Note: Descriptions are shown in the official language in which they were submitted.
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Cleaning Compositions and Tablets
Technical Field
The present invention relates to various uses for compressed clay material and
in
particular to tablets or cleaning compositions comprising compressed clay.
Background to the Invention
Clays have been used for several years in detergents to provide softening of
the fabrics
washed with the compositions. They have been described as materials which can
be dry-
added to the other detergent granules, or can be mixed with other ingredients.
EP-A-
313146 described agglomerates containing 60% to 99% clay, wax and a humectant,
which are added to a detergent composition.
Clay has also been mentioned to aid breaking up of tablets, which is for
example
described in EP-A-328880 and EP-A-799886.
The inventors have now found that when a clay material is compressed prior to
incorporation into a tablet or in a cleaning composition, improved
disintegration,
dispensing and/ or dissolution is achieved. They found for example that
tablets
comprising clay which is compressed prior to incorporation into a tablet,
disintegrate
more rapidly than tablets comprising the same clay material which has not been
compressed prior to incorporation into a tablet. They also found that in
particular the
amount of pressure used for the compression of the clay is of importance to
obtain clay
particles which aid disintegration, dispensing or dissolution.
The inventors also found that in cleaning compositions the compressed clay
component
improves the dispensing and/ or dissolution of the detergent ingredients. This
is believed
to be due to the disintegration initiated by the compressed clay, of product
lumps formed
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by caking or gelling of the product, in particular upon contact with water or
moisture,
such as in the dispensing drawer of a washing machine.
The inventors also found that when softening clays are compressed and than
incorporated
in cleaning compositions or tablets, not only improved disintegration,
dispensing or
dissolution is obtained, but also good softening of the fabrics. They found
that even
improved softening can be achieved compared to clay agglomerates comprising
binder
materials such as wax.
Summary of the invention
The present invention provides cleaning composition or component thereof
comprising a
compressed clay component.
The invention also relates to tablets, preferably cleaning tablets,
pharmaceutical tablets,
plant nutrient tablets, plant fertilizer tablets, comprising an active
ingredient and a
compressed clay component.
Also provided are tablets, compositions or components whereby the clay
component is
obtained by compression of a clay material with a pressure of at least 10 MPa.
The tablets, compositions or components are for example obtainable by
compressing a
clay material to form a compressed clay component and subsequently
incorporation of
the compressed clay component in the tablet, cleaning or detergent composition
or
component.
The tablets or compositions are preferably solid cleaning compositions or
tablets,
preferably laundry compositions or tablets.
The invention also relates to the use of a compacted clay component in a
granular
composition or tablet, in particular a cleaning composition or tablet plant
nutrient
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composition or tablet, plant fertilizer compositions or tablet, or
pharmaceutical
compositions or tablet, to improve the dissolution or disintegration of the
composition or
tablet.
Detailed description of the invention
Compressed clan component.
The compressed clay component herein can comprise any clay material known in
the art,
however preferably it comprises a clay material which can aid disintegration
or
dissolution or dispensing to some extent, without being compressed. When used
in
cleaning compositions or tablets herein, the clay material of the compressed
clay
component is preferably a clay material which provides softening of fabrics.
It should be understood for the purpose of the invention that the compressed
clay
component is compressed prior to incorporation in the compositions, components
or
tablets herein. However, the clay material of the compressed clay component
may be
mixed with other ingredients prior to compression, as described in more detail
hereinafter.
The compressed clay component can be obtained by any method comprising the
step of
submitting a clay material, optionally mixed with other ingredients, to a
pressure. For the
purpose of the invention, agglomeration of clay without any intentional,
application of
pressure, as known in the art for example from EP-A-313146, is not to be
understood as
a method of applying pressure on a clay material.
A preferred process comprises the steps of submitting the clay material to a
pressure of
at least lOMPa, or even at least 20MPa or even at least 40MPa. This can for
example be
done by tabletting or roller compaction of a clay material, optionally
together with one
or more other ingredients, to form a clay tablet or sheet, preferably followed
by size
reduction, such as grinding, of the compressed clay sheet or tablet, to form
compressed
clay particles. The particles can then be incorporated in a tablet or cleaning
composition.
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Tabletting methods and roller compaction methods are known in the art. For
example,
the compression of the clay can be done in a Lloyd 50K tablet press or with a
Chilsonator
roller compaction equipment, available from Fitzpatrick Company.
Various size reduction methods or grinding methods are also commonly known in
the art.
The size reduction step may comprise two or more individual size reduction or
grinding
phases, for example first breaking up the tablet or sheet into smaller lumps,
and then
grinding the lumps to form granules
The clay component is thus preferably in the form of granules. Preferably, at
least 90%
by weight of the particulate clay component has a particle size of from 150
microns to
2000 microns, more preferably from 200 microns to 1500 microns or even form
250
microns to 1200 microns. More preferably 90% of the particles has a particle
size of
from 400 microns to 1100 microns or even from 500 microns to 1000 microns. It
may be
preferred that substantially no fine particles of a particle size below 100
microns or even
below 150 microns are present.
Particles of the required particle size can for example be obtained by sieving
the particles
obtained by the size reduction or grinding step(s), by using sieves of the
applicable
particle size and collecting the fraction which remains on the sieve
corresponding to the
minimum particle size and which passes the sieve corresponding to the maximum
particle size.
The clay component may comprise additional ingredients, for example a binder
material.
Binder materials which can be used are those commonly used in tablets, as
described
herein after. Preferred binder materials for the clay component herein include
liquids
such as water, but also viscous or solid materials which can be melted at a
temperatures
whereby the clay is not affected. Preferred binders are oils, waxes, glycerol,
polyalkylene
glycols, (nonionic) surfactants and/or water.
Granulation aids, desiccants and/ or humectants may also be present.
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The clay component preferably comprises at least 40% or even at least 60% by
weight of
a clay material, including the water of hydration comprised in the clay
material.
Preferably, the clay component comprises at least 70% or even at least 80% or
even at
least 90% or even at least 95% by weight of the clay material. It may be
preferred that
the clay component consist of clay and water and minor ingredients which occur
naturally in the clay.
Highly preferred are smectite clays, as for example are disclosed in the US
Patents No.s
3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A-
299,575
and EP-A-313,146 all in the name of the Procter and Gamble Company.
The term smectite clays herein includes both the clays in which aluminium
oxide is
present in a silicate lattice and the clays in which magnesium oxide is
present in a silicate
lattice. Typical smectite clay compounds include the compounds having the
general
formula A12(Si205)2(OH)2.nH20 and the compounds having the general formula
Mg3(Si205)2(OH)2.nH20. Smectite clays tend to adopt an expandable three layer
structure.
Specific examples of suitable smectite clays include those selected from the
classes of
the montmorillonites, hectorites, volchonskoites, nontronites, saponites and
sauconites,
particularly those having an alkali or alkaline earth metal ion within the
crystal lattice
structure.
Preferred may be three-layer, expandable alumino-silicates which are
characterised by a
dioctahedral crystal lattice, while the expandable three-layer magnesium
silicates have a
trioctahedral crystal lattice.
As noted herein above, the clays employed in the compositions of the instant
invention
contain cationic counterions such as protons, sodium ions, potassium ions,
calcium ion,
magnesium ion, and the like. It is customary to distinguish between clays on
the basis of
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one canon predominantly or exclusively absorbed. For example, a sodium clay is
one in
which the absorbed cation is predominantly sodium. Such absorbed cations can
become
involved in exchange reactions with canons present in aqueous solutions. A
typical
exchange reaction involving a smectite-type clay is expressed by the following
equation:
smectite clay (Na) + NH40H _ smectite clay (NH4) + NaOH.
Since in the foregoing equilibrium reaction, one equivalent weight of ammonium
ion
replaces an equivalent weight of sodium, it is customary to measure cation
exchange
capacity (sometimes termed "base exchange capacity") in terms of
milliequivalents per
100 g. of clay (meq./100 g.). The cation exchange capacity of clays can be
measured in
several ways, including by electrodialysis, by exchange with ammonium ion
followed by
titration or by a methylene blue procedure, all as fully set forth in
Grimshaw, "The
Chemistry and Physics of Clays", pp. 264-265, Interscience (1971). The cation
exchange capacity of a clay mineral relates to such factors as the expandable
properties
of the clay, the charge of the clay, which, in turn, is determined at least in
part by the
lattice structure, and the like.
Smectites, such as nontonite, having an ion exchange capacity of around 70
meq/100 g.,
and montmorillonite, which has an ion exchange capacity greater than 70
meq/100 g.,
have been found to be useful herein, in that they are effectively deposited on
the fabrics
to provide the desired softening benefits. Accordingly, preferred clay
materials useful
herein can be characterised as expandable, three-layer smectite-type clays
having an ion
exchange capacity of at least about 50 meq/100 g.
