Note: Descriptions are shown in the official language in which they were submitted.
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PERFUMED DETERGENT TABLET
10
Technical field of the invention
The present invention relates to perfumed detergent tablets, especially those
adapted for use in washing machines, and to processes for making such tablets.
Background of the invention
Perfumed products are well-known in the art. However, consumer acceptance of
such perfumed products like laundry and cleaning products is determined not
only by the performance achieved with these products but also by the
aesthetics
associated therewith. The perfume components are therefore an important
aspect of the successful formulation of such commercial products.
In addition, a clay mineral compound is a desirable ingredient of such laundry
so and cleaning product, in particular those products which are in tablet
form.
Indeed, the clay can provide softening benefit but can also serve as a
disintegrant of such detergent tablets.
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However, a problem encountered with perfumed detergent tablets containing a
clay mineral compound is that the clay can have a detrimental effect on the
performance of the perfume contained therein. Hence, not to be bound by
theory,
it is believed that due to the close physical proximity given by the tablet,
the
perfume is absorbed into the clay where it can interact with heavy metal ions
and
acid or base sites within the clay which as result may cause a discoloration
of the
clay. Still, the interaction between the perfume and the clay may also result
in
the tablet having a less attractive odour.
Accordingly, it is an object of the invention to provide a perfumed detergent
tablet
comprising a clay mineral compound which exhibit good perfume performance
with reduced discoloration of the clay.
~5 Further, cleaning compositions in tablet form have often been proposed,
however
these have not (with the exception of soap bars for personal washing) gained
any
substantial success, despite the several advantages of products in a unit
dispensing form. One of the reasons for this may be that detergent tablets
require a relatively complex manufacturing process. In particular, it is often
2o desirable to provide the tablet with a coating and this adds to the
difficulties of
manufacture.
While tablets without a coating are entirely effective in use, they usually
lack the
necessary surface hardness to withstand the abrasion that is a part of normal
25 manufacture, packaging and handling. The result is that non-coated tablets
suffer from abrasion during these processes, resulting in chipped tablets and
loss
of active material.
Finally, coating of tablets is often desired for aesthetic reasons, to improve
the
30 outer appearance of the tablet or to achieve some particular aesthetic
effect.
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Numerous methods of tablet coating have been proposed, and many of these
have been suggested for detergent tablets. However, all of these methods have
certain disadvantages, as will be explained below.
GB-A-0 989 683, published on 22nd April 1965, discloses a process for
preparing
a particulate detergent from surfactants and inorganic salts; spraying on
water-
soluble silicate; and pressing the detergent particles into a solid form-
retaining
tablet. Finally, a readily water-soluble organic film-forming polymer (for
example,
polyvinyl alcohol) provides a coating to make the detergent tablet resistant
to
1o abrasion and accidental breakage.
EP-A-0 002 293, published on 13th June 1979, discloses a tablet coating
comprising hydrated salt such as acetate, metaborate, orthophosphate,
tartrate,
and sulphate.
EP-A-0 716 144, published on 12th June 1996, also discloses laundry detergent
tablets with water-soluble coatings which may be organic polymers including
acrylic/maleic co-polymer, polyethylene glycol, PVPVA, and sugar.
2o W09518215, published on 6th July 1995, provides water-insoluble coatings
for
solid cast tablets. The tablets are provided with hydrophobic coatings
including
wax, fatty acid, fatty acid amides, and polyethylene glycol.
EP-A-0 846 754, published on the 10t" of June 1998, provides a tablet having a
coating comprising a dicarboxylic acid, the coating material typically having
a
melting point of from 40°C to 200°C.
EP-A-0 846 755, published on the 10t" of June 1998, provides a tablet having a
coating comprising a material insoluble in water at 25°C, such as C12-
C22 fatty
3o acids, adipic acid or C8-C13 dicarboxylic acids.
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EP-A-0 846 756, published on the 10t" of June 1998, provides a tablet having a
coating comprising a disintegrant material and preferably an effervescent
material.
Recently, it has been found means by which coated tablets can be provided with
a coating so that they can be stored, shipped and handled without damage, the
coating being easily broken when the tablet is in the washing machine,
releasing
the active ingredients into the wash solution. Typical of such disclosure can
be
found in pending European patent applications EP 99870017.3, EP 99870018.1,
and EP 99870019.9.
However, whilst giving satisfactory results, it has now also been found that
where
a clay mineral compound is present in the coating of the detergent tablet, the
clay, for the same believed reasons stated above, can have a detrimental
effect
~5 on the performance of the perfume contained therein as well as on the
appearance of the coating, i.e. discoloration of the coating.
These problems have further been found more acute overtime, and more
particularly where the coating also comprises an acid having a melting point
of at
20 least 40°C, more particularly with a melting point of at least
145°C.
Accordingly, the detergent formulator is also faced with the problems of
providing
a coated tablet having a coating which has satisfactory appearance, is
sufficiently
hard to protect the tablet from mechanical forces when stored, shipped and
25 handled, and disperses readily in an aqueous solution whilst still giving
satisfactory perfume performance.
Further, the perfuming of detergent tablet is a concern to the detergent
formulator. Hence, the presence of the coating on the tablet can reduce the
3o diffusion of the perfume from the tablet resulting in a less attractive
odour.
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It has now surprisingly been found that the addition of a heavy metal ion
sequestrant to perfumed detergent tablet overcomes these problems.
5
Summary of the Invention
The present invention is a perfumed detergent tablet, the coating comprising a
1o clay mineral compound and a heavy metal ion sequestrant.
By "perfumed detergent tablet", it is meant that the perfume can be present in
the
coating if present, or in the detergent composition, or both.
Detailed Description of the Invention
Clay
2o An essential ingredient of the detergent tablet is a clay. The clay may be
present
in any of the detergent composition, the coating if present, or both.
