Note: Descriptions are shown in the official language in which they were submitted.
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Detergent Compositions
Technical Field
A process for preparing a detergent composition, said process
comprising spray drying a slurry of organic and inorganic material,
weight ratio of between 0.34 and 0.64 and said slurry having a
moisture content of between 2S % and SO % .
Background
Cleaning compositions designed for a number of different functions are
well known in the art, as reflected by the number of patents in this
field. Traditionally, such cleaning compositions comprise a number of
organic and inorganic materials, including for example, a surfactant
and a builder. Inorganic materials commonly employed in, especially
granular, detergent compositions include for example an alkali metal or
alkaline earth metal sulphate. Sulphate, despite being a common
component, does not perform any detersive function and is, in the
majority of instances, employed as a filler or bulking agent. It is thus
the aim of the present invention to provide a suitable detergent
composition comprising a reduced amount of sulphate.
Previously, it has been found that reducing or eliminating the sulphate
content of a detergent composition results in the detergent composition
being predisposed to ' caking' . Caked products do not flow efficiently
and are thus not acceptable to the consumer.
Surprisingly, it has been found that reduced sulphate detergent
compositions prepared by the process of the present invention are less
predisposed to caking than previously described reduced or nil-sulphate
compositions.
The applicants have surprisingly found that caking can be minimised
by formulating the detergent composition such that the weight ratio of
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organie.to inorganic material and the moisture content of the slurry of
organic and inorganic material in the crutcher (crutcher mix moisture
or CMM) are maintained within a predefined range. In a preferred
aspect the detergent compositions prepared by the process of the
present invention have density less than 599g/1.
It is further believed that an increase in CMM translates into improved
spraying of the slurry into the spray drying tower or atomisability.
Whilst it may be expected that this would reduce particle size and
therefore increase caking problems, we have surprisingly found that
selecting the organic to inorganic ratio and CMM within the predefined
limits described herein, potential for caking problems are reduced.
An additional benefit incurred from improved atomisability is the
reduction in density of the blown powder collected at the base of the
drying tower. The density of the blown powder can also be reduced by
injecting air into the organic/inorganic premix slurry. Air injection has
an effect akin to steam puffing. An advantage associated with the
reduction in density of the detergent compositions prepared by the
process of the present invention, is the cost saving incurred by
reducing the amount of a component that has little or no detersive
action and thus a proportional reduction in transportation cost.
Summary of the invention
According to the present invention there is provided a process for preparing a
detergent composition, said process comprising spray drying a slurry of
organic
and inorganic material, wherein air is injected into the slurry of organic and
inorganic
material and the ratio of organic to inorganic material is from 0.34 to 0.64,
and
said slurry having a moisture content of between 25% and 50%.
Detailed description of the invention
Organic Material
The detergent compositions prepared by the process of the present
invention comprise an organic material. Essentially any organic
material is envisaged for use herein. The preferred organic materials
used herein are surfactants.
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Surfactant
The detergent compositions of the invention contain one or more
surfactants selected from anionic, nonionic, non-ester cationic,
ampholytic, amphoteric and zwitterionic surfactants and mixtures
thereof. Preferred surfactants for use herein are the anionic
surfactants, most preferably Linear alkylbenzene sulfonates (LAS)
described below.
The surfactant is preferably present as a component of a surfactant
system at a level of from 0.1 % to 50 % , more preferably from 1 % to
40 % by weight, most preferably from 5 % to 30 % by weight of the
surfactant system.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic
classes, and species of these surfactants, is given in U.S.P. 3,929,b78
issued to Laughlin and Heuring on December 30, 1975. Further
examples are given in "Surface Active Agents and Detergents" (Vol. I
and II by Schwartz, Perry and Berch) . A list of suitable cationic
surfactants is given in U.S.P. 4,259,217 issued to Murphy on March
31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in combination with one or more anionic and/or
nonionic surfactants.
Anionic surfactant
Anionic surfactants are preferred components of the compositions
prepared by the process of the present invention. 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 , di- and
triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate surfactants.
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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 12-C 18 monoesters) diesters of
sulfosuccinate (especially saturated and unsaturated C6-C 14 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 sulfonate surfactant
Preferred anionic surfactants include the anionic sulfonate surfactants
suitable for use herein include the salts of CS-C20 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 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
hydroxyalkyl) 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 C 12-C 14 linear chain alkyl
sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the C 10-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
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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 ethoxymonosulfate surfactants.
Such mixtures have been disclosed in PCT Patent Application No. WO
93/18124.
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 polyethoxy polycarboxylate
surfactants include those having the formula RO-(CHR1-CHR2-O)-R3
wherein R is a C6 to C 1 g alkyl group, x is from 1 to 25, R 1 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.
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Alkali metal sarcosinate surfactant
Other suitable 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 alkenyl group, R1 is a C1-Cq, 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.
Alkoxylated nonionic surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein.
The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of
the nonionic condensates of alkyl phenols, nonionic ethoxylated
alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic
ethoxylate/propoxylate condensates with propylene glycol, and the
nonionic ethoxylate condensation products with propylene
oxide/ethylene diamine adducts.
Nonionic alkoxylated alcohol surfactant
The condensation products of aliphatic alcohols with from 1 to 25
moles of alkylene oxide, particularly ethylene oxide and/or propylene
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 2 to 10 moles of
ethylene oxide per mole of alcohol.
