Note: Descriptions are shown in the official language in which they were submitted.
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Detergent Compositions
Field of the Invention
This invention relates to bleach-containing, softening laundry
compositions comprising clay as a disintegrant and laundry bleach and laundry
enzymes, and in particular it relates to such compositions in the form of
tablets.
Background of the Invention
It is known to provide detergent compositions in the form of tablets made
by compacting a particulate detergent composition. Usually a small amount of
binder is included in the composition in order to promote the integrity of the
tablets.
Although it is necessary that the tablets should have good integrity before
use, it is necessary also that they should disintegrate rapidly during use,
when
contacted with wash water. It is known to include a disintegrant which will
promote disintegration of the tablet. Various classes of disintegrant are
known,
including the class in which disintegration is caused by swelling of the
disintegrant. Various swelling disintegrants have been proposed in the
literature, with the preference being directed predominantly towards starches,
celluloses and water soluble organic polymers. Inorganic swelling
disintegrants
such as bentonite clay have also been mentioned, for instance in EP-A-466,484.
In that disclosure, the same material acts as binder and disintegrant. It is
also mentioned therein that the disintegrant may give supplementary building,
anti-redeposition or fabric softening properties. The amount of disintegrant
is
preferably 1 to 5%. It is proposed in EP-A-466,484 that the tablet may have a
heterogeneous structure comprising a plurality of discrete regions, for
example
layers, inserts or coatings.
In W098/40463 it is proposed to introduce the disintegrant substantially
only in granular form.
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JP-A-9/87696 is concerned with tablets containing a non-ionic detergent
composition with a non-ionic surfactant as the main component and in
particular
is concerned with preventing the non-ionic surfactant from oozing out of the
tablets during storage, and it is also concerned with the fact that the non-
ionic
surfactant causes a loss in the softening effect that would be expected when a
softening clay is included. It describes the formation of tablets containing
finely
divided clay mineral, together with a finely divided oil absorbing carrier,
and a
disintegrant.
Modern detergent compositions often contain one or more laundry
enzymes and these tend to be sensitive to inactivation by conventional laundry
bleaches. It is known to reduce or prevent contact between bleach and other
components of the composition by encapsulating the bleach. Encapsulation
reduces the risk of inactivation of the enzyme by the bleach before the
detergent
composition can disperse in the wash medium.
Another problem in clay-containing detergent composition is that certain
ions in clay can tend to destabilise particular laundry bleaches, including
percarbonate bleaches.
Despite the technical problems associated with juxtaposing, on the one
hand, laundry enzymes and laundry bleach, and on the other hand, softening
clay and laundry bleach, detergent tablets combining all three components
would be highly desirable due to their special combination of fabric
whitening,
stain removal and fabric softening qualities. Accordingly it has been our
object
to provide laundry softening tablets which contain bleach, enzyme and clay and
which minimise the inactivation problems and which maximise the benefits of
including all these materials in the tablets.
Summary of the Invention
According to the invention there is provided a softening laundry detergent
tablet comprising clay, laundry surfactant, laundry enzyme and laundry bleach
wherein the tablet comprises one or more discrete first regions and one or
more discrete second regions, and
the clay is more highly concentrated in the or each first region than in the
or each second region, and
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the concentration of enzyme in the or each first region is higher than the
enzyme concentration in the or each second region, and
the concentration of bleach in the or each second region is higher than
the bleach concentration in the or each first region.
The amount of softening clay in the tablet is usually at least 5% by weight
of the tablet, preferably at least 8% and usually at least 10% but less than
25%,
more preferably less 20%, by weight of the tablet. Usually, the or each first
region comprises at least 5% (and often 10-30%) by weight (of the or each
first
region) of clay, and the concentration of clay in the or each first region is
at least
1.5 times, usually at least 2 (and preferably at least 5) times the
concentration of
clay in the or each second region.
The concentration of enzyme in the or each first region is usually at least
1.5 times and usually at least 2 times, and preferably at least 5 times, the
concentration of enzyme in the or each second region.
The concentration of bleach in the or each second region is higher than
the concentration of bleach in the or each first region. For instnace the
bleach
concentration in the or each second region is usually at least 1.5 times and
usually at least two times and preferably at least 5 or 10 times the
concentration
of bleach in the or each first region.
Preferably at least 80%, and preferably substantially all, of the clay is in
the or each first region.
Preferably at least 80%, and preferably substantially all, of the enzyme is
in the or each first region.
Preferably at least 80%, and preferably substantially all, of the bleach is in
the or each second region.
Detailed Description of the Invention
Most or all of the bleach in the tablet is preferably kept separate from
most or all of the softening clay in the tablet. If the bleach is encapsulated
to
protect it from the clay or if the bleach is stable to the clay then the or
each
second region can contain clay, for instance in a relatively low amount,
generally
below 3% by weight of the region. Preferably, however, the or each second
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region contains the bleach and is substantially free of clay, for instance
containing less than 20% of the total amount of clay and usually containing
less
than 3%, preferably less than 1 % and most preferably less than 0.5% (based on
the weight of the region) of the clay.