By clay mineral compound (or in abbreviation, "clay"), it is meant herein a
hydrous phyllosilicate, typically having a two or three layer crystal
structure. For
clarity, it is noted that the term clay mineral compound, as used herein,
excludes
sodium aluminosilicate zeolite builder compounds, which however, may be
included in the compositions of the invention as optional components. Further
description of clays may be found in Kirk-Othmer, Encyclopaedia of Chemical
Technology, 4th edition, Volume 6, page 381, as published by John Wiley and
Sons.
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The clay mineral compound is preferably a smectite clay compound. Smectite
clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632
and 4,062,647 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 AI2(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,
~5 saponites and sauconites, particularly those having an alkali or alkaline
earth
metal ion within the crystal lattice structure. Sodium or calcium
montmorillonite
are particularly preferred.
Suitable smectite clays, particularly montmorillonites, are sold by various
2o suppliers including English China Clays, Laviosa, Fordamin, Georgia Kaolin
and
Colin Stewart Minerals (CSM).
Preferred smectite clays are sold under the tradename of White Bentonite STP
by Fordamin and Detercal P7 by Laviosa Chemical Mineria SPA.
Clays for use herein may be subjected to an acid washing treatment with any
suitable mineral or organic acid. Such clays give rise to an acid pH on
dissolution in distilled water. A commercially available "acid clay" of this
type is
sold under the tradename Tonsil P by Sud Chemie AG.
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Substitution of small cations, such as protons, sodium ions, potassium ions,
magnesium ions and calcium ions, and of certain organic molecules including
those having positively charged functional groups can typically take place
within
the crystal lattice structure of the smectite clays. A clay may be chosen for
its
s ability to preferentially absorb one cation type, such ability being
assessed by
measurements of relative ion exchange capacity. The smectite clays suitable
herein typically have a cation exchange capacity of at least 50 meq/100g. U.S.
Patent No. 3,954,632 describes a method for measurement of cation exchange
capacity.
The crystal lattice structure of the clay mineral compounds may have, in a
preferred execution, a cationic fabric softening agent substituted therein.
Such
substituted clays have been termed 'hydrophobically activated' clays. The
cationic fabric softening agents are typically present at a weight ratio,
cationic
fabric softening agent to clay, of from 1:200 to 1:10, preferably from 1:100
to
1:20. Suitable cationic fabric softening agents include the water insoluble
tertiary
amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-
B-0 011 340.
2o A preferred commercially available "hydrophobically activated" clay is a
bentonite
clay containing approximately 40% by weight of a dimethyl ditallow quaternary
ammonium salt sold under the tradename Claytone EM by English China Clays
International.
Preferably, the clay which is present in the detergent composition is present
in an
intimate mixture or in a particle with a humectant and a hydrophobic compound,
preferably a wax or oil, such as paraffin oil. Preferred humectants are
organic
compounds, including propylene glycol, ethylene glycol, dimers or trimers of
glycol, most preferably glycerol. The particle is preferably an agglomerate.
so Alternatively, the particle may be such that the wax or oil and optionally
the
humectant form an encapsulate on the clay or alternatively, the clay be an
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encapsulate for the wax or oil and the humectant. It may be preferred that the
particle comprises an organic salt or silica or silicate.
In another embodiment, the clay in the detergent composition is preferably
mixed
with one or more surfactants and optionally builders and optionally water, in
which case the mixture is preferably subsequently dried. Preferably, such a
mixture is further processed in a spray-drying method to obtain a spray dried
particle comprising the clay.
It may also be preferred that the intimate mixture comprises a chelating
agent.
Depending on its end use, the clay will preferably be present in different
particles
size. Hence, when softening is desired, it is preferred that at least 50% by
weight, preferably substantially all (e.g. at least 90% or 95%) by weight of
the
~ o clay is present as granules. By granules, it is meant that the particles
of the clay
mineral compound which is present in the detergent composition are included as
components of agglomerate particles optionally containing other detergent
compounds. Where present as such components, the term "largest particle
dimension" of the clay mineral compound refers to the largest dimension of the
2o clay mineral component as such, and not to the agglomerated particle as a
whole. Typically, the granules will have a particle size of at least 100
micrometers, generally 100-1700 micrometers.
When a coating is present, it is often desired to have a clay as disintegrant
in the
25 coating. In this instance, the clay is preferably present in the coating,
having a
particle size of less than 75 Nm, more preferably of less than 53 Nm.
Preferably, the tablet is a softening tablet. By softening tablet, it is meant
that the
level of clay will typically be of at least 5%, preferably at least 8%, and
most
3o preferably at least 10% by weight of the tablet. The amount may be less
than
25%, usually less than 20%, and preferably not more than 15% by weight of the
tablet.
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Heavy metal ions seauestrants
The detergent compositions tablet of the invention also contains a heavy metal
ion sequestrant, that being either present in the coating if present or in the
detergent composition, or even in both the coating and the detergent
composition, preferably, it is present in both the coating and the detergent
composition or only in the detergent composition. By heavy metal ion
sequestrant, it is meant herein components which act to sequester (chelate)
heavy metal ions. These components may also have calcium and magnesium
chelation capacity, but preferentially they show selectivity to binding heavy
metal
ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to
20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and
~ s most preferably from 0.5% to 5% by weight of the tablet.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphonic acid or carboxylic acid functionalities, may be present either in
their
acid form or as a complex/salt with a suitable counter cation such as an
alkali or
2o alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures
thereof. Preferably any salts/complexes are water soluble. The molar ratio of
said
counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include organic
25 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
3o diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1
diphosphonate.
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Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic
acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid,
5 ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid
or
any salts thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
10 or mixtures thereof. Preferred EDDS compounds are the free acid form and
the
sodium or magnesium salt or complex thereof. Examples of such preferred
sodium salts of EDDS include Na2EDDS and Na3EDDS. Examples of such
preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
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-
2o carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in
EP-
A-516,102 are also suitable herein. The ~i-alanine-N,N'-diacetic acid,
aspartic
acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic
acid
sequestrants described in EP-A-509,382 are also suitable.