Nonionic ~olyh~~fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having
the structural formula R2CONR1Z wherein : R1 is H, C1-C4
hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or
a mixture thereof, preferable C 1-C4 alkyl, more preferably C 1 or C2
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alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a CS-C31
hydrocarbyl, preferably straight-chain CS-C 19 alkyl or alkenyl, more
preferably straight-chain C9-C17 alkyl or alkenyl, most preferably
straight-chain C 11-C 17 alkyl or alkenyl, or mixture thereof; and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least
3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z
preferably will be derived from a reducing sugar in a reductive
amination reaction; more preferably Z is a glycityl.
Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula:
R6CON{R7)2 wherein R6 is an alkyl group containing from 7 to 21,
preferably from 9 to 17 carbon atoms and each R7 is selected from the
group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -
(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic allcylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S.
Patent 4,565,647, Llenado, issued January 21, 1986, having a
hydrophobic group containing from 6 to 30 carbon atoms and a
polysaccharide, e.g., a polyglycoside, hydrophilic group containing
from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the
alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from
0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived
from glucose.
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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 10-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-Clg hydrocarbyl group, each
R1 is typically Cl-C3 alkyl, and R2 is a C1-CS hydrocarbyl group.
Preferred betaines are C 12_ 18 dimethyl-ammonio hexanoate and the
C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
Complex betaine surfactants are also suitable for use herein.
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Cationic surfactants
Suitable cationic ester surfactants used in this invention are preferably
water dispersible compound having surfactant properties comprising at
least one ester (ie -COO-) linkage and at least one cationically charged
group.
Other suitable cationic surfactants include the quaternary ammonium
surfactants selected from mono C6-C 16, preferably C6-C 10 N-alkyl or
alkenyl ammonium surfactants wherein the remaining N positions are
substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other
suitable cationic ester surfactants, including choline ester surfactants,
have for example been disclosed in US Patents No.s 4228042, 4239660
and 4260529.
Inorganic Material
The compositions prepared by the process of the present invention also
include an inorganic material. Essentially any inorganic material is
envisaged for use herein. Preferred inorganic marterials used herein
are builders, alkali metal and alkali earth metal silicates and sulphates.
The organic to inorganic ratio of the composition prepared by the
process of the present invetnion are between 0.34 and 0.6, preferably
between 0.343 and 0.555, most preferably between 0.36 and 0.48.
Water-soluble builder compound
The compositions prepared by the process of the present invention
preferably contain a detergency builder compound. Suitable builder
compound include water-soluble 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.
Suitable water-soluble builder compounds include the water soluble
monomeric polycarboxylates, or their acid forms, homo or
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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, borates,
phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric 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 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, diglycolic 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 CA 973771, 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. 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
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citrate/~itric 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 are useful water-soluble builders herein.
Suitable 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
Other suitable builder compounds include the partially soluble or
insoluble builder compounds, 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 % weight of the composition.
Examples of largely water insoluble builders include the «,dium
aluminosilicates.
Suitable aluminosilicate zeolites have 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 1.0 to 0.5 and x is at least 5, preferably from 7.5
to 276, more preferably from 10 to 264. The aluminosilicate material
are in hydrated form and are preferably crystalline, containing from
% 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. Zeolite A has the formula
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Na 12 ~'A102) 12 (5i02) 12~ . xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula
Nag6 [(A102)g6(Si02) 106 ~ 276 H20. Zeolite MAP, as disclosed in
EP-B-384,070 is a preferred zeolite builder herein.
Alkalinit,~vstem
Additional suitable inorganic materials also inlcude those used as
components of the alkalinity system. The alkalinity system were
present is at levels of from 1.5 % to 95 % , preferably from 5 % to 60 % ,
most preferably from 10 % to 40 % by weight of the composition
Components of an alkalinity system comprise components capable of
providing alkalinity species in solution. By alkalinity species it is
meant for the purposes of this invention: carbonate, bicarbonate,
hydroxide and the various silicate anions. Such alkalinity species can
be formed for example, when alkaline salts selected from alkali metal
or alkaline earth carbonate, bicarbonate, hydroxide or silicate,
including crystalline layered silicate, salts and any mixtures thereof are
dissolved in water. Alkali metal silicate salts are preferred components
of the detergent Impositions prepared herein.
Sul hate
The compositions prepared by the process of the present invention
preferably contain an alkali metal or alkali earth metal sulphate. A
preferred sulphate used herein is anhydrous sodium sulphate.
Preparation of the Detergent composition
The compositions of the present invention are prepared in a two stage
conventional spray drying process. Stage one comprises mixing the
organic and inorganic materials in a conventional large blender-type
piece of equipment, commonly known as a crutcher. The resulting
premix is in the form of a slurry having a moisture content (crutcher
mix moisture or CMM) of between 25 % and 50 % , preferably between
30 and 45 % , most preferably between 34 % and 43 % . The slurry is
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pumped to a height, such that it can be sprayed into the spray drying
tower of stage two.
The spray drying tower is heated to between 80 and 350°C. As the
organic and inorganic materials in the slurry fall in the tower, moisture
is driven off. Eventually particles of organic and inorganic material
collect at the base of the tower. Particles formed in the spray drying
tower are known as blown powder. In an additional stage, any
remaining components of the detergent composition may be dry mixed
with or sprayed onto the blown powder.
All equipment used in the crutching and spray drying process are
conventional. Variations of this process are also envisaged. In a
preferres embodiment of the present invention air is injected into the
crutcher mix before it is sprayed into the spray drying tower.
Additional detergent components
The additional organic or inorganic detergent components listed below
may be incorporated into the detergent composition. Where the
additional components are included as part of the slurry intended for
forming the blown powder, they are also to be included for calculation
of the organic to inorganic ratio.
