Note: Descriptions are shown in the official language in which they were submitted.
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WO 99/3121 PCT/1B98102050
Detergent Tablet
Technical Field
The present invention relates to a detergent tablet comprising a granular
component
wherein the granular component dissolves at a faster rate than the other
components
of the detergent tablet.
Back ound
Detergent tablets in tablet form are known in the art. Detergent compositions
in
tablet form hold several advantages over particulate detergent compositions,
such as
ease of handling, transportation and storage. It is the aim of detergent
tablet
manufacturers to make tablets that are sufficiently hard such that they do not
crumble or disintegrate on handling, transportation or storage.
Detergent tablets are traditionally prepared by the compression of a
particulate
detergent composition in a tablet press. The most common method used by
detergent manufacturers to increase tablet hardness is to increase the
compression
pressure at which the tablets are formed. It has however, been found that the
rate of
dissolution of a tablet generally decreases with increasing compression
pressure.
Slow dissolution of a tablet means that the components of the detergent tablet
are
delivered to the wash water slowly and over a longer period of time and thus
have
less time to provide a detersive benefit in the wash. EP-A- 504 091 describes
a
detergent tablet comprising citric acid which reacts with an alkali to form a
gas that
aids dissolution of the tablet.
It is the object of the present invention to provide a detergent tablet that
is hard
enough to withstand handling, transportation and storage but also dissolves
more
quickly than detergent tablets currently available on the market. It has been
found
that tablets incorporating a granular component having the average particle
size and
dissolution properties described herein, dissolve more quickly than tablets
currently
available on the market. It is believed that this is due to the fact that the
granular
component dissolves quickly in the wash water, leaving holes or channels in
the
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tablet. The holes or channels increase the surface area of the tablet that is
exposed to
the wash water, thereby increasing the dissolution rate of the tablet.
Summary of the Invention
According to the present invention there is provided a detergent tablet
comprising a
granular component having an average particle size of greater than 250p,m and
less
than 1200~m in diameter and wherein 10 grams of the granular component
dissolves
in I litre of deionised water at 25°C in 80 seconds or less.
Detailed Description of the Invention
Granular Component
The granular component of the present invention can be any component suitable
for
incorporation into a detergent tablet that has the average particle size and
meets the
dissolution criteria as described in more detail below.
The average particle size of the granular component is greater than 250pm and
less
than 1200~m in diameter. More preferably the average particle size of the
granular
component is in the range of from 300~m to 800pm, most preferably from 350~m
to
700p.m in diameter.
Particle size is calculated using a series of Tyler sieves. The series
consists of a
number of sieves each having a different aperture size. Samples of a granular
component are sieved through the series of sieves (typically 5 sieves). The
weight of
a sample retained in the sieve is plotted against the aperture size of the
sieve. The
average particle size of the granular component is defined as the aperture
size
through which 50% by weight of the sample would pass.
It is an essential feature of the present invention that the granular
component
dissolves rapidly on contact with water in comparison to other components of
the
detergent tablet. The detergent tablet of the present invention comprises a
granular
component, 10 grams of which dissolves in deionised water at 25°C in 80
seconds or
less. Preferably 10 grams of a granular component dissolves in deionised water
at
25°C in 75 seconds or less, more preferably 60 seconds or less, most
preferably 50
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WO 99131215 pCT/IB98/02050
seconds or less. The dissolution of the granular component is measured using
the
dissolution test method described below.
Dissolution test method
The rate of dissolution of the granular component is measured by taking
measurement of the conductivity of the water on which the granular component
is
dissolved.
For the purposes of the present invention, conductivity was measured using a
Jenway 4020 conductivity meter calibrated against a standard sample of known
conductivity; for example a O.O1M solution of potassium chloride provides
conductivity of 1.413 milli Siemens/cm.
l Og of a granular component is poured into a beaker containing 1 litre of
deionised
water. The resulting solution is continuously stirred at a rate of 700 rpm
using a
cm magnetic stirring rod. Conductivity re~ngs are taken at regular intervals
using the Jenway 4020 conductivity meter. Figure 1 is a graphical
representation of
dissolution of granular NaHEDP, available from Solutia, in deionised water
measured as conductivity of the deionised water over time. It can be seen from
figure 1 that granular NaHEDP dissolves according to the dissolution test
method
described herein in 60 seconds.
As the granular component starts to dissolve the conductivity of the solution
will
increase. Once all the granular component has dissolved the conductivity of
the
solution will reach a plateau and remain at approximately the same
conductivity
(allowing for minor fluctuations in the equipment). The granular component is
said
to have dissolved when the conductivity plateau has been reached.
Preferred granular components are organo phosphonates. A particularly
preferred
organo phosphonate is granular sodium 1-hydroxy ethane-1,1-diphosphonate
(NaHEDP; available from Solutia) or granular HEDP acid. Preferably the NaHEDP
or HEDP acid has an average particle size of between 300~m to 800Eur1, more
preferably from 350pm to 700~m in diameter, most preferably between 400~rn and
600~m in diameter. NaHEDP having the average particle size defined above,
dissolves according to the test method described above in 60 seconds or less,
more
preferably in 50 seconds or less.
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In another preferred aspect the granular component is an agglomerate. In this
embodiment l Og of the agglomerate dissolves in 1 litre of deionised water in
80
seconds or less, preferably 75 seconds or less or even 60 seconds or less.
Most
preferably the agglomerate dissolves in SO seconds or less. In a particularly
preferred embodiment the agglomerate comprises powdered NaHEDP having an
average particle size of less than 250 pm and a liquid binder. The liquid
binder can
comprise for example water, liquid silicate or a polymeric binder for example
polyethylene glycol or polypropylene glycol or mixtures thereof. Preferred
binders
comprise liquid NaHEDP, polyethylene glycol, polypropylene glycol or mixtures
thereof.
The granular component as defined above is preferably uniformly distributed
throughout the tablet. By uniform distribution it is meant that the granular
component is randomly dispersed throughout the tablet such that substantially
all of
the granular component does not for example, segregate and settle in only one
area
of the tablet. Uniform distribution is achieved by pre-mixing a granular
component
according to the present invention with other detergent components selected
from
those described below to form a detergent composition. The premixed detergent
composition is compressed using any suitable equipment, to form a detergent
tablet.
In an alternative embodiment of the present invention the detergent tablet is
a
multiple layer tablet comprising at least 2 layers of compressed detergent
components. In this embodiment a granular component is present as a component
of
at least one of the layers of the tablet.
In another preferred aspect of the present invention the detergent tablet
comprises
less than 10% free or unbound water, more preferably less than 8%, even more
preferably less than 5%, 4% or even 2% free or unbound water.
The granular component is preferably present at a level of from 0.1 % to 10% ,
more
preferably from 0.5% to 5%, most preferably from 0.5% to 3% by weight of the
detergent tablet.
The detergent tablet preferably dissolves in 10 minutes or less, more
preferably in 8
minutes or less, most preferably in 6 minutes or less determined according to
the
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DIiV 44990 test method using a dishwashing machine available from Bosch on the
normal 65°C washing programme with water hardness at 18°d.
Detergent Components
The detergent composition of the present invention comprises a granular
component
as an essential component thereof but may also additionally comprise a variety
of
detergent components including builder compounds, surfactants, enzymes,
bleaching
agents, alkalinity sources, lime soap dispersants, organic polymeric compounds
including polymeric dye transfer inhibiting agents, crystal growth inhibitors,
heavy
metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion
inhibitors, suds
suppressors; solvents, fabric softening agents, optical brighteners and
hydrotropes.
Highly preferred components of the detergent composition as described earlier
include a builder compound, a surfactant, an enzyme and a bleaching agent.
Builder compound
The tablet compositions of the present invention preferably contain a builder
compound, typically present at a level of from 1 % to 80% by weight,
preferably
from 10% to 70% by weight, most preferably from 20% to 60% by weight of the
composition.
Water-soluble builder compound
Suitable water-soluble builder compounds include the water soluble 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,
carbonates,
bicarbonates, borates, phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in
type although monomeric polycarboxylates are generally preferred for reasons
of
cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts
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6
of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing two carboxy groups include the water-soluble salts of succinic
acid,
malonic acid, (ethylenedioxy} diacetic acid, malefic acid, diglycoiic acid,
tartaric
acid, tartronic acid and fumaric acid, as well as the ether carboxylates and
the
sulfinyl carboxylates. 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 sulfosuccinate 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 polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran -
cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates,
2,2,5,5-
tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing
up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents
or mixtures thereof with their salts, e.g. citric acid or citratelcitric acid
mixtures
are also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can
produce borate under detergent storage or wash conditions can also be used but
are
not preferred at wash conditions less that about 50°C, especially less
than about
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PCT/1B98I02050
7
40°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates,
includinj sodium carbonate and sesqui-carbonate and mixtures thereof with
ultra-
fine calcium carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
Highly preferred builder compounds for use in the present invention are water-
soluble phosphate builders. Specific examples of water-soluble 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
polymerisation ranges from about 6 to 21, and salts of phytic acid.