2s 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-
3o hydroxypropylenediamine- N,N'-disuccinic acid (HPDDS) are also suitable.
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Most preferred heavy metal ions for use herein is alkali metal ethane 1-
hydroxy
diphosphonates, in particular when used in combination with diethylene
triamine
penta (methylene phosphonate).
Perfume
The tablets of the present invention may also optionally comprise a perfume
composition, that being either present in the coating if present or in the
detergent
composition, or even in both the coating and the detergent composition.
Suitable
perfumes herein include materials which provide an olfactory aesthetic benefit
1o such as to make such tablets more aesthetically pleasing to the consumer,
imparting a pleasant fragrance to fabrics treated therewith and/or cover any
"chemical" odor that the product may have.
As used herein, perfume includes fragrant substance or mixture of substances
including natural (i.e., obtained by extraction of flowers, herbs, leaves,
roots,
barks, wood, blossoms or plants), artificial (i.e., a mixture of different
nature oils
or oil constituents) and synthetic (i.e., synthetically produced) odoriferous
substances. Such materials are often accompanied by auxiliary materials, such
as fixatives, extenders, stabilizers and solvents. These auxiliaries are also
2o included within the meaning of "perfume", as used herein. Typically,
perfumes
are complex mixtures of a plurality of organic compounds.
Suitable perfumes are disclosed in U.S. Pat. 5,500,138, said patent being
incorporated herein by reference.
Examples of perfume ingredients useful in the perfume compositions include,
but
are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl
salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol;
2,6-
dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-
3o dimethyl-traps-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-
octanol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-hydroxy-4-
methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate;
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tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-propylphenyl)-
propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-
butan-2-one; 1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; para-
methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-3-
s oxo-cyclopentane carboxylate; undecalactone gamma.
Additional examples of fragrance materials include, but are not limited to,
orange
oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether;
methyl-beta-naphthylketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-
1o butylcyclohexyl acetate; alpha,alpha-dimethylphenethyl acetate;
methylphenylcarbinyl acetate; cyclic ethyleneglycol diester of tridecandioic
acid;
3,7-dimethyl-2,6-octadiene-1-nitrite; ionone gamma methyl; ionone alpha;
ionone
beta; petitgrain; methyl cedrylone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-
tetramethyl-naphthalene; ionone methyl; methyl-1,6,10-trimethyl-2,5,9-
15 cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-
acetyl-6-
tert-butyl-1,1-dimethyl indane; benzophenone; 6-acetyl-1,1,2,3,3,5-hexamethyl
indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal; 7-
hydroxy-
3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde;
formyl tricyclodecan; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid
20 lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-
benzopyrane; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-
[2,1 b]furan; cedrol; 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;
2-
ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol; caryophyllene
alcohol;
cedryl acetate; para-tert-butylcyclohexyl acetate; patchouli; olibanum
resinoid;
25 labdanum; vetivert; copaiba balsam; fir balsam; hydroxycitronellal and
indol;
phenyl acetaldehyde and indol;
More examples of perfume components are geraniol; geranyl acetate; linalool;
linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate;
dihydromyrcenol;
so dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl
acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl
acetate;
benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol;
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trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate;
vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal; 2-
methyl-3-
(p-isopropylphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal; 4-(4-methyl-3-
pentenyl)-3-cyclohexenecarbaldehyde; 4-acetoxy-3-pentyltetrahydropyran;
methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-
cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate;
phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal;
geranonitrile; citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol;
cedryl
methylether; isolongifolanone; aubepine nitrite; aubepine; heliotropine;
eugenol;
1o vanillin; diphenyl oxide; hydroxycitronellal ionones; methyl ionones;
isomethyl
ionomes; irones; cis-3-hexenol and esters thereof; indane musk fragrances;
tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones;
macrolactone musk fragrances; ethylene brassylate.
1 s The perfumes useful in the present invention compositions are
substantially free
of halogenated materials and nitromusks.
Preferably, the perfume composition contains less than 0.6% by weight of the
perfume composition of Schiff-base. The perfume for use herein is used at
levels
20 of up to 5 grams per tablet and preferably is substantially free of Schiff-
Base.
By "substantially free", it is meant that the perfume composition comprises
less
than 0.4 % by weight of Schiff Base, and more preferably is free of Schiff
base.
25 Schiff-Bases are the condensation of an aldehyde perfume ingredient with an
anthranilate. A typical description can be found in US 4853369. The Schiff
Bases
can be added directly to the perfume composition or can be formed in situ in
the
perfume composition by adding to it an Anthranilate such as Methyl or Ethyl
Anthranilate along with an aldehyde which can react with the Anthranilate to
form
3o the Schiff Base.
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Not to be bound by theory, it is believed that when this compound comes in
contact with the clay it can undergo reactions most likely catalysed by the
metal
ions present in the clay and that these reactions produce more highly coloured
by-products.
Typical of Schiff bases are selected from Schiffs base of 4-(4-hydroxy-4-
methylpentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate;
condensation products of: hydroxycitronellal and methyl anthranilate; 4-(4-
hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehyde and methyl
1o anthranilate; Methyl Anthranilate and HydroxyCitronellal commercially
available
under the tradename Aurantiol; Methyl Anthranilate and Methyl Nonyl
Acetaldehyde commercially available under the tradename Agrumea; Methyl
Anthranilate and PT Bucinal commercially available under the tradename
Verdantiol; Methyl anthranilate and Lyral commercially available under the
tradename Lyrame; Methyl Anthranilate and Ligustral commercially available
under the tradename Ligantral; and mixtures thereof.