Correspondingly, the amount of bleach in the or each first region is
preferably low, and preferably substantially all the bleach is in the or each
second region. Thus at least 80% of the bleach, and preferably substantially
all,
the bleach is generally in the or each second region.
The formulation of the first and second regions should be such that the or
each first region disperses into the wash water substantially quicker than the
or
each second region.
Although enzyme can be included in both regions, preferably most or all
of the enzyme is in the first region and thus preferably at least 80% by
weight of
the total amount of enzymes are in the or each first regions. Accordingly the
enzyme is dispersed into the wash water more rapidly than the bleach.
Typically, in a conventional wash process, at least 50% of the enzymes, and
preferably substantially all of the enzyme, are dispersed into the water at
least 5
minutes, and usually at least 10 minutes, before the corresponding proportions
of bleach are dispersed into the wash water.
The invention is of particular value when the bleach is a percarbonate
bleach, and in particular when it is not encapsulated. When using percarbonate
bleach, it is particularly desirable that the second regions containing the
percarbonate bleach should be substantially free, and preferably wholly free,
of
the clay.
When bleach activator is to be included in the tablet, it is preferred for the
bleach activator to be concentrated predominantly in the or each first
regions, so
that the concentration of bleach activator in the first regions is at least
1.5 times
and generally at least 2 times and most preferably at least 5 times the
concentration of bleach activator in the or each second region. Preferably the
or
each second region is substantially free, and generally wholly free, of bleach
activator.
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Since the tablets of the invention are softening laundry tablets, it is
preferred that the overall clay concentration in the tablet is relatively
high.
Usually, the clay concentration will be at least 5% by weight of the tablet.
Most
frequently, the clay content will be at least 8%, preferably at least 10%, by
weight of the tablet, but usually less than 25%, more preferably less than
20%,
and most preferably less than 15% clay by weight of the tablet.
It is preferred that the surfactant in the tablet is more highly concentrated
in the first regions, where most of the clay is located, than in the second
regions,
where there is less clay. Rapid disintegration of the first region then
ensures
that the surfactant is efficiently dispersed upon exposure of the tablet to
water.
Preferably therefore the amount of surfactant in the or each first region is
preferably at least 1.5 times, and usually 2 to 5 times, the amount of
surfactant
in the or each second region. Usually at least 50% and generally at least 60
or
70% but not more than about 80 or 90% of the total surfactant is in the first
region or regions with the balance being in the second region or regions.
If desired there can be one or more second regions having different
compositions from the other second regions.
The discrete first and second regions may be domains or other zones
within the tablet, for instance created by forming the tablet from a
particulate
mixture containing large granules, typically above 1 mm, wherein some or all
of
the large granules have one content and either the remainder of the large
granules or the remainder of the particulate mixture have one or more
different
contents, thereby forming the first regions and the second regions in the
tablet.
Typically the first regions contain 20 to 80%, often around 40 to 60% and
usually about 50%, by weight of the tablet with the second regions containing
the remainder.
Preferably the tablet is a multi-layer tablet, and each region of the tablet
is
a layer of the tablet. Preferably the tablet has at least 2 distinct layers,
most
preferably 3 layers. Different layers of the tablet may be colored; this is
particularly advisable for the first layer or other layers containing clay,
which
imparts an unattractive greyish tint on the tablet. Particularly preferred is
a
sandwich arrangement in which a single, middle layer of one type is sandwiched
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between identical layers of another type.
The tablets of the invention are of a size which is convenient for dosing in
a washing machine. The preferred size is 10 to 150g and the size can be
selected in accordance with the intended wash load and the design of the
washing machine which is to be used.
Tablet Manufacture
Detergent tablets of the present invention can be prepared simply by
mixing the solid ingredients together and compressing the mixture in a
conventional tablet press as used, for example, in the pharmaceutical
industry.
Preferably the principal ingredients, in particular gelling surfactants, 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 50000N, even more preferably of less
than 5000N and most preferably of less than 3000 N. Indeed, the most preferred
embodiment is a tablet compressed using a force of less than 2500N.
The particulate material 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/I 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 sentering, etc. Individual particles can also be
any
other particle, granule, sphere or grain.
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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.
The tablets may be manufactured by using any compacting process, such
as tabletting, briquetting, or extrusion, preferably tabletting. Suitable
equipment
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 (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.
Multi-layer tablets can be made by known techniques.
Coating
Solidity of the tablet according to the invention may be further improved
by making a coated tablet, the coating covering a non-coated tablet according
to
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the invention, thereby further improving the mechanical characteristics of the
tablet while maintaining or further improving dispersion.
In one embodiment of the present invention, the tablets may then be
coated so that the tablet does not absorb moisture, or absorbs moisture at
only
a very slow rate. The coating is 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.
Water solubility is measured following the test protocol of ASTM E1148-
87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
Suitable coating materials are dicarboxylic acids. 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 has a melting point preferably 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 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
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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.
