Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DETERGENT PARTICLES AI'rD PROCESSES FOR MAKING THEM
Field of the Invention
The present invention relates to particulate detergent compositions and an
improved
process for making such compositions. The detergent compositions of the
invention are suitable
for anv cleaning process, such as laundry and dishwashing detergent
compositions. Such
particulate compositions may be used directly in their particulate form or may
first be formed into
detergent tablets by any standard tabletting process such as compaction.
Background of the Invention
In order to meet the needs of the consumer. in addition to providing good
cleaning,
detergent compositions must meet many additional requirements including good
aesthetics, good
flow properties, good solubility- and good dispensing performance into wash
water. In order to
meet all of these requirements, the complexity of detergent compositions and
range of products
offered has growm. Formulation flexibility for producing such complex
compositions is therefore
extremely important and many methods for formulating detergent compositions
are already
known.
In view of the high performance requirements of the consumer, achieving
uniform dosage
of all of the detergent actives in the composition has increased importance,
in particular where
sophisticated detergent ingredients present in detergents at low levels make a
significant impact
on one of the performance features mentioned above. This problem is
exacerbated by the advent
of "compact" or low dosage granular detergent products. These low dosage
detergents are
currently in high demand as they conserve resources and can be sold is small
packages which are
more convenient for consumers prior to use. However, in a low dosage of
detergent, where
actives are present in very low levels, significant variability may occur in
the concentration of
such actives in each unit dosage. Performance problems have been identified
with some compact
detergent products and the present inventors have now found that this may be
due to formulation
variability where low level detergent ingredients which give a significant
impact on one or more
of the performance factors mentioned above may vary considerably from dose to
dose.
Summary of the Invention
The present invention therefore reduces these problems by providing a process
in which
such low dosage/high impact ingredients can be dispersed uniformly throughout
a detergent
formulation. Segregation is minimised without the need to incorporate high
levels of fillers to
form such low dosage/high impact ingredients into larger particles.
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In accordance with the present invention there is now provided a method for
making a
detergent particles comprising selecting detergent base particles having a
geometric mean
particle diameter from 500 - 2000 microns, in a moderate to low shear mixer
adhering detergent
active particulates to the detergent base particles, wherein the detergent
active particulates have a
geometric mean particle diameter no greater than 40% of the geometric mean
particle diameter of
the detergent base particles and comprise a detergent active selected from
perfumes. enzymes,
photobleaches, catalysts, soil release polymers, suds suppressors, bleaching
compounds,
whitening agents and layered silicates.
The present invention also provides detergent panicles produced by such a
process, and
detergent compositions incorporating these particles.
As used herein, it is intended to mean that a detergent active particulate is
bound to the
detergent base particulate, the two components subsequently appearing in a
detergent
composition as an individual detergent particle.
Detailed Description of the Invention
Physical Properties
The detergent active particulates preferably have a geometric mean particle
diameter
which is below 200~tm, preferably below 150~m and even below 100 Vim. The
geometric mean
particle diameter of the detergent active particulates is generally above I
O~tm preferably above 20
~tm and may even be above 40~m or above 60~m.
As used herein, the phrase "geometric mean particle diameter" means the
geometric mass median diameter of a set of discrete particles as measured by
any standard mass-
based particle size measurement technique, preferably by dry sieving. A
suitable sieving method
is in accordance with ISO 3118 (1976). A suitable device is the Ro-Tap testing
sieve shaker
Model B using 8 inch sieves of selected sizes. As used herein, the phrase
"geometric standard
deviation" or "span" of a particle size distribution means the geometric
breadth of the best-fitted
log-normal function to the above-mentioned particle size data which can be
accomplished by the
ratio of the diameter of the 84.13 percentile divided by the diameter of the
50~' percentile of the
cumulative distribution (Dg4_,3/D50)i See Gotoh et al, Powder Technolo~v
Handbook, pp. 6-11,
Marcel Dekker 1997.
The detergent base particles have a geometric mean particle diameter from 500
to
2000~m. The geometric mean particle diameter of the detergent base particles
is generally
greater than SSO~m or even greater than 600~m or 650~m. Preferably, the
geometric mean
particle diameter of the detergent base particles is below 1500~un.
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The detergent particles produced preferably have a geometric standard
deviation of from
1 to about 2, preferably from I .0 to 1. ~, more preferably from about 1.0 to
about I .4. Preferred
fully formulated detergents comprising the detergent particles also have such
a geometric
standard deviation.
Preferably the geometric mean particle diameter of the detergent active
particulates is no
greater than 20% of the geometric mean particle diameter of the detergent base
particles more
preferably no greater than 10% and may even be below 5% of the geometric mean
particle
diameter of the detergent base particles. Generally in the detergent
particles, no more than
25wrt% is derived from the detergent active particulates, preferably no
greater than 10 wt°io. The
invention may even be useful where the proportion of the detergent particles
derived from the
detergent active particulates is no greater than 5 or even no greater than 2
wt%.
As used herein the term "bulk densin-" refers to the uncompressed, untapped
powder bulk density, as measured by pouring an excess of particulate sample
through a funnel
into a smooth metal vessel (e.g. a 500m1 volume cylinder) scraping off the
excess off the heap
above the rim of the vessel, measuring the remaining mass of powder and
dividing the mass by
the volume of the vessel.
The bulk density of the detergent particles produced and also of the detergent
base
particles is generally above 200 g/1 and may be as high as 1500 g/1. It is
particularly preferred
that the bulk density a finished detergent composition comprising the
detergent particles
produced according to the present invention is greater than 550 g/1,
preferably greater than 600
g/1 or even above 650 g/1. The bulk density of the detergent particles
produced is therefore
generally from 400g/1 to 1100 g/1, generally above 500g/1 or even above 550 or
650g/1, generally
less than 1 OOOg/1 or below 900g/1. The invention may be particularly useful
for forming
detergent particles having a low bulk density such as below 550 or even below
500 or 450 g/1.
The detergent base particles for use in the method of the present invention
may comprise
a single detergent ingredient in particulate form or may be a pre-mix of
detergent ingredients.
Where the detergent base particles comprise a pre-mix, the separate detergent
ingredients may
simply be mixed together or may comprise a pre-formed particulate comprising
any combination
of two or more detergent ingredients, or mixtures thereof, optionally with
single detergent
ingredients. Suitable pre-formed particulates for the base particles may have
been formed by
spray-drying, agglomeration, marumerisation, extrusion or compaction, all of
which methods for
combining detergent ingredients are well-known in the art. Particularly
preferred pre-formed
particulates are powders obtained from spray-drying processes, agglomerates
and extrudates.
Spray-dried powders are particularly useful. Pre-formed particulates made
according to at least
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one low shear mixing step. for example in a fluidised bed. for example by
fluid bed
agglomeration are particularly preferred. Particularly preferred panicles are
as described in our
co-pending application filed today under reference number CW2158F.
Suitable spray-drying processes for forming such pre-formed particulates are
described
for example in EP-A-763594 or EP-A-437888. Suitable processes for forming pre-
formed
particulates which are agglomerates are described for example in W093/25378,
EP-A-367339,
EP-..A-420317 or EP-A-506184 and suitable processes for forming pre-formed
particulates by
extrusion are described for example in W091/02047.
Such pre-formed particulates may be added to the mixer in their wet or dry
state. They
are preferably added to the mixer in their dry state as addition in their wet
state may have an
adverse effect on flow into the mixer. Alternatively it may be preferred that
the pre-formed
particulates are formed in a first stage of a moderate to low shear mixer and
the detergent active
particulates are added in a second stage so that the pre-formed particulates
may be in a wet state
when they are contacted with the detergent active particulates. Thus, the pre-
formed particulate
may be for example an agglomerate, blown powder or extrudate which has not yet
undergone a
final drying stage.
Generally this means that a solvent used as a binding agent for the processing
is present
in higher amounts than are desirably present in a finished particulate
detergent. Generally the
solvent is water and wet particulates will have a free water content for
example of froml5 to 30
wt % of the pre-formed particulate. Often, however, the pre-formed particulate
will already have
undergone a drying step prior to addition to the mixer so that the water
content will be below 15
wt %, preferably below 10 wt %. Generally the free water content of the
detergent base particles
on entry into the mixer will be below 1 S wt %, preferably below 10 wt %.
It may be preferred that the detergent base particles comprise a surfactant or
mixture of
surfactants. Suitable surfactants are described below. The surfactant content
of the detergent
base particles or a pre-formed particulate component forming all or part of
the detergent base
particles is preferably from 5 to 80 % by weight of the particulate component.
Amounts of
surfactants above 10 or even above 30% may be preferred. Amounts of surfactant
below 70% or
even below 50% may be preferred. Where the detergent base pre-formed
particulate component
comprises surfactant, generally it will in addition comprise a builder or
alkalinity agent such as
sodium carbonate, zeolite, or phosphate. For example, each of these components
individually, or
in mixtures may be present in amounts above 5%, preferably above 10°~0
or even above 20% by
weight of the content of the pre-formed particulate component. Particularly
preferred builder
components are sodium carbonate and/or zeolite. Zeolite A and zeolite MAP are
both suitable.