Specific examples of water-soluble 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.
Partially soluble or insoluble builder compound
The compositions of the present invention may contain a partially soluble or
insoluble builder compound. Partially soluble and insoluble builder compounds
are
particularly suitable for use in tablets prepared for use in laundry cleaning
methods. Examples of partially water soluble builders include the crystalline
layered silicates as disclosed for example, in EP-A-0164514, DE-A-3417649 and
DE-A-3742043. Preferred are the crystalline layered sodium silicates of
general
formula
NaMSix02+1 .yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type preferably
have a
two dimensional 'sheet' structure, such as the so called b-layered structure,
as
described in EP 0 164514 and EP 0 293640.
Methods for preparation of crystalline layered silicates of this type are
disclosed in
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WO 99/31215 PCTIIB98/02450
DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in
the general formula above has a value of 2,3 or 4 and is preferably 2.
The most preferred crystalline layered sodium silicate compound has the
formula b-
Na2Si205 , known as NaSKS-6 (trade name), available from Hoechst AG.
The crystalline layered sodium silicate material is preferably present in
granular
detergent compositions as a particulate in intimate admixture with a solid,
water-
soluble ionisable material as described in PCT Patent Application No.
W092118594. The solid, water-soluble ionisable material is selected from
organic
acids, organic and inorganic acid salts and mixtures thereof, with citric acid
being
preferred.
Examples of largely water insoluble builders include the sodium
aiuminosilicates.
Suitable aluminosilicates include the aluminosilicate zeolites having the unit
cell
formula Naz[(A102)z(Si02)y]. xH20 wherein z and y are at least 6; the molar
ratio of z to y is from I .0 to 0.5 and x is at least 5, preferably from 7.5
to 276,
snore preferably from 10 to 264. The aluminosilicate material are in hydrated
form and are preferably crystalline, containing from 10% to 28%, more
preferably
from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials
are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite
X,
Zeolite HS and mixtures thereof.
A preferred method of synthesizing aluminosilicate zeolites is that described
by
Schoeman et al (published in Zeolite (1994) 14(2), 110-116), in which the
author
describes a method of preparing colloidal aluminosilicate zeolites. The
colloidal
aluminosilicate zeolite particles should preferably be such that no more than
5% of
the particles are of size greater than 1 ~m in diameter and not more than 5%
of
particles are of size less then 0.05 ~m in diameter. Preferably the
aluzriinosilicate
zeolite particles have an average particle size diameter of between
0.01 ~m and 1 Vim, more preferably between 0.05 p,m and 0.9 p,m, most
preferably
between 0.1 pm and 0.6 pm.
Zeolite A has the formula
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9
Na 12 [A102) to (Si02)12J. xH~O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(SiO~)106)~ 276 H20. Zeolite MAP, as disclosed in EP-B-384,070 is a
preferred zeolite builder herein.
Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
When
employed as a component of a detergent composition colloidal aluminosilicate
zeolites, especially colloidal zeolite A, provide enhanced builder performance
in
terms of providing improved stain removal. Enhanced builder performance is
also
seen in terms of reduced fabric encrustation and improved fabric whiteness
maintenance; problems believed to be associated with poorly built detergent
compositions.
A surprising finding is that mixed aluminosilicate zeolite detergent
compositions
comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium
ion
sequestration performance versus an equal weight of commercially available
zeolite
A. Another surprising finding is that mixed aluminosilicate zeolite detergent
compositions, described above, provide improved magnesium ion sequestration
performance versus an equal weight of commercially available zeolite A.
Surfactant
Surfactants are preferred components of the detergent compositions described
herein. Suitable surfactants are selected from anionic, cationic, nonionic
ampholytic and zwitterionic surfactants and mixtures thereof. Automatic
dishwashing machine products should be low foaming in character and thus the
foaming of the surfactant system for use in dishwashing methods must be
suppressed or more preferably be low foaming, typically nonionic in character.
Sudsing caused by surfactant systems used in laundry cleaning methods need not
be
suppressed to the same extent as is necessary for dishwashing. The surfactant
is
typically present at a level of from 0.2% to 30% by weight, more preferably
from
0.5% to 10% by weight, most preferably from 1% to S% by weight of the
compositions.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and
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WO 99/31215 PCTI1B98/02450
species of these surfactants, is Given in U.S.P. 3,929,678 issued to Laughlin
and
Heuring on December, 30, 1975. A list of suitable cationic surfactants is
given in
U.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants
typically included in automatic dishwashing detergent compositions is given
for
example, in EP-A-0414 549 and PCT Applications No.s WO 93/08876 and WO
93108874.
Nonionic surfactant
Essentially any nonionic surfactants useful for detersive purposes can be
included
in the compositions. Preferred, non-limiting classes of useful nonionic
surfactants
are listed below.
Nonionic ethoxylated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from
about 1
to about 25 moles of ethylene oxide are suitable for use herein. The alkyl
chain of
the aliphatic alcohol can either be straight or branched, primary or
secondary, and
generally contains from 6 to 22 carbon atoms. Particularly preferred are the
condensation products of alcohols having an alkyl group containing from 8 to
20
carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of
alcohol.
End-capped alkyl alkoxylate surfactant
A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped
poly(oxyalkylated) alcohols represented by the formula:
R10[CH2CH(CH3)OJx[CH2CH20Jy[CH2CH(OH)R2] (I)
wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from
about 4 to about 18 carbon atoms; R2 is a linear or branched aliphatic
hydrocarbon
radical having from about 2 to about 26 carbon atoms; x is an integer having
an
average value of from 0.5 to about 1.5, more preferably about 1; and y is an
integer having a value of at least about 15, more preferably at least about
20.
Preferably, the surfactant of formula I, at least about 10 carbon atoms in the
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11
terminal epoxide unit [CHOCH(OH)R~]. Suitable surfactants of formula I,
according to the present invention, are Olin Corporation's POLY-TERGENT~
SLF-18B nonionic surfactants, as described, for example, in WO 94/22800,
published October 13, 1994 by Olin Corporation.
Nonionic ethoxylated/propoxvlated fatty alcohol surfactant
The ethoxyiated C6-C 1 g fatty alcohols and C6-C 1 g mixed
ethoxylated/propoxylated fatty alcohols are suitable surfactants for use
herein,
particularly where water soluble. Preferably the ethoxylated fatty alcohols
are the
C 10-C 1 g ethoxylated fatty alcohols with a degree of ethoxylation of from 3
to 50,
most preferably these are the C 12-C I g ethoxylated fatty alcohols with a
degree of
ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty
alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of
ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
Nonionic EOlPO condensates with propylene glycol
The condensation products of ethylene oxide with a hydrophobic base formed by
the condensation of propylene oxide with propylene glycol are suitable for use
herein. The hydrophobic portion of these compounds preferably has a molecular
weight of from about 1500 to about 1800 and exhibits water insolubility.
Examples of compounds of this type include certain of the commercially-
available
PluronicTM surfactants, marketed by BASF.
Nonionic EO condensation products with propylene oxide/ethvlene 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.
Anionic surfactant
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12
Essentially any anionic surfactants useful for detersive purposes are
suitable.
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.
Anionic
sulfate surfactants are preferred.
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 1 ~-C 18 monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6 C14 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 and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C1~ acyl-N-(C1-C4
alkyl) and -N-(C1-C2 hydroxyallcyl) glucamine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched
chain
alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of
the C l 0-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles
of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a C 11-C 1 g, most preferably C 11-C 15 alkyl sulfate which has
been
ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene
oxide per
molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred
alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been
disclosed in PCT Patent Application No. WO 93/18124.
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13
:anionic sulfonate surfactant
:anionic sulfonate surfactants suitable for use herein include the salts of CS-
C~0
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or
secondary
alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates,
and any mixtures thereof.
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the
alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl
carboxyls'),
especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to C 1 g 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 20 % and M is a cation. Suitable alkyl poiyethoxy
polycarboxylate surfactants include those having the formula RO-(CHRI-CHR2-
O)-R3 wherein R is a C6 to C 1 g 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, and R3 is
selected
from the group consisting of hydrogen, substituted or unsubstituted
hydrocarbon
having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a
carboxyl unit connected to a secondary carbon. 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. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitablc anionic surfactants are the alkali metal sarcosinates of
formula R-
CON (R1) CH2 COOM, wherein R is a CS-C1~ linear or branched alkyl or
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14
alkenyl group, R 1 is a C 1-C,~ alkyl group and M is an alkali metal ion.