The preferred clays herein are available under various tradenames, for
example, Thixogel
#1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC
and
Volclay #325, from American Colloid Co., Skokie, Illinois; Black Hills
Bentonite
BH450, from International Minerals and Chemicals; and Veegum Pro and Veegum F,
from R.T. Vanderbilt. It is to be recognised that such smectite-type minerals
obtained
under the foregoing tradenames can comprise mixtures of the various discrete
mineral
entities. Such mixtures of the smectite minerals are suitable for use herein.
Montmorllonite clays are preferred herein, and sodium or calcium
montmorillonite are
particularly preferred to provide softening. Suitable smectite clays,
particularly
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montmorillonites, are sold by various suppliers including English China Clays,
Laviosa,
Georgia Kaolin and Colin Stewart Minchem. Gelwhite GP is an extremely white
form of
smectite clay and is therefore preferred when formulating white compositions
or tablets
herein. Volclay BC, which is a smectite-type clay mineral containing at least
3% of iron
(expressed as Fe203) in the crystal lattice, and which has a very high ion
exchange
capacity, is one of the most efficient and effective clays for use herein and
is preferred
from the standpoint of product performance.
Organophilic clays may also be used herein. These are hydrophobically modified
clays
which have organic ions replacing inorganic metal ions by ion exchange
processes
known in the art. These kinds of clay are readily mixable with organic solvent
and have
the capability to absorb organic solvent at the interlayers. Suitable examples
or
organophilic clays useful in the invention are Bentone SD-l, SD-2 and SD-3
from Rheox
of Highstown, N.J.
The particle size of the clay materials used to form the compressed clay
component
herein will depend on the final particle size of the clay component.
Preferably, the clay
material prior to compression has a particle size of from 0.01 ~.m to 800~.m,
more
preferably from l~,m m to 400 Vim, most preferably from S~m to 200 ~m or even
to 150
Vim.
It may be highly preferred that the compressed clay components, tablets,
components or
compositions herein comprise also one or more additional disintegrating agents
or
dispensing agents or wicking agents, in addition to the compressed clay
component.
Preferred disintegrating agents herein are those which will swell upon contact
with water
and break the tablet or granule comprising the disintegrating agent in small
pieces. This
will improve the dispersion or dispensing of the product in the solution.
Possible
disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
Examples
of suitable disintegrants include starch: natural, modified or pregelatinized
starch,
sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum,
pectin
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gum, tragacanth gum; croscarmylose sodium, crospovidone, cellulose,
carboxymethyl
cellulose, algenic acid and its salts including sodium alginate, silicone
dioxide,
polyvinylpyrrolidone, soy polysacharides, ion exchange resins and mixtures
thereof.
Highly preferred additional disintegrating agents for the granular detergent
compositions
of the invention but in particular for the tablets of the invention, are
preferably water-
swellable celluloses such as Solka-floc and Arbocel, and microcrystalline
cellulose such
as Lattice, available form FMC, and water soluble salts such as sodium
acetate.
Non compressed clays may also be present as additional ingredient of the
tablets or
cleaning compositions herein, in particular when the tablets or compositions
are used for
fabric softening.
Also preferred may be in the compressed clay components, tablets or
compositions of the
invention, to incorporate an effervescence system, capable of providing a gas
upon
contact with water. Preferably such a system comprises an acid source and a
carbonate
source, capable of reacting together in the presence of water to form carbon
dioxide gas.
Suitable acids to be used herein include solid organic, mineral or inorganic
acids, salts or
derivatives thereof or a mixture thereof. It may be preferred that the acids
are mono-, bi-
or tri-protonic acids. Such acids include mono- or polycarboxylic acids
preferably citric
acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid,
tartaric acid, malefic
acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are
preferably
used in their acidic forms, and it may be preferred that their anhydrous forms
are used, or
mixtures thereof. Derivatives also include ester of the acids. Surprisingly,
it has now
been found that by using tartaric, malefic and in particular malic acid as the
acid in the dry
effervescent granules, said granules deliver improved physical and/or chemical
stability
upon prolonged storage periods.
Suitable carbonate sources include carbonate, bicarbonate and percarbonate
salts, in
particular bicarbonate and/or carbonate. Suitable carbonates to be used herein
include
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carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like
amongst
which sodium and potassium carbonate are preferred. Suitable bicarbonates to
be used
herein include any alkali metal salt of bicarbonate like lithium, sodium,
potassium and
the like, amongst which sodium and potassium bicarbonate are preferred.
Bicarbonate
may be preferred to carbonate, because it is more-weigh effective, i.e., at
parity weigh
bicarbonate is a larger C02 "reservoir" than carbonate. However, the choice of
carbonate
or bicarbonate or mixtures thereof in the dry effervescent granules may be
made
depending on the pH desired in the aqueous medium wherein the dry effervescent
granules are dissolved. For example where a relative high pH is desired in the
aqueous
medium (e.g., above pH 9.5) it may be preferred to use carbonate alone or to
use a
combination of carbonate and bicarbonate wherein the level of carbonate is
higher than
the level of bicarbonate, typically in a weight ratio of carbonate to
bicarbonate from 0.1
to 10, more preferably from 1 to S and most preferably from 1 to 2.
The cleaning compositions, component or tablets may preferably contain a clay
flocculating agent, preferably present at a level of from 0.005% to 10%, more
preferably
from 0.05% to 5%, most preferably from 0.1 % to 2% by weight of the
composition.
The clay flocculating agent functions such as to bring together the particles
of clay
compound in the wash solution and hence to aid their deposition onto the
surface of the
fabrics in the wash. This functional requirement is hence different from that
of clay
dispersant compounds which are commonly added to laundry detergent
compositions to
aid the removal of clay soils from fabrics and enable their dispersion within
the wash
solution.
Preferred as clay flocculating agents herein are organic polymeric materials
having an
average weight of from 100,000 to 10,000,000, preferably from 150,000 to
5,000,000,
more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers
containing
monomeric units selected from alkylene oxide, particularly ethylene oxide,
acrylamide,
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acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine.
Homopolymers of, on
particular, ethylene oxide, but also acrylamide and acrylic acid are
preferred.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter
and
Gamble Company describe preferred organic polymeric clay flocculating agents
for use
herein.
Inorganic clay flocculating agents are also suitable herein, typical examples
of which
include lime and alum.
The flocculating agent is preferably present in a detergent base granule such
as a
detergent agglomerate, extrudate or spray-dried particle, comprising generally
one or
more surfactants and builders.
It may be preferred that clay material used to prepare the compressed clay
component
herein has a free moisture content of less than 30%, preferably less than 23%
or even less
than 18% or even less than 12%, which means that its free moisture content is
such that
when the 10 gram of the clay material is oven-dried at 105°C for 1 hour
under a draught,
the clay material looses less than 30% of its original weight, preferably less
than 23% or
even less than 18% or even less than 12%.
Tablets
The tablets herein can be any tablet used to deliver an active ingredient to a
medium
comprising a solvent. Preferred tablets forms are pharmaceutical tablets, to
deliver active
ingredients such as medicaments to a aqueous medium, tablets comprising plant
nutrients
or fertilisers or tablets comprising pesticides.
Highly preferred are detergent tablets, delivering detergent actives to the
cleaning
solution, such as preferably laundry or dish washing solutions or hard-surface
cleaning
solution. Preferred ingredients of cleaning tablets herein are described
hereinafter.
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It may be preferred that the tablet are laundry tablets which provide
softening of fabrics
in the wash.
When the tablets are cleaning or detergent tablets, they preferably comprise
the
compressed clay component at a level of from 0.05% to 30% by weight of the
tablet,
more preferably from 1% to 20% or even from 2% to 15% or even 3% to 12% by
weight.
The tablet may comprise a coating. The tablet may be coated so that the tablet
does not
absorb moisture, or absorbs moisture at only a very slow rate. The coating is
preferably
also strong so that moderate mechanical shocks to which the tablets are
subjected during
handling, packing and shipping result in no more than very low levels of
breakage or
attrition. Finally the coating is preferably brittle so that the tablet breaks
up when
subjected to stronger mechanical shock. Furthermore it is advantageous if the
coating
material is dispersed under alkaline conditions, or is readily emulsified by
surfactants.
This contributes to avoiding the problem of visible residue in the window of a
front-
loading washing machine during the wash cycle, and also avoids deposition of
particles
or lumps of coating material on the laundry load.
It may be preferred that the coating comprises one or more disintegrating
agent as
described herein, or even a compressed clay component herein.
