOCI : Sodium hypachlorite
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52
NaDCC : Sodium dichloroisocyanurate
NaOH : Sodium Hydroxide solution
KOH : Potassium Hydroxide solution
NaBz : Sodium Benzoate
SCS : Sodium Cumene Sulphonate
pH : Measured as a 1 % solution in distilled water at 20°C
Example 1
The following compact high density (0.96Kg/I) dishwashing detergent
compositions were prepared in accord with the present invention:
I II III IV V VI VII VIII
STPP - - 54.3 51.4 51.4 - - 50.9
Citrate 35.0 17.0 - - - 46.1 40.2 -
Carbonate - 17.5 14.0 14.0 14.0 - 8.0 32.1
Bicarbonate - - - - - 25.4 - -
Silicate 32.0 14.8 14.8 10.0 10.0 1.0 25.0 3.1
Metasilicate - 2.5 - 9.0 9.0 - - -
PB1 1.9 9.7 7.8 7.8 7.8 - - -
PB4 8.6 - _ _ _ _ _ _
Percarbonate - - - - - 6.7 11.8 4.8
Nonionic 1.5 2.0 1.5 1.7 1.5 2.6 1.9 5.3
1 II III IV V VI VII VI11
TAED 5.2 2.4 - - - 2.2 - 1.4
HEDP - 1.0 - - - - - -
DETPMP - 0.6 - - - - - -
MnTACN - - - - - - 0.008 -
PAAC - - 0.008 0.01 0.007 - - -
BzP _ _ _ - 1.4 - _ _
Paraffin 0.5 0.5 0.5 0.5 0.5 0.6 - -
Phosopholipase0.01 0.05 0.5 0.5 1.0 0.5 0.05 0.5
Protease 0.072 0.072 0.029 0.053 0.046 0.026 0.059 0.06
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53
Amylase 0.012 0.0120.006 0.012 0.013 0.009 0.017 0.03
Lipase - 0.001- 0.005 - - - _
BTA 0.3 0.3 0.3 0.3 0.3 - 0.3 0.3
MAIAA - _ _ _ _ - 4.2 -
480N 3.3 6.0 - - - - - O,g
Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1
Sulphate 7.0 20.0 5.0 2.2 0.8 12.0 4.6 -
pH 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9
Miscellaneous Up
and water to
100%
Exam~~le
2
The following of bulkensity
granular d
dishwashing
detergent
compositions
1.02Kg/L on
were prepared
in accord
with the
present
inventi
1 11 III IV V VI VII VII
STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6
Carbonate 30.5 30.5 31.0 30.0 23.0 39.4 4.2 45.0
Silicate 7.4 7.4 7.5 7.2 13.3 3.4 43.7 12.4
Metasilicate- - 4.5 5.1 - - - -
Percarbonate- - - - - 4.0 - -
PB1 4.4 4.2 4.5 4.5 - - - -
NADCC - - - - 2.0 - 1.6 1.0
Nonionic 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3
1 II lil IV V VI VII VII
TAED 1.0 - - - - 0.8- - -
PAAC - 0.0040.004 0.004 - - - -
BZP _ _ - 1.4 - _ _ _
Paraffin 0.2 0.3 0.2 0.3 - - -
Phospholipase1.0 1.05 0.5 1.0 0.5 0.1 0.5 1.0
Lipase 0.005 - 0.001 - - - - -
Protease 0.036 0.0150.03 0.028 - 0.03 - -
Amylase 0.003 0.0030.01 0.006 0.02 0.01 0.015 0.015
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54
BTA 0.1 0.1 0.1 0.1 - - - -
Perfume 0.2 0.2 0.2 0.2 0.1 0.2 0.2 -
Sulphate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6
pH 10.8 10.8 11.3 11.3 10.7 11.5 12.7 10.9
Miscellaneous and Up to 100%
water
Example 3
The following
detergent composition
tablets were
prepared in accord
with
the present inventionby mpressionof a hwashingdetergent
co granular
dis
composition at 3KN/cm2 head
a pressure of using rotary