The detergent compositions prepared by the process of the present
invention may contain a variety of additional detergent components.
The precise nature of these components, and levels of incorporation
thereof will depend on the physical form of the composition, and the
precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more
detergent components selected from additional surfactants, additional
builders, alkalinity system, bleach, organic polymeric compounds,
enzymes, enzyme stabilising system, suds suppressors, lime soap
dispersants, soil suspension and anti-redeposition agents and corrosion
inhibitors.
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Organic peroxyacid bleaching system
A optional feature of detergent compositions prepared herein, is an
organic peroxyacid bleaching system. In one preferred execution the
bleaching system 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 execution 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.
inor anic perhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen
peroxide. These salts are normally incorporated in the form of the
alkali metal, preferably sodium salt at a level of from 1 % to 40 % by
weight, more preferably from 2 % to 30 % by weight and most
preferably from 5 % to 25 % by weight of the 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. Suitable coatings comprise
inorganic salts such as alkali metal silicate, carbonate or borate salts or
mixtures thereof, or organic materials such as waxes, oils, or fatty
soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form
of the monohydrate of nominal formula NaB02H202 or the
tetrahydrate NaB02H202.3H20.
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Alkali metal percarbonates, particularly sodium percarbonate are
preferred perhydrates herein. Sodium percarbonate is an addition
compound having a formula corresponding to 2Na2C03.3H202, and
is available commercially as a crystalline solid.
Potassium peroxymonopersulfate is another inorganic perhydrate salt
of use in the detergent compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with
hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
Generally peroxyacid bleach precursors may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such
that on perhydroloysis the structure of the peroxyacid produced is
O
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
15 % by weight, most preferably from 1.5 % to 10 % by weight of the
detergent 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.
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Leaving roups
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). However, if L is too reactive, this activator will
be difficult to stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
Y R3 R3Y
-O ~ , -O ~ Y , and -O
O O
-N-C-R~ II
-N-C -C H-R4
' ~ ,
I R3 Y
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O O Y O
C H2-C ~--C w
_O-C-R~ -N\C,NRa _N~C/NR4
' II II
O O
3
R O Y
-O-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, and Y is H or a solubilizing
group. Any of R 1, R3 and R4 may be substituted by essentially any
functional group including, for example alkyl, hydroxy, alkoxy,
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I7
halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium
groups
The preferred solubilizing groups are -SO -M + , -CO -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 canon 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.
A~l nercarboxylic acid bleach nrecursc,~s
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,N1NI 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, 2 and 6 carbon
atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
Other preferred alkyl percarboxylic acid precursors include sodium
3,5,5-tri-methyl hexanoyioxybenzene sulfonate (iso-NOBS), sodium
nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene
sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl perox acid precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable
herein, including those of the following general formulae:
R~ -C-N-R2-C-L R~ -N-C-R2-C-L
O R5 O or R5 O O
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
18
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an
alkylene 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. Amide substituted bleach activator
compounds of this type are described in EP-A-0170386.
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, and the benzoylation products of sorbitol,
glucose, and all saccharides with benzoylating agents, and those of the
imide type including N-benzoyl succinimide, tetrabenzoyl ethylene
diamine and the N-benzoyl substituted ureas. Suitable imidazole type
perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl
benzimidazole. Other useful N-acyl group-containing perbenzoic acid
precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and
benzoyl pyroglutamic acid.
Cationic perox ay cid 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
ammmonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the solid
detergent compositions as a salt with a suitable anion, such as a halide
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
CA 02269475 2002-02-14
19
precurs:m compound may be 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; U.K. 1,382,594; EP 475,512, 458,396 and
284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in
WO 95/29160, and United States Patent Nos. 5,686,015; 5,460,747;
5,578,136 and 5,584,888.
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. Preferred cationic peroxyacid precursors of the N-acylated
caprolactam class include the trialkyl ammonium methylene benzoyl
caprolactams and the trialkyl ammonium methylene alkyl
caprolactams.
Benzoxazin organic peroxacid 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
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
CA 02269475 2002-02-14
P~eformed or anic perox, acid
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 1 % to 15 % by weight, more preferably from 1 % to 10 % by
weight of the 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 R5 O or
R~ -N-C-R2-C-OOH
R5 10
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. Amide substituted organic
peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides,
especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid
and diperoxyhexadecanedioc acid. and diperazelaic acid, and
diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also
suitable herein.
Bleach catalwst
The compositions optionally contain a transition metal containing
bleach catalyst. One suitable type of bleach catalyst is a catalyst system
comprising a heavy metal canon of defined bleach catalytic activity,
such as copper, iron, cobalt or manganese canons, an auxiliary metal
cation having little or no bleach catalytic activity, such as zinc or
aluminum canons, and a sequestrant having defined stability constants
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
21
for the .catalytic and auxiliary metal cations, particularly
ethylenediaminetetraacetic acid, ethylenediaminetetre
{methylenephosphonic acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. 4,430,243.
Other 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)2-(PF6}2, MnIII2(u-O) 1 (u-OAc)2( 1,4, 7-
trimethyl-1,4,7-triazacyclononane}2-(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2_(1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(C104)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-tetramethyl-1,4,7-
triazacyclononane, and mixtures thereof.
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). Still another.ry ne 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. Other examples include binuclear Mn complexed with
tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u_
O}2MnIVN4)+and [BipY2MnIII(u_p}2MnIVbipY2)-(C104}3.