Suitable coating materials are carboxylic acids, preferably dicarboxylic
aicds. Particularly
suitable dicarboxylic acids are selected from the group consisting of oxalic
acid, malonic
acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
azelaic acid,
sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and
mixtures
thereof. The coating material preferably has a melting point of from
40°C to 200°C.
The coating can be applied in a number of ways. Two preferred coating methods
are a)
coating with a molten material and b) coating with a solution of the material.
In a), the coating material is applied at a temperature above its melting
point, and
solidifies on the tablet. In b), the coating is applied as a solution, the
solvent being dried
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to leave a coherent coating. The substantially insoluble material can be
applied to the
tablet by, for example, spraying or dipping. Normally when the molten material
is
sprayed on to the tablet, it will rapidly solidify to form a coherent coating.
When tablets
are dipped into the molten material and then removed, the rapid cooling again
causes
rapid solidification of the coating material. Clearly substantially insoluble
materials
having a melting point below 40°C are not sufficiently solid at ambient
temperatures and
it has been found that materials having a melting point above about
200°C are not
practicable to use. Preferably, the materials melt in the range from
60°C to 160°C, more
preferably from 70°C to 120°C.
By "melting point" is meant the temperature at which the material when heated
slowly in,
for example, a capillary tube becomes a clear liquid.
A coating of any desired thickness can be applied according to the present
invention. For
most purposes, the coating forms from 1% to 10%, preferably from 1.5% to 5%,
of the
tablet weight.
It may be preferred that the tablets herein comprise one or more binders. For
example,
non gelling binders can be integrated to the particles forming the tablet in
order to further
facilitate dispersion.
If non gelling binders are used, suitable non-gelling binders include
synthetic organic
polymers such as.polyethylene glycols, polyvinylpyrrolidones, polyacrylates
and water-
soluble acrylate copolymers. The handbook of Pharmaceutical Excipients second
edition, has the following binders classification: Acacia, Alginic Acid,
Carbomer,
Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum,
Hydrogenated vegetable oil type I, Hydroxyethyl cellulose, Hydroxypropyl
methylcellulose, Liquid glucose, Magnesium aluminum silicate, Maltodextrin,
Methylcellulose, polymethacrylates, povidone, sodium alginate, starch and
zero. Most
preferable binders also have an active cleaning function in the laundry wash
such as
cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary
compounds,
bishexamethylene triamines, or others such as pentaamines, ethoxylated
polyethylene
amines, malefic acrylic polymers.
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Non-gelling binder materials are preferably sprayed on and hence have an
appropriate
melting point temperature below 90°C, preferably below 70°C and
even more preferably
below 50°C so as not to damage or degrade the other active ingredients
in the matrix.
Most preferred are non-aqueous liquid binders (i.e. not in aqueous solution)
which may
be sprayed in molten form. However, they may also be solid binders
incorporated into the
matrix by dry addition but which have binding properties within the tablet.
Non-gelling binder materials are preferably used in an amount within the range
from 0.1
to 15% of the composition, more preferably below 5% and especially if it is a
non
laundry active material below 2% by weight of the tablet.
It is preferred that gelling binders, such as nonionic surfactants are avoided
in their liquid
or molten form. Nonionic surfactants and other gelling binders are not
excluded from the
compositions, but it is preferred that they be processed into the detergent
tablets as
components of particulate materials, and not as liquids.
Tablet Manufacture
Detergent or cleaning tablets herein can be prepared simply by mixing the
solid
ingredients, including the compressed clay, together and compressing the
mixture in a
conventional tablet press as used, for example, in the pharmaceutical
industry. Preferably
the principal ingredients are used in particulate form. Any liquid
ingredients, for example
surfactant or suds suppressor, can be incorporated in a conventional manner
into the solid
particulate ingredients.
The ingredients such as builder and surfactant can be spray-dried in a
conventional
manner and then compacted at a suitable pressure. Preferably, the tablets
according to the
invention are compressed using a force of less than 100000N, more preferably
of less
than SOOOON, even more preferably of less than 20000N and most preferably of
less than
10000 N. However, when coating agents are used to coat the tablet core, even
lower
forces can be used to make the core of the tablet, such as for example below
SOOON or
even below 3000N.
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The particulate material, not being the compressed clay component, used for
making the
tablet of this invention can be made by any particulation or granulation
process. An
example of such a process is spray drying (in a co-current or counter current
spray drying
tower) which typically gives low bulk densities 600g/1 or lower. Particulate
materials of
higher density can be prepared by granulation and densification in a high
shear batch
mixer/granulator or by a continuous granulation and densification process
(e.g. using
Lodige(R) CB and/or Lodige(R) KM mixers). Other suitable processes include
fluid bed
processes, compaction processes (e.g. roll compaction), extrusion, as well as
any
particulate material made by any chemical process like flocculation,
crystallisation
centering, etc. Individual particles can also be any other particle, granule,
sphere or grain.
The components of the particulate material may be mixed together by any
conventional
means. Batch is suitable in, for example, a concrete mixer, Nauta mixer,
ribbon mixer or
any other. Alternatively the mixing process may be carried out continuously by
metering
each component by weight on to a moving belt, and blending them in one or more
drums) or mixer(s). Non-gelling binder can be sprayed on to the mix of some,
or all of,
the components of the particulate material. Other liquid ingredients may also
be sprayed
on to the mix of components either separately or premixed. For example perfume
and
slurries of optical brighteners may be sprayed. A finely divided flow aid
(dusting agent
such as zeolites, carbonates, silicas) can be added to the particulate
material after
spraying the binder, preferably towards the end of the process, to make the
mix less
sticky.
As described above for the compressed clay component, the tablets containing
the
compressed clay component, such as detergent tablets, may be manufactured by
using
any compacting process, such as tabletting, briquetting, or extrusion,
preferably
tabletting. Suitable equipment, which can also be used to make the compressed
clay
component herein, includes a standard single stroke or a rotary press (such as
Courtoy(R), Korch(R), Manesty(R), or Bonals(R)). The tablets prepared
according to this
invention preferably have a diameter of between 20mm and 60mm, preferably of
at least
35 and up to 55 mm, and a weight between 25 and 100 g. The ratio of height to
diameter
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(or width) of the tablets is preferably greater than 1:3, more preferably
greater than 1:2.
The compaction pressure used for preparing these tablets need not exceed
100000
kN/m2, preferably not exceed 30000 kN/m2, more preferably not exceed 5000
kN/m2,
even more preferably not exceed 3000kN/m2 and most preferably not exceed
1000kN/m2. In a preferred embodiment according to the invention, the tablet
has a
density of at least 0.9 g/cc, more preferably of at least 1.0 g/cc, and
preferably of less
than 2.0 g/cc, more preferably of less than 1.5 g/cc, even more preferably of
less than
1.25 g/cc and most preferably of less than 1.1 g/cc.
Mufti-layer tablets can be made by known techniques.
Cleaning compositions and components
The compressed clay component can be used in any composition or component
thereof,
to improve the dissolution or disintegration thereof, in particular in
cleaning
compositions, pharmaceutical compositions, plant nutrient compositions or
paint
fertilizer compositions, provided that these compositions allow incorporation
of a
granular clay component. Thus, generally the compositions will be solid
compositions,
in particular granular compositions.
Highly preferred compositions are cleaning compositions or component thereof.
The compositions.can take a variety of physical forms including granular,
flake, pastille
and bar and even liquid forms. Liquids may be aqueous or non-aqueous and may
be in
the form of a gel. The compositions may be pre-treatment compositions or may
be
conventional washing detergents. The compositions are particularly granular
detergent
compositions , preferably the so-called concentrated compositions adapted to
be added to
a washing machine by means of a dispensing device placed in the machine drum
with the
soiled fabric load.
Such granular detergent compositions or components thereof can be made via a
variety of
methods, including spray-drying, dry-mixing, extrusion, agglomerating and
granulation..
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Cleaning compositions or components herein, and also the cleaning tablets
described
above, preferably comprise the clay at a level of from 0.05% to 30% by weight
of the
tablet, more preferably from 1% to 20% or even from 2% to 15% or even 3% to
12% by
weight.
The compressed clay component may be comprised in a detergent granule.
However, it may be preferred that the compressed clay is present as a separate
granular
component of the composition, to aid dissolution, dispersion or dispensing of
the
composition, in particular in the event that caking or gelling occurs upon
contact with
water. This may in particular occur when the compositions comprise gelling
ingredients
such as nonionic surfactants. The incorporation of the compressed clay
component as
separate granule may in particularly be preferred when the compressed clay
component
has the preferred larger particle sizes, 90% by weight being from 400 to 1100
microns or
even from S00 to 1000 microns.