Preferred
examples are the myristyl and oleoyl methyl sarcosinates in the form of their
sodium salts.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants
and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8
to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from
2
to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to
3;
and each RS is an alkyl or hydroxyalkyl group containing from 1 to 3, or a
polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
Preferred
are C 1 p-C 1 g alkyl dimethylamine oxide, and C 10-18 acylamido alkyl
dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions
hereof. These surfactants can be broadly described as derivatives of secondary
and tertiary amines, derivatives of heterocyclic secondary and tertiary
amines, or
derivatives of quaternary ammonium, quaternary phosphonium or tertiary
sulfonium compounds. Betaine and sultaine surfactants are exemplary
zwitterionic
surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R is a C6-C 1 g hydrocarbyl group, each R1 is typically C 1-C3 alkyl,
and
R2 is a C1-CS hydrocarbyl group. 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.
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WO 99!31215 PCT/IB98I02050
Cationic surfactants
Cationic ester surfactants used in this invention are preferably water
dispersible
compound having surfactant properties comprising at least one ester (i.e. -COO-
)
linkage and at least one canonically charged group. Other suitable cationic
ester
surfactants, including choline ester surfactants, have for example been
disclosed in
US Patents No.s 4228042, 4239660 and 4260529.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected
from mono C6-C 16, preferably C6-C 1 p N-alkyl or alkenyl ammonium surfactants
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Enzymes
The detergent tablet compositions may comprise an enzyme. Said enzymes include
enzymes selected from cellulases, hemicellulases, peroxidases, proteases,
gluco-
amylases, amylases, xylanases, lipases, phospholipases, esterases, cunnases,
pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, Q-glucanases,
arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
A preferred combination is a cleaning composition having cocktail of
conventional
applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase
in
conjunction with one or more plant cell wall degrading enzymes.
The cellulases usable in the present invention include both bacterial or
fungal
cellulose. 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, 361078384 and
W096/02653 which disclose fungal cellulases 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
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16
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 SOKDa, an isoelectric point of S.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
Trichodenna
longibrachiatum described in W094/21801, Genencor, published September 29,
1994. 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
W091/21801. Other suitable cellulases for fabric care and/or cleaning
properties
are described in W096/34092, W096/17994 and W095/24471.
Said cellulases are normally incorporated in the detergent composition at
levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Peroxidase enzymes are used in combinatiowwith 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-CS substitued alkyl syringates) and
phenols. Sodium percarbonate or perborate are preferred sources of hydrogen
peroxide.
Said cellulases andlor peroxidases are normally incorporated in the detergent
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17
composition at levels from 0.0001% to 2% of active enzyme by weight of the
detergent composition.
Other preferred enzymes that can be included in the detergent 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. lipolvticum 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 ~d LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR(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 95/22615 by Novo Nordisk and
in WO 94/03578, WO 95!35381 and WO 96/00292 by Unilever.
Also suitable are cutinases [EC 3.1. i .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).
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. licheniformis (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
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18
enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASE~~, DL,'RAZYM'~ and SAVINASE~ from Novo and MAXATASE~~
NiAXACAL~, PROpERASE't 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, filed October 13, 1994.
Also suitable for the present invention are proteases described in patent
applications
EP 251 446 and WO 91106637, protease BLAP~ described in W09I/02792 and
their variants described in WO 95/23221.
See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93/18140 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 and increased
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19
hydrolysis is available as described in WO 95/07791 to Procter & 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 detergent compositions of the
present invention a level of from 0.0001% to 2%, preferably from O.OOI% to
0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the
composition.
Amylases (a and/or J3) 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 AIS, 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; W0/91/00353;
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 W094I18314, published August 18, 1994 and W096105295,
Genencor, published February 22, 1996 and amylase variants having additional
modification in the immediate parent available from Novo Nordisk A/S,
disclosed
in WO 95/10603, published April 95. Also suitable are amylases described in EP
277 216, W095/26397 and W096/23873 (all by Novo Nordisk).
Examples of commercial a-amylases products are Purafect Ox Am~ 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 are variants of the above enzymes, described in W096123873
(Novo Nordisk). Other amylolytic enzymes with improved properties with respect
to the activity level and the combination of thenmostability and a higher
activity
level are described in W095/35382.
The amylolytic enzymes are incorporated in the detergent compositions of the
present invention a level of from 0.0001 % to 2%, preferably from 0.00018% to
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WO 9913IZI5 PCT/IB98/02050
0.06%, more preferably from 0.00024°'o to 0.048% pure enzyme by weight
of the
composition.
The above-mentioned enzymes 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,
alkalophilic, acidophilic; halophilic, etc.). Purified or non-purified forms
of these
enzymes may be used. Also included by definition, are mutants of native
enzymes.
Mutants can be obtained e.g. by protein and/or genetic engineering, chemical
andlor physical modifications of native enzymes. Common practice as well is
the
expression of the enzyme via host organisms in which the genetic material
responsible for the production of the enzyme has been cloned.
Said enzymes are normally incorporated in the detergent composition at levels
from
0.0001% to 2% of active enzyme by weight of the detergent composition. The
enzymes can be added as separate single ingredients (grills, granulates,
stabilized
liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes
e.g. cogranulates ).
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers which are described in Copending European Patent application
92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation
scavengers are ethoxylated tetraethylene polyamines.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place
et
al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme
materials useful for liquid detergent formulations, and their incorporation
into such
formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981.
Enzymes for use in detergents can be stabilised by various techniques. Enzyme
stabilisation techniques are disclosed and exemplified in U.S. 3,600,319,
August
17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas.
Enzyme stabilisation systems are also described, for example, in U.S.
3,519,570.
A useful Bacillus, sp. AC13 giving proteases, xyianases and cellulases, is
described
in WO 9401532 A to Novo.
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Bleaching went
A highly preferred component of the detergent composition is a bleaching
agent.
Suitable bleaching agents include chlorine and oxygen-releasing bleaching
agents.
In one preferred aspect the oxygen-releasing bleaching agent contains a
hydrogen
peroxide source and an organic peroxyacid bleach precursor compound. The
production of the organic peroxyacid occurs by an in situ reaction of the
precursor
with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide
include inorganic perhydrate bleaches. In an alternative preferred aspect a
preformed organic peroxyacid is incorporated directly into the composition.
Compositions containing mixtures of a hydrogen peroxide source and organic
peroxyacid precursor in combination with a preformed organic peroxyacid are
also
envisaged.
Inorganic perhydrate bleaches
The compositions in accord with the invention preferably include a hydrogen
peroxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide
sources include the inorganic perhydrate salts.
The inorganic perhydrate salts are normally incorporated in the form of the
sodium
salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30%
by
weight and most preferably from S% to 25% by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts
are
normally the alkali metal salts. The inorganic perhydrate salt may be included
as
the crystalline solid without additional protection. For certain perhydrate
salts
however, the preferred executions of such granular compositions utilize a
coated
form of the material which provides better storage stability for the
perhydrate salt
in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaBO~H~O~ or the tetrahydrate NaB02H20~.3H20.
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22
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates for inclusion in compositions in accordance with the invention.
Sodium percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid. Sodium
percarbonate, being a hydrogen peroxide addition compound tends on dissolution
to release the hydrogen peroxide quite rapidly which can increase the tendency
for
localised high bleach concentrations to arise. The percarbonate is most
preferably
incorporated into such compositions in a coated form which provides in-product
stability.
A suitable coating material providing in product stability comprises mixed
salt of a
water soluble 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 I :
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 from 0.1 to 3, preferably n is from 0.3 to 1.0
and
most preferably n is from 0.2 to 0.5.
Another suitable coating material providing in product stability, comprises
sodium
silicate of Si02 : Na20 ratio from 1.8 : 1 to 3.0 : 1, preferably 1.8:1 to
2.4:1,
and/or sodium metasilicate, preferably applied at a level of from 2% to 10%,
(normally from 3% to 5%) of Si02 by weight of the inorganic perhydrate salt.
Magnesium silicate can also be included in the coating. Coatings that contain
silicate and borate salts or boric acids or other inorganics are also
suitable.
Other coatings which contain waxes, oils, fatty soaps can also be used
advantageously within the present invention.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility
in
the compositions herein.
Peroxvacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid
bleach
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WO 99/31215 PCT/IB98/02050
23
precursors may be represented as
O
X-C- L
where L is a leaving group and X is essentially any functionality, such that
on
perhydrolysis the structure of the peroxyacid produced is
0
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of
from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most
preferably from 1.5% to 5% by weight of the compositions.
Suitable peroxyacid bleach precursor compounds 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, lactams and acylated
derivatives
of imidazoles and oximes. Examples of useful materials within these classes
are
disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988,
864798, 1147871, 2143231 and EP-A-0170386.
Leaving, r~oups
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis reaction to occur within the optimum time frame (e.g., a wash
cycle). Howcver, if L is too reactive, this activator will be difficult to
stabilise for
use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
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24
Y R3 R 51'
-O C , -O ~~ Y , and -O
O
I I
-N-C-R -N N -N-C-CH-R
R s ' ~ ~ R3 Y ,
i
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
0 C H -CO Y C
t -N\CiN~ -N C a
jNR
' II II
O O
R3 O Y
-0-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing
from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon
atoms, R4 is H or R3, RS is an alkenyl chain containing from 1 to 8 carbon
atoms
and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by
essentially any functional group including, for example alkyl, hydroxy,
allcoxy,
halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04 M+,
-N~(R3)4X and O<--N(R3)3 and most preferably -S03 M+ and -C02 M+
wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a
cation
which provides solubility to the bleach activator and X is an anion which
provides
solubility to the bleach activator. Preferably, M is an alkali metal, ammonium
or
substituted ammonium cation, with sodium and potassium being most preferred,
and X is a halide, hydroxide, methylsulfate or acetate anion.
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?5
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted
and unsubstituted benzoyl oxybenzene sulfonates, including for example
bertzoyl
oxybenzene sulfonate:
~ 0II
1~l
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides
with benzoylating agents, including for example:
OAc
Ac0 \~n
~~; OAc
/ OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted
areas.
Suitable imidazole type perbenzoic acid precursors include N-benzoyl
irnidazole
and N-benzoyl benzimidazole and other useful N-acyl group-containing
perbenzoic
acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl
tetraacyl peroxides, and the compound having the formula:
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26
0 0
o~
d a~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
o~
0
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
O
I I
O C-C H2-C H2
6- II I
R C-NCH --f CH
2 21n
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.
Perbenzoic acid derivative precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
perhydrolysis.
Suitable substituted perbenzoic acid derivative precursors include any of the
herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by
essentially any non-positively charged (i.e.; non-cationic) functional group
including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and
amide
groups.
A preferred class of substituted perbenzoic acid precursor compounds are the
amide
substituted compounds of the following general formulae:
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27
R~ C-N -R2--- C-L R~ -- N C -R2-C-L
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R5 is H
or
an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be
essentially any leaving group. R1 preferably contains from 6 to 12 carbon
atoms.
R2 preferably contains from 4 to 8 carbon atoms. R1 may be aryl, substituted
aryl or alkylaryl containing branching, substitution, or both and may be
sourced
from either synthetic sources or natural sources including for example, tallow
fat.
Analogous structural variations are permissible for R2. The substitution can
include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent
groups
or organic compounds. R5 is preferably H or methyl. R1 and R5 should not
contain more than 18 carbon atoms in total. Amide substituted bleach activator
compounds of this type are described in EP-A-0170386.
Cationic peroxvacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid
part of a suitable peroxyacid precursor compound with a positively charged
functional group, such as an ammonium or alkyl ammonium group, preferably an
ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically
present in the compositions as a salt with a suitable anion, such as for
example a
halide ion or a methylsulfate ion.
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may he an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528;
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WO 99131215 PCT/IB98/02058
28
U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Suitable cationic peroXyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-
(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
0
~O~S03
~+
A preferred cationically substituted alkyl oxybenzene sulfonate has the
formula:
O ~ S03_
~ ~'~'~~ O
Preferred cationic peroxyacid precursors of the N-acylated caprolactam class
include the trialkyl ammonium methylene benzoyl caprolactams, particularly
trimethyl ammonium methylene benzoyl caprolactam:
O
O ,
''
I~~i'~ N
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl caprolactams:
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WO 99/31215 PCT/IB98/02050
29
O O
N
N , (CH~)n
where n is from 0 to 12, particularly from 1 to 5.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Alkvl nercarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid on
perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the
N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group
contains
from 1 to 6 carbon atoms, particularly those compounds in which the alkylene
group contains l, ? and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is
particularly preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyioxybenzene
sulfonate (HOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl
glucose.
Amide substituted alkyl peroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable,
including those of the following general formulae:
R~ -C -N-R2-C-L R~ -N-C-R2-C-L
II ~ I.
O R5 O or R~ O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
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group containing from 1 to 14 carbon atoms, and RS is H or an alkyl group
containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1
preferably contains from 6 to 1' carbon atoms. R2 preferably contains from 4
to
8 carbon atoms. R1 may be straight chain or branched alkyl containing
branching, substitution, or both and may be sourced from either synthetic
sources
or natural sources including for example, tallow fat. Analogous structural
variations are permissible for R2. The substitution can include alkyl,
halogen,
nitrogen, sulphur and other typical substituent groups or organic compounds.
RS
is preferably H or methyl. Rl and RS should not contain more than 18 carbon
atoms in total. Amide substituted bleach activator compounds of this type are
described in EP-A-0170386.
Benzoxazin organic peroxyacid precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example in EP-A-332,294 and EP-A-482,807, particularly those having the
formula:
O
II
,,C-R~
'N
including the substituted benzoxazins of the type
R2 C
~O
R4 N C -R~
R5
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS
may be the same or different substituents selected from H, halogen, alkyl,
alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an
alkyl
group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
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3I
O
II
CEO
C
''
N
Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more
preferably from 1% to 10% by weight ofthe composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
R~ -C-N-R2-C-OOH
O R'~ O or
R~ -N-C---RZ-C-OOH
R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2
is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon
atoms, and RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10
carbon
atoms. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably
contains from 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl,
substituted aryl or alkylaryl containing branching, substitution, or both and
may be
sourced from either synthetic sources or natural sources including for
example,
tallow fat. Analogous structural variations are permissible for R2. The
substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other
typical
substituent groups or organic compounds. RS is preferably H or methyl. R1 and
RS should not contain more than 18 carbon atoms in total. Amide substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides; especially
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32
diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic
peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic acid,
and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Metal-containin3 bleach catalyst
The bleach 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.
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
aluminium
cations, and a sequestrant having defined stability constants for the
catalytic and
auxiliary metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof.
Such catalysts are disclosed in U.S. Pat. 4,430,243.
Preferred types of bleach catalysts include the manganese-based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples
of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)~-
(PF6}2, MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(CI04)2, MnN4(u-0)6(1,4,7-tnazacyclononane)4-(C104)2, MnIIIMnIV4(u-
O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CI04)3, and mixtures
thereof. Others are described in European patent application publication no.
549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-
triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-
triazacyclononane, 1,2,4,7-tetrarnethyl-1,4,7-
triazacyclononane, and mixtures thereof.
The bleach catalysts useful in the compositions herein may also be selected as
appropriate for the present invention. For examples of suitable bleach
catalysts
see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat.
5,194,416 which teaches mononuclear manganese (IV) complexes such as
Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PF6).
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Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a
water-soluble complex of manganese (III), and/or (IV) with a ligand which is a
non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol,
xylithoi,
arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures
thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
ligands are of the formula:
R2 R3
R ~ -N=C-B-C=N-R4
wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-
membered ring. Said ring can further be substituted. B is a bridging group
selected from O, S. CRSR6, NR~ and C=O, wherein R5, R6, and R~ can each be
H, alkyl, or aryl groups, including substituted or unsubstituted groups.
Preferred
ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole,
pyrazole,
and triazole rings. Optionally, said rings may be substituted with
substituents such
as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the
ligand 2,2'-
bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-
bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts
include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt
(II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-
bispyridylamine)202C104,
Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine)
iron(II)
perchlorate, and mixtures thereof.
Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-
N-
dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2Mn~(u-
O)2MnNbtPY2J-(C104)3~
While the structures of the bleach-catalyzing manganese complexes of the
present invention have not been elucidated, it may be speculated that they
comprise chelates or other hydrated coordination complexes which result
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34
from the interaction of the carboxyl and nitrogen atoms of the ligand
with the manganese cation. Likewise, the oxidation state of the
manganese cation during the catalytic process is not known with
certainty, and may be the (+II), (+III), (+IV) or (+V) valence state.