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The detergent base particles preferably also comprises an organic builder such
as a poly
carboxylic acid andior salt such as citric acid. tartaric acid. malic acid,
succinic acid and their
salts or a polymeric polycarboxylate such as polymers based on acrylic acids
or malefic acids or
co-polymers thereof. Such components are generally present in the particle at
levels below 15 wt
of the particulate component, preferably below 10 W % of the particulate
component.
Other preferred ingredients in the pre-formed particulate component are
chelants such as
phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as
described below.
These components are preferably present in the detergent base particles in
amounts below ~ wt
or even below 2 wt ° o. Suds supressors andior soil release polymers
and/or bleach activators are
also preferred ingredients in pre-formed particulates.
Where the particulate components are detergent raw materials, any particulate
detergent
ingredient is suitable. These may be solid surfactants or soaps. or water
soluble or dispersable
polymeric materials, enzymes. bleaching components such as bleach activators
or bleach salts
such as peroxy salts. Highly suitable single ingredients in particulate form
include inorganic
components, particularly water-soluble inorganic components such as builders
and bleach salts
such as alkali metal percarbonates and/or perborates. These ingredients are
discussed in more
detail below .
Suitable detergent ingredients for incorporation either into the detergent
particles
themselves, or for post-addition to formulate a fully formulated detergent
composition are
discussed below.
The detergent active particulates are selected from perfumes, enzymes,
photobleaches,
catalysts, soil release polymers, suds suppressors, bleaching compounds,
whitening agents and
layered silicates.
Perfumes
Preferred detergent active particulates comprise perfume. Any perfume or
perfume
composition can be used. However, it must be solid or in combination with
other components so
that it has a solid form. For example it may be loaded onto a particulate
carrier such as zeolite, or
any other known solid carrier, for example as described in W094/16046,
ES93000006, EP-A-
535942, and EP-A-294206. More preferably it is present in encapsulated form.
Suitable
encapsulates are described for example in W094/12613, EP-A-539025, EP-A-
478326, EP-A-
383406, EP-A-382464, EP-A-346034, EP-A-70719. Particularly preferred
encapsulates comprise
starch.
Preferred perfumes contain at least one component with a low molecular weight
volatile
component, e.g. having a molecular weight of from 150 to 450 or preferably
350. Preferably, the
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perfume component comprises an oxygen-containing functional group. Preferred
functional
groups are aldehyde, ketone, alcohol or ether functional groups or mixtures
thereof.
Enzymes
The detergent active particulates may comprise one or more enzymes. Suitable
enzymes
include the commercially available lipases, cutinases, amylases. neutral and
alkaline proteases,
cellulases, endolases, esterases, 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
tradenames Alcalase, Savinase, Primase, Durazvm, and Esperase by Novo
Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-Brocades,
those sold by Genencor International, and those sold under the tradename
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, 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 Termamyl,
Duramyl and BAN by Novo Industries A/S. Preferred amylase enzymes may be those
described
in PCT/ US 9703635, and in W095/26397 and W096/23873. 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.
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 based on the content in the final detergent composition. 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. including Pseudomonas pseudoalcalieenes or
Pseudomas
fluorescens. Lipase from chemically or genetically modified mutants of these
strains are also
useful herein. A preferred lipase is derived from Pseudomonas
pseudoalcalieenes, which is
described in EP-B-0218272. Another preferred lipase is obtained by cloning the
gene from
Humicola lanuy'nosa and expressing the gene in Aspereillus 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 name Lipolase. This lipase
is also described
in U.S. Patent 4,810,414. Huge-Jensen et al, issued March 7, 1989.
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Photobleaches
Preferred detergent active particulates comprise photobleach particles.
Preferred photo-
bleaches herein comprise a compounds having a porphin or porphvrin structure.
Porphin and
porphvrin, in the literature, are used as synonyms, but conventionally porphin
stands for the
simplest porphyrin without any substituents; wherein porphyrin is a sub-class
of porphin. The
references to porphin in this application will include porphyrin. The porphin
structures
preferably comprise a metal element or canon, preferably Ca, Mg, P. Ti, Cr,
Zr, In. Sn or Hf,
more preferably Ge, Si or Ga, or more preferably A1 , most preferably Zn. It
can be preferred that
the photo-bleach or component is substituted with substituents selected from
alkyl groups such as
methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as
pvridyl, pyridyl-N-oxide,
phenyl, naphthyl and anthracyl moieties.
The photo-bleaching compound or component can have solubilizing groups as
substituents.
Alternatively, or in addition hereto the photo-bleaching agent can comprise a
polymeric
component capable of solubilizing the photo-bleaching compound, for example
PVP, PVNP, PVI
or co-polymers thereof or mixtures thereof.
Highly preferred photo-bleaching compounds have a phthalocyanine structure,
which
preferably have the metal elements or canons described above. The
phthalocyanines can be
substituted, suitable examples include the phthalocyanine structures which are
substituted at one
or more of the l -4, 6. 8-11, 13, 15-18, 20, 22-25, 27 atom positions.
One preferred group of photobleaches comprise a polymeric component and a
photobleaching component integrated with one another, whereby the weight ratio
of polymeric
component to photobleaching component is from 1:1 to 1000:1, preferably 20:1
to 100:1.
Particularly preferred polymeric compounds are formed from monomeric units
selected from N-
vinylpyrolidone, N-vinylacetamide, N-vinyl imidazole, N-vinyl oxazolidone, N-
vinyltriazole, 4-
vinylpyridine arid 4-vinylpyrilidine-N-oxide. Preferred photo-bleaching
compounds are metals,
preferably zinc, phthalocyamines or aluminium. Such photo-bleaches are
described in GB
2329397A.
Soil Release Polymers
Preferred soil release polymers (SRPs) typically have hydrophilic segments to
hydrophilize
the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic
segments to
deposit upon hydrophobic fibers and remain adhered thereto through completion
of washing and
rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can enable stains
occurring subsequent to treatment with the SRP to be more easily cleaned in
later washing
procedures. Preferred SRPs include oligomeric terephthalate esters, typically
prepared by
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_g_
processes involving at least one transesterification/oligomerization, often
with a metal catalyst
such as a titanium(IV) alkoxide. Such esters may be made using additional
monomers capable of
being incorporated into the ester structure through one. nvo, three, four or
more positions,
without, of course, forming a densely crosslinked overall structure.
Suitable SRPs include a sulfonated product of a substantially linear ester
oligomer
comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy
repeat units and
allyl-derived sulfonated terminal moieties covalently attached to the
backbone, for example as
described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P.
Gosselink. Such ester
oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the
product of (a) with
dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage
transesterification/oligomerization procedure; and (c) reacting the product of
(b) with sodium
metabisulfite in water. Other SRPs include the nonionic end-capped 1,2-
propylene/polyoxyethylene terephthalate polyesters ofU.S. 4,711,730. December
8, 1987 to
Gosselink et al., for example those produced by
transesterification/oligomerization of poly-
(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other
examples of
SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of
U.S. 4,721,580,
January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"),
PG, DMT and
Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester
oligomeric
compounds of U.S. 4,702,857. October 27, 1987 to Gosselink, for example
produced from DMT,
methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or
PG, Me-
capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially
sulfoaroyl, end-
capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado,
Gosselink et al.,
the latter being typical of SRPs useful in both laundry and fabric
conditioning products, an
example being an ester composition made from m-sulfobenzoic acid monosodium
salt, PG and
DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRPs also
include: simple copolymeric blocks of ethylene terephthalate or propylene
terephthalate with
polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to
Hays, May 25,
1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such
as the hydroxyether
cellulosic polymers available as METHOCEL from Dow; the Cl-C4 alkyl celluloses
and C4
hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et
al.; and the methyl
cellulose ethers having an average degree of substitution (methyl) per
anhydroglucose unit from
about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120
centipoise measured
at 20°C as a 2% aqueous solution. Such materials are available as
METOLOSE SM 100T"' and
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METOLOSE SM200T"', which are methyl cellulose ethers manufactured by Shin-etsu
Kagaku
Ko~vo KK.
Additional classes of SRPs include those described in U.S. 4,201.824, Violland
et al. and
U.S. 4,240,918 Lagasse et al.; and SRA's with carboxylate terminal groups made
by adding
trimellitic anhydride to known SRP's to convert terminal hydroxyl groups to
trimellitate esters.
With the proper selection of catalyst, the trimellitic anhydride forms
linkages to the terminals of
the polymer through an ester of the isolated carboxylic acid of trimellitic
anhydride rather than by
opening of the anhydride linkage. Either nonionic or anionic SRPs may be used
as starting
materials as long as they have hydroxyl terminal groups which may be
esterified. See U.S.
4,525,524 Tung et al., and U.S. 4,201,824, Violland et al.