When the compressed clay component is incorporated in a detergent granule, it
is clear
that the detergent granule will be of a larger particle size than the clay
component. The
clay component may be particularly useful in compositions comprising detergent
granules of an mean particle size of above 350 microns, preferably above 400
or even
500 microns or even above 600 or even 700 microns.
The term mean particle size as defined herein is calculated by sieving a
sample of the
composition into a number of fractions (typically 5 fractions) on a series of
sieves,
preferably Tyler sieves. The weight fractions thereby obtained are plotted
against the
aperture size of the sieves. The mean particle size is taken to be the
aperture size through
which 50% by weight of the sample would pass.
In a preferred embodiment, the composition preferably comprises whereof (not
including
the compressed clay granules when present as separate granular components) at
least
60%, more preferably at least 80% by weight have an average particle size, by
weight, of
from 450 microns to 1400 microns, preferably from 500 or even 600 microns to
1100
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microns or even 700 to 1000 microns. It may even be preferred that the
compositions
comprises less than 20% or even less than 10% or even less than 5% by weight
of
particulate components (not including the compressed clay granules when
present as
separate granular components) of a particle size of less than 200 microns, or
even less
than 350 microns or even less than 425 microns; it may also be preferred the
composition
comprise less than 20% or even less thanl0% or even less than 5% by weight of
the
composition, of particulate components (not including the compressed clay
granules
when present as separate granular components) of a particle size of more than
1700
microns, or even more than 1400 microns or even more than 1180 microns.
The detergent compositions or component thereof may also comprise additional
disintegrating agents and/ or effervescence sources.
Additional ingredients of cleaning compositions and tablets
The compositions and detergent tablets in accord with the invention contain
additional
detergent components. The precise nature of these additional components, and
levels of
incorporation thereof will depend on the physical form of the composition or
component,
and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional
detergent
components selected from surfactants, bleaches, bleach catalysts, alkalinity
systems,
builders, phosphate-containing builders, organic polymeric compounds, enzymes,
suds
suppressors, lime soap, dispersants, soil suspension and anti-redeposition
agents soil
releasing agents, perfumes, brightners, photobleaching agents and additional
corrosion
inhibitors.
Surfactant
The compositions in accord with the invention preferably contain one or more
surfactants
selected from anionic, nonionic, cationic, ampholytic, amphoteric and
zwitterionic
surfactants and mixtures thereof.
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A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes,
and species of
these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Hearing
on
December 30, 1975. Further examples are given in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable
cationic
surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are
generally used in
combination with one or more anionic and/or nonionic surfactants.
Anionic Surfactant
The compositions in accord with the present invention preferably comprise 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.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate
surfactant,
preferably a linear or branched alkyl benzene sulfonate and alkyl
ethoxylsulfates, as
described herein, preferably combined with a cationic surfactants as described
herein.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 1 g
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Anionic Sulfate Surfactant
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Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, the CS-C1~ acyl-N-(C1-C4 alkyl)
and -N-(C1-
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C 10-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a C11-
C 1 g, most preferably C 11-C 15 alkyl sulfate which has been ethoxylated with
from 0.5 to
7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures
have been
disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfonate Surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20 linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane
sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl
glycerol
sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates,
and any mixtures
thereof.
Anionic Carboxylate Surfactant
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Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially
certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to C 1 g alkyl group, x ranges from O to 10, and
the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is
0 is less than 20 % and M is a ration. Suitable alkyl polyethoxy
polycarboxylate
surfactants include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is
a C6
to C 1 g alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting
of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted
or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl
unit connected to a secondary carbon. Preferred secondary soap surfactants for
use herein
are water-soluble members selected from the group consisting of the water-
soluble salts
of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic
acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps may also be included as suds suppressors.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(R1) CH2 COOM, wherein R is a C5-C1~ linear or branched alkyl or alkenyl
group, R1
is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are
the myristyl
and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The
ethoxylated and
propoxylated nonionic surfactants are preferred.
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Preferred alkoxylated surfactants can be selected from the classes of the
nonionic
condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic
ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate
condensates
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
Nonionic Alkoxylated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred are
the condensation products of alcohols having an alkyl group containing from 8
to 20
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic Polyhydroxy Fattv Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the
structural
formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy
propyl, ethoxy, propoxy, or a mixture thereof, preferable Cl-C4 alkyl, more
preferably
C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a CS-C31
hydrocarbyl,
preferably straight-chain CS-C 1 g alkyl or alkenyl, more preferably straight-
chain Cg-C 1 ~
alkyl or alkenyl, most preferably straight-chain C 11-C 1 ~ alkyl or alkenyl,
or mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at
least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably
ethoxylated or propoxylated) thereof. Z preferably will be derived from a
reducing sugar
in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Fatty Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula:
R6CON(R~)2
wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17
carbon
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22
atoms and each R7 is selected from the group consisting of hydrogen, C1-C4
alkyl, C1-
C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic Alkylpolysaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from 6
to 30
carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing
from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to
18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The
glycosyl is
preferably derived from glucose.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and
the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to S, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and C 10-18
acylamido
alkyl dimethylamine oxide.
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A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions 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. Betaine and sultaine surfactants are exemplary zwitterionic
surfactants for
use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R
is a C6-C 1 g hydrocarbyl group, each R1 is typically C 1-C3 alkyl, and R2 is
a C 1-C5
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Cationic Surfactants
Suitable cationic surfactants to be used in the detergent herein include the
quaternary
ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono
C6-
C 16, preferably Cg-C l 0 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.
Another suitable group of cationic surfactants which can be used in the
detergent compositions or components thereof herein are cationic ester
surfactants.
The cationic ester surfactant is a, preferably water dispersible, compound
having
surfactant properties comprising at least one ester (i.e. -COO-) linkage and
at least one
canonically charged group.
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Suitable cationic ester surfactants, including choline ester surfactants, have
for example
been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are
separated
from each other in the surfactant molecule by a spacer group consisting of a
chain
comprising at least three atoms (i.e. of three atoms chain length), preferably
from three to
eight atoms, more preferably from three to five atoms, most preferably three
atoms. The
atoms forming the spacer group chain are selected from the group consisting of
carbon,
nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any
nitrogen
or oxygen atom in said chain connects only with carbon atoms in the chain.
Thus spacer
groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages
are
excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-
CH2-
linkages are included. In a preferred aspect the spacer group chain comprises
only carbon
atoms, most preferably the chain is a hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant
preferably of the
general formula I:
Rl /ApRa
~N+/ X_
R2~ ~R3
(
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about 14
carbon atoms; R2 and R3 are each independently alkyl groups containing from
one to
about three carbon atoms, preferably methyl, most preferably both R2 and R3
are methyl
groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X- is an
anion such
as chloride, bromide, methylsulfate, sulfate, or the like, to provide
electrical neutrality; A
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is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from
0 to about
30, preferably 2 to about 1 S, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group,
having no
greater than 6 carbon atoms whereby the -OH group is separated from the
quaternary
ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred
ApR4
groups are -CH2CH20H, -CH2CH2CH20H, -CH2CH(CH3)OH and -
CH(CH3)CH20H, with-CH2CH20H being particularly preferred. Preferred R1 groups
are linear alkyl groups. Linear R1 groups having from 8 to 14 carbon atoms are
preferred.
Another highly preferred cationic mono-alkoxylated amine surfactants for use
herein are
of the formula
R~\ /(CH2CH2O)2-5 H
\N+ XO
CH3/ \CH3
wherein R1 is C 10-C 1 g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl,
preferably C 10 and C 12 alkyl, and X is any convenient anion to provide
charge balance,
preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or
i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in
detergent
compositions of the invention is preferably from 0.1 % to 20%, more preferably
from
0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
Cationic bis-alkoxylated amine surfactant
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26
The cationic bis-alkoxylated amine surfactant preferably has the general
formula II:
ApR3
R\
\N+~ X_
R2~ ~A,qR4
wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18
carbon
atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10
to about
14 carbon atoms; R2 is an alkyl group containing from one to three carbon
atoms,
preferably methyl; R3 and R4 can vary independently and are selected from
hydrogen
(preferred), methyl and ethyl, X- is an anion such as chloride, bromide,
methylsulfate,
sulfate, or the like, sufficient to provide electrical neutrality. A and A'
can vary
independently and are each selected from C1-C4 alkoxy, especially ethoxy,
(i.e., -
CH2CH20-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30,
preferably 1
to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most
preferably both
p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are
of the
formula
R\ +/CH2CH20H
N X
CH3/ \CH2CH20H
wherein R 1 is C 10-C 1 g hydrocarbyl and mixtures thereof, preferably C 10, C
12, C 14
alkyl and mixtures thereof. X is any convenient anion to provide charge
balance,
preferably chloride. With reference to the general cationic bis-alkoxylated
amine
structure noted above, since in a preferred compound R1 is derived from
(coconut) C12-
C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each
monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include
compounds of the
formula:
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27
R~ ~(CHZCHZO)pH
N+ X
R2~ ~(CH2CH20)qH
wherein R1 is C 1 p-C 1 g hydrocarbyl, preferably C 1 p-C 14 alkyl,
independently p is 1 to
about 3 and q is 1 to about 3, R2 is Cl-C3 alkyl, preferably methyl, and X is
an anion,
especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20)
units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and
[CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr
and/or
i-Pr units.