The tablet coatings are preferably very hard and provide extra strength to
the tablet.
In a preferred embodiment of the present invention the fracture of the
coating in the wash is improved by adding a disintegrant in the coating. This
disintegrant will swell once in contact with water and break the coating in
small
pieces. This will improve the dispersion of the coating in the wash solution.
The
disintegrant is suspended in the coating melt at a level of up to 30%,
preferably
between 5% and 20%, most preferably between 5 and 10% by weight. 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 gum, tragacanth gum; croscarmylose
Sodium, crospovidone, cellulose, carboxymethyl cellulose, algenic acid and its
salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone,
soy
polysacharides, ion exchange resins and mixtures thereof.
Tensile Strength
Depending on the composition of the starting material, and the shape of
the tablets, the used compacting force may be adjusted to not affect the
tensile
strength, and the disintegration time in the washing machine. This process may
be used to prepare homogenous or layered tablets of any size or shape.
For a cylindrical tablet, the tensile strength corresponds to the diametrical
fracture stress (DFS) which is a way to express the strength of a tablet, and
is
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determined by the following equation
- 2F
~ Dt
Where F is the maximum force (Newton) to cause tensile failure (fracture)
measured by a VK 200 tablet hardness tester supplied by Van Kell industries,
Inc. D is the diameter of the tablet, and t the thickness of the tablet.
(Method Pharmaceutical Dosage Forms : Tablets Volume 2 Page 213 to
217). A tablet having a diametral fracture stress of less than 20 kPa is
considered to be fragile and is likely to result in some broken tablets being
delivered to the consumer. A diametral fracture stress of at least 25 kPa is
preferred.
This applies similarly to non cylindrical tablets, to define the tensile
strength, whereby the cross section normal to the height of the tablet is non
round, and whereby the force is applied along a direction perpendicular to the
direction of the height of the tablet and normal to the side of the tablet,
the side
being perpendicular to the non round cross section.
Effervescent
In another preferred embodiment of the present invention the tablets
further comprises an effervescent.
Effervescency as defined herein means the evolution of bubbles of gas
from a liquid, as the result of a chemical reaction between a soluble acid
source
and an alkali metal carbonate, to produce carbon dioxide gas,
i.e. C6H80~ + 3NaHC03 Na3C6H50~ + 3C02 + 3H20
Further examples of acid and carbonate sources and other effervescent
systems may be found in : (Pharmaceutical Dosage Forms : Tablets Volume 1
Page 287 to 291 ).
An effervescent may be added to the tablet mix in addition to the
detergent ingredients. The addition of this effervescent to the detergent
tablet
improves the disintegration time of the tablet. The amount will preferably be
between 5 and 20 % and most preferably between 10 and 20% by weight of the
tablet. Preferably the effervescent should be added as an agglomerate of the
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different particles or as a compact, and not as separated particles.
Due to the gas created by the effervescency in the tablet, the tablet can
have a higher D.F.S. and still have the same disintegration time as a tablet
without effervescency. When the D.F.S. of the tablet with effervescency is
kept
the same as a tablet without, the disintegration of the tablet with
effervescency
will be faster.
Further dispersion aid could be provided by using compounds such as
sodium acetate or urea. A list of suitable dispersion aid may also be found in
Pharmaceutical Dosage Forms: Tablets, Volume 1, Second edition, Edited by
H.A. Lieberman et all, ISBN 0-8247-8044-2.
Binders
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 zein. 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.
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,
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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.
Clays
The clay minerals used to provide the softening properties of the instant
compositions can be described as expandable, three-layer clays, i.e., alumino-
silicates and magnesium silicates, having an ion exchange capacity of at least
50 meq/100g. of clay. The term "expandable" as used to describe clays relates
to the ability of the layered clay structure to be swollen, or expanded, on
contact
with water. The three-layer expandable clays used herein are those materials
classified geologically as smectites.
There are two distinct classes of smectite-type clays; in the first,
aluminum oxide is present in the silicate crystal lattice; in the second class
of
smectites, magnesium oxide is present in the silicate crystal lattice. The
general
formulas of these smectites are AI2(Si205)2(OH)2 and Mg3(Si205) (OH)2 for the
aluminum and magnesium oxide type clay, respectively. It is to be recognised
that the range of the water of hydration in the above formulas can vary with
the
processing to which the clay has been subjected. This is immaterial to the use
of the smectite clays in the present invention in that the expandable
characteristics of the hydrated clays are dictated by the silicate lattice
structure.
Furthermore, atom substitution by iron and magnesium can occur within the
crystal lattice of the smectites, while metal cations such as Na+, Ca++, as
well
as H+, can be co-present in the water of hydration to provide electrical
neutrality.
Except as noted hereinafter, such cation substitutions are immaterial to the
use
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of the clays herein since the desirable physical properties of the clays are
not
substantially altered thereby.