Preferably, the perfume composition is free of perfume ingredients selected
from
Methyl Anthranilate and HydroxyCitronellal commercially available under the
tradename Aurantiol; Methyl Anthranilate and Methyl Nonyl Acetaldehyde
commercially available under the tradename Agrumea; Methyl Anthranilate and
PT Bucinal commercially available under the tradename Verdantiol; Methyl
anthranilate and Lyral commercially available under the tradename Lyrame;
Methyl Anthranilate and Ligustral commercially available under the tradename
Ligantral; and mixtures thereof.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned
above
are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether,
dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of
such
3o solvents, diluents or carriers incorporated in the perfumes is preferably
kept to
the minimum needed to provide a homogeneous perfume solution.
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Tablets of the present invention as well as coated tablets according to the
invention provide improved fabric perfume deposition.
5 Preferably, the perfume composition is present in an amount of 0.001 % to
10%,
preferably from 0.005% to 5%, more preferably from 0.01 % to 3%, and even
more preferably from 0.02% to 2% by weight of the tablet.
The perfume can be incorporated to the tablet by any conventional means known
1o to the skilled person. One preferred means is by spray-on of the perfume
composition onto the tablet.
Detergent ingredients
The tablets may comprise components such as surfactants, enzymes, detergent
15 etc.... Typical tablet compositions for the preferred embodiment of the
present
invention are disclosed in the pending European applications of the Applicant
n°
96203471.6, 96203462.5, 96203473.2 and 96203464.1 for example. Elements
typically entering in the composition of detergent tablets or of other forms
of
detergents such as liquids or granules are detailed in the following
paragraphs.
Detersive surfactants
Surfactant are typically comprised in a detergent composition. The dissolution
of
surfactants is favoured by the addition of the highly soluble compound.
Nonlimiting examples of surfactants useful herein typically at levels from
about
1 % to about 55%, by weight, include the conventional C11 _C1 g alkyl benzene
sulfonates ("LAS") and primary, branched-chain and random C10_C20 alkyl
sulfates ("AS"), the C1 p_C1 g secondary (2,3) alkyl sulfates of the formula
CH3(CH2)x(CHOSOg_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
so a water-solubilizing cation, especially sodium, unsaturated sulfates such
as oleyl
sulfate, the C10_C1g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy
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sulfates), C10_C1g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C10-18 glycerol ethers, the C10_C1g 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_C1g alkyl ethoxylates ("AE") including
the so-called narrow peaked alkyl ethoxylates and Cg-C12 alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12_C18
betaines and sulfobetaines ("sultaines"), C10-C1g amine oxides, and the like,
can also be included in the overall compositions. The C10-C1g N-alkyl
1o polyhydroxy fatty acid amides can also be used. Typical examples include
the
C12-C1g N-methylglucamides. See WO 9,206,154. 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
15 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 surfactants are listed in standard texts. In a preferred
embodiment, the tablet comprises at least 5% per weight of surfactant, more
preferably at least 15% per weight, even more preferably at least 25% per
2o weight, and most preferably between 35% and 45% per weight of surfactant.
Non eq Mina binders
Non gelling binders can be integrated in detergent compositions to further
facilitate dissolution.
2s 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,
3o Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type
I,
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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,
they may also be solid binders incorporated into the matrix by dry addition
but
which have binding properties within the tablet.
~5 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
2o 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.
Builders
Detergent builders can optionally be included in the compositions herein to
assist
2s 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.
3o 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
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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-
s 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
1o 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
15 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.
2o 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
crisperring agent in granular formulations, as a stabilizing agent for oxygen
2s 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
3o builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
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19
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
s from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
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:
Nal2[(A102)12(Si02)12]'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.
2o 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
2s 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.
3o 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.
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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.
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
15 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.
2o 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.
so 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.
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21
Fatty acids, e.g., C12-C1g 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 sudsing, which
should be
s 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
1o 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.
Bleach
15 The detergent compositions herein may optionally 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
2o 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
25 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
3o 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
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22
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-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
~ 5 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.
2o 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
25 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.
3o 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
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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
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)oxybenzene
~o sulfonate, (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
R6-O N-C H2-C H ~C H R6-O N C H2 ~ H2
~C H2-C H2 2 ~C H2-C H2
2o 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
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mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October
8, 1985, incorporated herein by 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 U.S. Pat. 5,246,621,
U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European
~ 5 Pat. App. Pub. Nos. 549,271 A1, 549,272A1, 544,440A2, and 544,490A1;
Preferred examples of these catalysts include MnlV2(u-O)3(1,4,7-trimethyl-
1,4,7-
triazacyclononane)2(PFg)2, Mnlll2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)2, MnlV4(u-O)g(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,
2o MnIU(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PFg), 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;
2s 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
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preferably from about 1 ppm to about 500 ppm, of the catalyst species in the
laundry liquor.
Enzymes
5 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
~5 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
2o 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
25 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
so 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
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26
European Patent Application 130,756, published January 9, 1985) and Protease
B (see European Patent Application Serial No. 87303761.8, filed April 28,
1987,
and European Patent Application 130,756, Bott et al, published January 9,
1985).
Amylases include, for example, a-amylases described in British Patent
Specification No. 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
~ s 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
2o 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
2s 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.
3o 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
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27
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
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
~ 5 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.
Flocculating agent
The detergent composition may 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
3o detergent compositions to aid' the removal of clay soils from fabrics and
enable
their dispersion within the wash solution.
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28
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, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and
ethylene
imine. Homopolymers of, on particular, ethylene oxide, but also acrylamide and
1o 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
2o a detergent agglomerate, extrudate or spray-dried particle, comprising
generally
one or more surfactants and builders.
It may be preferred that the flocculating agent is also comprised in the
particle or
granule comprising the clay.
