Note: Descriptions are shown in the official language in which they were submitted.
CA 0223220', 1998-03-16
CM1463F
Deter~ent particle
Technicàl Field
The present invention relates to an agglomerated or extruded detergent particle,comprising perborate bleach, an acid source and one or more surfactants, for use in
detergent compositions which are suitable for use in laundry washing methods. The
invention also relates to a process for making the agglomerated or extruded detergent
1 0 particle.
Back~round to the Invention
There is a trend amongst commercially available granular detergents towards higher
15 bulk densities and towards granular detergent compositions which have a higher
content of detergent active ingredients, such as bleach. Such detergents offer greater
convenience to the consumer and at the same time reduce the amount of packaging
materials which will, ultimately, be disposed of. However, traditional detergentformulations and processes to produce the final detergent powder are not always
20 satisfactory or suitable for these detergents, with higher active ingredient
concentration.
Amongst consumers there is also a need for detergents which provide improved
bleachable stain removal. Therefore, in the recent past detergents have been
25 developed which contain various types of bleaches, which can be incorporated at
high levels.
The (high density) detergents, comprising high levels of bleach and surfactant can
lead to poor solubility properties, arising from low rate of dissolution or the
30 formation of gels, and thus to poor dispensing of the product, either from the
dispensing drawer of a washing m~rhine, or from a dosing device placed with the
laundry inside the m~chine. This poor dispensing is often caused by gelling of
particles, which have high levels of surfactant and/ or bleach, upon contact with
water. The gel prevents a proportion of the detergent powder from being solubilized
35 in the wash water which reduces the effectiveness of the powder. This is a particular
problem at low water pressures and/or at lower washing temperature.
CA 0223220~ 1998-03-16
EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal
percarbonate to improve the dispensing profile and dissolution rate of a detergent.
Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the
percarbonate bleach.
EP-A-0 639 639 contains a similar disclosure in this respect.
Other ways to improve dispensing include the use of an effervescence system. If the
detergent contains an effervescence system then the generation of a gas such as
carbon dioxide pushes the particles of the d~lelgelll apart, and prevents them from
gelling.
The use of effervescence to improve the dispensability of granular materials has been
used extensively in ph~ ceutical preparations. The most widely used effervescentsystem in this respect is citric acid in combination with bicarbonate. The use of this
simple effervescent system has also been described for improving the dispersibility
of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2,184,946.
EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of
350 to 1500 microns.
US -A-5, 114,647 discloses a s~niti.~ing composition comprising granules of alkali
metal carbonate and aliphatic carboxylic acid of a particle size of 150 to 2,000microns.
EP-A-0 333 223 discloses a bathing plepal~lion comprising fumaric acid having anaverage particle size of 50-500 microns.
The Applicants have found that one of the specific problems associated with poor30 dispensing of detergent compositions which contain ble~.~hing agents and
particularly perborate monohydrate bleach, is that localised high concentrations of
bleach form which may contact the fabric and cause spot bleaching of coloured
fabrics. Secondly, poorly dispensed surfactants tend to deposit on the fabric and the
machine. This can lead to fabric damage. These problems can be encountered
35 especially with detergent compositions comprising high levels of surfactants and
perborate, especially perborate (monohydrate). However, these high concentrations
CA 0223220S 1998-03-16
are often required for an optimal stain/soil removal and suspension and bleachable
stain removal.
The Applicants now have found that this problem can be solved or reduced when an5 acid source is agglomerated with or extruded along with the surfactants, or a part
thereof, and the perborate bleach to form an agglomerated or extruded d~lelgent
particle. In the detergent comprising this agglomerated or extruded particle, an alkali
source should be present, capable of producing a gas when reaction with the acidic
source. We have found that agglomerating or extruding of such an acid source with
10 surfactant(s) and bleach, when there is an alkali source present in the detergent
composition, improves the solubility and/or dispersion of the surfactant(s) and the
perborate bleach in the wash water and elimin~tes or reduces the problems of fabric
damage by high concentrate bleach and of solid detergent particles or surfactants
rem~ining in the washing m~chine and on washed clothes. It is believed that the acid
15 reacts rapidly with the alkali in the wash water to release the gas. This helps disperse
the perborate bleach and the detergent in general surfactants and minimi~e the
formation of high concentrations of bleach and of insoluble clumps.
The improved dispensing of the surfactant(s) and the perborate bleach can amount to
20 an overall improved and more efficient performance.
Furthermore, the detergent residues in the dispensing drawer or dispensing device are
reduced.
25 All documents cited in the present description are, in relevant part, incorporated
herein by reference.
Summary of the Invention
30 According to the present invention there is provided an agglomerate or extruded
detergent particle comprising a perborate component, one or more surfactants and an
acid source. Optionally other detergent ingredient can be present in the agglomerate
or extrudate. The agglomerated or extruded dt;telgent particle can be included in
delelgellts comprising an alkali source capable of reacting with the acid source to
35 produce a gas. According to the present invention there is also provided a process for
making the agglomerate or extruded detergent particle.
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Detailed Description of the Invention
s
A~lomerate or extruded particle
The agglomerate or extruded detergent particle of the present invention contains one
or more surfactants and an acid source and a perborate component, which are
described below.
The amount of each component in the agglomerate or extruded detergent particle can
vary depending on the application of the particle and on the nature of the finaldetergent composition comprising the particle. For example, when the particle will be
used in a detergent composition comprising one or more of the same ingredients as
the particle, the level thereof in the particle can be reduced.
The level of surfactant in the particle is preferably from 15% to 95%, more
preferably from 25% to 60%, most preferably from 30% to 50% by weight of the
particle.
The level of acid source in the particle is preferably from 1% to 40%, more
preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably
from 7% to 15% by weight of the particle
The level of perborate component in the particle is preferably from 10% to 70%,
more preferably from 15% to 50%, most preferably from 20% to 40% by weight of
the particle.