Perhvdrate Bleaches
An preferred additional components of the compositions is a perhydrate bleach,
such as
metal perborates, metal percarbonates, particularly the sodium salts.
Perborate can be
mono or tetra hydrated. Sodium percarbonate has the formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic
perhydrate
salt of use in the detergent compositions herein.
Organic Peroxyacid Bleaching System
A preferred feature of the composition is an organic peroxyacid bleaching
system. In one
preferred execution the bleaching system contains a hydrogen peroxide source
and an
organic peroxyacid bleach precursor compound. The production of the organic
peroxyacid occurs by an in situ reaction of the precursor with a source of
hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate
bleaches,
such as the perborate bleach of the claimed invention. In an alternative
preferred
execution a preformed organic peroxyacid is incorporated directly into the
composition.
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Compositions containing mixtures of a hydrogen peroxide source and organic
peroxyacid
precursor in combination with a preformed organic peroxyacid are also
envisaged.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydroloysis the structure of the peroxyacid produced is
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of from
0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most
preferably
from 1.5% to 10%~by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and
EP-A-0170386.
Leaving Groups
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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 ~ Y , and -O
1 O 4
-N-C-R -N N -N-C-CH-R
R3 ~--~ ~ R3 Y ,
I
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
O Y O
-NCH2 CNR _ ~%NR4
-O-C-R1 \C/ 4 Nw
II O
O
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R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or
R3, and Y is H or a solubilizing group. Any of 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 cation,
with
sodium and potassium being most preferred, and X is a halide, hydroxide,
methylsulfate
or acetate anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains
from 1
to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred. The
TAED is preferably not present in the agglomerated particle of the present
invention, but
preferably present in the detergent composition, comprising the particle.
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31
Other preferred alkyl percarboxylic 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 Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein,
including
those of the following general formulae:
R~ CNR2CL R~ -NC~R2-CL
O R5 O or R5 O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to 10
carbon atoms and L can be essentially any leaving group. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable
O-acylated perbenzoic acid precursor compounds include the substituted and
unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of
sorbitol,
glucose, and all saccharides with benzoylating agents, and those of the imide
type
including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-
benzoyl
substituted ureas. Suitable imidazole type perbenzoic acid precursors include
N-benzoyl
imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine
and benzoyl
pyroglutamic acid.
Cationic Peroxyacid Precursors
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Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part
of a suitable peroxyacid precursor compound with a positively charged
functional group,
such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl
ammonium group. Cationic peroxyacid precursors are typically present in the
solid
detergent compositions as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as
described
hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl
percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594; EP
475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in 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.
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Benzoxazin Organic Peroxyacid Precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example
in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
O
I I
CEO
I
N C-R~
wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed Organic Peroxyacid
The detergent composition may contain, in addition to, or as an alternative
to, an organic
peroxyacid bleach precursor compound, a preformed organic peroxyacid ,
typically at a
level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight
of the
composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R~ CNR2COOH R~ NCR2COOH
O R5 O or R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide
substituted
organic peroxyacid compounds of this type are described in EP-A-0170386.
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Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid and
diperoxyhexadecanedioc
acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach Catalyst
The composition can contain a transition metal containing bleach catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a
transition metal
cation of defined bleach catalytic activity, such as copper, iron or manganese
cations, an
auxiliary metal cation having little or no bleach catalytic activity, such as
zinc or
aluminum cations, and a sequestrant having defined stability constants for the
catalytic
and auxiliary metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts
thereof. Such
catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in U.S.
Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include
Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, Mn~2(u-O)1(u-
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, Mn~4(u-O)6(1,4,7-
triazacyclononane)4-(C104)2, Mn~MnN4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)3, and mixtures thereof. Others are described in
European
patent application publication no. 549,272. Other ligands suitable for use
herein include
1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-
methyl-
1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and
mixtures
thereof.
The bleach catalysts useful herein may also be selected as appropriate for the
present
invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612
and U.S.
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Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear
manganese (IV)
complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-
soluble complex of manganese (III), and/or (IV) with a ligand which is a non-
carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred
ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso-
erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals,
including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the
formula:
R2 R3
R~ -N=C-B-C=N-R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring.
Said ring can further be substituted. B is a bridging group selected from O,
S. CRSR6,
NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups,
including
substituted or unsubstituted groups. Preferred ligands include pyridine,
pyridazine,
pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally,
said rings may
be substituted with substituents such as alkyl, aryl, alkoxy, halide, and
nitro. Particularly
preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts
include Co, Cu,
Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred
catalysts
include Co(2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt
(II),
trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)202C104, Bis-
(2,2'-
bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II)
perchlorate, and
mixtures thereof.
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Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-
dentate
ligands, including N4Mn~(u-O)2MnNN4)+and [Bipy2Mn~(u-O)2Mn~bipy2]-
(C104)3.
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application, publication no. 224,952, (absorbed manganese on aluminosilicate
catalyst),
U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium
salt),
U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex
catalyst),
German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191
(transition metal-containing salts), U.S. 4,430,243 (chelants with manganese
canons and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
The bleach catalyst is typically used in a catalytically effective amount in
the
compositions and processes herein. By "catalytically effective amount" is
meant an
amount which is sufficient, under whatever comparative test conditions are
employed, to
enhance bleaching and removal of the stain or stains of interest from the
target substrate.
The test conditions will vary, depending on the type of washing appliance used
and the
habits of the user. Some users elect to use very hot water; others use warm or
even cold
water in laundering operations. Of course, the catalytic performance of the
bleach
catalyst will be affected by such considerations, and the levels of bleach
catalyst used in
fully-formulated detergent and bleach compositions can be appropriately
adjusted. As a
practical matter, and not by way of limitation, the compositions and processes
herein can
be adjusted to provide on the order of at least one part per ten million of
the active bleach
catalyst species in the aqueous washing liquor, and will preferably provide
from about 1
ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate
this point
further, on the order of 3 micromolar manganese catalyst is effective at
40°C, pH 10
under European conditions using perborate and a bleach precursor. An increase
in
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37
concentration of 3-5 fold may be required under U.S. conditions to achieve the
same
results.
Water-Soluble Builder Compound
The compositions in accord with the present invention 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 1 S%
to
40% by weight of the composition.
The detergent compositions of the invention preferably 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% 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,
tartronic acid and
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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,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates
described in Netherlands Application 7205873, and the oxypolycarboxylate
materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
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 of the composition.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed
citrates described in British Patent No. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can produce
borate under detergent storage or wash conditions are useful water-soluble
builders
herein.
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
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sodium polymeta/phosphate in which the degree of polymerization ranges from
about 6
to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The compositions in accord with 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 of the composition.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(A102)z(Si02)y]. xH20
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least
5, preferably from 7.5 to 276, more preferably from 10 to 264. The
aluminosilicate
material are in hydrated form and are preferably crystalline, containing from
10% to
28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurnng materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof. Zeolite A has the formula:
Na 12 [A102) 12 (5102)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 of the compositions.
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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 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. Other
methods
of establishing d50 values are disclosed in EP 384070A.
Heavy metal ion seguestrant
The compositions of the invention preferably contain as an optional component
a heavy
metal ion sequestrant. By heavy metal ion sequestrant it is meant herein
components
which act to sequester (chelate) heavy metal ions. These components may also
have
calcium and magnesium chelation capacity, but preferentially they show
selectivity to
binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 10%,
preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most
preferably
from 0.3% to 2% by weight of the compositions or component
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Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic
acid.
Other suitable heavy metal ion sequestrant 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.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-
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 (3-
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 1,1 hydroxyethane diphosphonic acid or the alkali
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metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof.
Enzyme
Another preferred ingredient useful in the 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 commercially available protease enzymes include those sold under the
tradenames Alcalase, Savinase, Primase, Durazym, 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 obtained from a special
strain of B
licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred
commercially
available amylases include for example, those sold under the tradename
Rapidase by
Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by
Novo Industries A/S. Highly preferred amylase enzymes maybe 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 of the
composition.