Further suitable bleach catalysts are described, for example, in
European patent application 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),
CA 02269475 2002-02-14
22
U.S. 4,'119,557 (ferric complex catalyst), German Pat. specification
2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-
containing salts), U.S. 4,430,243 (chelants with manganese canons and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
E_nzyme
Suitable enzymatic materials include the commercially available
lipases, cutinases, amylases, neutral and alkaline proteases, esterases,
cellulases, pectinases, lactases and peroxidases conventionally
incorporated into detergent compositions. Preferred enzymes are
discussed in US Patents 3,519,570 and 3,533,139.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective
amount" . The term "cleaning effective amount" refers to any amount
capable of producing a cleaning, stain removal, whitening,
deodorizing, or freshness improving effect on substrates. In practical
terms for current commercial preparations, typical amounts are up to 5
mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per
gram of the detergent composition. Stated otherwise, the compositions
herein will typically comprise from 0.001 % to 5 % , preferably from
0.01 % to 1 % by weight of a commercial enzyme preparation.
Preferred commercially available protease enzymes include those sold
under the trademarks Alcalase, Savinase, Primase, Durazym, and
Esperase by Novo Industries A/S (Denmark), those sold under the
trademarks Maxatase, Maxacal and Maxapem by Gist-Brocades, those
sold by Genencor International, and those sold under the trademarks
Opticlean and Optimase by Solvay Enzymes. As well as Protease A as
disclosed in EP 130,756 A, January 9, 1985 and Protease B as
disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A,
January 9, 1985. 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.
CA 02269475 2002-02-14
23
Other preferred proteases include those of WO 95/10591 A to Procter
& Gamble. When desired, a protease having decreased absorption and
increased hydrolysis is available as described in WO 95/07791 to
Procter and Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 94/25583 to Novo.
In more detail, an especially 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, +210, +216, +217, +218, +222, +260,
+265, and/or +274 according to the numbering of Bacillus
amyloliguefaciens subtilisin, as described in the patents of
A. Baeck, et al, entitled "Protease-Containing Cleaning Compositions" '
having US Patent No. 5,679,630, and C. Ghosh, et al, "Bleaching
Compositions Comprising Protease Enzymes" having US Patent No.
5,677,272.
Protease enzyme may be incorporated into the compositions in
accordance with the invention at a level of from 0.0001 % to 4 % active
enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a
special strain of B licheniformis, described in more detail in GB-
1,269,839 (Novo). Preferred commercially available amylases include
for example, those sold under the trademark Rapidase by Gist-
Brocades, and those sold under the trademarks Termamyl fungamyl and
BAN by Novo Industries A/S.
Engineering of enzymes for improved stability, e.g., oxidative
stability, is known. See, for example J. Biological Chem., Vol. 260,
No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of
CA 02269475 2002-02-14
24
the present compositions can make use of amylases having improved
stability in detergents such as automatic dishwashing types, especially
improved oxidative stability as measured against a reference-point of
TERMAMYL~ in commercial use in 1993. These preferred amylases
herein share the characteristic of being "stability-enhanced" amylases,
characterized, at a minimum, by a measurable improvement in one or
more of: oxidative stability, e.g., to hydrogen peroxide /
tetraacetylethylenediamine in buffered solution at pH 9-10; thermal
stability, e.g., at common wash temperatures such as about 60°C; or
alkaline stability, e.g., at a pH from about 8 to about 11, measured
versus the above-identified reference-point amylase. Stability can be
measured using any of the art-disclosed technical tests. See, for
example, references disclosed in WO 94/02597. Stability-enhanced
amylases can be obtained from Novo or from Genencor International.
One class of highly preferred amylases herein have the commonality of
being derived using site-directed mutagenesis from one or more of the
Bacillus amylases, especially the Bacillus a-amylases, regardless of
whether one, two or multiple amylase strains are the immediate
precursors. Oxidative stability-enhanced amylases vs. the above-
identified reference amylase are preferred for use, especially in
bleaching, more preferably oxygen bleaching, as distinct from chlorine
bleaching, detergent compositions herein. Such preferred amylases
include (a) an amylase according to the above-identified WO
94/02597, Novo, Feb. 3, 1994, as further illustrated by a mutant in
which substitution is made, using alanine or threonine, preferably
threonine, of the methionine residue located in position 197 of the B.
licheniformis alpha-amylase, known as TERMAMYL~, or the
homologous position variation of a similar parent amylase, such as B.
amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b) stability-
enhanced amylases as described by Genencor International in a paper
entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th
American Chemical Society National Meeting, March 13-17 1994, by
C. Mitchinson. Therein it was noted that bleaches in automatic
dishwashing detergents inactivate alpha-amylases but that improved
oxidative stability amylases have been made by Genencvr from B
licheniformis NCIB8061. Methionine (Met) was identified as the most
likely residue to be modified. Met was substituted, one at a time, in
CA 02269475 2002-02-14
positions 8, 15, 197, 256, 304, 366 and 438 leading to specific
mutants, particularly important being M 197L and M 197T with the
M 197T variant being the most stable expressed variant. Stability was
measured in CASCADE~ and SUNLIGHT~; (c) particularly
preferred amylases herein include amylase variants having additional
modification in the immediate parent as described in WO 95/10603 A
and are available from the assignee, Novo, as DURAMYL~. Other
particularly preferred oxidative stability enhanced amylase include
those described in WO 94/18314 to Genencor International and WO
94/02597 to Novo. Any other oxidative stability-enhanced amylase can
be used, for example as derived by site-directed mutagenesis from
known chimeric, hybrid or simple mutant parent forms of available
amylases. Other preferred enzyme modifications are accessible. See
WO 95/09909 A to Novo.
Other amylase enzymes include those described in WO 95/26397.