1 a standard press:
12
I II III IV V VI
STPP - 48.8 49.2 38.0 - 46.8
C itrate 26.4 - - - 31.1 -
Carbonate - 5.0 14.0 15.4 14.4 23.0
Silicate 26.4 14.8 15.0 12.6 17.7 2.4
Phospholipase 0.5 0.7 0.5 0.7 0.005 0.5
Protease 0.058 0.072 0.041 0.033 0.052 0.013
Amylase 0.01 0.03 0.012 0.007 0.016 0.002
Lipase 0.005 - - - - -
PB1 1.6 7.7 12.2 10.6 15.7 -
PB4 6.9 - - - - 14.4
Nonionic 1.5 2.0 1.5 1.6 0.8 6.3
PAAC - - 0.02 0.009 - -
1 II III IV V VI
MnTACN - - - - 0.007 -
TAED 4.3 2.5 - - 1.3 1.8
HEDP 0.7 - - 0.7 - 0.4
DETPMP 0.6 - - - - -
Paraffin 0.4 0.5 0.5 0.5 - -
BTA 0.2 0.3 0.3 0.3 - -
PA30 3.2 - - - - -
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WO 99/01531 PCT/US97/11399-
M~~ - _ _ _ 4.5 0.5
Perfume - - 0.05 0.05 0.2 0.2
Sulphate 24.0 13.0 2.3 - 10.7 3.4
Weight of tablet 25g 25g 20g 30g 18g 20g
pH 10.6 10.6 10.7 10.7 10.9 11.2
Miscellaneous and waterUp to 100%
Example 4
The following liquid dishwashing detergent compositions of density
1.40Kg/L were prepared in accord with the present invention
I I1 III IV
STPP 17. 5 17.5 17.2 16.0
Carbonate 2.0 - 2.4 -
Silicate 5.3 6.1 14.6 15.7
NaOCI 1.1 1.1 1.1 1.2
Polygen/carbopol 1.1 1.0 1.1 1.2
Nonionic - - 0.1 -
NaBz 0.7 0.8 - -
Phospholipase 0.005 0.1 0.05 0.05
Amylase 0.01 0.005 0.0025 0.05
NaOH - 1.9 - 3.5
KOH 2.8 3.5 3.0 -
pH 11.0 11.7 10.9 11.0
Sulphate, miscellaneousand water up to
100%
Examqple ~
The following liquid rinse aid compositions were prepared in accord with the
present invention
1 II III
Nonionic 12.0 - 14.5
Nonionic blend - 64.0 -
C itric 3.2 - 6. 5
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56
HEDP 0.5 - -
PEG - 5.0 -
SCS 4.8 - 7.0
Phospholipase 0.05 0.1 1.0
Amylase 0.005 0.003 0.01
Ethanol 6.0 8.0 -
pH of the liquid 2.0 7.5
Example 6
The following liquid manualdishwashing were
detergent
compositions
prepared in accord with nvention
the present i
I II III IV V
Alkyl (1-7) ethoxy sulfate 28.5 27.4 19.2 34.1 34.1
Amine oxide 2.6 5.0 2.0 3.0 3.0
C12 glucose amide - - 6.0 - -
Betaine 0.9 - - 2.0 2.0
Xylene sulfonate 2.0 4.0 - 2.0 -
Neodol C11E9 - - 5.0 -
Poiyhydroxy fatty acid amide- - - 6.5 6.5
Sodium diethylene yenta - - 0.03 - -
acetate
(40%)
Diethylenetriamine yenta - - - 0.06 0.06
acetate
Sucrose - - - 1.5 1.5
Ethanol 4.0 5.5 5.5 9.1 9.1
Alkyl Biphenyl oxide disulfonate- - - - 2.3
I II III IV V
Calcium formate - - - 0.5 1.1
Ammonium citrate 0.06 0.1 - - -
Sodium chloride - 1.0 - - -
Magnesium chloride 3.3 - 0.7 -
Calcium chloride - - 0.4 - -
CA 02294839 1999-12-30
WO 99/01531 PCTNS97/11399 -
57
Sodium sulfate - - 0.06 - -
Magnesium sulfate 0.08 - - - -
Magnesium hydroxide - - - 2.2 2.2
Sodium hydroxide - - - 1.1 1.1
Hydrogen peroxide 200ppm 0.16 0.006 - -
Phospholipase 0.01 0.05 0.5 1.0 0.005
Amylase 0.03 0.005 0.01 0.005 0.015
Protease 0.5 0.15 0.10 0.08 0.05
Perfume 0.18 0.09 0.09 0.2 0.2
Water and minors Up to
100%