Suitable soil release polymers may be selected from: (a) alkyl and
hydroxyalkyl ethers of
cellulose containing from one to four carbon atoms in the alkyl moiety and
having a molar degree
of substitution of from 1.5 to 2.7 and a number average molecular weight of
from 2000 to
100000; (b) polymers comprising ethylene terephthalate and polyethylene oxide
terephthalate at a
mole ratio of from 1:10; (c) polymers comprising propylene terephthalate and
polyethylene oxide
terephthalate at a mole ratio of from 1:10 to 10:1, said polyethylene oxide
terephthalate
containing polyethylene oxide units with a number average molecular weight of
from 500 to
10000 and said soil release agent having a number average molecular weight of
from 1000 to
100000; and (d) polymers comprising ethylene terephthalate and/or propylene
terephthalate in
any ratio and polyethylene oxide and/or polypropylene oxide inany ratio such
that the mole ratio
of ethylene terephthalate plus propylene terephthalate to polyethylene oxide
plus polypropylene
oxide is from 1:10 to 10:1, said polyethylene oxide units and said
polypropylene oxide units each
having a number average molecular weight of from 250 ti 10000 and said soil
release agent
having a number average molecular weight of from 1000 to 100000; and mixtures
thereof; as
described in more detail in EP-A-271312.
Suds Supressors
The detergent active particulates may comprise suds supressors. Suitable suds
suppressing systems may comprise essentially any known antifoam compound,
including, for
example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or
soap.
By antifoam compound it is meant herein any compound or mixtures of compounds
which act such as to depress the foaming or sudsing produced by a solution of
a detergent
composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam
compounds defined herein as any antifoam compound including a silicone
component. Such
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silicone antifoam compounds also t~rpically 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 anti foam compounds include the monocarboxvlic fatty acids and
soluble
salts thereof as 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 C1 g-C40
ketones (e.g. stearone) N-allylated amino triazines such as tri- to hexa-
alkylmelamines or di- to
tetra alkyldiamine chlorniazines 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. A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination polydimethyl siloxane, at
a level
of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam
compound; and 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% 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 1:1.1, at a level of from 0.5% to 10%. such as DC0544,
commercially
available from Dow Corning; and
(c) an inert carrier fluid compound, most preferably comprising a C16-CI 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°ro, 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
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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 atoms,
or a mixture thereof. with a melting point of from 45°C to 80°C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane
or
mixtures of silicone. such as polydimethylsiloxane, aluminosilicate and
polycarboxylic polymers.
such as copolymers of laic and acrylic acid.
Bleaching Compounds
The detergent active particulates may comprise one or more bleaching
compounds.
Suitable bleaching compounds include bleach activators, pre-formed peracids
and peracid salts
such as alkali metal percarbonate and/or perborate. The chemical nature of
these components is
discussed in more detail below in the section entitled "Detergent
Ingredients". Preferred bleach
compounds are bleach activators such as TAED, NOBS, ISONOBS etc, as discussed
below, and
the persalts such as alkali metal percarbonate and/or perborate. Sodium salts
are particularly
preferred.
Whitenin~Agents
Suitable whitening agents include hydrophilic optical brighteners such as
include those
having the structural formula:
R~ R,
ON H ~I N O
N OON O ~_~ O N 00 ~T
ON H H N \
R2 S~3M S~3M R~
wherein RI 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',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-2-
yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular br-
ightener species is
commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy
Corporation.
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Tinopal-CBS-a and Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in
the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxvethyl-N-2-
methylamino and
M is a canon such as sodium, the brightener is 4.4'-bis[(4-anilino-6-(N-2-
hvdroxyethyl-N-
methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
This particular
brightener species is marketed as Tinopal 5BM-GXT"' 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 are
sold by Ciba Geigy
Corporation as Tinopal-DMS-XTM and Tinopal AMS-GXTM
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Layered Silicates
Suitable crystalline layered silicates are described for example in US
4,664,839.
Crystalline layered silicates rich in delta-phase are preferred. such as those
described in
W097/I 9156.
Cata~s
The detergent active particulates may also comprise catalyst particulates.
Suitable
catalysts include transition metal-containing bleach catalyst. One suitable
type of bleach catalyst
is a catalyst system comprising a heavy metal cation of defined bleach
catalytic activiy, such as
copper, iron or manganese cations, an auxiliary metal canon having little or
no bleach catalytic
activity, such as zinc or aluminium cations, and a sequestrant/chelant having
defined stability
constants for the catalytic and auxiliary metal cations, particularly
ethylenediamine tetraacetic
acid, ethylenediamine tetra(methylenephosphonic acid) and water-soluble salts
thereof. Such
catalysts are disclosed in US 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in US
5,246,621 and US 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-
trimethul-1,4,7-
triazacyclononane)2-(C1O4)2, MnIV4(u-O)6(1,4,7-triaxacyclononane)4-(C1O4)2,
MnIIIMnIV4(u-O)1(u-Oac)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C1O4)3,
and mixtures
thereof. Others are described in EP-A-549272. Other suitable ligands include
1,5,9-trimethyl-
1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-
triazacyclonanone,
1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see US 4,246,612 and US 5.227,084.
See also
US 5,194,416 which teaches nononuclear manganese (IV) complexes such as
Mn(1,4,7-trimethyl-
1,4,7-triazacyclonanone)(OCH3)3-(PF6). Still another type ofbleach catalyst as
disclosed in US
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 [Bipy2Mn)ZI(u-O)2MnNbipy2]-(C1O4)3.
Further suitable bleach catalysts are described for example in EP 408131
(cobalt complex
catalysts) EP 384503 and 306089 (metallo-porphyrin catalysts) US4,728,455
(manganese/multidentate ligand catalyst) US 4,711,748 and EP 224952 (absorbed
manganese on
aluminosilicate catalyst) US 4.601,845 (aluminosilicate support with manganese
and zinc or
magnesium salt) US 4,626,373 (manganese/ligand catalyst), US 4,119,557 (ferric
complex
catalyst), German Patent specification 2054019 (cobalt chelant catalyst),
Canadian 866191
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WO 00/78908 PCT/US00/16916
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(transition metal-containing salts), US 4.430.243 (chelants with manganese
cations and non-
catalytic metal cations), and US 4,728.455 (manganese gluconate catalysts).
The preferred detergent active particulates comprise perfume, photobleach
and/or
catalyst. Perfume and/or photobleaches are particularly preferred. In a
particularly preferred
aspect of the invention, the detergent active particulates comprise
encapsulated perfume. In a
further particularly preferred aspect of the invention, the detergent active
particulates comprise
photobleach.
The preferred proportion of detergent active particulates to detergent base
powder will
vary dependent upon the relative particle sizes of these two components.
Preferably in the final
detergent composition the weight percentage of any one of the detergent active
particulates will
be no greater than l Owt%, preferably below 5 wt°io or even below 2 or
1 w~t% of the detergent
base particles. In particular where the proportion of detergent active
particulates is as low as 5 or
2 or 1 W°ro of the detergent base powder, preferably the geometric mean
particle size of the
detergent active particulates is no greater than 20%, preferably no greater
than 10 % or even
below 5 or even 2 or 1 % of the geometric mean panicle size of the detergent
base particles.
The detergent particles themselves may contain all of the ingredients of a
full formulated
detergent or may be mixed with additional detergent components such as
individual detergent
ingredients in particulate form or pre-formed detergent panicles as described
above which may
form part of the detergent base particles. The individual detergent
ingredients in particulate form
may be any of the detergent ingredients described below, in a particulate
form. Preferably,
detergent compositions of the present invention comprise more than 30 wt%,
more preferably
more than 50 wt°io or even as high as 80 or 90 wt% or even 95 wt% of
the detergent particles
according to the present invention. The higher the level of detergent
particles of the present
invention, the greater the benefits of the invention in terms of promoting
uniform dosages of
detergent from a package of particulate detergent or in a unit dosage which is
formed into a
tablet.
The processes of the invention may comprise the step of adding to the mixer a
binder to
facilitate production of the desired detergent particles. Generally such a
binder will be liquid in
the form of a solution or melt and will be added by spraying either directly
into the mixer or onto
the particulate components as they travel into the mixer. Preferably the
binder is added directly
into the mixer for example by spraying. The binder is added for purposes of
enhancing
agglomeration by providing a binding or sticking agent for detergent
components. The binder
may be any conventional detergent binding agent, preferably selected from the
group consisting
of water, anionic surfactants, nonionic surfactants, polyethylene glycol,
polyvinyl pyrrolidone,
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polyacrvlates, organic acids or their salts such as citric acid or citric
salts. and mixtures thereof.
Other suitable binder materials includine those listed herein are described in
Beerse et al, US
Patent number 5108646 (Procter and Gamble Company), the disclosure of which is
incorporated
herein by reference. The binder must be compatible with the detergent active
particulate as will
be appreciated by persons skilled in the an. Thus, where the stability of the
detergent active
particulate is adversely affected by water, the binder will be substantially
water-free.