Preferably, at least one anionic surfactant is present. In a pl~f~lled embodiment a
nonionic surfactant and an anionic surfactant are present. In a further preferred
embodiment an anionic and a cationic and optionally a nonionic surfactant are
present. When a cationic sllrf~t~nt is present, preferably a silicate or alumino silicate
35 co.~ ing material is present.
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Preferably, magnesium sulphate is present in the particle, preferably at a level of
from 0.1% to 8%, more preferably of from 0.2% to 5%, most preferably from 0.3%
to 3% by weight of the particle.
5 Preferably, the particle does not comprise a bleach activator and/ or crystalline
layered silicate.
The agglomerate or extruded particle can optionally comprise additional detergent
ingredients. Preferred optional ingredients in the particle can be builders (alumino
10 silicates, polymeric carboxylates), an alkali source, bleach activators and bleach
catalysts.
Surfactant
15 The level of surfactant in the particle is preferably from 15% to 95%, more
preferably from 25% to 60%, most preferably from 30% to 50% by weight of the
particle.
When the particle is comprised in a detergent composition, the total level of
20 surfactant in the d~lergellt composition is preferably of from 1% to 90%, preferably
3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most
preferably 12% to 25% by weight ofthe detergent composition.
The surfactant in the agglomerate or extruded particle is selected from anionic,25 nonionic and cationic surfactants and mixtures thereof.
Optionally, ampholytic, amphoteric and zwitterionic surfactants can be present in the
particle.
30 A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and
species of these surfactants, is given in U.S.P. 3,929,678 issued to T ~lghlin 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
35 31, 1981.
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Anionic surfactant
The agglomerated or extruded detergent particle in accordance with the present
invention preferably comprise one or more anionic surfactants. Essentially any
5 anionic surfactants useful for detersive purposes can be comprised in the detergent
composition. 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.
The level of anionic surfactant is preferably from 10% to 95%, more preferably from
20% to 60%, most preferably from 25% to 50% by weight of the particle.
In detergent compositions, comprising the particle, the total level of anionic
surfactant is preferably from 2% to 40%, more preferably from 4% to 30%, even
more preferably from 5% to 25%, most preferably from 6% to 15% by weight ofthe
composltlon.
Other anionic surfactants include the isethionates such as the acyl isethionates, N-
20 acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated
C12-C1 8 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
25 resin acids present in or derived from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surf~t~nt.c suitable for use herein include the linear and branched
30 primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol
snlf~tes, alkyl phenol ethylene oxide ether slllf~tes, the Cs-C17 acyl-N-(C1-C4 alkyl)
and -N-(C1-C2 hydroxyalkyl) gluc~mine sulfates, and sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic
nonsulfated compounds being described herein).
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Alkyl sulfate surfactants are preferably selected from the linear and branched primary
C 1 o-C 18 alkyl sulfates, more preferably the C1 1 -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 C1o-C1g 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 1 1 -C l 8, most preferably C 1 1 -C 1 5 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.
15 Anionic sulfonate surfactant
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
20 glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and
any mixtures thereof.
Anionic carboxylate surfactant
25 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
30 CH2COO-M+ wherein R is a C6 to C 1 8 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-(CHRl-CHR2-O)-R3 wherein R is
a C6 to C 18 alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
35 consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic
acid radical, and mixtures thereof, and R3 is selected from the group consisting of
CA 0223220~ 1998-03-16
hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbonatoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a5 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-
l-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 suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
(Rl) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group,
15 R1 is a C1-C4 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.
Cationic surfactants
20 Another pr~r~lled surfactant of the invention is one or more cationic surfactants.
Suitable cationic surf~ct~nt~ include the qll~tern~ry ammonium surfactants selected
from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants
wherein the renl~ining N positions are substituted by methyl, hydroxyethyl or
hydroxy~ropyl groups. Another pier~ll~ cationic surfactant is an C6-C 18 alkyl or
25 alkenyl ester of an q~l~tçrn~ry ammonium alcohol, such as qll~t~?rn~ry choline esters.
The level of cationic surfactant is preferably from 1% to 20%, more preferably from
2% to 15%, most preferably from 4% to 10% by weight ofthe particle.
30 In detergent compositions, comprising the particle, the level of cationic surfactant is
preferably from 0.2% to 20%, more preferably from 0.5% to 15%, even more
preferably from 1% to 10%, most preferably from 1% to 5% by weight ofthe
composltlon.
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Nonionic surfactant
The detergent composition of the present invention preferably contains a nonionic
surfactant. Essentially any nonionic surfactant can be used herein.
The level of nonionic surfactant is preferably from 5% to 60%, more preferably from
10% to 45%, most preferably from 15% to 35% by weight ofthe particle.
In detergent compositions, comprising the particle, the level of nonionic surfactant is
preferably from 1% to 30%, more preferably from 2% to 25%, even more preferably
from 3% to 15%, most preferably from 4% to 12% by weight ofthe composition.
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
cond~n~tes 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 ~ mine adducts.
Nonionic alkoxylated alcohol surfactant
The con-lPnc~tion 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 cont~ining from 8 to
20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural
formulaR2CONR1Z 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
CA 0223220~ 1998-03-16
,
preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-
C3 1 hydrocarbyl, preferably straight-chain Cs-C 19 alkyl or alkenyl, more preferably
straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-chain Cl 1 -C 17 alkyl
or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear
5 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.
10 Nonionic fatty acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula: R6CoN(R7)2
wherein R6 is an alkyl group cont~inin~ 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 -(C2H4O)XH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group cont~ining from 6 to
30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
cont~ining from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula
R20(CnH2nO)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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11
Optional surfactants
Amphoteric surfactant
5 Optional amphoteric surfactants for use in the particle or detergent compositions,
comprising the particle, include the amine oxide surfactants and the alkyl
amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(oR4)XN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~ining from 8 to
26 carbon atoms; R4 is an alkylene or hydroxyalkylene group C~ g from 2 to 3
carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3; and each
R5 is an alkyl or hydroxyalkyl group cont~ining from 1 to 3, or a polyethylene oxide
15 group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are Clo-Clg alkyl
dimethylamine oxide, and Clo 1 8 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
Optionally, zwitterionic surfactants can be incorporated into the particle or detergent
compositions comprising the particle. These s~ ct~nt~ can be broadly described as
25 derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary
and tertiary ~mines, or derivatives of quaternary ammonium, q~-~t~rn~ry
phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are
exemplary zwitterionic surfactants for use herein.