Specific amylase enzymes for use in the detergent compositions of the
present invention include a-amylases characterized 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. (Such Phadebas~ a-amylase activity assay is described at
pages 9-10, WO 95/26397.) Also included herein are a-amylases
which are at least 80% homologous with the amino acid sequences
shown in the SEQ ID listings in the references. Amylase enzyme may
be incorporated into the composition in accordance with the invention
at a level of from 0.0001 % to 2 % active enzyme by weight of the
composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of
from 0.0001 % to 2 % by weight, preferably 0.001 % to 1 % by weight,
most preferably from 0.001 % to 0.5 % by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for
example, from a lipase producing strain of Humicola sp.,
Thermom.~ces sp. or Pseudomonas sp. including Pseudomonas
CA 02269475 2002-02-14
26
~seudoalcaligenes or Pseudomas fluorescens. Lipase from chemically
or genetically modified mutants of these strains are also useful herein.
A preferred lipase is derived from Pseudomonas pseudoalcaligenes,
which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from
Humicola lanuginosa and expressing the gene in Asper illus oryza, as
host, as described in European Patent Application, EP-A-0258 068,
which is commercially available from Novo Industri A/S, Bagsvaerd,
Denmark, under the trade mark Lipolase. This lipase is also described
in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Cutinase enzymes suitable for use herein are described in WO 88/09367
A to Genencor.
Peroxidase enzymes may be used in combination with oxygen sources;
e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution
bleaching" or prevention of transfer of dyes or pigments removed from
substrates during the wash to other substrates present in the wash
solution. Known peroxidases include horseradish peroxidase,
ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed in WO
89/09813 A to Novo.
Enzyme Stabilizing S, s~~ tem
A preferred component of enzyme-containing compositions is an
enzyme stabilising system. When present the enzyme stabilising system
is at levels of from 0.001 % to 10 % , preferably from 0.005 % to 8 % ,
most preferably from 0.01 % to 6 % , by weight of the composition.
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.
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
27
Heavy metal ion sequestrant
The detergent compositions prepared by the process 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.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene
phosphonates), alkali metal ethane 1-hydroxy disphosphonates and
nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta
(methylene 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.
Other suitable heavy metal ion sequestrants for use herein are
iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
28
glycery~ imino diacetic acid, described in EP-A-317,542 and EP-A-
399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and
aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid
sequestrants described in EP-A-516,102 are also suitable herein. The ~i
-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic
acid-N-monoacetic acid and iminodisuccinic acid sequestrants
described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-
510,331 describes suitable sequestrants derived from collagen, keratin
or casein. EP-A-528, 859 describes a suitable alkyl iminodiacetic acid
sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-
tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid
(GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also
suitable.
Organic polymeric compound
Organic polymeric compounds are optional components of the
detergent compositions prepared in accord with the invention, and are
preferably present as components of any particulate components where
they may act such as to bind the particulate component together. By
organic polymeric compound it is meant herein essentially any
polymeric organic compound commonly used as dispersants, and anti-
redeposition and soil suspension agents in detergent compositions,
including any of the high molecular weight organic polymeric
compounds described as clay flocculating agents herein.
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
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
29
separat~c~ from each other by not more than two carbon atoms.
Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MWt 2000-5000 and their
copolymers with malefic anhydride, such copolymers having a
molecular weight of from 20,000 to 100,000, especially 40,000 to
80,000.
The polyamino compounds are useful herein including those derived
from aspartic acid such as those disclosed in EP-A-305282, EP-A-
305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid,
acrylic acid, polyaspartic acid and vinyl alcohol, particularly those
having an average molecular weight of from 5,000 to 10,000, are also
suitable herein.
Other organic polymeric compounds suitable for incorporation in the
detergent compositions herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulose,
hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene
glycols, particularly those of molecular weight 1000-10000, more
particularly 2000 to 8000 and most preferably about 4000.
Suds suppressing system
The detergent compositions of the invention may comprise a suds
suppressing system. Where present such a sytem is found 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 and 2-alkyl alcanol antifoam compounds.
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
By antifoam compound it is meant herein any compound or mixtures of
compounds which act such as to depress the foaming or sudsing
produced by a solution of a detergent composition, particularly in the
presence of agitation of that solution.
Particularly preferred antifoarn compounds for use herein are silicone
antifoam compounds defined herein as any antifoam compound
including a silicone component. Such silicone antifoam compounds
also typically contain a silica component. The term "silicone" as used
herein, and in general throughout the industry, encompasses a variety
of relatively high molecular weight polymers containing siloxane units
and hydrocarbyl group of various types. Preferred silicone antifoam
compounds are the siloxanes, particularly the polydimethylsiloxanes
having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty
acids and soluble salts thereof. These materials are described in US
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids, and salts thereof, for use as suds
suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably 12 to 18 carbon atoms. Suitable salts include the alkali
metal salts such as sodium, potassium, and lithium salts, and
ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high
molecular weight fatty esters (e.g. fatty acid triglycerides}, fatty acid
esters of monovalent alcohols, aliphatic Clg-C40 ketones (e.g.
stearone) N-alkylated amino triazines such as tri- to hexa-
alkylmelamines or dl- to tetra alkyldiamine chlortriazines formed as
products of cyanuric chloride with two or three moles of a primary or
secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis
stearic acid amide and monostearyl di-alkali metal (e.g. sodium,
potassium, lithium} phosphates and phosphate esters.