When present, the weight ratio of clay to the flocculating polymer is
preferably
from 1000:1 to 1:1, more preferably from 500:1 to 1:1, most preferably from
300:1 to 1:1, or even more preferably from 80:1 to 10:1, or in certain
applications
even from 60:1 to 20:1.
Other components which are commonly used in detergent compositions and
which may be incorporated into detergent tablets include chelating agents,
soil
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29
release agents, soil antiredeposition agents, dispersing agents, suds
suppressors, fabric softeners, dye transfer inhibition agents and mixtures
thereof.
Hiqhly soluble Compounds
The tablet may comprise a highly soluble compound. Such a compound could be
formed from a mixture or from a single compound. A highly soluble compound is
defined as follow:
A solution is prepared as follows comprising de-ionised water as well as 20
grams per litre of a specific compound:
1- 20 g of the specific compound is placed in a Sotax Beaker. This beaker is
placed in a constant temperature bath set at 10°C. A stirrer with a
marine
propeller is placed in the beaker so that the bottom of the stirrer is at 5 mm
above the bottom of the Sotax beaker. The mixer is set at a rotation speed of
200 turns per minute.
15 2- 980 g of the de-ionised water is introduced into the Sotax beaker.
3- 10 s after the water introduction, the conductivity of the solution is
measured,
using a conductivity meter.
4- Step 3 is repeated after 20, 30, 40, 50, 1 min, 2 min, 5 min and 10 min
after
step 2.
20 5- The measurement taken at 10 min is used as the plateau value or maximum
value.
The specific compound is highly soluble according to the invention when the
conductivity of the solution reaches 80% of its maximum value in less than 10
seconds, starting from the complete addition of the de-ionised water to the
25 compound. Indeed, when monitoring the conductivity in such a manner, the
conductivity reaches a plateau after a certain period of time, this plateau
being
considered as the maximum value. Such a compound is preferably in the form of
a flowable material constituted of solid particles at temperatures comprised
between 10 and 80°Celsius for ease of handling, but other forms may be
used
3o such as a paste or a liquid.
Example of highly, soluble compounds include Sodium di isoalkylbenzene
sulphonate (DIBS) or Sodium toluene sulphonate.
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Cohesive Effect
The tablet may comprise a compound having a Cohesive Effect on the
particulate material of a detergent matrix forming the tablet. The Cohesive
Effect
on the particulate material of a detergent matrix forming the tablet or a
layer of
the tablet is characterised by the force required to break a tablet or layer
based
on the examined detergent matrix pressed under controlled compression
conditions. For a given compression force, a high tablet or layer strength
indicates that the granules stuck highly together when they were compressed,
so
~o that a strong cohesive effect is taking place. Means to assess tablet or
layer
strength (also refer to diametrical fracture stress) are given in
Pharmaceutical
dosage forms : tablets volume 1 Ed. H.A. Lieberman et al, published in 1989.
The cohesive effect is measured by comparing the tablet or layer strength of
the
~ 5 original base powder without compound having a cohesive effect with the
tablet
or layer strength of a powder mix which comprises 97 parts of the original
base
powder and 3 parts of the compound having a cohesive effect. The compound
having a cohesive effect is preferably added to the matrix in a form in which
it is
substantially free of water (water content below 10% (pref. below 5%)). The
2o temperature of the addition is between 10 and 80C, more pref. between 10
and
40C.
A compound is defined as having a cohesive effect on the particulate material
according to the invention when at a given compacting force of 3000N, tablets
with a weight of 50g of detergent particulate material and a diameter of 55mm
2s have their tablet tensile strength increased by over 30% (preferably 60 and
more
preferably 100%) by means of the presence of 3% of the compound having a
cohesive effect in the base particulate material.
An example of a compound having a cohesive effect is Sodium di
isoalkylbenzene sulphonate.
3o When integrating a highly soluble compound having also a cohesive effect on
the
particulate material used for a tablet or layer formed by compressing a
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31
particulate material comprising a surfactant, the dissolution of the tablet or
layer
in an aqueous solution is significantly increased.
In a preferred embodiment, at least 1% per weight of a tablet or layer is
formed
from the highly soluble compound, more preferably at least 2%, even more
preferably at lest 3% and most preferably at least 5% per weight of the tablet
or
layer being formed from the highly soluble compound having a cohesive effect
on the particulate material.
1o It should be noted that a composition comprising a highly soluble compound
as
well as a surfactant is disclosed in EP-A-0 524 075, this composition being a
liquid composition.
A highly soluble compound having a cohesive effect on the particulate material
15 allows to obtain a tablet having a higher tensile strength at constant
compacting
force or an equal tensile strength at lower compacting force when compared to
traditional tablets. Typically, a whole tablet will have a tensile strength of
more
than SkPa, preferably of more than 10kPa, more preferably, in particular for
use
in laundry applications, of more than 15kPa, even more preferably of more than
20 30 kPa and most preferably of more than 50 kPa, in particular for use in
dish
washing or auto dish washing applications; and a tensile strength of less than
300 kPa, preferably of less than 200 kPa, more preferably of less than 100
kPa,
even more preferably of less than 80 kPa and most preferably of less than 60
kPa. Indeed, in case of laundry application, the tablets should be less
2s compressed than in case of auto dish washing applications for example,
whereby
the dissolution is more readily achieved, so that in a laundry application,
the
tensile strength is preferably of less than 30 kPa.
This allows to produce tablets or layers which have a solidity and mechanical
3o resistance comparable to the solidity or mechanical resistance of
traditional
tablets while having a less compact tablet or layer thus dissolving more
readily.
Furthermore, as the compound is highly soluble, the dissolution of the tablet
or
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32
layer is further facilitated, resulting in a synergy leading to facilitated
dissolution
for a tablet according to the invention.
Tablet Manufacture
s The tablet may comprise several layers. For the purpose of manufacture of a
single layer, the layer may be considered as a tablet itself.