30 Suitable betaines are those compounds having the formula R(R')2N+R2COO-
wherein R is a C6-C1g hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2
is a Cl-Cs hydrocarbyl group. Preferred betaines are C12 18 dimethyl-ammonio
hexanoate and the C10-l8 acylamidopropane (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
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12
Acid source
In accordance with the present invention, an acid source, or source of acidity, is
present in the agglomerate or extruded detergent particle. When comprised in a
5 detergent composition, the detergent composition contains an alkali source, capable
of reacting with the acid source to produce a gas. Optionally, the alkali source or part
thereof can be comprised in the particle.
The level of the acid source in the particle is preferably from 1% to 40%, more
preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably
from 7% to 15% by weight of the particle.
In detergent compositions comprising the particle, the level of the source of acidity
is preferably present of from 0.1% to 50%, more preferably from 0.5% to 25%, even
more preferably from 1% to 12%, most preferably from 1% to 7% weight of the
composltlon.
Preferably, 80% or more of the acid source has a particle size in the range of from
about 150 microns to about 710 microns, with at least about 37% by weight of the20 acid source having a particle size of about 350 microns or less. In a plef~lled
embodiment 100% of the acid source has a particle size of about 710 microns or less.
Alternatively, greater than about 38%, more preferably 38.7%, of the particulate acid
source has a particle size of about 350 microns or less.
25 The particle size of the acid source is calculated by sieving a sample of the source of
acidity on a series of Tyler sieves. For example, a Tyler sieve mesh 100 corresponds
to an ap~ ule size of 150 microns. The weight fractions thereby obtained are plotted
against the aperture size of the sieves.
30 The acid source may be any suitable organic, mineral or inorganic acid, or a
derivative thereof, or a mixture thereof. The acid source may be a mono-, bi- or tri-
protonic acid. Preferred derivatives include a salt or ester of the acid. The source of
acidity is preferably non-hygroscopic, which can improve storage stability. However,
monohydrates acids can also be useful herein. Organic acids and their derivatives are
35 preferred. The acid is preferably water-soluble. Suitable acids include citric, glutaric,
CA 0223220~ 1998-03-16
13
succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid,
or a salt or an ester thereof. Citric acid is especially preferred.
5 Perborate component
Another essential ingredient of the agglomerate or extruded detergent particle of the
present invention is a perborate component, which is capable of bleaching.
10 The level of perborate component in the particle is preferably from 10% to 70%,
more preferably from 15% to 50%, most preferably from 20% to 40% by weight of
the particle.
In detergent compositions comprising the particle, the perborate is preferably present
at a level of from 1% to 40% by weight, more preferably from 6% to 25% by
weight, most preferably from 13% to 20% by weight of the compositions.
The perborate is preferably in the form of a salt, normally in the form of the alkali
metal, preferably sodium salt.
The perborate bleach is preferably sodium perborate in the form of the monohydrate
or tetrahydrate, which can be represented respectively with the nominal formula
NaBO2H2O2 and NaB~2H2~2 3H2o
25 The perborate bleach may be included as the crystalline solid without additional
protection. However, ple~lled executions of certain granular compositions utilize a
coated form of the perborate bleach 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
30 materials such as waxes, oils, or fatty soaps.
Source of Alkali
In accordance with the present invention, when the agglomerate or extruded
35 detergent particle is present in a detergent composition, an alkali source is generally
present in the detergent composition such that it has the capacity to react with the
CA 0223220~ 1998-03-16
14
acid source to produce a gas. Preferably this gas is carbon dioxide, and therefore the
alkali is a carbonate, or a suitable derivative thereof.
Optionally, the alkali source, or part thereof can be present in the particle.
The detergent composition comprising the particle of the present invention,
preferably contains from about 2% to about 75%, preferably from about 5% to about
60%, most preferably from about 10% to about 30% by weight of the alkali source.When the alkali source is present in the particle, the agglomerate or extrudate
preferably contains from about 5% to about 60%, more preferably from 10% to 50%,most preferably from 15% to 35% of the alkali source.
In a preferred embodiment, the alkali source is a carbonate. Examples of pl~r~ dcarbonates are the ~lk~line earth and alkali metal carbonates, including sodium
carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine
calcium carbonate such as are disclosed in German Patent Application No. 2,321,001
published on November 15, 1973. Alkali metal percarbonate salts may also be
included in the detergent compositions and are also suitable sources of carbonate
species and are described below in more detail.
Other suitable sources will be known to those skilled in the art.
The alkali source may also comprise other components, such as a silicate. Suitable
silicates include the water soluble sodium silicates with an SiO2: Na2O ratio of from
1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most
preferred. The silicates may be in the form of either the anhydrous salt or a hydrated
salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most pl~;r~lled silicate.
Alkali metal persilicates are also suitable sources of silicate herein.
Process for makin~ of the a~lomerate particle
The agglomerate detergent particle can be prepared via a process comprising the
steps of:
i) allmixing one or more detergent surfactants, the perborate component and an acid
source and optionally other detergent ingredientsto form a mixture; and
CA 0223220~ 1998-03-16
ii) agglomerating the mixture to form agglomerated particles.
Typically, such a process involves mixing an effective amount of powder, including
5 the acid source, with a high active surfactant paste in one or more agglomerators such
as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, preferably
two, such as those m~nllf~tllred 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. Preferably a high shear10 mixer is used, such as a Lodige CB (Trade Name). Most preferably, a high shear
mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade
Name) and a Lodige KM (Trade name) or Schugi KM (Trade Name). Optionally,
only one or more low shear mixer are used. Preferably, the agglomerates are
thereafter dried and/ or cooled.