CA 02269475 2002-02-14
31
A preferred suds suppressing system comprises
(a) antifoam compound, preferably silicone antifoam compound,
most preferably a silicone antifoam compound comprising in
combination
(i) polydimethyl siloxane, at a level of from 50 % to 99 % ,
preferably 75 % to 95 % by weight of the silicone antifoam
compound; and
(ii) silica, at a level of from 1 % to 50% , preferably 5 % to
25 % by weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a
level of from 5 % to 50 % , preferably 10 % to 40 %a by weight;
(b) a dispersant compound, most preferably comprising a silicone
glycol rake copolymer with a polyoxyalkylene content of 72-
78 % and an ethylene oxide to propylene oxide ratio of from
1:0.9 to 1:1. I , at a level of from 0.5 % to 10 % , preferably 1 %
to 10% by weight; a particularly pTMferred silicone glycol rake
copolymer of this type is DC0544, commercially available from
DOW Corning under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a '
C 16-C 1 g ethoxylated alcohol with a degree of ethoxylation of
from 5 to 50, preferably 8 to 15, at a level of from 5 % to 80%,
preferably 10 % to 70 % , by weight;
A highly preferred particulate suds suppressing system is described in
EP-A-0210731 and comprises a silicone antifoam compound and an
organic carrier material having a melting point in the range 50°C to
85°C, wherein the organic carrier material comprises a monoester of
glycerol and a fatty acid having a carbon chain containing from 12 to
20 carbon atoms. EP-A-0210721 discloses other preferred particulate
suds suppressing systems wherein the organic carrier material is a fatty
acid or alcohol having a carbon chain containing from 12 to 20 carbon
CA 02269475 1999-04-20
WO 98/18895 PCT/US97/18424
32
atoms, or a mixture thereof, with a melting point of from 45 °C to
80°C.
Clav softening_s stem
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.
The detergent compositions herein may also comprise from 0.01 % to
% , 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.
a) Polvamine N-oxide~y~~ers
Polyamine N-oxide polymers suitable for use herein contain units
having the following structure formula
P
I
(I)
R
CA 02269475 2002-02-14
33
wherein P is a polymerisable unit, and
00 O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination thereof whereto the nitrogen of
the N-O group can be attached or wherein the nitrogen of the N-O
group is part of these groups.
The N-O group can be represented by the following general
structures
O
O
(R1) x -N-(R2)Y
(R3)z or N_(R 1 )x
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1
and wherein the nitrogen of the N-0 group can be attached or wherein
the nitrogen of the N-O group forms part of these groups. The N-O
group can be part of the polymerisable unit (P) or can be attached to
the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part'of the
polymerisable unit comprise polyamine N-oxides wherein R is selected
from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of
said polyamine N-oxides comprises the group of polyamine N-oxides
wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyciic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine,
quinoline, acridine and derivatives thereof.
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Other suitable polyamine N-oxides are the polyamine oxides whereto
the N-O group is attached to the polymerisable unit. A preferred class
of these polyamine N-oxides comprises the polyamine N-oxides having
the general formula (I) wherein R is an aromatic,heterocyclic or
alicyclic groups wherein the nitrogen of the N-O functional group is
part of said R group. Examples of these classes are polyamine oxides
wherein R is a heterocyclic compound such as pyrridine, pyrrole,
imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided
the material has the desired water-solubility and dye-suspending
power. Typically, the average molecular weight is within the range of
500 to 1000,000.
b) Co~olvmers of N-vinvlpvrrolidone and N-vinvlimidazole
Suitable herein are coploymers of N-vinylimidazole and N-
vinylpyrrolidone having an average molecular weight range of from
5,000 to 50,000. The preferred copolymers have a molar ratio of N-
vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
cLPolyvinylpyrrolidone
The detergent compositions herein may also utilize
polyvinylpyrrolidone ("PVP") having an average molecular weight of
from 2,500 to 400,000. Suitable polyvinylpyrrolidones are
commercially available from ISP Corporation, New York, NY and
Montreal, Canada under the product names PVP K-15 (viscosity
molecular weight of 10,000), PVP K-30 (average molecular weight of
40,000), PVP K-60 (average molecular weight of 160,000), and PVP
K-90'(average molecular weight of 360,000). PVP K-15 is also
available from ISP Corporation. Other suitable polyvinylpyrrolidones
which are commercially available from BASF Cooperation include
Sokalari HP 165 and Sokalan HP 12.
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d) Poly~invloxazolidone
The detergent compositions herein may also utilize
polyvinyioxazolidones as polymeric dye transfer inhibiting agents. Said
polyvinyloxazolidones have an average molecular weight of from
2,500 to 400,000.
e) Polyvinylimidazole
The detergent compositions herein may also utilize polyvinylimidazole
as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles
preferably have an average molecular weight of from 2,500 to
400, 000.
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Ontica)'bri htener
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:
R~ RZ
N H H N
N O~-IV O C C O N --~O 1V
H I-i
R2~ S03M S03M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 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, R1 is anilino, R2 is N-2-bis-hydroxyethyl
and M is a canon such as sodium, the brightener is 4,4',-His[(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 trademark 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, R1 is anilino, R2 is N-2-hydroxyethyl-N-
2-methylamino and M is a canon such as sodium, the brightener is
4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the trademark
Tinopal SBM-GX by Ciba-Geigy Corporation.
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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-6-
morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium
salt. This particular brightener species is commercially marketed
under the trademark 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 ingredients
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 present compositions preferably have a pH measured as a 1
solution in distilled water of at least 10.0, preferably.from 10.0 to
12.5, most preferably from 10.5 to 12Ø
Form of the compositions
The compositions in accordance with the invention can take a variety
of physical forms including granular, tablet forms. The compositions
are particularly the so-called concentrated granular detergent
compositions adapted to be added to a washing machine by means of a
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38
dispensing device placed in the machine drum with the soiled fabric
load.