The three-layer, expandable alumino-silicates useful herein are further
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 one cation 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 cations 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. The ion exchange capacity of clays varies
widely in the range from about 2 meq/100 g. for kaolinites to about 150
meq/100 g., and greater, for certain clays of the montmorillonite variety.
Illite
clays have an ion exchange capacity somewhere in the lower portion of the
range, i.e., around 26 meq/100 g. for an average illite clay.
Illite and kaolinite clays, with their relatively low ion exchange capacities,
are preferably not used as the clay in the instant compositions. Indeed, such
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illite and kaolinite clays constitute a major component of clay soils and, as
noted
above, are removed from fabric surfaces by means of the instant compositions.
However, 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 in the instant
compositions in that they are deposited on the fabrics to provide the desired
softening benefits. Accordingly, clay minerals 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.
While not intending to be limited by theory, it appears that advantageous
softening (and potentially dye scavenging, etc.) benefits of the instant
compositions are obtainable and are ascribable to the physical characteristics
and ion exchange properties of the clays used therein. That is to say,
experiments have shown that non-expandable clays such as the kaolinites and
the illites, which are both classes of clays having an ion exchange capacities
below 50 meq/100 g., do not provide the beneficial aspects of the clays
employed in the instant compositions.
The smectite clays used in the compositions herein are all commercially
available. Such clays include, for example, montmorillonite, volchonskoite,
nontronite, hectorite, saponite, sauconite, and vermiculite. The 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.
While any of the smectite-type clays having a cation exchange capacity of
at least about 50 meq/100 g. are useful herein, certain clays are preferred.
For
example, Gelwhite GP is an extremely white form of smectite clay and is
therefore preferred when formulating white granular detergent compositions.
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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 in
laundry compositions and is preferred from the standpoint of product
performance.
Appropriate clay minerals for use herein can be selected by virtue of the
fact that smectites exhibit a true 14A x-ray diffraction pattern. This
characteristic
pattern, taken in combination with exchange capacity measurements performed
in the manner noted above, provides a basis for selecting particular smectite-
type minerals for use in the granular detergent compositions disclosed herein.
The clay is preferably mainly in the form of granules, with at least 50%
(and preferably at least 75% or at least 90%) being in the form of granules
having a size of at least 100~m up to 1800~m, preferably up to 1180~m,
preferably 150-850pm. Preferably the amount of clay in the granules is at
least
50%, usually at least 70% or 90%, of the weight of the granules.
Detersive surfactants
Non-limiting examples of surfactants useful herein typically at levels from
about 1 % to about 55%, by weight, anionics such as sulphonates, sulphates and
ether sulphates. These include the conventional C11-C18 alkyl benzene
sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl
sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula
CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2)y(CHOS03-M+) CH2CH3 where x
and (y + 1 ) are integers of at least about 7, preferably at least about 9,
and M is
a water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl
sulfate, the C10-C18 alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy
sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EOq-5
ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl
polyglycosides and their corresponding sulfated polyglycosides, and C12-C18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including
the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol
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alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18
betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like,
can also be included in the overall compositions. The C10-C18 N-alkyl
polyhydroxy fatty acid amides can also be used. Typical examples include the
C12-C18 N-methylglucamides. See WO 92/06154. Other sugar-derived
surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-
C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18
glucamides can be used for low sudsing. C10-C20 conventional soaps may also
be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be
used. Mixtures of anionic and nonionic surfactants are especially useful.
Other
conventional useful anionic, amphoteric, nonionic or cationic surfactants are
listed in standard texts.
In preferred embodiments, the tablet comprises at least 5% by weight of
surfactant, more preferably at least 15% by weight, even more preferably at
least 25% by weight, and most preferably between 35% and 55% by weight of
surfactant. The amount of anionic is preferably at least 1.5 times, generally
at
least 2 or 3 times, the total amount of other surfactants.
Builders
Detergent builders can optionally be included in the compositions herein
to assist in controlling mineral hardness. Inorganic as well as organic
builders
can be used. Builders are typically used in fabric laundering compositions to
assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition.
Inorganic or P-containing detergent builders include, but are not limited
to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including
bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However,
non-phosphate builders are required in some locales. Importantly, the
compositions herein function surprisingly well even in the presence of the so-
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called "weak" builders (as compared with phosphates) such as citrate, or in
the
so-called "underbuilt" situation that may occur with zeolite or layered
silicate
builders.
Examples of silicate builders are the alkali metal silicates, particularly
those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered
silicates,
such as the layered sodium silicates described in U.S. Patent 4,664,839,
issued
May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline
layered
silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike
zeolite builders, the Na SKS-6 silicate builder does not contain aluminum.
NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. It can be
prepared by methods such as those described in German DE-A-3,417,649 and
DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein,
but
other such layered silicates, such as those having the general formula
NaMSix02x+1.yH20 wherein M is sodium or hydrogen, x is a number from 1.9 to
4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used
herein.
Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-
Na2Si05 (NaSKS-6 form) is most preferred for use herein. Other silicates may
also be useful such as for example magnesium silicate, which can serve as a
crispening agent in granular formulations, as a stabilizing agent for oxygen
bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on November 15, 1973.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently marketed
heavy duty granular detergent compositions, and can also be a significant
builder ingredient in liquid detergent formulations. Aluminosilicate builders
include those having the empirical formula:
Mz(zA102)y].xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the
range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
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Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In
an
especially preferred embodiment, the crystalline aluminosilicate ion exchange
material has the formula:
Na~2[(A102)~2(Si02)~2].xH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be
used herein. Preferably, the aluminosilicate has a particle size of about 0.1-
10
microns in diameter.
Organic detergent builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of
polycarboxylate
compounds. As used herein, "polycarboxylate" refers to compounds having a
plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid
form,
but can also be added in the form of a neutralized salt. When utilized in salt
form, alkali metals, such as sodium, potassium, and lithium, or
alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed
in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S.
Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of
U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether
polycarboxylates also include cyclic compounds, particularly alicyclic
compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
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Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene or
vinyl
methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid, the various alkali metal, ammonium and
substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such
as
mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are polycarboxylate builders of particular importance for heavy
duty
liquid detergent formulations due to their availability from renewable
resources
and their biodegradability. Citrates can also be used in granular
compositions,
especially in combination with zeolite and/or layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present invention are
the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful
succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and
salts thereof. A particularly preferred compound of this type is
dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in European Patent
Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be
incorporated into the compositions alone, or in combination with the aforesaid
builders, especially citrate and/or the succinate builders, to provide
additional
builder activity. Such use of fatty acids will generally result in a
diminution of
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sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and
especially in the formulation of bars used for hand-laundering operations, the
various alkali metal phosphates such as the well-known sodium
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be
used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and
other known phosphonates (see, for example, U.S. Patents 3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
0
The detergent compositions herein may contain bleaching agents or
bleaching compositions containing a bleaching agent and one or more bleach
activators. When present, bleaching agents will typically be at levels of from
about 1 % to about 30%, more typically from about 5% to about 20%, of the
detergent composition, especially for fabric laundering. If present, the
amount of
bleach activators will typically be from about 0.1 % to about 60%, more
typically
from about 0.5% to about 40% of the bleaching composition comprising the
bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents
useful for detergent compositions in textile cleaning, hard surface cleaning,
or
other cleaning purposes that are now known or become known. These include
oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g.,
sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of bleaching agent that can be used without restriction
encompasses percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium monoperoxyphthalate
hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-
4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching
agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20,
1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985,
European Patent Application 0,133,354, Banks et al, published February 20,
1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
Highly preferred bleaching agents also include 6-nonylamino-6-
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oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6,
1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen
bleaching compounds include sodium carbonate peroxyhydrate and equivalent
"percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,
manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an
average particle size in the range from about 500 micrometers to about 1,000
micrometers, not more than about 10% by weight of said particles being smaller
than about 200 micrometers and not more than about 10% by weight of said
particles being larger than about 1,250 micrometers. Optionally, the
percarbonate can be coated with silicate, borate or water-soluble surfactants.
Percarbonate is available from various commercial sources such as FMC,
Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are
preferably combined with bleach activators, which lead to the in situ
production
in aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various nonlimiting examples of
activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to
Mao
et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS)
and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures
thereof can also be used. See also U.S. 4,634,551 for other typical bleaches
and activators useful herein.
Highly preferred amido-derived bleach activators are those of the
formulae:
R1 N(R5)C(O)R2C(O)L or R1 C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or
alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and
L is
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any suitable leaving group. A leaving group is any group that is displaced
from
the bleach activator as a consequence of the nucleophilic attack on the bleach
activator by the perhydrolysis anion. A preferred leaving group is phenyl
sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent
4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October
30,
1990, incorporated herein by reference. A highly preferred activator of the
benzoxazin-type is:
O
II
CEO
I
~C
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
II II
O C-C H2-C H \ O C-C H2- ~ H2
R6-C-NBC H2-C H2 C H2 R6-C-NBC H2-C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about 12 carbon atoms. Highly preferred lactam activators include
benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl
caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl
valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-
trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent
4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by
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reference, which discloses acyl caprolactams, including benzoyl caprolactam,
adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also known in
the art and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718,
issued July 5, 1977 to Holcombe et al. If used, detergent compositions will
typically contain from about 0.025% to about 1.25%, by weight, of such
bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a
manganese compound. Such compounds are well known in the art and include,
for example, the manganese-based catalysts disclosed in US-A-5,246,621, US-
A-5,244,594; US-A-5,194,416; US-A-5,114,606; and EP-A-549,271, EP-A-
549,272, EP-A-544,440, and EP-A-544,490; Preferred examples of these
catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2,
Mnlll2(u-O)1 (u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2,
MnIV4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)1 (u-OAc)2-
(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-
triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based
bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of manganese with various complex ligands to enhance
bleaching is also reported in the following United States Patents: 4,728,455;
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and
5,227,084.