An other agglomeration process involves mixing of various components of the final
agglomrate in different stages, using an fluidised bed. For example, a preferredparticle in accord with the present invention can be agglomerated by addition,
preferably by spraying on, of nonionic, anionic surf~ct~nt~ and optionally a wax, or
20 mixtures thereof, to the acid source in powdered form and other optional ingredients.
Then, additional components, including the perborate bleach and optinally the alkali
source or part thereof, can be added and agglomerated in one or more stages, thus
forming the final agglomerate particle.
25 Preferably, no bleach activator and/ or crystalline layered silicate is added to the
agglomerate mix in the agglomeration process for making the particle of the
invention.
The agglomerate particles may take the form of flakes, prills, marumes, noodles,30 ribbons, but preferably take the form of granules. A plef~lled way to process the
particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high
active surfactant pastes and to control the particle size of the resulting agglomerates
within specified limits. Typical particle sizes are from 0.10 mm to 5.0 mm in
diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40
35 mm to 1.00 mm in diameter.
CA 0223220~ 1998-03-16
16
A high active surfactant paste comprising a mix of, typically, from 50% by weight to
95% by weight, preferably 70% by weight to 85% by weight of surfactant, and
optionally it can contain an appropriate acid source. The paste may be pumped into
the agglomerator at a temperature high enough to m~int~in a pumpable viscosity, but
5 low enough to avoid degradation of the anionic surfactants used. An operating
telllpcldlllre of the paste of 50~C to 80~C is typical. Such pastes and methods for
making and processing such pastes is for example described in WO 93/03128.
In an especially preferred embodiment of the present invention, the detergent
10 composition has a density of greater than about 600 g/l and is in the form of powder
or a granulate.
Process for makin~ the extruded particle
15 Extruded particles can generally be prepared by mixing the various components,
optionally addition of powdered components and/or slip additives, forcing the
obtained mixture by pressure through the extruder holes of the required diameter or
less, cutting of the extruded paste into extrudates (granules) of the required length
and rounding the extrudates. WO 91/13678 and WO 91/02047 describe such
20 processes.
In more detail the extruded particles can be made as follows. The detergent
ingredients can be mixed into one paste. Preferably, the various detergent
components are pre-mixed in dirr~lelll pastes, preferably two, whereby the acid
25 source preferably is present in a dirr~,le.l~ pre-mixed past than the alkali source if
present in the particle, especially when the alkaline source is a carbonate or
bicarbonate.
In a highly plefcll~d embo~liment one pre-mixed paste comprises the perborate
30 component and part of the surfactant, preferably the anionic surfactant if present, and
additional components such as zeolite and cationic surfactant, and one pre-mixedpaste comprises the acid source and part of the surfactant, preferably the nonionic
surfactant. The premixed pastes will then be mixed to form one paste.
35 Optionally, water and additional detergent components, such as slip additives,
additional bleach, enzymes, optionally bleach activators, stabilisers and soap can be
CA 0223220~ 1998-03-16
17
added to the pre-mixed paste or pastes or to the paste as a whole, simultaneously with
or shortly after the mixing process has started.
Preferably the paste obtained is coated with a slip material prior to or simultaneously
5 with the introduction of the paste in the extruder. A variety of compounds are known
to be useful herein as slip additives. Preferred slip additives are those compounds
which also have a secondary detergent function, such as certain anionic and nonionic
surfactants, polymeric polycarboxylates, polyvinyl alcohols.
10 Under pressure (20 bar or more) the paste or coated paste is then passed through the
holes (of the extruder) of the required diameter or less, whereafter the extruded
granules are cut in to granules of the required length (about 0.1 mm to 2.0 mm,
preferably about 0.4 mm to 1.0 mm).
Typical particle diameter sizes (width) are from 0.10 mm to 5.0 mm, preferably from
0.25 mm to 3.0mm, most preferably from 1.00 mm to 2.50.
The viscosity of the paste should be controlled to avoid caçking of the paste in the
extruder or during mixing and to avoid the paste from blocking the extruder. By
20 constant ples~ule, the viscosity is best controlled by heating and cooling the paste
and/ or the extruder.
Optionally, the obtained extrudates are rounded, to obtain round or spherical
particles.
Preferably, the thus obtained particles are dusted with a powder, preferably zeolite,
and dried, to form equally shaped granules, and to avoid agglomeration of the
granules.
30 Additional ingredients
The agglomerate or extruded detergent particle and/ or the detelgell~ compositions,
comprising the particle of the invention, may also contain additional ingredients or
components. The precise nature of these additional ingredients, and levels of
CA 0223220~ 1998-03-16
18
.
incorporation thereof will depend on the physical form of the final composition, and
the precise nature of the washing operation for which it is to be used.
The detergent particle preferably comprises as an additional ingredient one or more
S builders, preferably alumino silicates and/ or organic polycarboxylate polymers,
alkali sources, bleach activators or bleach catalysts, or mixtures thereof.
The detergent compositions, comprising the particle of the invention, preferablycontain one or more additional detergent components selected from surfactants as10 described above, additional acid sources, additional bleaches, builders, organic
polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil
suspension and anti-redeposition agents and corrosion inhibitors.
Water-soluble builder compound
The particle and/ or the detergent compositions of the present invention can contain a
water-soluble builder compound, typically present in deLelg~ compositions 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 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,
25 and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type
although monomeric polycarboxylates are generally plere,~ed for reasons of cost and
performance.
Suitable carboxylates cont~inin~ one carboxy group include the water soluble salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates cont~ining
two carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid
35 and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates Co"t~ il-g three carboxy groups include, in particular, water-
CA 0223220~ 1998-03-16
.