The mean particle size of the components of granular compositions in
accordance with the invention should preferably be such that no more
that 5 % of particles are greater than 1.7mm in diameter and not more
than 5 % of particles are less than 0. l5mm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the composition into a number of fractions (typically 5
fractions) on a series of Tyler sieves. The weight fractions thereby
obtained are plotted against the aperture size of the sieves. The mean
particle size is taken to be the aperture size through which 50 % by
weight of the sample would pass.
Density of the detergent composition is measured by means of a simple
funnel and cup device consisting of a conical funnel moulded rigidly on
a base and provided with a flap valve at its lower extremity to allow
the contents of the funnel to be emptied into an axially aligned
cylindrical cup disposed below the funnel. The funnel is 130 mm high
and has internal diameters of 130 mm and 40 mm at its respective
upper and lower extremities. It is mounted so that the lower extremity
is 140 mm above the upper surface of the base. The cup has an
overall height of 90 mm, an internal height of 87 mm and an internal
diameter of 84 mm. Its nominal volume is 500 ml.
To carry out a measurement, the funnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to overfill the
cup. The filled cup is removed from the frame and excess powder
removed from the cup by passing a straight edged implement eg; a
knife, across its upper edge. The filled cup is then weighed and the
value obtained for the weight of powder doubled to provide a bulk
density in g/Iitre. Replicate measurements are made as required.
CA 02269475 2002-02-14
39
A~~lornerate particles
Components used herein in granular compositions may be in the form
of an agglomerate particle, which may take the form of flakes, prills,
marumes, noodles, ribbons, but preferably take the form of granules.
The most preferred way to process the particles is by agglomerating
powders (e.g. aluminosilicate, carbonate) with high active pastes and
to control the particle size of the resultant agglomerates within
specified limits. Such a process involves mixing an effective amount of
powder with a high active paste in one or more agglomerators such as
a pan agglomerator, a Z-blade mixer or more preferably an in-line
mixer such as those manufactured by Schugi (Holland) BV, 29
Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige
Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9,
Postfach 2050, Germany. Most preferably a high shear mixer is used,
such as a Lodige CB (Trade Mark).
A high active paste comprising from 50% by weight to 95% by weight,
preferably 70 % by weight to 85 % by weight of surfactant is typically
used. The paste may be pumped into the agglomerator at a temperature
high enough to maintain a pumpable viscosity, but low enough to avoid
degradation of the surfactant used. An operating tempera::re of the
paste of 50°C to 80°C is typical.
Laundry washing 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 composition in accord with the invention. By an
effective amount of the detergent composition it is meant from 40g to
300g of product dissolved or dispersed in a wash solution of volume
from 5 to 65 litres, as are typical product dosages and wash solution
volumes commonly employed in conventional machine laundry
methods.
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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 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. Especially preferred dispensing devices for use
with the composition of the invention have been described in the
following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-
0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland
published in Manufacturing Chemist, November 1989, pages 41-46
also describes especially preferred dispensing devices for use with
granular laundry products which are of a type commonly know as the
"granulette". Another preferred dispensing device for use with the
compositions of this invention is disclosed in PCT Patent Application
No. W094/11562.
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41
Especially preferred dispensing devices are disclosed in European
Patent Application Publication Nos. 0343069 & 0343070. The latter
Application discloses a device comprising a flexible sheath in the form
of a bag extending from a support ring defining an orifice, the orifice
being adapted to admit to the bag sufficient product for one washing
cycle in a washing process. A portion of the washing medium flows
through the orifice into the bag, dissolves the product, and the solution
then passes outwardly through the orifice into the washing medium.
The support ring is provided with a masking arrangemnt to prevent
egress of wetted, undissolved, product, this arrangement typically
comprising radially extending walls extending from a central boss in a
spoked wheel configuration, or a similar structure in which the walls
have a helical form.
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.
Packaging for the compositions
Commercially marketed executions of the bleaching compositions can
be packaged in any suitable container including those constructed from
paper, cardboard, plastic materials and any suitable laminates.
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Abbreviations used in Examples
In the detergent compositions, the abbreviated component
identifications have the following meanings:
LAS : Sodium linear C 12 alkyl benzene sulfonate
Nonionic 45E7 A C 14-15 Predominantly linear primary
:
alcohol condensed with an average of
7 moles
of ethylene oxide
QAS : R2.N+(CH3)3 with R2 = C12 - C14
STPP : Anhydrous sodium tripolyphosphate
Carbonate : Anhydrous sodium carbonate with a particle
size between 200pm and 900pm
Silicate : Amorphous Sodium Silicate (Si02:Na20;
2.0
ratio)
Sodium sulfate : Anhydrous sodium sulfate
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Protease : Proteolytic enzyme of activity 4KNPU/g sold
by NOVO lndustries A/S under the trademark
Savinase
Alcalase : Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g
sold by NOVO Industries A/S under the
trademark Carezyme
Amylase . Amylolytic enzyme of activity 60KNU/g sold
by NOVO Industries A/S under the trademark
Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold
by NOVO Industries A/S under the trademark
Lipolase
PB 1 : Anhydrous sodium perborate bleach of
nominal formula NaB02.H202
TAED : Tetraacetylethylenediamine
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480N : Random copolymer of 3:7 acrylic/methacrylic
acid, average molecular weight about
3,500
DTPA(A) : Diethylene triamine pentaacetic acid
PhotoactivatedSulfonated Zinc Phthlocyanine encapsulated
: in
bleach dextrin soluble polymer
SRP : Sulfobenzoyl end capped esters with
oxyethylene oxy and terephthaloyl backbone
Silicone
antifoam : Polydimethylsiloxane foam controller
with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller
to
said dispersing agent of 10:1 to 100:1.