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 0.1 ppm to about 700 ppm, more
preferably from about 1 ppm to about 500 ppm, of the catalyst species in the
laundry liquor.
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Enz
Enzymes can be included in the formulations herein for a wide variety of
fabric laundering purposes, including removal of protein-based, carbohydrate-
based, or triglyceride-based stains, for example, and for the prevention of
refugee dye transfer, and for fabric restoration. The enzymes to be
incorporated
include proteases, amylases, lipases, cellulases, and peroxidases, as well as
mixtures thereof. Other types of enzymes may also be included. They may be
of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast
origin. However, their choice is governed by several factors such as pH-
activity
and/or stability optima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes are preferred,
such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to
about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active
enzyme per gram of the composition. Stated otherwise, the compositions herein
will typically comprise from about 0.001 % to about 5%, preferably 0.01 %-1 %
by
weight of a commercial enzyme preparation. Protease enzymes are usually
present in such commercial preparations at levels sufficient to provide from
0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of proteases are the subtilisins which are obtained
from particular strains of B. subtilis and B. licheniforms. Another suitable
protease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold by Novo Industries A/S
under the registered trade name ESPERASE. The preparation of this enzyme
and analogous enzymes is described in British Patent Specification No.
1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based
stains that are commercially available include those sold under the tradenames
ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE
by International Bio-Synthetics, Inc. (The Netherlands). Other proteases
include
Protease A (see EP-A-130,756, published January 9, 1985) and Protease B
(see European Patent Application 87303761.8, filed April 28, 1987, and EP-A-
130,756, Bott et al, published January 9, 1985).
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Amylases include, for example, -amylases described in GB-A-1,296,839
(Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo
Industries.
The cellulase usable in the present invention include both bacterial or
fungal cellulase. Preferably, they will have a pH optimum of between 5 and
9.5.
Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
issued March 6, 1984, which discloses fungal cellulase produced from Humicola
insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus
belonging to the genus Aeromonas, and cellulase extracted from the
hepatopancreas of a marine mollusk (Dolabella Auricula Solander). suitable
cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-
2.247.832. CAREZYME (Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in
Japanese Patent Application 53,20487, laid open to public inspection on
February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter
referred to as "Amano-P." Other commercial lipases include Amano-CES,
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum
NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and
further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and
Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The
LIPOLASE enzyme derived from Humicola lanuginosa and commercially
available from Novo (see also EPO 341,947) is a preferred lipase for use
herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g.,
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching," i.e. to prevent transfer of dyes or pigments removed
from
substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase. Peroxidase-containing detergent compositions are disclosed, for
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example, in PCT International Application WO 89/099813, published October
19, 1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139,
issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S.
Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent
4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for
liquid detergent formulations, and their incorporation into such formulations,
are
disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes
for use in detergents can be stabilized by various techniques. Enzyme
stabilization techniques are disclosed and exemplified in U.S. Patent
3,600,319,
issued August 17, 1971 to Gedge, et al, and European Patent Application
Publication No. 0 199 405, Application No. 86200586.5, published October 29,
1986, Venegas. Enzyme stabilization systems are also described, for example,
in U.S. Patent 3,519,570.
Flocculants
Most clay flocculating polymers are fairly long chained polymers and co-
polymers derived from such monomers as ethylene oxide, acrylamide, acrylic
acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and
ethylene imine. Gums, like guar gum, are suitable as well.
Preferred are polymers of ethylene oxide, acrylamide or acrylic acid.
These polymers dramatically enhance the deposition of a fabric softening clay
if
their molecular weights are in the range of from 100 000 to 10 million.
Preferred
are such polymers having a weight average molecular weight of from 150000 to
million.
The most preferred polymer is poly (ethylene oxide). Molecular weight
distributions can be readily determined using gel permeation chromatography,
against standards of poly (ethylene oxide) of narrow molecular weight
distributions.
The amount of flocculant is preferably 0.5-10% by weight of the tablet,
most preferably about 2 to 6%.
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The flocculant is preferably mainly in the form of granules, with at least
50% by weighty (and preferably at least 75% and most preferably at least 90%)
being in the form of granules having a size of at least 100~m up to 1800~.m,
preferably up to 1180~m and most preferably 150-850~m Preferably the amount
of flocculant in the granules is at least 50%, generally at least 70% or 90%,
of
the weight of the granules.
Other components which are commonly used in detergent compositions
and which may be incorporated into the detergent tablets of the present
invention include chelating agents, soil release agents, soil antiredeposition
agents, dispersing agents, brighteners, suds suppressors, fabric softeners,
dye
transfer inhibition agents and perfumes.
It should be noted that when a clay material is compressed prior to
incorporation
into a tablet or in a cleaning composition, improved disintegration or
dispensing
is achieved. For example, 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. In particular the amount of pressure used for the compression of the
clay
is of importance to obtain clay particles which aid disintegration or
dispensing.