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 aminosuccinatesdescribed 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 cont~ining 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 cont~ining
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 cont~ining up to three carboxy groups per
molecule, more particularly citrates.
Borate builders, as well as builders cont~ining 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
The particle and/ or the detergent compositions of the present invention may contain
a partially soluble or insoluble builder compound, typically present in the detergent
composition 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.
In the particle, the partially soluble or insoluble builder compound is preferably
present at a level of from 5% to 85% by weight, preferably from 15% to 60% by
weight, most preferably from 20% to 50% weight of the particle.
CA 0223220~ 1998-03-16
Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y].
xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x
is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate material are in hydrated form and are preferably crystalline,
containing from 10% to 28%, more preferably from 18% to 22% water in bound
form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials
are available under the design~tions Zeolite A, Zeolite B, Zeolite P, Zeolite X,Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 [AlO2) 12 (SiO2)l2] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86
[(Alo2)g6(sio2)lo6]- 276 H2O.
Preferably, the particle of the invention does not comprise a crystalline layered
silicate. However, pl~fe~.~d crystalline layered silicates for use in the detegrent
compositions herein have the general formula
NaMSixO2x+l YH2o
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514 and methods for their p.~palalion are disclosed in DE-A-3417649 and DE-
30 A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or
4 and is preferably 2. The most preferred material is ~-Na2Si20s, available fromHoechst AG as NaSKS-6.
Additional perhydrate bleaches
CA 0223220~ 1998-03-16
In addition to the perborate bleach, metal percarbonates, particularly sodium
percarbonate is an optional perhydrate which can be incorporated into the particle or
detergent composition of the invention. Sodium percarbonate is an addition
compound having a formula corresponding to 2Na2CO3.3H2O2, and is available
5 commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate salt of use in the detergent compositions herein.
10 Or~anic peroxYacid bleachin~ system
A pl~el~lled feature of detergent compositions of the invention is an organic
peroxyacid bleaching system. In one ~efe,l~d execution the bleachin~ system
contains a hydrogen peroxide source and an organic peroxyacid bleach precursor
15 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, such as the perborate bleach of the
claimed invention. In an alternative p~ef~ d execution a plefollned organic
peroxyacid is incorporated directly into the composition. Compositions cont~inin~
20 mixtures of a hydrogen peroxide source and organic peroxyacid precursor in
combination with a preformed organic peroxyacid are also envisaged.
Peroxyacid bleach precursor
25 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
CA 0223220~ 1998-03-16
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,l 147871, 2143231 and EP-A-0170386.
Leaving ~roups
15 The leaving group, hereinafter L group, must be sufficiently reactive for theperhydrolysis 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.
25 Preferred L groups are selected from the group consisting of:
--O~ ~~Y and --O~
--N--C--R1 --N N --N--C--CH--R4
IR3 ~ ' R3 Y
CA 0223220~ 1998-03-16
23
R3 r
-O--CH=C--CH=CH2 --O--CH=C--CH=CH2
1~l Y 1~l
-O--C--R1 --N/ ~NR4 --N /NR4
11 0
R3 0 Y
--O--C=CHR4 , and IN i--CH--R4
R3 o
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~ining from 1
to 14 carbon atoms, R3 is an alkyl chain cont~ining from 1 to 8 carbon atoms, R4 is
H or R3, 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,
10 hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl
ammmonium groups.
The preferred solubilizing groups are -SO3 M, -CO2 M, -SO4 M, -N (R3)4X
and o<--N(R3)3 and most preferably -SO3-M+ and -CO2-M+ wherein R3 is an alkyl
15 chain co~ il-g 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.
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid on
25 perhydrolysis.
CA 0223220~ 1998-03-16
24
Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
,N,NlNl tetra acetylated alkylene ~ mines wherein the alkylene group contains
from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is
5 particularly preferred. The TAED is preferably not present in the agglomeratedparticle of the present invention, but preferably present in the detergent composition,
comprising the particle.
Other p.efel.~d alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl
10 hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursors
15 Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including those of the following general formulae:
R1~C N~R2 C L R1 N~C~R2- C~L
,
O R5 0 or R5 0 0
20 wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group cont~ining from 1 to 14 carbon atoms, and R5 is H or an alkyl group
cont~ining 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
30 unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products ofsorbitol, 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
CA 0223220~ 1998-03-16
group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone,
dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic peroxyacid precursors
s
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid
10 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 precursor compound may be an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
20 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 pler~ d cationic peroxyacid precursors are described in UK Patent
Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650,
08/298904 and 08i298906.
30 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
35 methylene alkyl caprolactams.
CA 0223220~ 1998-03-16
26
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 forrnula:
col
[~N"C R1
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
10 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 1% to 15% by weight, more
15 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:
R1 C N R2 C OOH
O R5 o or
- R1 N C R2 C OOH
R5 0 0
wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an alkylene, arylene, and alkarylene group cont~inin~ from 1 to 14 carbon atoms, and
25 RS is H or an alkyl, aryl, or alkaryl group co~ il-g 1 to 10 carbon atoms. Amide
substituted organic peroxyacid compounds of this type are described in EP-A-
0170386.
CA 0223220~ 1998-03-16
27
,
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and
diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalyst
The particle and/ or the compositions optionally contain a transition metal cont~ining
bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a
heavy metal cation of defined bleach catalytic activity, such as copper, iron orm~ng~nese cations, an auxiliary metal cation having little or no bleach catalytic
activity, such as zinc or aluminum cations, and a sequestrant having defined stability
constants for the catalytic and auxiliary metal cations, particularly
ethylene~i~minetetraacetic acid, ethylene~i~minetetra(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 m~ng~n~se-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-(ClO4)2, MnIV4(u-
O)6(1,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-O) 1 (u-OAc)2 (1,4,7-
trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof. Others are
described in European patent application publication no. 549,272. Other ligands
suitable for use herein include 1,5,9-trimethyl- 1,5,9-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 m~ng~nese (IV)complexes such as Mn(1,4,7-trimethyl-1,4,7-tri~7~cyclononane)(OCH3)3 (PF6). Still
another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble
complex of m~ng~nese (III), and/or (IV) with a ligand which is a non-carboxylatepolyhydroxy compound having at least three consecutive C-OH groups. Other
examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate
lig~n-l~, including N4MnIII(u-0)2MnIVN4)+and [Bipy2MnIII(u-0)2MnIVbipy2]-
(C104)3.