Due to the ligands' possible six points of attachment to the manganese
cation, it may be reasonably speculated that mufti-nuclear species andlor
"cage" structures may exist in the aqueous bleaching media. Whatever
the form of the active Mwligand species which actually exists, it
functions in an apparently catalytic manner to provide improved
bleaching performances on stubborn stains such as tea, ketchup, coffee,
wine, juice, and the like.
Other bleach catalysts are described, for example, in European patent
application, publication no. 408,131 (cobalt complex catalysts),
European patent applications, publication nos. 384,503, and 306,089
(metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate
ligand catalyst), U.S. 4,711,748 and European patent application,
publication no. 224,952, (absorbed manganese on aluminosilicate
catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and
zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst),
U.S. 4,119,557 (ferric complex catalyst), German Pat. specification
2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metaI-
containing salts), U.S. 4,430,243 (chelants with manganese cations and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
Other preferred examples include cobalt (III) catalysts having the
formula:
Co[~3)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 Iigand; q is
0
or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q
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35
+ 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 ? 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 co-ordination sites stabilise 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~3)n(M~)mJ 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 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)SCIJ Yy, and
especially [Co(NH3)SC1JCI2.
More preferred are the present invention compositions which utilize
cobalt (III) bleach catalysts having the formula:
[Co(~3)n(M)m(B)bJ 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
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36
2 (preferably 1 ); B is a ligand co-ordinated 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,
I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate,
bromide, PF6-, BF4-, B(Ph)4 , phosphate, phosphite, silicate, tosylate,
methanesulfonate, and combinations thereof. Optionally, T can be
protonated if more than one anionic group exists in T, e.g., HP042-,
HC03-, H~P04-, 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.) andlor anionic polymers (e.g.,
polyacrylates, polymethacrylates, etc.).
The M moieties include, but are not limited to, for example, F-, S04'2,
NCS-, SCN-, S203-2, NH3, P043-, and carboxylates (which preferably
are mono-carboxylates, but more than one carboxylate may be present in
the moiety as 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-, HZP04 ,
HOC(O)CH~C(O)O-, etc.) Preferred M moieties are substituted and
unsubstituted Cl-C3p carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen
and C 1-C30 (preferably C 1-C 1 g) unsubstituted and substituted alkyl, C6-
C30 (preferably C6-C1 g) unsubstituted and substituted aryl, and C3-C30
(preferably CS-C 1 g) unsubstituted and substituted heteroaryl, wherein
substituents are selected from the group consisting of -NR'3, -NR'4+, -
C(O)OR', -OR', -C(O)NR'~, wherein R' is selected from the group
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37
consisting of hydrogen and C 1-C6 moieties. Such substituted R
therefore include the moieties -(CHI jnOH 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 ? to about 5.
Most preferred Nl are carboxylic acids having the formula above wherein
R is selected from the group consisting of hydrogen, methyl, ethyl,
propyl, straight or branched C4-C 1 ~ 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, palmitic,
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. Inor~. Bioinorg.
Mech., (1983), 2, pages 1-94. For example, Table 1 at page 17,
provides the base hydrolysis rates (designated therein as kpH) for cobalt
pentaamine catalysts complexed with oxalate (kOH= 2.5 x 10-4 M-1 s-1
(25°C)), NCS- (kOH= 5.0 x 10-4 M-1 s-1 (25°C)), formate (kOH=
5.8
x 10-4 M-1 s-1 (25°C)), and acetate (kpl.l= 9.b x 10''~ 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)SOAcJCI2; as well as [Co(NH3)50AcJ(OAc)2;
[Co(NH3)50AcJ(PF6)2; [Co(NH3)gOAc](S04); [Co
~3)SOAcJ(BF4)2; and [Co(NH3)50AcJ(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
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38
7,1989, .1. Chem. Ed. ( 1989), 66 ( 12 ), 1043-45; The Synthesis and
Characterization of Inorganic Compounds, W.L. 3olly (Prentice-Hall;
1970), pp. 461-3; Inbrs. Chem., 18, 1497-1502 (1979); Inor~.
Chem., ''1, 2881-2885 (1982); Inor~. Chem., 18, 2023-2025 (1979);
Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry,
56, 22-2~ (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".
Water-soluble sulfate salt
The detergent tablet composition optionally contains a water-soluble sulfate
salt.
Where present the water-soluble sulfate salt is at the level of from 0.1% to
40%,
more preferably from 1% to 30%, most preferably from 5% to 25% by weight of
the compositions.
The water-soluble sulfate salt may be essentially any salt of sulfate with any
counter cation. Preferred salts are selected from the sulfates of the alkali
and
alkaline earth metals, particularly sodium sulfate.
Alkali Metal Silicate
A preferred component of the detergent composition is an alkali metal
silicate. A
preferred alkali metal silicate is sodium silicate having an Si02:Na20 ratio
of from
1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2Ø Sodium silicate
is
preferably present at a level of less than 20%, preferably from 1% to 15%,
most
preferably from 3% to 12% by weight of Si02. The alkali metal silicate may be
in the form of either the anhydrous salt or a hydrated salt.
Hydrocarbon oils
Another preferred detergent component for use in the present invention is a
hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons
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having a number of carbon atoms in the range of from 20 to 50; preferred
hydrocarbons are saturated and/or branched; preferred hydrocarbon oil selected
from predominantly' branched Cos_45 species with a ratio of cyclic to
noncyclic
hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1. A preferrred
hydrocarbon oil is paraffin. A paraffin oil meeting the characteristics as
outlined
above, having a ratio of cyclic to noncyclic hydrocarbons of about 32:68, is
sold
by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
Water-soluble bismuth compound
The compositions prepared by the process of the present invention suitable for
use
in dishwashing methods may contain a water-soluble bismuth compound,
preferably present at a level of from 0.005% to 20%, more preferably from 0.01
to 5%, most preferably from 0.1 % to 1 % by weight of the compositions.
The water-soluble bismuth compound may be essentially any salt or complex of
bismuth with essentially any inorganic or organic counter anion. Preferred
inorganic bismuth salts are selected from the bismuth trihalides, bismuth
nitrate and
bismuth phosphate. Bismuth acetate and citrate are preferred salts with an
organic
counter anion.
Corrosion inhibitor compound
The compositions of the present invention and suitable for use in dishwashing
methods may contain corrosion inhibitors preferably selected from organic
silver
coating agents, particularly paraffin, nitrogen-containing corrosion inhibitor
compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
Organic silver coating agents are described in PCT Publication No. W094/16047
and copending European application No. EP-A-690122. Nitrogen-containing
corrosion inhibitor compounds are disclosed in copending European Application
no. EP-A-634,478. Mn(II) compounds for use in corrosion inhibition are
described in copending European Application No. EP-A-672 749.
Organic silver coating agent may be incorporated at a level of from 0.05% to
10%,
preferably from 0.1% to 5% by weight of the total composition.
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The functional role of the silver coating agent is to form 'in use' a
protective
coating layer on any silverware components of the washload to which the
compositions of the invention are being applied. The silver coating agent
should
hence have a high affinity for attachment to solid silver surfaces,
particularly when
present in as a component of an aqueous washing and bleaching solution with
which the solid silver surfaces are being treated.
Suitable organic silver coating agents herein include fatty esters of mono- or
polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon
chain.
The fatty acid portion of the fatty ester can be obtained from mono- or poly-
carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon
chain.
Suitable examples of monocarboxylic fatty acids include behenic acid, stearic
acid,
oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic
acid,
butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and
(3,(f-
dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-
butyl-malonic acid, isocitric acid, citric acid, malefic acid, malic acid and
succinic
acid.
The fatty alcohol radical in the fatty ester can be represented by mono- or
polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
Examples of suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl
and
lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl
alcohol,
diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or
sorbitan.
Preferably, the fatty acid and/or fatty alcohol group of the fatty ester
adjunct
material have from 1 to 24 carbon atoms in the alkyl chain.
Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan
esters
wherein the fatty acid portion of the ester normally comprises a species
selected
from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
The glycerol esters are also highly preferred. These are the mono-, di- or tri-
esters of glycerol and the fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include: stearyl
acetate,
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41
palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and
tallowyl
proprionate. Fatty acid esters useful herein include: xylitol monopalmitate,
pentaerythritol monostearate, sucrose monostearate, glycerol monostearate,
ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters
include
sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan
monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan
dilaurate,
sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed
tallowalkyl sorbitan mono- and di-esters.
Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol
monobehenate, and glycerol distearate are preferred glycerol esters herein.
Suitable organic silver coating agents include triglycerides, mono or
diglycerides,
and wholly or partially hydrogenated derivatives thereof, and any mixtures
thereof.