Detergent tablets 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.
In particular for laundry tablets, 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 suitable for laundry
2o compressed using a force of less than 2500N, but tablets for auto dish
washing
may also be considered for example, whereby such auto dish washing tablets
are usually more compressed than laundry tablets.
The particulate material used for making a tablet can be made by any
25 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~
CB
3o and/or Lodige~ KM mixers). Other suitable processes include fluid bed
processes, compaction processes (e.g. roll compaction), extrusion, as well as
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33
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.
s 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
~ s 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
2o includes a standard single stroke or a rotary press (such as Courtoy~,
Korch~,
Manesty0, or Bonals~). 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
25 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 kNlm2, 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
30 1.0 g/cc, and preferably of less than 2.0 g/cc, more preferably of less
than 1.5
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34
g/cc, even more preferably of less than 1.25 g/cc and most preferably of less
than 1.1 g/cc.
Multi layered tablets are typically formed in rotating presses by placing the
matrices of each layer, one after the other in matrix force feeding flasks. As
the
process continues, the matrix layers are then pressed together in the pre-
compression and compression stages stations to form the multilayer layer
tablet.
With some rotating presses it is also possible to compress the first feed
layer
before compressing the whole tablet.
~o
Hydrotrope compound
A highly soluble compound having a cohesive effect may be integrated to a
detergent tablet, whereby this compound is also a hydrotrope compound. Such
hydrotrope compound may be generally used to favour surfactant dissolution by
~5 avoiding gelling. A specific compound is defined as being hydrotrope as
follows
(see S.E. Friberg and M. Chiu, J. Dispersion Science and Technology, 9(5&6),
pages 443 to 457, (1988-1989)):
1. A solution is prepared comprising 25% by weight of the specific compound
and 75% by weight of water.
20 2. Octanoic Acid is thereafter added to the solution in a proportion of 1.6
times
the weight of the specific compound in solution, the solution being at a
temperature of 20°Celsius. The solution is mixed in a Sotax beaker with
a stirrer
with a marine propeller, the propeller being situated at about 5mm above the
bottom of the beaker, the mixer being set at a rotation speed of 200 rounds
per
25 minute.
3. The specific compound is hydrotrope if the the Octanoic Acid is completely
solubilised, i.e . if the solution comprises only one phase, the phase being a
liquid phase.
It should be noted that in a preferred embodiment of the invention, the
3o hydrotrope compound is a flowable material made of solid particles at
operating
conditions between 15 and 60° Celsius.
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Hydrotrope compounds include the compounds listed thereafter:
A list of commercial hydrotropes can be found in McCutcheon's Emulsifiers and
Detergents published by the McCutcheon division of Manufacturing
5 Confectioners Company.
Compounds of interest also include:
1. Nonionic hydrotrope with the following structure:
R - O - (CH2CH20)x( CH -CH20)yH
CH3
where R is a C8-C10 alkyl chain, x ranges from 1 to 15, y from 3 to 10.
2. Anionic hydrotropes such as alkali metal aryl sulfonates. This includes
alkali
metal salts of benzoic acid, salicylic acid, bezenesulfonic acid and its many
derivatives, naphthoic acid and various hydroaromatic acids. Examples of these
are sodium, potassium and ammonium benzene sulfonate salts derived from
~5 toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, tetralin
sulfonic
acid, naphtalene sulfonic acid, methyl- naphtalene sulfonic acid, dimethyl
naphtalene sulfonic acid, trimethyl naphtalene sulfonic acid=
Other examples include salts of dialkyl benzene sulfonic acid such as salts of
di
isopropyl benzene sulfonic acid, ethyl methyl benzene sulfonic acid, alkyl
2o benzene sulfonic acid with an alkyl chain length with 3 to 10, (pref. 4 to
9), linear
or branched alkyl sulfonates with an alkyl chain with 1 to 18 carbons.
3. Solvent hydrotropes such as alkoxylated glycerines and alkoxylated
glycerides, esters slakoxylated glycerines, alkoxylated fatty acids, esters of
glycerin, polyglycerol esters. Preferred alkoxylated glycerines have the
following
25 structure:
R
Hy-0(-0HyCH-0-~"H
R
CHp-0(-CHZGH-0-~"H
R
CHrO(-CHZCH-0-~,H
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36
where I, m and n are each a number from 0 to about 20, with I+m+n = from about
2 to about 60, preferably from about 10 to about 45 and R represents H, CH3 or
C2Hs
Preferred alkoxylated glycerides have the following struture
HpC,-R~
H I Ry R3
Hp~-O-(CHyCH-O)-H
where R1 and R2 are each C"COO or -(CH2CHR3-O),-H where R3 = H, CH3 or
C2H5 and I is a number from 1 to about 60, n is a number from about 6 to about
24.
4. Polymeric hydrotropes such as those described in EP636687:
R R~
-(CHz- )X - (CHz- )v
E Rz
where E is a hydrophilic functional group,
R is H or a C1-C10 alkyl group or is a hydrophilic functional group;
R1 is H a lower alkyl group or an aromatic group,
R2 is H or a cyclic alkyl or aromatic group.
The polymer typically has a molecular weight of between about 1000 and
1000000.
5. Hydrotrope of unusual structure such as 5-carboxy-4-hexyl-2-cyclohexene-1-
yl
octanoic acid (Diacid~).
Use of such compound in the invention would further increase the dissolution
2o rate of the tablet, as a hydrotrope compound facilitates dissolution of
surfactants,
for example. Such a compound could be formed from a mixture or from a single
compound.
Tensile Strength
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37
For the purpose of measuring tensile strength of a layer, the layer may be
considered as a tablet itself.
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 or
layer,
and is determined by the following equation
~o Tensile strength = 2 F/ ~cDt
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 or layer, and t the thickness of the
tablet or
layer. For a non round tablet, ~D may simply be replaced by the perimeter 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.