CA 0223220~ 1998-03-16
28
Further suitable bleach catalysts are described, for example, in European patentapplication No. 408,131 (cobalt complex catalysts), European patent applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455
(m~ng~nese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application, publication no. 224,952, (absorbed m~ng~nese on aluminosilicate
catalyst), U.S. 4,601,845 (aluminosilicate support with m~ng~nese and zinc or
m~gnesium salt), U.S. 4,626,373 (m~n~nese/ligand catalyst), U.S. 4,119,557 (ferric
complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst)10 C~n~ n 866,191 (transition metal-cont~inin~. salts), U.S. 4,430,243 (chelants with
m~ng~nese cations and non-catalytic metal cations), and U.S. 4,728,455 (m~ng~nPse
gluconate catalysts).
Heavy metal ion sequestrant
The particle and or the detergent compositions, comprising the particle 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
20 magnesium chelation capacity, but pr~rerelltially they show selectivity to binding
heavy metal ions such as iron, m~n~nese 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
25 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 ~ mine tri (methylene phosphonate) hexamethylene diamine
tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
35 Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid
and polyaminocarboxylic acids such as ethylene~i~minotetracetic acid,
CA 0223220~ 1998-03-16
29
ethylenetriamine pentacetic acid, ethylene~i~rnine disuccinic acid, ethylene~ mine
diglutaric acid, 2-hydroxypropylene~ mine disuccinic acid or any salts thereof
Especially prer~lled is ethylene.li~-nine-N,N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or5 mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid,
described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-
10 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
,B-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 describessuitable 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'-
20 disuccinic acid (GADS), ethylenetli~mine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylene~ min~-N-N'-disuccinic acid (HPDDS) are also suitable.
EnzYme
25 Another plef~lled ingredient useful in the detergent compositions, comprising the
particle, is one or more additional enzymes. Optionally, the enzymes or part thereof
cam be present in the agglomerated or extruded particle of the invention.
Preferred additional enzymatic materials include the commercially available lipases,
30 cutinases, amylases, neutral and ~lk~line proteases, esterases, cellulases, pectinases,
lactases and peroxidases conventionally incorporated into detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the
35 tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries
A/S (Denrnark), those sold under the tr~dçn~rne Maxatase, Maxacal and Maxapem
CA 0223220~ 1998-03-16
-
by Gist-Brocades, those sold by Genencor International, and those sold under thetr~clen~me Opticlean and Optimase by Solvay Enzymes. 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
tradename Rapidase by Gist-Brocades, and those sold under the tradename
10 Termamyl and BAN by Novo Industries A/S. 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 from0.001% to 0.5% by weight ofthe compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a
lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp.
20 including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase fromchemically or genetically modified mutants of these strains are also useful herein. A
preferred lipase is derived from Pseudomonas pseudoalcali~enes. which is described
in Granted European Patent, EP-B-0218272.
25 Another plefelled lipase herein is obtained by cloning the gene from Humicolal~nu~inosa and ~ressing the gene in Asper~illus oryza, as host, as described in
European Patent Application, EP-A-0258 068, which is commercially available fromNovo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase
is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Or~anic polymeric compound
Organic polymeric compounds are preferred additional components of the particle
and/ or the d~lel~ ll compositions, comprising the particle in accord with the
35 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
CA 0223220~ 1998-03-16
polymeric compound it is meant herein essentially any polymeric organic compoundcommonly used as dispersants, and anti-redeposition and soil suspension agents in
dete~gent 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 I % to 10% by weight of the compositions.
10 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 ofthe lattertype are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers
with maleic anhydride, such copolymers having a molecular weight of from 20,000
to 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 cont~ining monomer units selected from maleic 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.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition
agent, for use herein, can be the ethoxylated cationic monoamines and ~i~mines of
the formula:
CA 0223220~ 1998-03-16
CH3 CH3
X i OCH2CH2) N+ CH2---CH2~CH2)a b N CH2 2
(CH2CH20 -)~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl
or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for
cationic mono~mines (b=0), n is at least 16, with a typical range of from 20 to 35; for
cationic diamines (b=1), n is at least about 12 with a typical range of from about 12
to about 42.
Other di~l~cr~a~ / anti-redeposition agents for use herein are described in EP-B-
10 011965 and US 4,659,802 and US 4,664,848.
Suds suppressing system
The detergent compositions, when formulated for use in m~hine washing
15 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
20 known antifoam compound, including, for example silicone antifoam compounds
and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mi~lulcs of compounds
which act such as to depress the foaming or sudsing produced by a solution of a
25 detergent composition, particularly in the presence of agitation of that solution.
Particularly prcf~llcd antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component. Such silicone antifoam compounds also typically contain a silica
30 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
CA 0223220~ 1998-03-16
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
10 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 C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
15 hexa-alkylmel~mine~ or di- to tetra alkyldiamine chlortriazines formed as products of
cyanuric chloride with two or three moles of a primary or secondary amine
cont~ining 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.
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 silicalsilicone antifoam compound is incorporated at a level of from 5%
to 50%, preferably 10% to 40% by weight;
35 (b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide
CA 0223220~ 1998-03-16
-
- 34
to propylene oxide ratio of from 1 :0.9 to 1: 1.1, at a level of from 0.5% to
10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol
rake copolymer of this type is DCO544, commercially available from DOW
Corning under the tradename DCO544;
s
(c) an inert carrier fluid compound, most preferably comprising a C 16-c 18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly plerell~d particulate suds su~plessing system is described in EP-A-0210731
and comprises a silicone antifoam compound and an organic carrier m~teri~l 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 cont~ining
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 oralcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or a mixture
thereof, with a melting point of from 45~C to 80~C.