Thus, in one aspect of the invention, a first feed stream of detergent base
powder is fed
into the mixer and in addition a second feed stream comprising a detergent
active particulates is
fed into the mixer and binder is also present in the mixer. The binder may be
fed directly via a
third stream into the mixer or it may be contacted with the detergent base
particles or detergent
active particulates prior to one or both of these feed streams entering the
mixer, for example the
detergent active particulate (or a proportion of the base particles] may be
entrained in the binder.
Where the mixer is divided into different zones, the three components may be
fed into the same
zone or optionally may be fed into different zones. In a preferred embodiment
of the invention,
the detergent base particles and detergent active particulates will be pre-
mixed prior to addition
of the binder.
In a further preferred aspect of the invention, after mixing of the detergent
base particles
and detergent active particulates, so that adhesion of the two components has
taken place, a
further liquid component is applied to the outside of the particles produced.
This further coating
may be the same chemical composition as the binder or may be any of the other
coating materials
or detergent ingredients described below.
The moderate to low shear mixer to be used in the present invention may be for
example
a Lodige KM (trademark) (Ploughshare) moderate speed mixer, or mixer made by
Fukae, Draes,
Schugi or similar brand mixers which mix with only moderate to low shear. The
Lodige KM
(ploughshare) moderate speed mixer which is a preferred mixer for use in the
present invention
comprises a horizontal hollow static cylinder having a centrally mounted
rotating shaft around
which several plough-shaped blades are attached. Preferably, the shaft rotates
at a speed of from
about 1 S rpm to about 140 rpm, more preferably from about 80 rpm to about 120
rpm. The
grinding or pulverizing is accomplished by cutters, generally smaller in size
than the rotating
shaft, which preferably operate at about 3600 rpm. Other mixers similar in
nature which are
suitable for use in the process include the Lodige PloughshareT"" mixer and
the Drais~ K-T 160
mixer. Generally, in the processes of the present invention, the shear will be
no greater than the
shear produced by a Lodige KM mixer with the tip speed of the ploughs below 10
m/s, or even
below 8mls or even lower.
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Preferably, the mean residence time of the various starting detergent
ingredients in the
low or moderate speed mixer is preferably in range from about 0.1 minutes to
about 30 minutes,
most preferably the residence time is about 0.5 to about ~ minutes. In this
way, the density of the
resulting detergent agglomerates is at the desired level.
Other suitable mixers for use in the present invention are low or very low
shear mixers
such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and
fluid bed
agglomerators.
Fluid bed agglomerators are particularly preferred. Typical fluidised bed
agglomerators
are operated at a superficial air velocity of from 0.1 to 4 m/s, either under
positive or negative
pressure. Inlet air temperatures generally range from -10 or 5°C up to
250°C. I-Iowever inlet air
temperatures are generally below 200°C, or even below 150°C. The
fluidized bed granulator is
preferably operated such that the flux number FN of the fluid bed is at least
about 2.~ to about
4.5. Flux number (FIvTm) is a ratio of the excess velocity (Ue) of the
fluidisation gas and the
particle density (pp) relative to the mass flux (q,;q) of the liquid sprayed
into the bed at a
normalized distance (D°) of the spraying device. The flux number
provides an estimation of the
operating parameters of a fluidized bed to control granulation within the bed.
The flux number
may be expressed either as the mass flux as determined by the following
formula:
FNm = log~oL {PaUe)/9nq~
or as the volume flux as determined by the formula:
FN,. = logio~{Ua/q~aq~
where q,,,;g is the volume of spray into the fluid bed. Calculation of the
flux number and a
description of its usefulness is fully described in WO 98/58046 the disclosure
of which is herein
incorporated by reference.
In addition, the fluidized bed is generally operated at a Stokes number of
less than about
1, more preferably from about 0.1 to about 0.5. The Stokes number is a measure
of particle
coalescence for describing the degree of mixing occurring to particles in a
piece of equipment
such as the fluid bed. The Stokes number is measured by the formula:
Stokes number = 4pvd/9u
wherein p is the apparent particle density, v is the excess velocity, d is the
mean particle
diameter and a is the viscosity of the binder. The Stokes number and a
description of its
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usefulness is described in detail in ~'l'O 99/03964, the disclosure of which
is herein incorporated
by reference.
Thus, where the mixer is a fluid bed mixer, detergent base particles of the
present
invention are passed into a fluid bed optionally having multiple internal
"stages" or "zones". A
stage or zone is any discrete area within the fluid bed, and these terms are
used interchangeably
herein. The process conditions within a stage may be different or similar to
the other stages in
the fluid bedldryer. It is understood that two adjacent fluid beds are
equivalent to a single fluid
bed having multiple stages. The various feed streams of detergent base
particles and detergent
active particulates can be added either at the same or at the different
stages, depending on, for
example, the particle size and moisture level of the feed stream. Feeding
different streams to
different stages can minimize the heat load on the fluid bed. and optimize the
particle size and
increase uniformity of the shape of the detergent particles produced.
The bed is typically fluidized with heated air in order to dry or partially
dry moisture
such as the binder liquids from the ingredients in the fluid bed. Where binder
is sprayed into the
fluid bed the spraying is generally achieved via nozzles capable of delivering
a fine or atomized
spray of the binder to achieve intimate nixing with the particulates.
Typically, the droplet size
from the atomizer is less than about 2 times the particle size. This
atomization can be achieved
either through a conventional two-fluid nozzle with atomizing air, or
alternatively by means of a
conventional pressure nozzle. To achieve this type of atomization, the
solution or slurry rheology
is may have a viscosity of less than about 500 centipoise, preferably less
than about 200
centipoise at the point of atomization. While the nozzle location in the fluid
bed may be in most
any location, the preferred location is a positioning that allows a vertical
down spray of any
liquid components such as binder. This may be achieved for example, using a
top spray
configuration. To achieve best results, the nozzle location is placed at or
above the f7uidized
height of the particles in the fluid bed. The fluidized height is typically
determined by a weir or
overflow gate height. The agglomeration/granulation zone of the fluid bed may
be followed by
an optional coating zone, followed by a drying zone and a cooling zone. Of
course, one of
ordinary skill in the art will recognize that alternative arrangements are
also possible to achieve
the resultant particles of the present invention.
Typical conditions within a fluid bed apparatus of the present invention
include: (i) a
mean residence time from about 1 to about 20 minutes, (ii) a depth of
unfluidised bed of from
about 100 to about 600 mm, (iii) a droplet spray size of less than 2 times the
mean particle size in
the bed, which is preferably not more than about 100 micron more preferably
not more than 50
microns, (iv) spray height generally from 150 to 1600 mm of spray height from
the fluid bed
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plate or preferably 0 to 600mm from the top of the fluid bed , (v) from about
O.l to about 4.0 m/s.
preferably 1.0 to 3.Orrvs of f7uidizing velocity and (vi) from about 12 to
about 200 °C of bed
temperature, preferably 15 to 100°C. Once again. one of ordinary skill
in the art will recognise
that the conditions in the fluid bed may vary depending on a number of
factors.
The detergent particles produced in the mixer can be further processed by
adding a
coating agent to improve the particle colour, increase the particle whiteness
or improve the
particle flowability after the detergent particles exit the mixer or the dryer
if an optional drying
step is added subsequently to the mixer or in a later stage in the mixer, to
obtain the high density
granular detergent compositions produced by the processes of the invention.
Those skilled in the
art will appreciate that a wide variety of methods may be used to dry as well
as cool the exiting
detergent without departing from the scope of the invention. Since the mixer
can be operated at
relatively low temperatures, the need for cooling apparatus is generally not
required in the
present process which thereby further reduces manufacturing costs of the final
product.
Another optional processing step includes continuously adding a coating agent
such as
zeolite and/or fumed silica to the mixer to facilitate free f7owabiliy of the
resulting detergent
particles and to prevent over agglomeration. Such coating agents generally
have a mean particle
size below 100 microns, preferably below 60 microns, even more preferably
below 50 microns.
Any coating stage may take place either immediately after formation of the
detergent
particles of the invention either before or after any drying step and
optionally after the detergent
particles have been mixed with additional detergent ingredients for forming a
fully formulated
detegent composition. Preferably any such coating agent will also have
detergent active
properties. A particularly preferred coating agent is a surfactant or aqueous
solution of
surfactant.
Detergent ingredients which are suitable as ingredients of the base powder,
and/or as
ingredients of the detergent active particulates and/or as ingredients of any
additional ingredients
added to the detergent particles of the present invention to form the fully
formulated detergent
compositions of the invention are described below.
Deter eg nt Ingredients
Surfactant
Suitable surfactants for use in the invention are anionic, nonionic,
ampholytic, and
zwitterionic classes of these surfactants, is given in U.S.P. 3,929,678 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.
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Preferably. the detergent particle of the present invention and compositions
comprising
such particles comprises an additional anionic surfactant. Essentially any
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 and sulfonate surfactants are
preferred.