2o 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.
Tablet Dispensing
The rate of dispensing of a detergent tablet can be determined in the
following
way:
Two tablets, nominally 50 grams each, are weighed, and then placed in the
3o dispenser of a Baucknecht~ WA9850 washing machine. The water supply to the
washing machine is.set to a temperature of 20 °C and a hardness of 21
grains
per gallon, the dispenser water inlet flow-rate being set to 8 I/min. The
level of
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38
tablet residues left in the dispenser is checked by switching the washing on
and
the wash cycle set to wash program 4 (white/colors, short cycle). The
dispensing
percentage residue is determined as follows:
dispensing = residue weight x 100 / original tablet weight
The level of residues is determined by repeating the procedure 10 times and an
average residue level is calculated based on the ten individual measurements.
In
this stressed test a residue of 40 % of the starting tablet weight is
considered to
be acceptable. A residue of less than 30% is preferred, and less than 25% is
more preferred.
It should be noted that the measure of water hardness is given in the
traditional
"grain per gallon" unit, whereby 0.001 mole per litre = 7.0 grain per gallon,
representing the concentration of Ca2+ ions in solution.
Effervescent
~5 Detergent tablets may further comprise 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. CgH8O7 + 3NaHC03 ~ Na3CgH507 + 3C02 T + 3H20
2o 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
25 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 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
3o 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
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39
same as a tablet without, the disintegration of the tablet with effervescency
will
be faster.
Further dissolution aid could be provided by using compounds such as sodium
acetate or urea. A list of suitable dissolution 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.
Coating
Solidity of a tablet may be improved by making a coated tablet, the coating
covering a non-coated tablet, thereby further improving the mechanical
characteristics of the tablet while maintaining or further improving
dissolution.
This very advantageously applies to mufti-layer tablets, whereby the
mechanical
characteristics of a more elastic layer can be transmitted via the coating to
the
~ 5 rest of the tablet, thus combining the advantage of the coating with the
advantage of the more elastic layer. Indeed, mechanical constraints will be
transmitted through the coating, thus improving mechanical integrity of the
tablet.
In one embodiment of the present invention, the tablets may then be coated so
2o 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 quickly when subjected to stronger
mechanical
25 shock. Furthermore it is advantageous if the coating material is dissolved
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 undissolved
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".
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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 dissolution of the coating in
the
5 wash solution. Typically, 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.
Clay mineral compound, as above described, is a disintegrant for use herein.
~o
Other possible disintegrants which may be use in addition to the clay
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
15 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, polymers containing cationic (e.g.
quaternary ammonium) groups, amine-substituted polyacrylates, polymerised
2o cationic amino acids such as poly-L-lysine, polyallylamine hydrochloride)
and
mixtures thereof. '
Preferably, the coating material has a melting point of at least 40°C,
preferably of
from 40°C to 200 °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.
Preferably, the coating material which has a melting point of at least
40°C is an
3o acid. Acid having a melting temperature of at least 40°C are for
example
dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from
the
group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid,
adipic
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41
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic
acid,
dodecanedioic acid, tridecanedioic acid and mixtures thereof. Most preferred
is
adipic acid.
More preferably, the coating comprises a crystallised structure. By
crystallised, it
should be understood that the coating comprises a material which is solid at
ambient temperature (25°C) and has a structure exhibiting some order.
This can
be detected typically by usual crystallography techniques e.g. X-ray analysis,
on
the material itself. In a more preferred embodiment, the material forming the
1o crystallised structure does not co-crystallised or only partially with the
optional
component which is liquid at 25°C mentioned above. Indeed, it is
preferred that
the optional component remains in the liquid state at 25°C in the
coating
crystalline structure in order to provide flexibility to the structure and
resistance to
mechanical stress. Most preferably, the above mentioned acid having a melting
15 temperature of at least 40°C comprises a crystallised structure.
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.
2o Preferably, an acid having a melting point of more than 90°C such as
azelaic,
sebacic acid, dodecanedioic acid. However, for the purpose of the present
invention, the use of sebacic acid is less preferred as it provides a
detrimental
odour to the resulting product. According to the invention, it was found that
an
acid having a melting point of more than 145°C such as adipic was found
2s particularly suitable.
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.
so 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
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42
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. During the solidification phase, the coating undergoes some internal
stress (e.g. shrinkage upon cooling) and external stress (e.g. tablet
relaxation).
This will likely cause some cracks in the structure such as edge splitting if
the
coating material is too brittle to withstand these mechanical stress, which is
the
case when a coating is solely made from components solid at 25°C. Thus,
it is
preferred that the coating comprises a component which is liquid at
25°C. Hence,
it is believed that this liquid component will allow the coating to better
withstand
and absorb mechanical stress by rendering the coating structure more flexible.
The component which is liquid at 25°C is preferably added to the
coating
materials in proportions of less than 10% by weight of the coating, more
preferably less than 5% by weight, and most preferably of less than 3% by
weight. The component which is liquid at 25°C is preferably added to
the coating
materials in proportions of more than 0.1 % by weight of the coating, more
preferably more than 0.3% by weight, and most preferably of more than 0.5% by
weight.
Examples of optional components which are liquid at 25°C includes
polyethylene
glycols, thermal oil, silicon oil, esters of dicarboxylic acids, mono
carboxylic
acids, paraffin, triacetin, perfumes or alkaline solutions. For example,
particularly
good results were obtained by use of NaOH solution as alkaline solution.
It is preferred that the structure of the components which is liquid at
25°C is close
to the material forming the crystallised structure, so that the structure is
not
excessively disrupted.