Clay softening system
The particle and/ or 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 claysare disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
European Patents Nos. 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.
Polymeric dye transfer inhibitin~ a~ents
The particle, but preferably the detergent compositions may also comprise from
0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transferinhibiting agents.
CA 0223220~ 1998-03-16
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.
S a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula:
(I) Ax
R
wherein P is a polymerisable unit, and
00 0
A is NC, CO, C, -O-, -S-, -N-; x is O or1;
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 orwherein the nitrogen of the N-O group is part of these groups.
20 The N-O group can be represented by the following general
structures:
o
o
(R1) X-N-(R2)
(R3)z or N-(R1 )x
25 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-O group can be attached or wherein the nitrogen of the N-O group forms
CA 0223220~ 1998-03-16
36
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 heterocyclic
group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,10 acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O groupis attached to the polymerisable unit. A pl~rt;,led class of these polyamine N-oxides
comprises the polyamine N-oxides having the general formula (I) wherein R is an
15 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.
20 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.
25 b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone havingan average molecular weight range of from 5,000 to 50,000. The plefe,~ed
copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to
30 0.2.
c) Polyvinylpyrrolidone
The delelgellt compositions herein may also utilize polyvinylpyrrolidone ("PVP")35 having an average molecular weight of from 2,500 to 400,000. Suitable
polyvinylpyrrolidones are commercially valuable from ISP Corporation, New York,
CA 0223220~ 1998-03-16
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 of360,000). PVP K-15 is also available from ISP Corporation. Other suitable
5 polyvinylpyrrolidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone
10 The detergent compositions herein may also utilize polyvinyloxazolidones as
polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an
average molecular weight of from 2,500 to 400,000.
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.
20 Optical bri~htener
The detergent compositions herein also optionally contain from about 0.005% to 5%
by weight of certain types of hydrophilic optical brighteners.
25 Hydrophilic optical brighteners useful herein include those having the structural
formula:
N~ ~C=C~N~
R2 SO3M SO3M Rl
30 wherein Rl 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,
CA 0223220~ 1998-03-16
38
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
5 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, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylaminoand 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)amino]2,2'-stilbenedisulfonic acid
disodium salt. This particular brightener species is commercially marketed under the
15 tr~den~me Tinopal 5BM-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-6-morphilino-s-triazine-2-yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
20 commercially marketed under the tr~den~me Tinopal AMS-GX by Ciba Geigy
Corporation.
Cationic fabric softening agents
25 Cationic fabric softening agents can also be incorporated into the particle and/or the
compositions. Suitable cationic fabric softening agents include the water insoluble
tertiary amines or dilong chain amide materials as disclosed in GB-A-I 514 276 and
EP-B-0 011 340.
30 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
CA 0223220~ 1998-03-16
39
Other optional ingredients suitable for inclusion in the particle and the detergent
compositions include perfumes, colours and filler salts, with sodium sulfate being a
preferred filler salt.
CA 0223220~ 1998-03-16
pH of the compositions
The final detergent 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
5 10.5 to 12Ø
Form of the a~glomerated or extruded particle and deter~ent compositions thereof
Surfactant a~lomerate particles
The particles may take the form of flakes, prills, marumes, noodles, ribbons, but
preferably take the form of granules. The most ~l~r~ d way to process the particles,
as described above, is by agglomerating or mixing and extruding powders (e.g.
aluminosilicate, optionally carbonate) with high active surfactant pastes and to15 control the particle size of the resultant particles within specified limits.
Form of the compositions
The compositions, comprising the particle, can take a variety of physical forms
20 including granular, tablet and bar. The compositions can be of the form of the so-
called concentrated granular detergent compositions adapted to be added to a
washing m~ ine by means of a dispensing device placed in the machine drum with
the soiled fabric load.
25 The mean particle size of the base composition of granular compositions in
accordance with the invention can be from 0.1 mm to 5.0 mm, but it 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 0.1 Smm in diameter.
30 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.
CA 0223220~ 1998-03-16
41
The bulk density of granular detergent compositions is typically of at least 500g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by
means of a simple funnel and cup device consisting of a conical funnel moulded
rigidly on a base and provided with a flap valve at its lower extremity to allow the
contents of the funnel to be emptied into an axially aligned cylindrical cup disposed
below the funnel. The funnel is 130 mm high and has internal diameters of 130 mmand 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
10 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
15 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/litre. Replicate measurements are made as required.
Laundry washin~ method
Machine laundry methods herein typically comprise treating soiled laundry with an
aqueous wash solution in a washing machine having dissolved or dispensed thereinan effective amount of a m~rhine laundry detergent composition in accord with the
invention. By an effective amount of the detergent composition it is meant from 40g
25 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 m~rhine laundry methods.
In a plefell~d use aspect a dispensing device is employed in the washing method.30 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.
35 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
CA 0223220~ 1998-03-16
42
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 thisproduct 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
10 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.
15 Preferred dispensing devices are reusable and are designed in such a way thatcontainer integrity is m~int~ined 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
20 in Manufacturing Chemist, November 1989, pages 41-46 also describes especially
plcfel~cd dispensing devices for use with granular laundry products which are of a
type commonly know as the "granulette". Another plcrellcd dispensing device for
use with the compositions of this invention is disclosed in PCT Patent Application
No. WO94/11562.
Especially ~;,lefellcid 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
30 one washing cycle in a washing process. A portion of the washing medium flowsthrough 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 m~king arrangement to prevent egress of wetted, undissolved, product, this
arrangement typically comprising radially e~t~n~ling walls extending from a central
35 boss in a spoked wheel configuration, or a similar structure in which the walls have a
helical form.
CA 0223220~ 1998-03-16
.