The anionic surfactants may be present in the detergent particle in amounts
below 25 w
or even below 20 wrt % but in a final detergent composition comprising the
particle, is
preferably present at a level of from 0.1 % to 60%. more preferably from 1 to
40%, most
preferably from 5% to 30% by weight.
Other anionic surfactants include the anionic carboxylate surfactants such as
alkyl ethoxy
carboxylates, alkyl polyethoxy polycarboxvlates and soaps ("allyl carboxyls")
such as 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-I-
octanoic acid and
2-pentyl-I-heptanoic acid. Certain soaps may also be included as suds
suppressors. Other
suitable anionic surfactants are the alkali metal sarcosinates of formula R-
CON (R1) CH2
COOM, wherein R is a CS-C I ~ linear or branched alkyl or alkenyl group, R 1
is a C I -C4 alkyl
group and M is an alkali metal ion. Other anionic surfactants include
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 C12-C18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-C14 diesters), N-
acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable,
such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived from
tallow oil.
Anionic sulfate 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-CIA acyl-N-(CI-C4 alkyl) and -N-
(CI-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 CI0-
CI g alkyl sulfates,
more preferably the CI I-CIS branched chain alkyl sulfates and the CIA-C14
linear chain alkyl
sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the
group consisting of the
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C10-C 18 allyl sulfates which have been ethoxylated with from 0.5 to 20 moles
of ethylene oxide
per molecule. More preferably, the allyl ethoxvsulfate surfactant is a C11-
Clg, most preferably
C11-CI5 alkyl sulfate which has been ethoxylated with from 0.5 to 7,
preferably from 1 to 5.
moles of ethylene oxide per molecule.
Preferred surfactant combinations are mixtures of the preferred alkyl sulfate
and/ or
sulfonate and alkyl ethoxysulfate surfactants optionally with cationic
surfactant. Such mixtures
have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactants suitable for use herein include the salts of C5-
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.
Essentially any alkoxvlated nonionic surfactant or mixture is 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.
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are particularly
suitable for use herein.
Particularly preferred are the condensation products of straight or branched,
primary or secondary
alcohols having an alkyl group containing from 6 to 22 carbon atoms with from
2 to 10 moles of
ethylene oxide per mole of alcohol.
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONRIZ wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl,
ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl: and R2 is a C5-
C31 hydrocarbyl;
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxyls
directly connected to the chain, or an alkoxylated derivative (preferably
ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing sugar in a
reductive
amination reaction; more preferably Z is a glycityl.
Suitable alkylpolysaccharides for use herein are disclosed in LT.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from 6
to 30 carbon
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atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing from 1.3 to 10
saccharide units. Preferred alkylpolyglycosides have the formula:
R2O(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.
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 R5 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 CIO-Clg alkyl dimethylamine oxide, and CIO-18
acylamido alkyl
dimethylamine oxide.
Zwitterionic surfactants can also be incorporated into the detergent
compositions in
accord with the invention. 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.
Betaines such as C12-18 dimethyl-ammonio hexanoate and the CIO-18
acylamidopropane (or
ethane) dimethyl (or diethyl) betaines and sultaine surfactants are exemplary
2witterionic
surfactants for use herein.
Suitable cationic surfactants to be used herein include the quaternary
ammonium
surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C16,
preferably C6-
Cl0 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions
are substituted
by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-
alkoxylated and
bis-alkoxylated amine surfactants.
Cationic ester surfactants such as choline ester surfactants, have for example
been
disclosed in US Patents No.s 4228042, 4239660 and 4260529 are also suitable as
are
cationic mono-alkoxylated amine surfactants preferably of the general formula
I:
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WO 00/78908 PCT/US00/16916
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R'
/((CH2)2-a0)~-tH
N+ /
CH3/ \CH3
wherein R 1 is C 10-C 1 g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl, preferably
C10 and C12 alkyl, and X is any convenient anion to provide charge balance,
preferably chloride
or bromide. The levels of the cationic mono-alkoxylated amine surfactants in
the detergent
compositions of the invention are generally from 0.1 % to 20%, preferably from
0.2% to 7°io, most
preferably from 0.3% to 3.0% by weight.
Cationic bis-alkoxvlated amine surfactant such as
+/CH~CH20H
X
CH / \CH2CH20H
3
are also useful, wherein R1 is C10-Clg hydrocarbyl and mixtures thereof,
preferably C10, C12
C14 alkyl and mixtures thereof. X is any convenient anion to provide charge
balance, preferably
chloride.
Bleach Activator
The detergent particles or detergent compositions containing them preferably
comprise a
bleach activator, preferably comprising an organic peroxyacid bleach
precursor. It may be
preferred that the composition comprises at least two peroxy acid bleach
precursors, preferably at
least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic
peroxy acid
bleach precursor, as defined herein. The production of the organic peroxyacid
occurs then by an
in situ reaction of the precursor with a source of hydrogen peroxide. The
bleach activator may
alternatively, or in addition comprise a preformed peroxy acid bleach.
It is preferred that the bleach activator is present in the detergent
particle. It may be
preferred that the bleach activator is present as a separate, admixed
particle. Preferred
hydrophobic peroxy acid bleach precursor preferably comprise a compound having
an oxy-
benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ or NACA-OBS.
Preferred
hydrophilic peroxy acid bleach precursors preferably comprises TAED.
Peroxyacid Bleach Precursor
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Peroxvacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhvdrolysis 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
For the purpose of the invention, hydrophobic peroxyacid bleach precursors
produce a
peroxy acid of the formula above wherein X is a group comprising at least 6
carbon atoms and a
hydrophilic peroxyacid bleach precursor produces a peroxvacid bleach of the
formula above
wherein X is a group comprising 1 to 5 carbon atoms.
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 RsY
-O ~ , -O U Y , and -O
1 O 4
-N-C-R -N N -N-C-CH-R
I ' , I I
R3 ~ R3 Y
I
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
,
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O Y O
-NCH2-C\NR4 _N~ ~NR4
-~C-R ~C/ ,
' II
O
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein RI 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 R1, R3 and R4 may be substituted by
essentially any functional
group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl,
amide and
ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X and
O<--N(R3)3 and most preferably -S03 M+ and -C02 M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a 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 canon, with sodium and
potassium being most
preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Peroxyacid bleach precursor compounds are preferably present in final
detergent
compositions at a level of from 0.5% to 30% by weight, more preferably from 1
% to 15% by
weight, most preferably from 1.5% to 10% by weight. The ratio of hydrophilic
to hydrophobic
bleach precursors, when present, is preferably from 10:1 to 1:10, more
preferably from 5;1 to 1:5
or even from 3:1 to 1:3. 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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Allyl 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 t'~pe include the N-,IvT,IvTINI
tetra acet<~lated
alkylene diamines wherein the all.~~lene group contains from 1 to 6 carbon
atoms, particularly
those compounds in which the alkylene group contains I, 2 and 6 carbon atoms.
Tetraacetyl
ethylene diamine (TAED) is particularly preferred as hydrophilic peroxy acid
bleach precursor.
Other preferred alkyl percarboxvlic acid precursors include sodium 3,5.5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS),
sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ -CNR2C-L R~ NCR2CL
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon
atoms, R2 is an
alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon
atoms, and R5 is H
or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can
be essentially any
leaving group. RI preferably contains from about 6 to 12 carbon atoms. R2
preferably contains
from about 4 to 8 carbon atoms. RI may be straight chain or branched alkyl,
substituted aryl or
alkylaryl containing branching, substitution, or both and may be sourced from
either synthetic
sources or natural sources including for example, tallow fat. Analogous
structural variations are
permissible for R2. R2 can include alkyl, aryl, wherein said RZ may also
contain halogen,
nitrogen, sulphur and other typical substituent groups or organic compounds.
RS is preferably H
or methyl. R1 and R5 should not contain more than 18 carbon atoms total. Amide
substituted
bleach activator compounds of this type are described in EP-A-0170386. It can
be preferred that
RI and RS forms together with the nitrogen and carbon atom a ring structure.
Preferred examples of bleach precursors of this type include amide substituted
peroxyacid precursor compounds selected from (6-octanamido-
caproyl)oxybenzenesulfonate, (6-
decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-
nonanamidocaproyl)oxy
benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
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Perbenzoic acid precursor compounds which provide perbenzoic acid on
perhydrolysis
benzoxazin organic peroxyacid precursors, as disclosed for example in EP-A-
332294 and EP-A-
482807 and cationic peroxvacid precursor compounds which produce cationic
peroxyacids on
perhydrolysis are also suitable. Cationic peroxyacid precursors are described
in U.S. Patents
4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127.82: 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 peroxvacid precursors are described in UK
Patent
Application No. 9407944.9 and US Patent Application Nos. 08!298903, 08/298650,
08; 298904
and 08/298906.
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.