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Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001 % to
2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001
% to
0.5% by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example,
from a lipase
producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including
Pseudomonas pseudoalcali eg nes or Pseudomas fluorescens. Lipase from
chemically or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas pseudoalcaligenes, which is described in Granted
European
Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanu~inosa and expressing the gene in Aspergillus 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.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the
compositions
herein and are preferably present as components of any particulate components
where
they may act such as to bind the particulate component together. By organic
polymeric
compound it is meant herein essentially any polymeric organic compound
commonly
used as dispersants, and anti-redeposition and soil suspension agents in
detergent
compositions, including any of the high molecular weight organic polymeric
compounds
described as clay flocculating agents herein, including quaternised
ethoxylated (poly)
amine clay-soil removal/ anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%,
most
preferably from 0.5% to 10% by weight of the compositions.
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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.
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:
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CH3 i H3
X~-OCH2CH2)n N+-CH2-CH2-(-CH2)a N+-CH2CH20-~X
(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.
Other dispersants/ anti-redeposition agents for use herein are described in EP-
B-011965
and US 4,659,802 and US 4,664,848.
Suds Sunnressine Svstem
The detergent compositions of the invention, when formulated for use in
machine
washing compositions, may comprise a suds suppressing system present at a
level of
from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to
3%
by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds and 2-
alkyl
alcanol antifoam compounds.
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.
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46
Such silicone antifoam compounds also typically contain a silica component.
The term
"silicone" as used herein, and in general throughout the industry, encompasses
a variety
of relatively high molecular weight polymers containing siloxane units and
hydrocarbyl
group of various types. Preferred silicone antifoam compounds are the
siloxanes,
particularly the polydimethylsiloxanes having trimethylsilyl end blocking
units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and
soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September
27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof,
for use as
suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,
preferably
12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as
sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty
esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic
C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to
hexa-
alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products
of cyanuric
chloride with two or three moles of a primary or secondary amine containing 1
to 24
carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-
alkali metal
(e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably
a
silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam
compound; and
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47
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from
5% to 50%, preferably 10% to 40% 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%,
preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake
copolymer of this type is DC0544, commercially available from DOW Corning
under the tradename DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C16-C18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to
1 S, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-
0210731
and comprises a silicone antifoam compound and an organic Garner material
having a
melting point in the range 50°C to 85°C, wherein the organic
carrier material comprises a
monoester of glycerol and a fatty acid having a carbon chain containing from
12 to 20
carbon atoms. EP-A-0210721 discloses other preferred particulate suds
suppressing
systems wherein the organic Garner 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.
Polymeric Dye Transfer Inhibiting Agents
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48
The compositions herein may also comprise from 0.01% to 10 %, preferably from
0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers
can be
cross-linked polymers.
Optical Bri~htener
The compositions herein also optionally contain from about 0.005% to 5% by
weight of
certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R~ R2
N H_H N O
N OOIj O C C O NOO N
rN H H NO
R2/ S03M S03M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a cation
such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-
2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener
species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-
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49
Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred
hydrophilic
optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
hydroxyethyl-
N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium
salt. This
particular brightener species is commercially marketed under the tradename
Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon
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
commercially
marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy
Corporation.
Polymeric Soil Release Agent
Polymeric soil release agents, hereinafter "SRA", can optionally be employed
in the
present compositions. If utilized, SRA's will generally comprise from 0.01 %
to 10.0%,
typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of the
compositions.
Preferred SRA's 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 occurnng subsequent to treatment with the SRA to be more easily
cleaned
in later washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by
processes
involving at least one transesterification/oligomerization, often with a metal
catalyst such
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as a titanium(IV) alkoxide. Such esters may be made using additional monomers
capable
of being incorporated into the ester structure through one, two, three, four
or more
positions, without, of course, forming a densely crosslinked overall
structure.
Suitable SR.A's 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 SRA's include the
nonionic
end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.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 SRA's 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.
SRA's 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
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51
derivatives such as the hydroxyether cellulosic polymers available as METHOCEL
from
Dow; the C1-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 SM100 and METOLOSE
SM200, which are the trade names of methyl cellulose ethers manufactured by
Shin-etsu
Kagaku Kogyo KK.
Additional classes of SR.A's include: (I) nonionic terephthalates using
diisocyanate
coupling agents to link polymeric ester structures, see U.S. 4,201,824,
Violland et al. and
U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups
made by
adding trimellitic anhydride to known SRA'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 SRA's 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.. Other
classes
include: (III) anionic terephthalate-based SRA's of the urethane-linked
variety, see U.S.
4,201,824, Violland et al.;
Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention
include perfumes, spray-on and encapsulates, colours and filler salts, with
sodium sulfate
being a preferred filler salt.
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Abbreviations used in 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
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS : Sodium C 1 x-C 1 y 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(C2H4OH) with R2 = C 12 - C 14
QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = Cg - C11
SADS : Sodium C~4-C22 alkyl disulfate of formula
2-(R).C4 H~.-
1,4-(S04-)2 where R = C,~C1$
MBAS : C 12 - C 18 midbranched alkyl sulphate surfactant
with an
average branching of 1.5 methyl or ethyl branching groups
MES : x-sulpho methylester of C~g fatty acid
APA : Cg - 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 : C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA : C 16-C 1 g alkyl N-methyl glucamide
TPKFA : C 16-C 1 g topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
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Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12~27H20 having a primary particle
size in the range from 0.1 to 10 micrometers
(weight
expressed on an anhydrous basis)
NaSKS-6 : Crystalline layered silicate of formula b-
Na2Si205
Citric acid : Anhydrous citric acid
Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle
size between
200~m and 900~m
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size
distribution between 400~m 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 425~m
and 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular
weight about 70,000
MA/AA (1) : Copolymer of 4:6 maleic/acrylic acid, average
molecular
weight about 10,000
AA : Sodium polyacrylate polymer of average molecular
weight
4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether Methyl cellulose ether with a degree of polymerization
: of
650 available from Shin Etsu Chemicals
Enz~nes:
Protease : Proteolytic enzyme, having 3.3% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Savinase
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Protease I : Proteolytic enzyme, having 4% by weight of active
enzyme, as described in WO 95/10591, sold by Genencor
Int. Inc.
Alcalase : Proteolytic 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 : Amylolytic enzyme, having 1.6% by weight of active
enzyme, sold by NOVO Industries A/S under the
tradename Termamyl 120T
Amylase II : Amylolytic enzyme, as disclosed in PCT/ US9703635
Lipase : Lipolytic enzyme, having 2.0% by weight of active
enzyme, sold by NOVO Industries A/S under the
tradename Lipolase
Endolase : Endoglucanase enzyme, having 1.5% by weight of active
enzyme, sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB 1 : Anhydrous sodium perborate bleach of nominal formula
NaB02.H202
Percarbonate : Sodium percarbonate of nominal formula
2Na2C03.3H202
DOBS : Decanoyl oxybenzene sulfonate in the form of the sodium
salt
DPDA : Diperoxydodecanedioc acid
NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium
salt, optionally comprising a disintegrating agent
NACA-OBS : (6-nonamidocaproyl) oxybenzene sulfonate, optionally
comprising a disintegrating agent
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LOBS : Dodecanoyloxybenzene sulfonate in the form of the
sodium salt
DOBS : Decanoyloxybenzene sulfonate in the form of the
sodium salt
DOBA : Decanoyl oxybenzoic acid
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 in the
form of its sodium salt.
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
TEPAE . : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidosole, with an average molecular
weight of
20,000
PVP : Polyvinylpyrolidone polymer, with an average
molecular
weight of 60,000
PVNO : Polyvinylpyridine N-oxide polymer, with
an average
molecular weight of 50,000
PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an average molecular weight of 20,000
QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H40))n, wherein n = from 20
to 30
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Clay 1 : Compressed montmorillonite clay, 90% having a particle
size of from 400 microns to 100 microns, compressed
with a pressure of 20 MPa
Clay 2 : Compressed bentonite clay, 90% having a particle size of
from 400 microns to 100 microns, compressed with a
pressure of 20MPa
Clay 3 : Any clay according to example 1
SRP 1 : Anionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short
block polymer
Cellulose : cellulose such as Solka-floc or Arbocel or
microcrystalline cellulose such as Lattice, form FMC.