43
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 aspolyethylene 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 l~min~tPs A preferred pack~gin~ execution is described in
European Application No. 94921505.7.
Abbreviations used in following Examples
In the detergent compositions, the abbreviated component identifications have the
following m~ninp~
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C 14-C 15 linear alkyl sulfate
CxyEzS : Sodium Clx-Cly branched alkyl sulfate condensed
with z moles of ethylene oxide
C45E7 : A C14 15 predomin~ntly linear primary alcohol
condensed with an average of 7 moles of ethylene oxide
C25E3 : A C12 15 branched primary alcohol condensed with an
average of 3 moles of ethylene oxide
C25E5 : A C12 15 branched primary alcohol condensed with an
average of 5 moles of ethylene oxide
CA 0223220~ 1998-03-16
CEQ : RlCOOCH2CH2.N+(CH3)3 with Rl = C11-C13
QAS : R2.N+(CH3)2(c2H4OH) with R2 = C12 ~ C14
Soap : Sodium linear alkyl carboxylate derived from an
80/20 mixture of tallow and coconut oils.
TFAA : C 16-c 18 alkyl N-methyl glucamide
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102SiO2)12. 27H20 having a primary particle
size in the range from 0.1 to 10 micrometers
NaSKS-6 : Crystalline layered silicate of formula
o -Na2Si205
Citric acid : Anhydrous citric acid
Carbonate : Anhydrous sodium carbonate with a particle size
between 200 ~lm and 900~1m
Bicarbonate : Anhydrous sodium bicarbonate with a particle size
distribution between 40011m and 1200~1m
Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
Sodium sulfate : Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a
particle size distribution between 425~1m and 850~m
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 Industries A/S under the tradename 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 tr~dçn~me
Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename
Termamyl 60T
CA 0223220~ 1998-03-16
Lipase : Lipolytic enzyme of activity 1 00kLU/g sold by
NOVO Industries A/S under the tradename
Lipolase
Endolase : Endoglunase enzyme of activity 3000 CEVU/g
sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20-H202
PB 1 : Anhydrous sodium perborate monohydrate bleach of
nominal formula NaBo2.H2o2
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03 3H202
NOBS : Nonanoyloxybenzene sulfonate in the forrn of the
sodium salt.
TAED : Tetraacetylethylene~ mine
DTPMP: Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under the
Trade name Dequest 2060
Photoactivated : Sulfonated Zinc Phthlocyanine encapsulated in bleach
dextrin soluble polymer
Brightener l : Disodium4,4'-bis(2-sulphostyryl)biphenyl
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene
oxy and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
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.
Alkalinity : % weight equivalent of NaOH, as obtained using the
alkalinity release test method described herein.
CA 0223220~ 1998-03-16
46
In the following Examples all levels are quoted as % by weight of the composition:
Example 1
The following detergent formulations according to the present invention were
prepared:
A B
Blown Powder
Zeolite A 15.0
Sodium sulfate - -
LAS 3.0
CEQ 2.0 1.3
DTPMP 0.4
CMC 0.4
MA/AA 4.0
Agglomerates
PB1 15.0 10.0
C45AS - 11.0
LAS 6.0
TAS 3.0
Silicate 4.0
Zeolite A 10.0 13.0
CMC - 0-5
MA/AA - 2.0
Citric Acid 4.0 3.0
Spray On
Perfume 0.3 0.5
C 45 E 7 4.0 4.0
C 25 E3 2.0 2.0
Dry additives
T A E D 4.0 2.0
MA/AA - 3.0
NaSKS-6 - 12.0
CA 02232205 1998-03-16
47
Bicarbonate 7.0 5.0
Carbonate 17.0 14.0
PVPVI/PVNO 0.5 0.5
Alcalase 0.5 0.9
Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam 5.0 5.0
Dry additives
Sodiurn sulfate 0.0 2.0
Balance (Moisture and Miscellaneous) 100.0 100.0
Density (g/litre) 700 700
CA 0223220~ 1998-03-16
48
Example 2
The following high density and bleach-cont~ining detergent formulations, according
to the present invention were prepared:
C D
Blown Powder
Zeolite A 15.0 15.0
Sodium sulfate 0.0 0.0
LAS 3.0 3.0
QAS - 1.5
CEQ 2.0 2.0
DTPMP 0.4 0.4
CMC 0.4 0.4
MA/AA 4.0 2.0
Agglomerates
PB1 15.0 15.0
LAS 4.0 4.0
TAS 2.0 1.0
C24E5 2.0 2.0
Silicate 3.0 4.0
Citric Acid 2.0 3.0
Zeolite A 8.0 8.0
Carbonate - 6.0
Magnesium sulphate 0.3 0.4
Spray on
Perfume 0.3 0.3
C45E7 2.0 2.0
Dry additives
Citrate 5.0 2.0
Bicarbonate
Carbonate 16.0 10.0
TAED 6.0 5.0
Polyethylene oxide of MW 5,000,000 - 0.2
CA 02232205 1998-03-16
49
Bentonite clay - 10.0
Protease 1.0 1.0
Lipase 0.4 0.4
Amylase 0.6 0.6
Cellulase 0.6 0.6
Silicone antifoam 5.0 5.0
Dry additives
Sodium sulfate 0.0 0.0
Balance (Moisture and 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850
CA 0223220~ 1998-03-16
Example 3
The following high density detergent formulations, according to the present
invention were prepared:
E F
Agglomerate
LAS 7.5
PB1 12.0
PB4 - 15.0
C45AS - 14.0
CEQ - 3.5
Zeolite A 15.0
citric acid 1.5 2.0
Carbonate 4.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
C24E5 5.0 5.0
Spray On
Perfume 0.5 0.5
Dry Additives
Zeolite - 6.0
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 1.4 1.4
Lipase 0.4 0.4
Cellulase 0.6 0.6
Arnylase 0.6 0.6
CA 02232205 1998-03-16
51
Silicone antifoarn 5.0 5.0
Brightener 1 0.2 0.2
Brightener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