The particles or compositions of the present invention may contain, in
addition to, or as
an alternative to an organic peroxyacid bleach precursor compound, a preformed
organic
peroxyacid , typically at a level of from 0.1% to 15% by weight, more
preferably from 1% to
10% by weight. A preferred class of organic peroxyacid compounds are the amide
substituted
compounds as described in EP-A-0170386. Other organic peroxyacids include
diacyl and
tetraacylperoxides, especially diperoxydodecanedioc acid,
diperoxvtetradecanedioc acid and
diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and
diperbrassylic acid and
N-phthaloylaminoperoxicaproic acid are also suitable herein.
Peroxide Source
Inorganic persalts are a preferred source of peroxide. Preferably these salts
are present at
a level of from 0.01% to 50% by weight, more preferably of from 0.5% to 30% by
weight of the
particle or composition of the invention. 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.
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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.
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 suitable for use
herein.
Chelants
As used herein, chelants refers to detergent ingredients which act to
sequester (chelate)
heavy metal ions. These components may also have calcium and magnesium
chelation capacit)~,
but preferably selectively bind heave metal ions such as iron, manganese and
copper.
Chelants are generally present in the detergent particle or final detergent
composition at a
level of from 0.005% to 10%, preferably from 0.1% to 5°0, more
preferably from 0.25% to 7.5%
and most preferably from 0.3% to 2% by weight of the compositions or component
Suitable chelants include organic phosphonates, such as the amino alkylene
poly
(alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and
nitrilo trimethylene
phosphonates, preferably, diethylene triamine penta (methylene phosphonate),
ethylene diamine
tri (methylene phosphonate) hexamethylene diamine tetra (methylene
phosphonate) and hydroxy-
ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1
hydroxyethane
dimethylene phosphonic acid.
Other suitable chelants for use herein include nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine disuccinic
acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic
acid or any salts
thereof, and 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-
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 ~-
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 alos
suitable. Glycinamide-
N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred
are diethylenetriamine pentacetic acid, ethylenediamine-N.N'-disuccinic acid
(EDDS) and 1,l
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hvdroxyethane diphosphonic acid or the alkali metal, alkaline earth metal.
ammonium, or
substituted ammonium salts thereof, or mixtures thereof. In particular the
chelating agents
comprising a amino or amine group can be bleach-sensitive and are suitable in
the compositions
of the invention.
Water-Soluble Builder Compound
The component or compositions herein preferably contain a water-soluble
builder
compound, typically present in detergent compositions at a level of from 1 %
to 80% by weight,
preferably from 10% to 60% by weight, most preferably from 15% to 40% by
weight.
The detergent compositions of the invention may comprise phosphate-containing
builder
material. Preferably present at a level of from 0.5% to 60%, more preferably
from 5% to 50%,
more preferably from 8°~o to 40%. The phosphate-containing builder
material preferably
comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium
tripolyphosphate.
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, 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, tarnonic acid and
fumaric acid, as well as
the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or
their acids 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, lactoxvsuccinates described in British Patent No. 1,389,732,
and aminosuccinates
described in Netherlands Application 7205873, and the oxypolycarboxylate
materials such as 2-
oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
The most preferred
polycarboxylic acid containing three carboxy groups is citric acid, preferably
present at a level of
from 0.1% to 15%, more preferably from 0.5% to 8% by weight.
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
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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 hydroxy carboxylates containing up
to three carboxy
groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders and 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
tripolvphosphates, 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.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids or their salts in which the polycarboxylic
acid comprises at
least two carboxyl radicals separated from each other by not more than two
carbon atoms.
Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such
salts are
polyacrylates of MWt 1000-5000 and their copolymers with malefic anhydride,
such copolymers
having a molecular weight of from 2000 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.
Partially Soluble or Insoluble Builder Compound
The panicles or detergent compositions of the present invention may contain a
partially
soluble or insoluble builder compound, typically present in detergent
compositions at a level of
from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most
preferably from 8% to
40% weight. Examples of largely water insoluble builders include the sodium
aluminosilicates.
As mentioned above, it may be preferred in one embodiment of the invention,
that only small
amounts of alumino silicate builder are present.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. x120
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
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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:
Na 12 [A102) 12 (Si02)12~. xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106~~
276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1 % to 80%, more preferably
from 15%
to 40% by weight. Zeolite MAP is described in EP 384070A (Unilever). It is
defined as
an alkali metal alumino-silicate of the zeolite P type having a silicon to
aluminium ratio
not greater than 1.33, preferably within the range from 0.9 to 1.33 and more
preferably
within the range of from 0.9 to 1.2. Of particular interest is zeolite MAP
having a silicon
to aluminium ratio not greater than 1.15 and, more particularly, not greater
than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size,
expressed as a median particle size d50 value of from 1.0 to 10.0 micrometres,
more
preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0
micrometres. The
d50 value indicates that 50% by weight of the particles have a diameter
smaller than that
figure. The particle size may, in particular be determined by conventional
analytical
techniques such as microscopic determination using a scanning electron
microscope or by
means of a laser granulometer, described herein. Other methods of establishing
d50 values
are disclosed in EP 384070A.
Other Deter eg nt Ingredients
A preferred ingredients of the compositions herein are dyes and dyed particles
or
speckles, which can be bleach-sensitive. The dye as used herein can be a dye
stuff or an aqueous
or nonaqueous solution of a dye stuff. It may be preferred that the dye is an
aqueous solution
comprising a dyestuff, at any level to obtain suitable dyeing of the detergent
particles or speckles,
preferably such that levels of dye solution are obtained up to 2% by weight of
the dyed particle.
or more preferably up to 0.5% by weight, as described above. The dye may also
be mixed with a
non-aqueous carrier material, such as non-aquous liquid materials including
nonionic surfactants.
Optionally, the dye also comprising other ingredients such as organic binder
materials, which
may also be a non-aqueous liquid.
The dyestuff can be any suitable dyestuff. Specific examples of suitable
dyestuffs include
E104 - food yellow 13 (quinoline yellow), E110 - food yellow 3 (sunset yellow
FCF), E131 -
food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue
2 (brilliant blue
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FCF), E140 - natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment
green 7
(chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV
paste (trade
name) and,% or Pigmasol Green (trade name).
Another preferred ingredient of the particles or compositions of the invention
is a
perfume or perfume composition. Any perfume composition can be used herein.
The perfumes
may also be encapsulated. Preferred perfumes containing at least one component
with a low
molecular weight volatile component , e.g. having a molecular weight of from
150 to 450 or
preferably 350. Preferably, the perfume component comprises an oxygen-
containing functional
group. Preferred functional groups are aldehyde, ketone, alcohol or ether
functional groups or
mixtures thereof.
Another highly preferred ingredient useful in the particles or compositions
herein is one
or more additional enzymes. Preferred additional enzymatic materials include
the commercially
available lipases, cutinases, amylases, neutral and alkaline proteases,
cellulases, endolases,
esterases, pectinases, lactases and peroxidases conventionally incorporated
into detergent
compositions. Suitable enzymes are discussed in US Patents 3,519,570 and
3,533,139.
Preferred enzymes are discussed above with respect to the detergent active
particulates.
The same enzymes are preferred as components of the detergent base powder or
as additional
detergent ingredients added to the detergent particles of the invention to
form a fully formulated
detergent.
The detergent particles or compositions herein also preferably contain from
about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners,
preferably as a
detergent active particulate component as mentioned above. Examples are
commercially
marketed by Ciba Geigy Corporation as Tinopal-LTNPA-GXT"' and Tinopal-CBS-XTM.
Others
include Tinopal 5BM-GXT"', Tinopal-DMS-XT"' and Tinopal AMS-GXTM by Ciba Geigy
Corporation.
Photo-Bleachine Agent
As described above, photo-bleaching agents are preferred ingredients of the
compositions
and are preferably present in the form of the detergent active particulates as
discussed above.
However, they may optionally be present in the detergent base particles or as
additional detergent
ingredients for addition to the detergent particles of the invention for
forming the fully
formulated detergnet compositions of the invention.
Oreanic Polymeric lnQredients
Organic polymeric compounds are preferred additional herein and are preferably
present
as components of any particulate components where they may act such as to bind
the particulate
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component together. Bv 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, including
quaternised
ethoxylated (poly) amine clay-soil removali anti-redeposition agent in accord
with the invention.
Organic polymeric compound is typically incorporated in the finished detergent
compositions of the invention at a level of from 0.01°~o to 30%,
preferably from 0.1°~o to 15%,
most preferably from 0.5% to 10% by v~~eight of the compositions or component.
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. Highly
preferred polymeric components herein are cotton and non-cotton soil release
polymer according
to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807,
Gosselink et al., and in
particular according to US application no.60/051517.
Another organic compound, which is a preferred clay dispersant/ anti-
redeposition agent,
for use herein, can be the ethoxylated cationic monoamines and diamines of the
formula:
H3 ~ H3
X-~OCH2CH2)n i +-CH2-CH2~-CH2)a N+-CH2CH~0-~X
b
(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 monoamines
(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.