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
Photo-bleach : agent comprising zinc or alumino phthalocyanine and
polyvinylpyrrolidinone of average molecular weight of
30,000 to50,000, at a weight ratio of 1:80 to 1:120,
encapsulated with starch and with a sugar derivative
Example 1
A compressed clay component was prepared by placing 20 gram of a clay, for
example a bentonite or montmorillonite clay, whereof 90% of the particles had
a particle
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57
size of below 110 microns, in a die having a diameter of 5.4 cm and
compressing the clay
into a tablet of about 10 cm thick, by applying a force of 45 kN, using a
Lloyd SOK tablet
press. The obtained tablet was broken in parts and the parts were added to a
Combimax
700 food processor, to thus grind the parts to form the particulate compressed
clay
component. These particles were sieved to obtain the fraction whereof 95% by
weight
had a particle size from 500 microns to 1000 microns.
The same process was repeated but then by applying a force of 25kN.
The same process was repeated, both when using a force of 25kN and 45kN, but
then
compressing an agglomerated bentonite or montmorillonite clay also comprising
10% by
weight of the agglomerate of a wax and 5% by weight of the agglomerate of a
humectant.
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Example 2
Detergent tablets:
Ex Ex Ex C Ex D Ex Ex F
A B E
Clay 3 8.0 10.0 14.5 11.0 15.0 4.0
Flocculant Agglomerate2.0 1.5 5.8 3.0
(PEO, zeolite, MA/AA,
water)
Anionic agglomerates38 24 38 24 38 24
Cationic agglomerates5.0 5.0 5.0 5.0 5.0 5.0
Sodium percarbonate8 8 8 8 8 8
Bleach activator 2.31 2.31 2.31 2.31 2.31 2.31
agglomerates
Sodium carbonate 2.67 45.33 17.00 31.00 10.86 37.14
EDDS/Sulphate particle0.19 0.19 0.19 0.19 0.19 0.19
Tetrasodium salt 0.34 0.34 0.34 0.34 0.34 0.34
of
Hydroxyethane Diphosphonic
acid
Fluorescer 0.15 0.15 0.15 0.15 0.15 0.15
Zinc Phthalocyanine0.027 0.027 0.027 0.027 0.027 0.027
sulphonate encapsulate
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Soap powder 1.40 1.40 1.40 1.40 1.40 1.40
Suds suppressor 2.6 2.6 2.6 2.6 2.6 2.6
3.0 2.0 1.5 - - 3.0
Cellulose
Citric acid 4.0 4.0 4.0 4.0 4.0 4.0
Protease 0.45 0.45 0.45 0.45 0.45 0.45
Sodium acetate 0.3 0.5 2.0 - 3.0 -
Cellulase 1.0 0.20 0.30 0.50 0.50 1.20
Amylase 0.20 0.20 0.20 0.20 0.20 0.20
Binder
Cationic Polymer 0.75 0.75 0.75 0.75 0.75 0.75
PEG 4000 1.25 1.25 1.25 1.25 1.25 1.25
Anionic agglomerates 1 comprise of 40% anionic surfactant, 27% zeolite and 33%
carbonate.
Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and 32%
carbonate.
Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24%
sulphate.
Bleach activator agglomerates comprise of 81 % TAED, 17% acrylic/maleic
copolymer
(acid form) and 2% water.
Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of
58% of
Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19%
water.
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Zinc phthalocyanine sulphonate encapsulates are 10% active,
Suds suppressor comprises of 11.5% silicone oil; 59% of zeolite and 29.5% of
water.
Example 3
Detergent composition in granular form according to the invention:
G H I J K L
Agglomerate
LAS 7.0 5.0 10.0 14.0 2.0 -
C245AS 3.0 2.0 2.0 2.0 2.5 2.5
Clay 3 10.0 5.0 - - - -
C45AE3S 1.0 1.0 1.0 - - 0.5
C28AS 2.0 1.0 2.0 1.0 0.5 3.5
Silicate 0.2 - 1.0 - 0.3 0.8
Sodium carbonate 6.0 3.0 8.0 - 3.0 3.0
MBAS - 2.0 - - S.0 8.0
SKS-6 0.7 4.0 - 0.5 1.0 2.0
HEDP/EDDS 0.1 0.7 0.3 - - 0.5
Zeolite A 10.0 6.0 6.0 12.0 9.0 10.0
CMC 0.5 - 0.3 0.8 - 0.5
Agglomerate
TAED 5.0 3.0 - 2.0 4.0 3.0
CMC or MA/AA 1.0 0.5 - 0.5 1.0 1.0
Clay 3 - - - - 2.0
Agglomerate
Zeolite A 2.0 1.0 - 1.0 - 2.0
Sud suppressor 0.5 0.5 0.3 0.2 0.1 0.2
MA/AA 0.5 - - 0.2 - 0.2
Agglomerate
QAS 1.0 0.5 1.0 - 1.0 -
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Zeolite 2.0 1.0 - - 2.0 -
Carbonate 0.5 1.0 - - - -
MA/AA - 0.1 - - - -
PEO S.0 - 1.5 3.0 2.0
Clay 3 - - - 10.0 4.0 5.0
Dry add
QEA 1.0 0.5 - - 1.0 -
Clay 3 5.0 2.0 12.0 10.0 8.0 2.0
HEDP/DTPA/EDDS 0.3 0.5 - 0.5 0.5 0.5
MA/AA 1.0 2.0 3.0 - 2.0 2.0
Mg sulphate 0.1 0.2 - - - 0.3
Brightener 0.1 - 0.2 0.2 - 0.2
Zeolite 1.0 2.0 3.0 4.0 5.0 2.0
SKS-6/silicate 10.0 6.0 S.0 10.0 10.0 12.0
Enzymes 0.5 0.8 0.3 1.2 1.2 1.0
CMC 0.2 - 0.3 - 0.5 0.5
Soap 0.5 - - 0.5 1.0 -
NACA OBS - 3.0 - - - 3.0
Photobleach 0.1 0.1 0.5 - 0.2 -
Speckles 0.5 0.2 0.7 - 0.3 -
Carbonate 6.0 5.0 2.0 - 8.0 7.0
Sodium chloride 0.2 - 0.5 - 0.5 -
Sodium sulphate 2.0 3.0 - 8.0 - 3.0
Percarbonate 18.0 10.0 - 22.0 20.0 10.0
Citric acid 1.0 0.5 2.0 3.0 2.0 -
Spray on
AES - 0.5 - - 2.0 -
Perfume 0.2 0.1 0.5 0.2 0.2 0.2
Brightener 0.1 0.2 0.1 0.1 0.1 0.1
Photobleach - - - - - 0.01
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Example 4
Detergent composition according to the invention, in granular form:
M N O P Q R
Spray dried powder
Base: LAS 7.0 6.0 3.0 - 4.0 -
MBAS - - - 5.0 - -
SADS - - - - 3.0
Tallow alkyl sulphate 1.0 - 1.0 1.0 - 1.0
C245AS - - 0.5 - - 1.0
Sodium sulphate 3.0 5.0 3.0 2.0 - 3.0
C24AE35 - 0.5 - 0.5 - 0.7
Clay 1 or 2 10.0 - - - - -
PEO 0.5 1.5 3.0 4.0 5.0 2.0
Sodium carbonate 3.0 6.0 1.0 3.0 5.0 3.0
Sodium sulphate - 1.0 2.0 2.0 - 5.0
Zeolite A 16.0 10.0 5.0 10.0 6.0 -
MA/AA 1.0 - 1.0 0.5 1.0 -
Mg sulphate 0.1 0.1 - 0.1 - 0.1
Brightener 0.2 0.1 - - 0.3 0.5
Chelant 0.5 0.5 - 0.3 0.2 0.4
Water 0.2 0.1 0.1 0.05 0.05 0.3
Agglomerate
LAS - 3.0 5.0 2.0 - 5.0
C45AS - 2.0 3.0 2.0 - -
Carbonate - 5.0 7.0 5.0 - -
Sulphate - 3.0 - 2.0 - 3.0
Zeolite A - 4.0 8.0 3.0 - 9.0
Photobleach - 0.05 0.05 - -
Dry add
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QEA 1.0 1.0 1.0 - 1.0
Sudsuppressor 0.5 0.5 0.5 1.0 0.2 0.3
Percarbonate/perborate 20.0 14.0 - 22.0 18.0 10.0