Further, when softening clays are compressed and then incorporated in cleaning
compositions or tablets, not only improved disintegration or dispensing is
obtained, but also good softening of the fabrics.
Preferably, the clay component is obtained by compression of a clay material.
A preferred process comprises the steps of submitting the clay material to a
pressure of at least 10MPa, or even at least 20MPa or even 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.
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
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press or with a Chilsonator roller compaction equipment, available form
Fitzpatrick Company.
Example 1
A detergent base powder of composition A (see table 1 ) was prepared as
follows. All the particulate materials of base composition A were mixed
together
in a mixing drum to form a homogenous particulate mixture. During this mixing
the binder was sprayed on. The base powder of composition A was mixed in a
mixing drum and diluted with the described mounts of smectite clay extrudate
which had been formed using the following process. 500g of the clay were
mixed with 250g distilled water. The resulting mix was fed to a Dome extruder
with a screw set at a rpm of 80. The resulting mix was then screened using
ASTM screen sets. The extrudates made were then dried in a Sherwood
Scientific fluid bed dryer set at 90°C for 30 min. The dried
extrudates were
screened and the oversize (particles larger than 1700~m) and the fines
(particles
smaller than 150~m) were removed from the mix.
Tablets were then made the following way 42.8g of the mixture was
introduced into a mould of circular shape with a diameter of 5.4cm and
compressed to give a tablet tensile strength (or diametrical fracture stress)
of 15
kPa.
The tablet was placed in a perforated 10cm diameter metallic cage with a
mesh size of 5mm x 5mm. The cage was paced in a pool of 51 of demineralised
water at 20°C and rotated at a rate of 80rpm. The residue left in the
cage after a
residence time of 3 min in the pool of water is determined by weighing. The
level of residues is calculated as follows:
residue = residue weight/original tablet weight x 100
The lower the residue number the better the tablet disintegration.
In this example, the tablet consisted of composition A.
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Example 2
Example 1 was repeated but the tablets were formed of composition B as
indicated in table 1.
Example 3
Example 1 was repeated with tablets prepared as follows: 21.4g of
powder of composition A was first introduced into a mould of circular shape
with
a diameter of 5.4cm, 21.4g of powder of composition B was then added to the
mould and the mix compressed to give a tablet tensile strength (or diametrical
fracture stress) of 15 kPa. In this example, the tablet is formed of a layer
of A
and a layer of B.
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Table 1: Detergent Base Powder Composition
Ex A Ex B
Clay Extrudate 14.33 -
Flocculant Agglomerate 3.8 3.8
Anionic agglomerates 1 38 38
Cationic agglomerates 5.0 5.0
Sodium percarbonate - 8
Bleach activator agglomerates 2.31 2.31
Sodium carbonate 25.00 32.18
EDDS/Sulphate particle 0.19 0.19
Tetrasodium salt of Hydroxyethane Diphosphonic0.34 0.34
acid
Fluorescer 0.15 0.15
Zinc Phthalocyanine sulphonate encapsulate0.027 0.027
Soap powder 1.40 1.40
Suds suppressor 2.6 2.6
Citric acid 4.0 4.0
Protease 0.45 -
Cellulase 0.20 -
Amylase 0.20 -
Binder
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Cationic Polymer 0.75 0.75
PEG 4000 1.25 1.25
Clay extrudate comprise 97% of montmorillonite clay and 3% water.
Flocculant raw material is polyethylene oxide with an average molecular weight
of 300,000.
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.
Layered silicate comprises of 95% SKS 6 and 5% silicate.
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.
Zinc phthalocyanine sulphonate encapsulates are 10% active.
Suds suppressor comprises of 11.5% silicone oil; 59% of zeolite and 29.5% of
water.
Example 1 gave the lowest residue, but the whole tablet disintegrated
together. Example 2 gave the highest residue. The clay-containing layer in
Example 3 disintegrated fast, but the other layer disintegrated slowly, giving
a
residue between the other examples. Thus the enzyme was all released quickly
and the bleach slowly.
Other examples include tablets made from a powder of the
following composition:
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Examples A and B
Table A: Detergent base powder composition
Ex A Ex B
(%) (%)
Clay Extrudate 14.00 14.00
Flocculant Agglomerate 3.8 3.8
Anionic agglomerates 1 32 38
Anionic particle 2 2.27 2.27
Cationic agglomerates 4.0
Sodium percarbonate 8.0 10.0
Bleach activator agglomerates2.31 2.8
Sodium carbonate 21.066 16.57
EDDS/Sulphate particle 0.19 0.19
Tetrasodium salt of 0.34 0.34
Hydroxyethane Diphosphonic
acid
Fluorescer 0.15 0.15
Zinc Phthalocyanine 0.027 0.027
sulphonate encapsulate
Soap powder 1.40 1.40
Suds suppressor 2.6 2.6
Citric acid 4.0 4.0
Protease 0.45 0.45
Cellulase 0.20 0.20
Amylase 0.20 0.20
Perfume 1.00 1.00
Binder
Pluriol 1000 2.0 2.0
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Clay extrudate comprise 97% of CSM Quest 5A clay and 3% water
Flocculant raw material is polyethylene oxide with an average
molecular weight of 300,000
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
Layered silicate comprises of 95% SKS 6 and 5% silicate
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.