Suitable sources of fatty acid esters include vegetable and fish oils and
animal fats.
Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil,
olive oil,
peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm
oil and
corn oil.
Waxes, including microcrystalline waxes are suitable organic silver coating
agents
herein. Preferred waxes have a melting point in the range from about
35°C to
about 110°C and comprise generally from 12 to 70 carbon atoms.
Preferred are
petroleum waxes of the paraffin and microcrystalline type which are composed
of
long-chain saturated hydrocarbon compounds.
Alginates and gelatin are suitable organic silver coating agents herein.
Dialkyl amine oxides such as C1~-C20 methylamine oxide, and dialkyl quaternary
ammonium compounds and salts, such as the C 12-C20 methylammonium halides
are also suitable.
Other suitable organic silver coating agents include certain polymeric
materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
700,000, polyethylene glycols (PEG) with an average molecular weight of from
600 to 10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone
and N-vinylimidazole, and cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose are examples of such
polymeric
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42
materials.
Certain perfume materials, particularly those demonstrating a high
substantivity for
metallic surfaces, are also useful as the organic silver coating agents
herein.
Polymeric soil release agents can also be used as an organic silver coating
agent.
Suitable polymeric soil release agents include those soil release agents
having: (a)
one or more nonionic hydrophile components consisting essentially of (i)
polyoxyethylene segments with a degree of polymerization of at least 2, or
(ii)
oxypropylene or polyoxypropylene segments with a degree of polymerization of
from 2 to 10, wherein said hydrophile segment does not encompass any
oxypropylene unit unless it is bonded to adjacent moieties at each end by
ether
linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and
from 1
to about 30 oxypropylene units, said hydrophile segments preferably comprising
at
least about 25% oxyethylene units and more preferably, especially for such
components having about 20 to 30 oxypropylene units, at least about 50%
oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3
oxyalkylene terephthalate segments, wherein, if said hydrophobe components
also
comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3
oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or
oxy
C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester)
segments,
preferably polyvinyl acetate, having a degree of polymerization of at least 2,
or
(iv} C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures
therein,
wherein said substituents are present in the form of C1-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a
combination of
(a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of from about 200, although higher levels can be used,
preferably
from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6
alkylene hydrophobe segments include, but are not limited to, end-caps of
polymeric soil release agents such as M03S{CH2)nOCH2CH20-, where M is
sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued
January 26, 1988 to Gosselink.
Polymeric soil release agents useful herein also include cellulosic
derivatives such
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43
as hydroxyether cellulosic polymers, copolymeric blocks of ethylene
terephthalate
or propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate, and the like. Such agents are commercially available and
include
hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release
agents for use herein also include those selected from the group consisting of
C1-
C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued
December 28, 1976 to Nicol, et al.
Soil release agents characterized by polyvinyl ester) hydrophobe segments
include
graft copolymers of polyvinyl ester), e.g., C1-C6 vinyl esters, preferably
polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as
polyethylene oxide backbones. See European Patent Application 0 219 048,
published April 22, 1987 by Kud, et al.
Another suitable soil release agent is a copolymer having random blocks of
ethyl
ene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular
weight of this polymeric soil release agent is in the range of from about
25,000 to
about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and
U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another suitable polymeric soil release agent is a polyester with repeat units
of
ethylene terephthalate units contains 10-15% by weight of ethylene
terephthalate
units together with 90-80% by weight of polyoxyethylene terephthalate units,
derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
Another suitable polymeric soil release agent is a sulfonated product of a
substantially linear ester oligomer comprised of an oligomeric ester backbone
of
terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone. These soil release agents are described fully in
U.S.
Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
Other suitable polymeric soil release agents include the terephthalate
polyesters of
U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic
end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988
to Gosselink, and the block polyester oligomeric compounds of U.S. Patent
4,702,857, issued October 27, 1987 to Gosselink. Other polymeric soil release
agents also include the soil release agents of U.S. Patent 4,877,896, issued
October 31, 1989 to Maldonado et al, which discloses anionic, especially sul
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44
foarolyl, end-capped terephthalate esters.
Another soil release agent is an oligomer with repeat units of terephthaloyl
units,
sulfoisoterephthaloyl units, oxyethyieneoxy and oxy-1,2-propylene units. The
repeat units form the backbone of the oligomer and are preferably terminated
with
modified isethionate end-caps. A particularly preferred soil release agent of
this
type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units,
oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to
about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-
ethanesulfonate.
A preferred organic silver coating agent is a 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 from 1:10 to 2:1,
preferably from 1:5 to 1:1. A paraffin oil meeting these characteristics,
having a
ratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by
Wintershall,
Salzbergen, Germany, under the trade name WINOG 70.
NitroQgn-containing corrosion inhibitor compounds
Suitable nitrogen-containing corrosion inhibitor compounds include imidazole
and
derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those
imidazole derivatives described in Czech Patent No. 139, 279 and British
Patent
GB-A-1,137,741, which also discloses a method for making imidazole compounds.
Also suitable as nitrogen-containing corrosion inhibitor compounds are
pyrazole
compounds and their derivatives, particularly those where the pyrazole is
substituted in any of the l, 3, 4 or 5 positions by substituents Rl, R3, R4
and RS
where R1 is any of H, CH20H, CONH3, or COCH3, R3 and RS are any of C1-
C2p alkyl or hydroxyl, and R4 is any of H, NH2 or N02.
Other suitable nitrogen-containing corrosion inhibitor compounds include
benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-S-mercapto-1,2,3,4-tetrazole,
thionalide, morpholine, melamine, distearylamine, stearoyl stearamide,
cyanuric
acid, aminotriazole, aminotetrazole and indazole.
Nitrogen-containing compounds such as amines, especially distearylamine and
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ammonium compounds such as ammonium chloride, ammonium bromide,
ammonium sulphate or diammonium hydrogen citrate are also suitable.
Mn(II) corrosion inhibitor compounds
The compositions may contain an Mn(II) corrosion inhibitor compound. The
Mn(II) compound is preferably incorporated at a level of from 0.005% to 5% by
weight, more preferably from 0.01 % to 1 %, most preferably from 0.02% to 0.4%
by weight of the compositions. Preferably, the Mn(II) compound is incorporated
at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to
50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any
bleaching solution.
The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated
forms. Suitable salts include manganese sulphate, manganese carbonate,
manganese phosphate, manganese nitrate, manganese acetate and manganese
chloride. The Mn(II) compound may be a salt or complex of an organic fatty
acid
such as manganese acetate or manganese stearate.
The Mn(II) compound may be a salt or complex of an organic ligand. In one
preferred aspect the organic ligand is a heavy metal ion sequestrant. In
another
preferred aspect the organic ligand is a crystal growth inhibitor.
Other corrosion inhibitor compounds
Other suitable additional cotTOSion inhibitor compounds include, mercaptans
and
diols, especially mercaptans with 4 to 20 carbon atoms including lauryl
mercaptan,
thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are
saturated
or unsaturated C 10-C20 fatty acids, or their salts, especially aluminium
tristearate.
The C 1 ~-C20 hydroxy fatty acids, or their salts, are also suitable.
Phosphonated
octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also
suitable.
Copolymers of butadiene and malefic acid, particularly those supplied under
the
trade reference no. 07787 by Polysciences Inc have been found to be of
particular
utility as corrosion inhibitor compounds.
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Total .available Oxy,Qen (Av0) Level
It has been found that, for optimal anti-silver tarnishing performance, the
level of
available oxygen in the present compositions, measured in units of % available
oxygen by weight of the composition, is preferably controlled; the Ievel of
available oxygen should hence preferably be in the range from 0.3% to 2.5%,
preferably from 0.5% to 1.7%, more preferably from 0.6% to 1.5%, most
preferably from 0.7% to 1.2%, measured according to the method described
hereunder.
Rate of Release of Av0
The rate of release of available oxygen is preferably also controlled; the
rate of
release of available oxygen from the compositions herein preferably should be
such
that, when using the method described hereinafter, the available oxygen is not
completely released from the composition until after 3.5 minutes, preferably
the
available oxygen is released in a time interval of from 3.5 minutes to 10.0
minutes,
more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0
minutes to 8.5 minutes.
Method for Measuring Level of Total Available Oxyaen (Av0) and Rate of
Release of Av0 in a Detergent Composition
Method
1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, and the
stirrer speed is selected to ensure that the product is evenly dispersed
through the
solution.
2. The detergent composition (typically 8g of product which has been sampled
down from a bulk supply using a Pascal sampler), is added and simultaneously a
stop clock is started.