TAED 4.0 3.0 - - 2.0 3.5
NACA OBS - 3.0 - 4.2 2.5 -
Zeolite A 6.0 3.0 5.0 - 7.0 12.0
SKS-6/silicate 8.0 12. 0 5.0 9.0 - 8.0
Citric acid/citrate 2.0 1.0 3.0 - - 2.0
Speckle (carbonate) 0.3 0.5 0.4 - , - 0.5
Sodium carbonate 5.0 - 8.0 10.0 - 6.0
Sodium sulphate 10.0 5.0 - 3.0 - 14.0
Clay 2 or 3 - 15.0 12.0 4.0 6.0 10.0
Soap 0.5 0.5 - - 0.5 -
Enzymes 1.0 1.5 1.0 1.0 1.0 1.0
SRP 0.1 0.2 0.3 - 0.3 -
HEDP/EDDS/DTPA 0.5 0.5 - 0.2 0.8 0.3
Spray-on
AES - 3.0 1.5 - - -
Perfume 0.3 0.3 0.2 0.5 0.2 0.3
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Example 5
S T U V W X
Blown powder
LAS 23.0 8.0 7.0 9.0 7.0 7.0
TAS - - - - 1.0 -
C45AS 6.0 6.0 5.0 8.0 - -
C45AE35 - 1.0 1.0 1.0 - -
C45E35 - - - - 2.0 4.0
SADS 0.5 - _ -
Zeolite A 10.0 18.0 14.0 12.0 10.0 14.0
MA/AA - 0.5 - - - 2.0
MA/AA( 1 ) 7.0 - _ _ _ _
Clay 1 or 3 - - 6.0 10.0 - -
Sulfate 5.06.36.3 14.3 11.0 15.0 19.3
Silicate 10.0 1.0 1.0 1.0 1.0 1.0
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0
PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0
DTPA - 0.9 0.5 - - 0.5
Photobleach 2 - 0.05 0.005 - 0.3 0.5
Brightener 2 0.3 0.2 0.3 - 0.1 0.3
Spray-on
C45E7 - 2.0 - - 2.0 2.0
C25E9 3.0 - - - - -
C23E9 - - 1.5 2.0 - 2.0
Perfume 0.3 0.3 0.3 2.0 0.3 0.3
Agglomerates
C45AS - 5.0 5.0 2.0 - 5.0
LAS - 2.0 2.0 - - 2.0
PEO - 3.0 3.0 2.0 - 1.0
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Clay 3 3.0 - 7.0 - 5.0
Zeolite A - 7.5 7.5 8.0 - 7.5
Carbonate - 4.0 4.0 5.0 - 4.0
PEG 4000 - 0.5 0.5 - - 0.5
Misc (water etc) - 2.0 2.0 2.0 - 2.0
Dry additives
QAS (1) _ _ _ _ 1.0 -
Clay 2 or 3 3.0 - 6.0 - 11.0 6.0
Citric acid/ malic - - 5.0 3.0 2.0 5.0
aicd
PB4 - - - - 12.0 1.0
PBl - 4.0 3.0 - - -
Percarbonate 4.0 - - 2.0 - 10.0
Carbonate - 5.3 1.8 - 4.0 4.0
NOBS 4.0 - 6.0 - - 0.6
Methyl cellulose 0.2 - - - - -
SKS-6 8.0 - - - -
STS - - 2.0 - 1.0 -
Cumene sulfonic acid - 1.0 - - - 2.0
Photobleach 0.01 - - 0.1 0.1 -
Lipase 0.2 - 0.2 - 0.2 0.4
Cellulase 0.2 0.2 0.2 0.3 0.2 0.2
Amylase 0.2 - 0.1 - 0.2 -
Protease 0.5 0.5 0.5 0.3 0.5 0.5
PVPI - - - - 0.5 0.1
PVP - - - - 0.5 -
PVNO - - 0.5 0.3 - -
QEA - - - - 1.0 -
SRP1 0.2 0.5 0.3 - 0.2 -
Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -
Mg sulfate - - 0..2 - 0.2 -
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Silica 0.2 0.2 0.2 - 0.2 -
Misc/minors to 100%
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Example 6
The following nil bleach-containing detergent formulations of particular use
in the
washing of coloured clothing, according to the present invention were
prepared:
Y Z AA
Blown Powder
Zeolite A 15.0 1 S.0 -
Sulfate 0.0 5.0 -
LAS 3.0 3.0 -
DTPMP 0.4 0.5 -
CMC 0.4 0.4 -
MA/AA 4.0 4.0 -
Agglomerates
C45AS - - 11.0
LAS 6.0 S.0 -
TAS 3.0 2.0 -
Silicate 4.0 4.0 -
PEO 2.0 1.0 1.5
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Photobleach 2 - 0.005 -
Spray On
EFAA - 2.0 -
Perfume 0.3 0.3 0.5
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
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NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 S.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Alcalase 0.5 0.3 0.9
Lipase 0.4 0.4 0.4
Clay 3 11.0 7.0 10.0
Amylase 0.6 0.6 . 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Sulfate 0.0 9.0 0.0
Misc/minors to 100% 100.0 100.0 100.0
Density (g/litre) 700 700 700
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Example 7
The following is a composition in the form of a tablet or granular formulation
in accord
with the invention.
BB CC DD EE FF GG HH II JJ KK LL
Sodium 12.0 16.023.019.0 18.020.0 16.08.5 5 20.06.0
C11-
C13
alkylbenzenes
ulfonate
Sodium 4.5 - - - 4.0 - - -
C 14-
C15 alcohol
sulfate
C14_C15 _ _ _ _ _ _ _ _ _
alcohol
ethoxylate
(0.5) sulfate
Cia-Cis - - 2.0 - 1.0 1.0 1.0 - - - -
alcohol
ethoxylate
(3)
sulfate
Sodium 2.0 2.0 - 1.3 - - 5.0 5.5 4.0 - -
C 14-
C 15 alcohol
ethoxylate
(or
mixtures
of
different
ethoxylation
degree)
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C9-C,4 alkyl - - 1.0 0.5 2.0 - - - -
dimethyl
hydroxy
ethyl
quaternary
ammonium
salt
Tallow fatty - - - - 1.0 - - - -
acid
Tallow - - - - - - - - - - -
alcohol
ethoxylate
(50)
Sodium 23.025.0 14.022.020.0 10.020.0 30.020.0 25.025.0
tripolyphosph
ate / Zeolite
Sodium 25.022.0 35.020.028.0 41.030.0 30.025.0 45.024.0
carbonate
Sodium 0.5 0.5 0.5 0.5 - - - - - - -
Polyacrylate
(45 %)
Sodium - - 1.0 1.0 1.0 2.0 0.5 0.5 1.0 - -
polyacrylate/
maleate
polymer
Sodium 3.0 6.0 9.0 8.0 9.0 6.0 8.0 5.0 6.0 8.0 5.0
silicate
(1:6
ratio
Na0/Si02)(4
6%)
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Sodium - - - - - 2.0 3.0 - - - 8.0
sulfate
Sodium 5.0 S.0 10.0- 3.0 1.0 - 20.014.0 - -
perborate/
percarbonate
Polyethylene1.5 1.5 1.0 1.0 - - 0.5 - - - 0.5
glycol),
MW
4000 (SO%)
Sodium 1.0 1.0 1.0 - 0.5 0.5 0.5 0.5 0.5 - 0.5
carboxy
methyl
cellulose
Citric acid- - - - - - - - - - -
NOB S/ - 1.0 - - 1.0 0.7 - - - - -
DOBS
TAED / PAP 1.5 1.0 2.5 - 3.0 0.7 - 4.5 5.0 - -
Chelant 0.5 0.5 0.5 - 1.0 - - 0.5 0.5 -
SRP 1.5 1.5 1.0 1.0 - 1.0 - 1.0 1.0 - -
Clay 3 5.0 6.0 12.07.0 10.04.0 3.0 7.0 10.0 6.0 8.0
Flocculating0.2 0.2 3.0 2.0 0.1 1.0 0.5 2.0 0.5 1.0 0.5
agent PEO
Humectant - - - - 0.5 0.5 - - 0.5 - -
wax 0.5 - - - - 0.5 - - 0.5 - -
Cellulose 0.5 2.0 - - 3.0 2.0 - - 1.5 - 1.0
Sodium 2.0 1.0 3.0 - - - - 1.0 0.5 4.0 1.0
acetate
Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 5.0 5.0 8.0 10.0
Magnesium - - - - - 0.5 1.5 - - - -
sulphate
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Soap/ suds - - 0.5 0.5 0.8 0.6 1.0 1.0 0.8 0.5/1.0/
suppressor 0.0 0.0
Enzymes, - - - - 2.0 1.5 2.0 0.5 1.0 1.0 1.0
including
amylase,
cellulase,
protease
and
lipase
Speckle 2.5 1.1 0.5 1.4 - - 2.2 1.0 1.6 1.0
minors, 2.0 1.0 1.0 1.0 2.5 1.5 1.0 1.0 0.5 0.5 0.5
e.g.
perfume,
PVP,
PVPVI/PVN
O, brightener,
photo-bleach,