Zinc phthalocyanine sulphonate encapsulates are 10% active.
Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning);
59% of zeolite and 29.5% of water.
Example C (micronised citric acid)
In composition of example B, the citric acid used was replaced with
micronised citric acid. The citric acid used was ground with a coffee
grinder to the following psd prior to use.
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Max level of Max level of particles
particles bigger smaller than 150um
than
1.4 mm
Example 8% 12%
B
Min level of particles
smaller than 150um
Example ~ 80%
C
Example D-F (phosphated composition)
Ex D Ex E Ex F
(%) (%) (%)
Clay Extrudate 13.00 13.00 13.00
Flocculant 3.5 3.5 3.5
Agglomerate
Anionic particle 38.2 38.2 38.2
Sodium 8.0
percarbonate
Sodium perborate 8.0
monohydrate
Sodium perborate 8.0
tetrahydrate
Bleach activator 2.3 2.3 2.3
agglomerates
HPA sodium 15.4 15.4 15.4
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tripolyphosphate
Sodium carbonate 10.043 10.043 10.043
EDDS/Sulphate 0.19 0.19 0.19
particle
Tetrasodium salt 0.34 0.34 0.34
of
Hydroxyethane
Diphosphonic acid
Fluorescer 0.15 0.15 0.15
Zinc 0.027 0.027 0.027
Phthalocyanine
sulphonate
encapsulate
Soap powder 1.40 1.40 1.40
Suds suppressor 2.6 2.6 2.6
Citric acid 1.0 1.0 1.0
Protease 0.45 0.45 0.45
Cellulase 0.20 0.20 0.20
Amylase 0.20 0.20 0.20
Pertume 1.00 1.00 1.00
Binder
Pluriol 1000 2.0 2.0 2.0
r-
Clay extrudate comprise 97% of CSM Quest 5A clay and 3% water
Flocculant raw material is polyethylene oxide with an average
molecular weight of 300,000
Layered silicate comprises of 95% SKS 6 and 5% silicate
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 (ex Dow Corning);
59% of zeolite and 29.5% of water.
The anionic particle was a blown powder with the following
composition:
(%)
Sodium linear alkylbenzene17.7
sulphonate
Nonionic C35 7E0 2.0
Nonionic C35 3E0 5.9
Soap 0.5
Sodium tripolyphosphate, 47.8
(Rhodia-Phos HPA 3.5 from
Rhone Poulenc)
Sodium silicate 10.8
Sodium carboxymethly 0.4
cellulose
Acrylate / maleate 2.1
copolymer
Salts, moisture 12.9
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Examples G and H
Ex G Ex H
(%) (%)
Clay Extrudate 14.00 14.00
Flocculant Agglomerate 3.8 3.8
Anionic agglomerates 1 32 32
Anionic particle 2 2.27 2.27
Cationic agglomerates 4.0 4.0
Sodium percarbonate 8.0 8.0
Bleach activator agglomerates 2.31 2.31
Sodium carbonate 18.066 18.066
EDDS/Sulphate particle 0.19 0.19
Tetrasodium salt of 0.34 0.34
Hydroxyethane Diphosphonic
acid
Fluorescer 0.15 0.15
Zinc Phthalocyanine sulphonate 0.027 0.027
encapsulate
Soap powder 1.40 1.40
Suds suppressor 2.6 2.6
Arbocel TF-30-HG 5.0
Vivapur G22 5.0
Citric acid 2.0 2.0
Protease 0.45 0.45
Cellulase 0.20 0.20
Amylase 0.20 0.20
Perfume 1.00 1.00
Binder
Pluriol 1000 2.0 2.0
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Clay extrudate comprise 97% of CSM Quest 5A clay and 3% water
Flocculant raw material is polyethylene oxide with an average
molecular weight of 300,000
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
Layered silicate comprises of 95% SKS 6 and 5% silicate
Bleach activator agglomerates comprise of 81 % TAED (Tetra acetyl
ethylene diamine), 17% acrylic/maleic copolymer (acid form) and 2%
wate r.
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.
Zinc phthalocyanine sulphonate encapsulates are 10% active.
Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning);
59% of zeolite and 29.5% of water.
Arbocel TF-30-HG and Vivapur G22 are cellulose containing
disintegration agent from the Rettenmaier company
Example I-N
Example A-G are repeated by dipping the tablets made with the
indicated composition in a bath comprising 80 parts of adipic acid
mixed with 18.5 parts of CSM Quest 9 clay and 1.5 parts of Coasol
(Coasol being a diisobutyladipate).
The tablet may also comprise a high molecular weight
poly(ethyleneoxide), cellulosic disintegrant, and/ or acetate. It could
also further comprise high soluble salts.