In the following Examples all levels are quoted as % by weight of the
composition:
Example 1
Compositions B to D were prepared with accord to the present
invention. Composition A is a comparative composition known in the
art and X is a nil-sulphate composition.
A B C D X
Blown Powder
LAS 19.3 21.5 22.4 25.3 31.29
STPP 21.0 21.8. 24.3 27.5 34.05
Silicate 8.0 8.9 9.2 10.4 12.97
Sulphate 38.2 32.1 28.5 19.1 -
Dry Add
Carbonate 5.0 5.4 5.7 6.5 8.11
Perfume 0.06 0.07 0.07 0.08 0.10
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organi~/inor~anic 0.286 0.343 i 0.36? 0.444 0.665
ratio i
CMM' % 34 35 36 39 43
Density g/L 360 320 ~ 310 300 260
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Example 2
Compositions F to I were prepared with accord to the present
invention. Composition E is a comparative composition known in the
art and Y represents a nil-sulphate composition.
E F G H I Y
Blown Powder
LAS 19.3 20.4 21.3 23.4 25.38 27.41
QAS 0.63 0.65 0.67 0.70 0.82 0.89
STPP 25.0 27.1 27.6 30.3 32.88 35.51
Silicate 7.6 7.9 8.3 ~ 9.1 9.9 10.79
Sulphate 29.4 25.6 22.0 14.7 7.36
DTPA{A) 0.21 0.23 0.23 0.25 0.27 0.29
MA/AA 1.0 1.1 1.1 1.2 1.31 1.4
Dry Add
Carbonate 5.0 S.3 5.5 6.05 6.57 7.1
Protease 0.6 0.6 0.6 0.72 0.78 0.8
Lipase 0.15 0.16 0.17 0.18 0.19 0.21
Amylase 0.36 0.38 0.39 0.40 0.47 0.51
SRP 0.14 0.14 0.15 0.16 0.18. 0.19
organic/inorganic 0.338 0.369 0.381 0.476 0.554 0.648
ratio
CMM % 34 35 35 37 40 42
Density g/L 400 370 360 340 320 300
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Example 3
Compositions K and L were prepared with accord to the present
invention. Composition J is a comparative composition known in the
art and Z represents a nil-sulphate composition.
K L Z
Blown Powder
LAS 6.65 7.38 7.74 8.11
Silicate 6.7 7.4 7.80 8.17
MA/AA 0. 95 1. OS 1.11 1.1 S
DTPA(A) 0.27 0.28 0.31 0.33
STPP 25.7 28.53 29,95 31.36
Sulphate 19.9 8.9 4.49 -
Nonionic 45E7 4.7 5.27 5.53 5.79
Silicone antifoam 0.34 0.37 0.39 0.42
480N 0.04 0.04 0.05 0.05
Dry Add
Carbonate 11.4 12.65 13.28 13.91
Protease 0.47 0.53 0.54 0.57
Lipase 0.1 0.116 0.12 0.122
Amylase 0.38 0.42 0.44 0.46
S~ 0.1 0.111 0.12 0.122
Cellulase 0.08 0.09 0.09 0.09
PB 1 10.45 11.60 12.17 12.75
TAED 1.28 1.42 1.49 1.56
Photoactivated 0.003 0.003 0.003 0.003
organic/inorganic 0.249 0.354 0.358 0.401
ratio
CMM % 34 34 34 34
Density g/L 500 470 455 440
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Measurement of Cakin
The compositions prepared by the process of the present invention are
less predisposed to caking than other reduced and nil-sulphate
compositions previously documented. Caking potential is measured by
a standard test procedure for measuring cake strength. In general terms
the cake strength test is a measure of the force required to break a
detergent composition cake pre-packed at a specific pressure. The
'stickier' the detergent components, the greater the force required to
break the cake.
The cake strength measuring equipment consists essentially of a solid
perspex cylinder, with a polished surface (diameter 6.35cm, length
15.90cm), a hollow perspex sleeve with a polished inner surface (inner
diameter 6.35cm, wall thickness l.5cm, length 15.25cm), a perspex
disc lid (diameter 11.5cm and thickness 0.65cm), a 5 Kg weight and a
force gauge.
The sleeve and cylinder, the latter fitted inside the former, are placed
vertically on a flat surface. The cylinder/sleeve is filled with detergent
composition which has been stored at 35°C for 12 hours. The detergent
composition in the cylinder/sleeve is levelled using a straight edged
knife and the lid fitted on the top of the detergent. The 5 Kg weight is
then placed on the lid, such that the weight provides an even pressure
across the surface of the lid. The weight is left to compress the
detergent for 2 minutes. After 2 minutes, the weight is removed and
the sleeve slid downward, leaving a cake of detergent. The force gauge
is then directed to the centre of the lid and the force required to break
the cake is noted. The following scale is representative of consumer
perception.
Cake Strength / lbs Consumer Perception
0 excellent
very good
2 good
satisfactory
4/5 poor
6/7 unacceptable
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Table 1. represents cake strength data produced for the compositions
described in Example 2 (compositions E, F, G, H, I and Y)
E F G H I y
Cake Strength / lbs 0 0 0 1 2
CMM % 34 35 35 37 40 42
Table 1.
It can be seen from the data described in table 1, that the compositions
of the present invention have reduced potential for caking.