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Other dispersantsi anti-redeposition acents for use herein are described in EP-
B-011965
and US 4,659,80? and US 4.664,848.
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Suds Suppressin System
The suds supressing system is preferably also present in the form of the
detergent active
particulates as described above. Such components may however be present in the
detergent base
particles or as additional detergent ingredients for addition to the detergent
particles of the
invention for formulating a finished detergent composition.
Polymeric dye transfer inhibiting agents may also be present in the detergent
particles or
compositions of the invention. When present they are generally in amounts from
0.01 % to 10 %,
preferably from 0.05% to 0.5% based on the final detergent compositions and
are preferably
selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and
N-
vinylimidazole, polyvinylpyrrolidonepolvmers or combinations thereof, whereby
these polymers
can be cross-linked polymers.
Polymeric soil release agents, which are described above are also preferably
present as
detergent active particulates. However they may be present alternatively or in
addition, in the
detergent base particles or as additional detergent ingredients for addition
to the detergent
particles of the invention for formulating a finished detergent composition.
Other optional ingredients suitable for inclusion in the compositions of the
invention
include colours and filler salts, with sodium sulfate being a preferred filler
salt.
Highly preferred compositions contain from about 2% to about 10% by weight of
an
organic acid, preferably citric acid. Also, preferably combined with a
carbonate salt, minor
amounts (e.g., less than about 20% by weight) of neutralizing agents,
buffering agents, phase
regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants,
opacifiers, anti-
oxidants, bactericides and dyes, such as those described in US Patent
4.285,841 to Barrat et al.,
issued August 25, 1981 (herein incorporated by reference), can be present.
The detergent compositions can include as an additional component a chlorine-
based
bleach. However, since the detergent.compositions of the invention are solid,
most liquid
chlorine-based bleaching will not be suitable for these detergent compositions
and only granular
or powder chlorine-based bleaches will be suitable. Alternatively, a chlorine
based bleach can be
added to the detergent composition by the user at the beginning or during the
washing process.
The chlorine-based bleach is such that a hypochlorite species is formed in
aqueous solution. The
hypochlorite ion is chemically represented by the formula OCI-.
Those bleaching agents which yield a hypochlorite species in aqueous solution
include
alkali metal and alkaline earth metal hypochlorites, hypochlorite addition
products, chloramines,
chlorimines, chloramides, and chlorimides. Specific examples include sodium
hypochlorite,
potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium
hypochlorite,
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chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate,
sodium
dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric
acid, 1,3-
dichloro-~.5-dimethylhydantoin. N-chlorosulfamide, Chloramine T, Dichloramine
T. chloramine
B and Dichloramine B. A preferred bleaching agent for use in the compositions
of the instant
invention is sodium hypochlorite, potassium hypochlorite, or a mixture
thereof. A preferred
chlorine-based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are
available in solid
or concentrated form and are dissolved in water during preparation of the
compositions of the
instant invention. Some of the above materials are available as aqueous
solutions.
Laundry Washine 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 l Og 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.
Preferred washing machines may be the so-called low-fill machines.
In a preferred use aspect the composition is forntulated such that it is
suitable for hard-
surface cleaning or hand washing. In another preferred aspect the detergent
composition is a pre-
treatment or soaking composition, to be used to pre-treat or soak soiled and
stained fabrics.
Examples
Abbreviations used in the Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
branched AS . branched Sodium alkyl sulfate as described in W099/19454
CxyAS . Sodium C 1 x - C 1 y alkyl sulfate
C46SAS . Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS : Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide
CxyEz : C 1 x-C 1 y predominantly linear primary alcohol condensed with an
average of z moles of ethylene oxide
QAS : R2.N+(CH3)2(C2H40H) with R2 = C12 - C14
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QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11
APA : C8 - C10 amido propyl dimethyl amine
Soap : Sodium linear alkyl carboxylate derived from
an 80.!20 mixture of tallow
and coconut fatty acids
STS : Sodium toluene sulphonate
CFAA : C12-Cl4 (coco) alkyl N-methyl glucamide
TFAA . C16-C18 alkyl N-methyl glucamide
TPKFA : C 12-C 14 topped whole cut fatty acids
STPP . Anhydrous sodium tripolyphosphate
TSPP . Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(AlO2Si02)12.27H20 having a primary panicle
size in the range
from 0.1 to 10 micrometers (weight expressed
on an anhydrous basis)
NaSKS-6 : Crystalline layered silicate of formula d-
Na2Si205
Citric acid . Anhydrous citric acid
Borate : Sodium borate
Carbonate . Anvdrous sodium carbonate with a particle size
between 200~m and
900pm
Bicarbonate . Anhydrous sodium bicarbonate with a particle
size distribution between
400pm and 1200pm
Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1
)
Sulfate : Anhydrous sodium sulfate
Mg sulfate . Anhydrous magnesium sulfate
Citrate . Tri-sodium citrate dehydrate of activity 86.4%
with a particle size
distribution between 425pm and 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
m. W. about 70,000
MA/AA ( 1 ) . Copolymer of 4:6 maleic/acrylic acid, average
m. W. about 10,000
AA . Sodium polyacrylate polymer of average molecular
weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether l cellulose ether with a degree of polymerization
:Methy of 650 available from
Shin Etsu Chemicals
Protease . Proteolytic enzyme, having 3.3/o by weight
of active enzyme, sold by
NOVO Industries A/S under the tradename Savinase
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Protease I : Proteoh~tic enzyme. having 4% by weight of active enzyme, as
described
in VSO 95/10591. sold by Genencor Int. lnc.
Alcalase : Proteolvtic enzyme, having 5.3% by weight of active enzyme. sold by
NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of active enzyme, sold
by
NOVO Industries A/S under the tradename Carezyme
Amylase : Amylolyic enzyme, having I .6% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Termamyl 120T
Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme. sold by
NOVO Industries A/S under the tradename Lipolase
Lipase (1) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold
by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H2 O.H2O2-
PB1 . Anhydrous sodium perborate bleach of nominal formula NaB02.H 2O2
Percarbonate . Sodium percarbonate of nominal formula 2Na2C03.3H2O2
NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt
NAC-OBS : (6-nonamidocaproyl) oxybenzene sulfonate
TAED : Tetraacetylethylenediamine
DTPA . Diethylene triamine pentaacetic acid
DTPMP . Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename bequest 2060
EDDS . Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer sodium salt.
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach (1)
dextrin soluble
polymer
Photoactivated :Sulfonated alumino phthlocyanine encapsulated in bleach (2)
dextrin soluble
polymer
Brightener 1 : Disodium 4,4'-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
PEGx . Polyethylene glycol, with a molecular weight of x (typically 4,000)
PEO : Polyethylene oxide, with an average molecular weight of 50,000
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TEPAE : Tetraethylenepentaamine ethoxylate
PVI . Polwinvl imidosole, with an average molecular weight of 20.000
PVP : Polyvinylpvrolidone polymer, with an average
molecular weight of
60,000
PVNO . Polyvinylpvridine N-oxide polymer. with an average
molecular weight of
50,000
PVPVI : Copolymer of polvvinylpvrolidone and vinylimidazole,
with an average
molecular weight of 20,000
QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-
(C2H4 O))n, wherein n = from 20 to 30
SRP 1 . Anionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short block polymer
PEI . Polyethyleneimine with an average molecular weight
of 1800 and an
average ethoxylation degree of 7 ethyleneoxy
residues per nitrogen
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
Opacifier . Water based monostyrene latex mixture, sold by
BASF
Aktiengesellschaft under the tradename Lytron
621
Wax : Paraffin wax
HMSO . hexamethylene diamine tetra(ethylene oxide)24
The following are examples of the present invention.
EXAMPLE I
This Example illustrates a process according to this invention which produces
uniform
free flowing, good dispensing and dissolving detergent particles with
uniformity of colour and
particle shape. Multiple detergent starting ingredients are dry mixed in an
orbital vertical screw
mixer of 200kg batch size, and several batches prepared. This bulk premix is
added into a
horizontal rotating drum type mixer with internal baffles - a laboratory scale
example having
batch size 40kg. A proportion of premix is sampled and added to the mixer. The
smaller
particles which pose a segregation risk are dry mixed into the mixer.
Binding agent, C45AE7, is sprayed into the mixer using an air atomised nozzle.
The
product is left to mix for 2 minutes and anti-caking agent (zeolite A) is
added into the mixer and
mixed for a further 1 minute. The product is run into a storage box. Other
detergent additives
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such as enzymes, percarbonate and dyed carbonate speckles are post-added in a
mixing step with
other liquid additives such as perfume, to form the final detergent.