3. The temperature control should be adjusted so as to maintain a constant
temperature of 20°C throughout the experiment.
4. Samples are taken from the detergent solution at 2 minute time intervals
for
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47
?0 minutes. starting after 1 minute, and are titrated by the "titration
procedure"
described below to determine the level of available oxygen at each point.
Titration Procedure
An aliquot from the detergent solution (above) and 2m1 sulphuric acid are
added into a stirred beaker
3. Approximately 0.2g ammonium molybdate catalyst (tetra hydrate form) are
added
3. 3mls of 10% sodium iodide solutionare added
4. Titration with sodium thiosulphate is conducted until the end point. The
end point can be seen using either of two procedures. First procedure consists
simply in seeing the yellow iodine colour fading to clear. The second and
preferred procedure consists of adding soluble starch when the yellow colour
is
becoming faint, turning the solution blue. More thiosulphate is added until
the
end point is reached (blue starch complex is decolourised).
The level of AvO, measured in units of % available oxygen by weight, for the
sample at each time interval corresponds to the amount of titre according to
the
following equation
Vol S203(ml) x Molarity (S203) x 8
Sample mass (g)
Av0 level is plotted versus time to determine the maximum level of AvO, and
the
rate of release of Av0
Controlled rate of release - means
A means may be provided for controlling the rate of release of oxygen bleach
to
the wash solution.
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Means for controlling the rate of release of the bleach may provide for
controlled
release of peroxide species to the wash solution. Such means could, for
example,
include controlling the release of any inorganic perhydrate salt, acting as a
hydrogen peroxide source, to the wash solution.
Suitable controlled release means can include coating any suitable component
with
a coating designed to provide the controlled release. The coating may
therefore,
for example, comprise a poorly water soluble material, or be a coating of
sufficient
thickness that the kinetics of dissolution of the thick coating provide the
controlled
rate of release.
The coating material may be applied using various methods. Any coating
material
is typically present at a weight ratio of coating material to bleach of from
1:99 to
1:2, preferably from 1:49 to 1:9.
Suitable coating materials include triglycerides (e.g. partially) hydrogenated
vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides,
microcrystalline
waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth
metal
sulphates, silicates and carbonates, including calcium carbonate and silicas.
A preferred coating material, particularly for an inorganic perhydrate salt
bleach
source, comprises sodium silicate of Si02 : Na20 ratio from 1.8 : 1 to 3.0 :
1,
preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a
level
of from 2% to 10%, {normally from 3% to S%) of Si02 by weight of the
inorganic perhydrate salt. Magnesium silicate can also be included in the
coating.
Any inorganic salt coating materials may be combined with organic binder
materials to provide composite inorganic salt/organic binder coatings.
Suitable
binders include the C 10-C20 alcohol ethoxylates containing from 5 - 100 moles
of
ethylene oxide per mole of alcohol and more preferably the C15-C20 P~~'
alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole
of
alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
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49
700.000 and polyethylene glycols (PEG) with an average molecular wei?ht of
from
600 to ~ x 106 preferably 1000 to 400,000 most preferably 1000 to 10,000 are
examples of such polymeric materials. Copolymers of malefic anhydride with
ethylene, methylvinyl ether or methacrylic acid, the malefic anhydride
constituting
at least 20 mole percent of the polymer are further examples of polymeric
materials
useful as binder agents. These polymeric materials may be used as such or in
combination with solvents such as water, propylene glycol and the above
mentioned C 10-C20 alcohol ethoxylates containing from 5 - 100 moles of
ethylene
oxide per mole. Further examples of binders include the C 10-C20 mono- and
diglycerol ethers and also the C 1 p-C2p fatty acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their
salts are other examples of binders suitable for use herein.
One method for applying the coating material involves agglomeration. Preferred
agglomeration processes include the use of any of the organic binder materials
described hereinabove. Any conventional agglomerator/mixer may be used
including, but not limited to pan, rotary drum and vertical blender types.
Molten
coating compositions may also be applied either by being poured onto, or spray
atomized onto a moving bed of bleaching agent.
Other means of providing the required controlled release include mechanical
means
for altering the physical characteristics of the bleach to control its
solubility and
rate of release. Suitable protocols could include compression, mechanical
injection, manual injection, and adjustment of the solubility of the bleach
compound by selection of particle size of any particulate component.
Whilst the choice of particle size will depend both on the composition of the
particulate component, and the desire to meet the desired controlled release
kinetics, it is desirable that the particle size should be more than 500
micrometers,
preferably having an average particle diameter of from 800 to 1200
micrometers.
Additional protocols for providing the means of controlled release include the
suitable choice of any other components of the detergent composition matrix
such
that when the composition is introduced to the wash solution the ionic
strength
environment therein provided enables the required controlled release kinetics
to be
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achieved.
Alkalinity system
The compositions preferably contain an alkalinity system containing sodium
silicate
having an Si02 : Na20 ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4,
most
preferably 2.0, present preferably at a level of less than 20%, preferably
from 1
to 15%, most preferably from 3% to 12% by weight of Si02. The alkali metal
silicate may be in the form of either the anhydrous salt or a hydrated salt.
The alkalinity system also preferably contains sodium metasilicate, present at
a
level of at least 0.4% Si02 by weight. Sodium metasilicate has a nominal SiO~_
Na20 ratio of 1Ø The weight ratio of said sodium silicate to said sodium
metasilicate, measured as Si02, is preferably from 50:1 to 5:4, more
preferably
from 15:1 to 2:1, most preferably from 10:1 to 5:2.
Heav~r metal ion seq_uestrant
The detergent compositions of the invention preferably contain as an optional
component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is
meant herein components which act to sequester (chelate) heavy metal ions.
These
components may also have calcium and magnesium chelation capacity, but
preferentially they show selectivity to binding heavy metal ions such as iron,
manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to
20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and
most preferably from 0.5% to 5% by weight of the compositions.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphoric 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 organic
phosphonates,
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~1
such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among
the above species are diethyiene triamine penta (methyiene phosphonate),
ethylene
diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene
phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic
acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid,
ethylenediamine
diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts
thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof. Preferred EDDS compounds are the free acid form and the
sodium or magnesium salt or complex thereof.
C stal owth inhibitor component
The detergent compositions preferably contain a crystal growth inhibitor
component, preferably an organodiphosphonic acid component, incorporated
preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by
weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which
does not contain nitrogen as part of its chemical structure. This definition
therefore excludes the organo aminophosphonates, which however may be included
in compositions of the invention as heavy metal ion sequestrant components.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more
preferably a C2 diphosphonic acid, such as ethyiene diphosphonic acid., or
most
preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in
partially or fully ionized form, particularly as a salt or complex.
Enzyme Stabilizin~S~stem
Preferred enzyme-containing compositions herein may comprise from about
0.001% to about 10%, preferably from about 0.005% to about 8%, most
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preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing
system. The enzyme stabilizing system can be any stabilizing system which is
compatible with the "detersive enzyme. Such stabilizing systems can comprise
calcium ion, boric acid, propylene glycol, short chain carboxylic acid,
boronic
acid, chlorine bleach scavengers and mixtures thereof. Such stabilizing
systems
can also comprise reversible enzyme inhibitors, such as reversible protease
inhibitors.
Organic polymeric compound
Organic polymeric compounds may be added as preferred components of the
compositions in accord with the invention. By organic polymeric compound it is
meant essentially any polymeric organic compound commonly used as dispersants,
and anti-redeposition and soil suspension agents in detergent compositions.
Organic polymeric compound is typically incorporated in the detergent
compositions of the invention at a level of from 0.1 % to 30%, preferably from
0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
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 polyacrylates of
molecular weight 2000-10000 and their copolymers with 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 are the copolymers of acrylic acid and malefic anhydride having a
molecular weight of from 20,000 to 100,000.
Preferred commercially available acrylic acid containing polymers having a
molecular weight below 15,000 include those sold under the tradename Sokalan
PA30, PA20, PA15, PA 10 and Sokalan CP 10 by BASF GmbH, and those sold
under the tradename Acusol 45N by Rohm and Haas.
Preferred acrylic acid containing copolymers include those which contain as
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53
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 -
(CR~-CRl(CO-O-R3)]- wherein at least one of the substituents R1, R~ or R3,
preferably Rl or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R1 or R~
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
methacrylic acid monomer). The most preferred copolymer of this type has a
molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and
40% to 20% by weight of methacrylic acid.
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.
Clad softenin~ystem
The detergent compositions may contain a clay softening system comprising a
clay
mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite
clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and
4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name
of the Procter and Gamble Company describe suitable organic polymeric clay
flocculating agents.