Component % ~'~'eight of Total Feed
Drv materials added to the~remix
Detergent premix* 98.48%
Photobleach 0.02°ro
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Binding agent
C45AE7 alcohol ethoxylate 0.7%
Anti-caking agent
Zeolite A 0.1
* = comprising of sodium linear alkyl benzene sulphonate ( 13.4wrt%), zeolite
A (40°~0), sodium
sulphate (23.5%), sodium carbonate (8.4%), magnesium sulphate (0.7wt%), EDDS
(0.4wt%),
MA/AA (2.Swt%), soap (l.Swt%), QAS l(2.Owt%), HEDP (0.3wt%), optical
brightener
(O.Swt%), water (5.3wt%), diamine hexamethylene tetra (ethylene oxide) 24
(l.5wt%).
EXAMPLE II
This Example also illustrates the process of the invention and incorporates
the parameters
of Example I. A premix of dry detergent materials is prepared as in example 1,
of composition as
listed below. A proportion of premix is sampled and added to the mixer.
Binding agent,
C45AE7 mixed with PEG 4000, is sprayed into the mixer using an air atomised
nozzle. The
premix of increased cohesivity is left to mix for 1 minute. The smaller
particles which pose a
segregation risk are dry mixed into the mixer. The product is left to mix for
2 minutes and anti-
caking agent (zeolite A) is added into the mixer and mixed for a further 1
minute. The product is
run into a storage box. Other detergent additives such as enzymes,
percarbonate and dyed
carbonate speckles are post-added in a mixing step with other liquid additives
such as perfume, to
form the final detergent.
Component % Weight of Total Feed
Dry materials added to the premix
Detergent premix* 98.48%
Photobleach 0.02%
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Bindine agent
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C45AE7 alcohol ethoxvlate 1.0%
PEG4000 0.5%
Anti-caking a
Zeolite A 0.2%
EXAMPLE III
This Example also illustrates the process of the invention and incorporates
the parameters
of Example I. A premix of dry detergent materials is prepared as in example I,
of composition as
listed below. A proportion of premix is sampled and added to the mixer.
Binding agent,
C45AE5, is sprayed into the mixer using an air atomised nozzle. The premix of
increased
cohesivity is left to mix for I minute. The smaller particles which pose a
segregation risk are dry
mixed into the mixer. The product is left to mix for 2 minutes and anti-caking
agent (zeolite A) is
added into the mixer and mixed for a further 15 seconds. The product is run
into a storage box.
Other detergent additives such as enzymes, percarbonate and dyed carbonate
speckles are post-
added in a mixing step with other liquid additives such as perfume, to form
the final detergent.
Component % Weight of Total Feed
Dry materials added to the premix
Detergent premix* 97.78%
Photobleach 0.02%
Perfume encaps type 1 0.4%
Perfume encaps type 2 0.1
Binding aft
C45AE5 alcohol ethoxylate 1.5%
Anti-cakin~agent
Zeolite A 0.2%
EXAMPLE IV
This Example also illustrates the process of the invention and incorporates
the parameters
of Example I. A premix of dry detergent materials is prepared as in example 1,
of composition as
listed below. A proportion of premix is sampled and added to the mixer.
Bonding agent,
C45AE7, is sprayed into the mixer using an air atomised nozzle. The premix of
increased
cohesivity is left to mix for 1 minute. The smaller particles which pose a
segregation risk are dry
mixed into the mixer. A further spray-on of bonding agent is applied to fix
the small particles
firmly to the surface of the larger host particles. The product is left to mix
for 2 minutes and anti-
caking agent (zeolite A) is added into the mixer and mixed for a further I
minute. The product is
run into a storage box. Other detergent additives such as enzymes,
percarbonate and dyed
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carbonate speckles are post-added in a mixing step with other liquid additives
such as perfume, to
form the final detergent.
Component % Weight of Total Feed
Drv materials added to the_premix
Detergent premix* 98.2%
Photobleach 0.02%
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Binding fluid
C45AE7 alcohol ethoxylate 1.0%
Anti-caking agent
Zeolite A 0.08°~0
EXAWPLE V
This Example also illustrates the process of the invention and incorporates
the parameters
of Example I. A premix of dry detergent materials is prepared as in example 1,
of composition as
listed below. A proportion of premix is sampled and added to the mixer.
The fine segregatable particles are dispersed into a carrier fluid such as
C45AE7 in a
tank, using low shear agitation, mixed for 10 minutes. The suspension of fine
particles in fluid is
pumped to a spray nozzle and atomised onto the premix particles in the mixer.
The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is
added into
the mixer and mixed for a further 1 minute. The product is run into a storage
box. Other
detergent additives such as enzymes, percarbonate and dyed carbonate speckles
are post-added in
a mixing step with other liquid additives such as perfume, to form the final
detergent.
Component % Weight of Total Feed
Drv materials added to the premix
Detergent premix* 96.48%
Photobleach 0.02%
Binding fluid
C45AE7 alcohol ethoxylate 3.0%
Anti-caking agent
Zeolite A 0.5%
Further example compositions
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In the following examples all levels are quoted as % by weight of the full
finished detergent
composition:
TABLE
The following compositions are in accordance with the invention.
A B C D E F ParticleSpan E Sphericity
ize Colour(Mean)
(median, ifferenc
Vim) of
raw
material
compare
to
finished
compositi
n
1. S ra 50qm 1.8 .4 1.9
-
dried
ranules
LAS .0 .0 11.0 .0 .0 .0
AS 1.0
C45AS 1.0 1.0
C16-C17 .0 .0 .0
branched
S
DTPA, .5 .6 0.5 .7 1.0 .5
HEDP
nd/or
EDDS
MgS04 .5 .4 .5 .4 .5 .5
Sodium 10.0 .0 .0 .0 .0 10.0
arbonate
Sodium .0 .0 .0 5.0 .0 .0
ulphate
eolite 18.0 0.0 18.0 10.0 0.0 17.0
A
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IS KS-6
IMA/AA or 1.0 1.5 1.0 .6 1.0 0.6
(QAS 1 1.0 0.5 1.0 .8 1.0
Brightener 0.1 0.05 .05 0.06 0.05 0.05
IHMEO 0.5 .5 1.0 .5 1.0 1.0
I
ISoap 1.5 1.0 1.5 1.5
(Component
is within
the
~i remix
(Spray dried50.0 50.0 8.0 0.0 0.0 50.0
I
~granules
(1 )
(Nonionic 5.0
E7/AE5
Sodium .0 .0 .0 .0 5.0 OO~m 1.5 .0 1.5
carbonate
Sodium .0 1.0 350~m 1.6 .5 1.5
ulphate
QAS 1 .0 1.0 500~m .7 .0 .1
gglomerate
Nonionic 10.0 500~m 1.9 .3 1.8
gglomerate
SKS-6 / 12.0 350pm 1.8 14.6 1.9
LAS
gglomerate
Silicone .5 .5 .0 .5 .5 500~m .0 14.3 1.5
ntifoam
gglomerate
SRP 1 ,5 ~ .5 .3 500~m .0 10.4 .0
AED .5 .5 .0 550~m .5 11.4 .6
1 1
ggiomerate
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SKS-6 3.5 3.5 9.0 3.5 5.0 O~m 1.9 6.0 1.7
powder
AED 1.5 .0 80~m 1.7 9.5 1.6
powder
Premix
binder
pplied to
he premix
(2)
PEG 4000 5.0
PEG 1500 .0
S, LAS, 5.0 .0
MBAS
ater as 10.0 15.0
binder
(removed
on
vying)
Other
additives
os t-added
to make
the
final
detergent
formulation
. S ra -on
materials
Pertume .4 .2 .4 .4 .5 .3
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..
5. D
added
materials
Premix 0.0 5.0 55.0 65.0 0.0 0.0
(2)
Enzymes .0 1.5 1.0 1.3 1.2 1.5
(protease,
lipolase,
mylase,
cellulase)
NACAOBS 3.0 .5 .0 3.5 3.5 .5
Sodium 13.0 10.0 10.0 12.0 12.0 10.0
percarbonat
Photobfeach0.02 0.02 .02 0.02 0.02 0.02
Perfume .7 .5 .6 .8 .9 .4
ncapsulate
Citric .0 .0 .0 .0 .5 .0
acid
Sodium 1.0 1.0 1.0 .5 1.5 1.5
rbonate
peckle
eolite .1 .3
A
AED .p
gglomerate
Silicone .0
ntifoam
ggiomerate
. Coatin
pplied
to
premix
(2)
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Burkeite .0 5.0 8.0 5.0
(applied
in
30wt%
queous
olution)
Brightener .1 .1
15
Fillers
up to
100%
Finished
product
Median OOpm OOpm OO~m 800~m800pmOOp.m
particle
size
Span 1.4 1.2 1.4 1.2 1.4 1.6
(geometric
tandard
eviation)
Roundness 1.30 1.20 1.35 1.40 1.45 1.40
(mean)
hiteness 98.0 6.5 98.5 92.0 97.0 101.5
~IW=L-3b
Having thus described the invention in detail, it will be obvious to those
skilled in the an
that various changes may be made without departing from the scope of the
invention and the
invention is not to be considered limited to what is described in the
specification.