Lime soap dispersant compound
The compositions of the invention may contain a lime soap dispersant compound,
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. Preferred
lime soap disperant compounds are disclosed in PCT Application No.
W093108877.
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Suds suppressing system
The compositions of the invention, when formulated for use in machine washing
compositions, preferably comprise a suds suppressing system present at a level
of
from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1%
to 5% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known antifoam compound, including, for example silicone antifoam compounds,
2-alkyl and alcanol antifoam compounds. Preferred suds suppressing systems and
antifoam compounds are disclosed in PCT Application No. W093/08876 and EP-
A-705 324.
Polymeric dye transfer inhibitin~asents
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, polyvinylpyrrolidonepolymers or combinations thereof.
Optical brightener
The detergent compositions herein also optionally contain from about 0.005% to
5% by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural
formula:
Ri R2
N H H N
N OON O C-C O N \O N
~N H H N
R~ S03M S03M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
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5~
hydroxyethyl; Ro is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-
methylamino> morphilino, chloro and amino; and M is a salt-forming cation such
as sodium or potassium.
When in the above formula, R 1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
tradename
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the
preferred hydrophilic optical brightener useful in the detergent compositions
herein.
When in the above formula, Rl is anilino, R2 is N-?-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)aminoJ2,2'-
stilbenedisulfonic acid disodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy
Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anilino-b-morphilino-s-triazine-2-
yl)aminoJ2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX by Ciba
Geigy Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into compositions in
accordance with the present invention. Suitable cationic fabric softening
agents
include the water insoluble tertiary amines or dilong chain amide materials as
disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of
from
0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ing_,redients
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56
Other optional ingredients suitable for inclusion in the compositions of the
invention include perfumes, colours and filler salts, with sodium sulfate
being a
preferred filler salt.
pH of the compositions
The detergent compositions used in the present invention are preferably not
formulated to have an unduly high pH, in preference having a pH measured as a
1% solution in distilled water of from 8.0 to 12.5, more preferably from 9.0
to
11.8, most preferably from 9.5 to 11.5.
Machine dishwashing method
Any suitable methods for machine washing or cleaning soiled tableware,
particularly soiled silverware are envisaged.
A preferred machine dishwashing method comprises treating soiled articles
selected
from crockery, glassware, hollowware, silverware and cutlery and mixtures
thereof, with an aqueous liquid having dissolved or dispensed therein an
effective
amount of a detergent tablet composition in accord with the invention. By an
effective amount of the detergent tablet composition it is meant from 8g to
60g of
product dissolved or dispersed in a wash solution of volume from 3 to 10
litres, as
are typical product dosages and wash solution volumes commonly employed in
conventional machine dishwashing methods. Preferably the detergent tablets are
from 15g to 40g in weight, more preferably from 20g to 35g in weight.
Laundry washins method
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein
an effective amount of a machine laundry detergent tablet composition in
accord
with the invention. By an effective amount of the detergent tablet composition
it
is meant from 40g to 3008 of product dissolved or dispersed in a wash solution
of
volume from S to 65 litres, as are typical product dosages and wash solution
volumes commonly employed in conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method.
The dispensing device is charged with the detergent product, and is used to
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57
introduce the product directly into the drum of the washing machine before the
commencement of the wash cycle. Its volume capacity should be such as to be
able to contain sufficient detergent product as would normally be used in the
washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement
of the wash cycle of the washing machine water is introduced into the drum and
the
drum periodically rotates. The design of the dispensing device should be such
that
it permits containment of the dry detergent product but then allows release of
this
product during the wash cycle in response to its agitation as the drum rotates
and
also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may
possess a number of openings through which the product may pass.
Alternatively,
the device may be made of a material which is permeable to liquid but
impermeable to the solid product, which will allow release of dissolved
product.
Preferably, the detergent product will be rapidly released at the start of the
wash
cycle thereby providing transient localised high concentrations of product in
the
drum of the washing machine at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container integrity is maintained in both the dry state and during the wash
cycle.
Alternatively, the dispensing device may be a flexible container, such as a
bag or
pouch. The bag may be of fibrous construction coated with a water impermeable
protective material so as to retain the contents, such as is disclosed in
European
published Patent Application No. 0018678. Alternatively it may be formed of a
water-insoluble synthetic polymeric material provided with an edge seal or
closure
designed to rupture in aqueous media as disclosed in European published Patent
Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form
of water frangible closure comprises a water soluble adhesive disposed along
and
sealing one edge of a pouch formed of a water impermeable polymeric film such
as
polyethylene or polypropylene.
CA 02314484 2000-06-12 ,
WO 99/31215 PCTIIB98/02050
58
Examples
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
STPP : Sodium tripolyphosphate
Citrate : Tri-sodium citrate dihydrate
Bicarbon : Sodium hydrogen carbonate
ate
Carbonat : Anhydrous sodium carbonate having average particle size of 4?S~m to
a 700pm and dissolving in approximately 180 seconds according to the
dissolution test method described herein
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio = 1.6-3.2) having
average particle size of SOOpm to 700pm and dissolving in
approximately 210 seconds according to the dissolution test method
described herein
Metasili : Sodium metasilicate (Si02:Na20 ratio = 1.0)
cate
PB 1 Anhydrous sodium perborate monohydrate
:
PB4 : Sodium perborate tetrahydrate of nominal fonmula
NaB02.3H20.H202
PercarboAnhydrous sodium percarbonate of nominal formula
.
pate 2.Na2C03,3H202
PlurafacC 13-C 15 mixed ethoxylatedlpropoxylated fatty
: alcohol with an
average degree of ethoxylation of 3.8 and an average
degree of
propoxylation of 4.5, sold under the tradename
Plurafac
TAED Tetraacetyl ethylene diamine
:
NaHED Granular sodium Ethane I-hydroxy-1,1-diphosphonate
. having average
P particle size of between 400wm and SOOpm and dissolving
in
approximately 60 seconds according to the dissolution
test Fnethod
described herein.
DETPM Diethyltriamine penta (methylene) phosphonate,
: marketed by
P monsanto under the tradename bequest 2060
MnTAC Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane.
:
N
CA 02314484 2000-06-12
WO 99/3121 ~ PCT/IB98/02050
~9
PAAC Pentaamine acetate cobalt (III) salt
:
ParaffinParaffin oil sold under the tradename Winog 70
: by Wintershall.
ProteaseProteolytic enzyme
:
Amylase Amylolytic enzyme.
:
BTA : Benzotriazole
PA30 Polyacrylic acid of average molecular weight approximately
: 4,500
MA/AA Randon copolymer of 4:1 acrylatelmaleate, average
: molecular weight
about 70,000
480N Random copolymer of 7:3 acrylate/methacrylate,
: average molecular
weight about 3,500
SulphateAnhydrous sodium sulphate having average particle
: size of from 425p
m to 700pm and dissolving in 90 seconds according
to the dissolution
test method described herein
pH : Measured as a i % solution in distilled water
at 20C
In the following examples all levels are quoted as % by weight of the
composition:
The following tablet detergent composition examples A to F in accord with the
present invention were prepared by compression of a granular dishwashing
detergent
composition at a pressure of l3KNicm2 using a standard I2 head rotary press:
A B C D E F
STPP - 48.80 49.2 34.0 - 46.8
0 0
Citrate 26.40 - - - 31.1 -
0
Carbonate - 5.0 14.0 15.4014.4 23.0
0
Silicate 26.40 14.80 15.0 10.6017.7 2.40
0
Protease 1.76 2.20 1.26 1.0 1.60 0.40
Am lase 1.20 I.50 1.50 0.85 2.0 0.30
PB 1 1.56 7.69 12.2 12.2 15.7
0 0
PB4 6.92 - - - - 14.4
0
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WO 99/31215 PCT/1898/02050
60
Nonionic 1.~0 2.0 1.~0 2.2 0.80 6.30
P AAC - - 0.01 0.009 - -
6
MnTACN - - - - 0.00 -
7
TAED 4.33 2.50 - - 1.30 1.84
HEDP 0.67 1.2 1.8 0.92 0.89 0.40
DETPMP 0.65 - - - - -
Paraffin 0.42 0.50 0.5 0.55 - -
BTA 0.24 0.30 0.3 0.33 - -
PA30 3.2 - - - - -
MA/AA - - - - 4.51 0.55
Perfume - - 0.05 0.05 0.20 0.2
Sul hate 24.75 13.0 2.67 16.89 9.7 3.41
Misclwater to
balance
wei ht of tablet 25 25 20 30 18 20
H ( 1 % solution)10.60 10.6010.7 10.8 10.9 1
I
.2