3o In another embodiment, the optional component which is liquid at
25°C may
advantageously have a functionality in the washing of laundry, for example
silicone oil which provides suds suppression benefits or perfume oil. When
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43
present, the perfume oil may be the perfume composition as per described
herein, or a different perfume composition to that already contained by the
tablet,
provided it contains less than 0.6% by weight of Schiff-Base.
s The coating may also comprise materials other than the optional component
which is liquid at 25°C. Hence, further preferred, is the addition of
reinforcing
fibres to the coating in order to further reinforce the structure.
In a most preferred embodiment, the crystallised structure is made of adipic
acid,
the component which is liquid at 25°C being available under the name
CoasoIT"~
from Chemoxy International, being a blend of the di-isobutyl esters of the
glutaric, succinic and adipic acid. The advantage of the use of this component
being the good dispersion in the adipic acid to provide flexibility. It should
be
noted that disintegration of the adipic acid is further improved by the
adipate
content of CoasoIT"".
According to a preferred embodiment of the invention, the coating comprises an
acid having a melting temperature of at least 145°C, such as adipic
acid for
example, as well as a clay, such as a bentonite clay for example, whereby the
2o clay is used as a disintegrant and also to render the structure of adipic
acid more
favourable for water penetration, thus improving the dispersion of the adipic
acid
in a aqueous medium. Preferred are clays present in the coating and having a
particle size of less than 75 pm, more preferably of less than 53 Nm, in order
to
obtain the desired effect on the structure of the acid. Preferred clays are
25 bentonite clays. Indeed the acid has a melting point such that traditional
cellulosic disintegrants undergo a thermal degradation during the coating
process, whereas such clays are found to be more heat stable. Further,
traditional cellulosic disintegrant such as NymceIT"' for example are found to
turn
brown at these temperatures.
In another preferred embodiment, the coating further comprises reinforcing
fibres. Such fibres have been found to improve further the resistance of the
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44
coating to mechanical stress and minimise the splitting defect occurence. Such
fibres are preferably having a length of at least 100 Nm, more preferably of
at
least 200 pm and most preferably of at least 250 pm to allow structure
reinforcement. Such fibres are preferably having a length of at less than 500
Nm,
more preferably of less than 400 pm and most preferably of less than 350 Nm in
order not to impact onto dispersion of the coating in an aqueous medium.
Materials which may be used for these fibres include viscose rayon, natural
nylon, synthetic nylon (polyamides types 6 and 6,6), acrylic, polyester,
cotton and
derivatives of cellulose such as CMCs. Most preferred is a cellulosic material
available under the trade mark Solka-FIocT"" from Fibers Sales & Development.
It
should be noted that such fibres do not normally need pre-compression for
reinforcing the coating structure. Such fibres are preferably added at a level
of
less than 5% by weight of the coating, more preferably less than 3% by weight.
Such fibres are preferably added at a level of more than 0.5% by weight of the
~ s coating, more preferably more than 1 % by weight.
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.
Tablet coatings are very hard and provide extra strength to the tablet.
Process
A preferred process for making a tablet according to the invention comprises
the
2s steps of:
(a) forming a core by compressing a particulate material, the particulate
material
comprising surfactant and detergent builder;
(b) applying a coating material to the core, the coating material being in the
form
of a melt;
(c) allowing the molten coating material to solidify;
characterised in that the coating comprises a clay.
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Another preferred process for making a tablet according to the invention
comprises the steps of
(a) forming a core by compressing a particulate material, the particulate
material
5 comprising surfactant and detergent builder;
(b) applying a coating material to the core, the coating material being
dissolved in
a solvent or water;
(c) allowing the solvent or water to evaporate;
characterised in that the coating comprises a clay.
The compounds disclosed above for a product are advantageously packed in a
packaging system.
A packaging system may be formed from a sheet of flexible material. Materials
suitable for use as a flexible sheet include mono-layer, co-extruded or
laminated
films. Such films may comprise various components, such as poly-ethylene, poly-
propylene, poly-styrene, poly-ethylene-terephtalate. Preferably, the packaging
system is composed of a poly-ethylene and bi-oriented-poly-propylene co-
2o extruded film with an MVTR of less than 5 g/day/m2. The MVTR of the
packaging
system is preferably of less than 10 g/day/m2, more preferably of less than 5
g/day/m2. The film (2) may have various thicknesses. The thickness should
typically be between 10 and 150 Vim, preferably between 15 and 120 ~.m, more
preferably between 20 and 100 Vim, even more preferably between 25 and 80
~.m and most preferably between 30 and 40 Vim.
A packaging material preferably comprises a barrier layer typically found with
packaging materials having a low oxygen transmission rate, typically of less
than
300 cm3/m2/day, preferably of less than 150 cm3/m2/day, more preferably of
less
than 100 cm3/m2/day, even more preferably of less than 50 cm3/m2/day and most
3o preferably of less than 10 cm3/m2/day. Typical materials having such
barrier
properties include bi oriented polypropylene, poly ethylene terephthalate,
Nylon,
polyethylene vinyl alcohol) , or laminated materials comprising one of these,
as
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46
well as SiOx (Silicium oxydes), or metallic foils such as aluminium foils for
example. Such packaging material may have a beneficial influence on the
stability of the product during storage for example.
Among the packing method used are typically the wrapping methods disclosed in
W092/20593, including flow wrapping or over wrapping. When using such
processes, a longitudinal seal is provided, which may be a fin seal or an
overlapping seal, after which a first end of the packaging system is closed
with a
first end seal, followed by closure of the second end with a second end seal.
The
packaging system may comprise re-closing means as described in W092/20593.
In particular, using a twist, a cold seal or an adhesive is particularly
suited.
Indeed, a band of cold seal or a band of adhesive may be applied to the
surface
of the packaging system at a position adjacent to the second end of the
packaging system, so that this band may provide both the initial seal and re-
closure of the packaging system. In such a case the adhesive or cold seal band
may correspond to a region having a cohesive surface, i.e. a surface which
will
adhere only to another cohesive surface. Such re-closing means may also
comprise spacers which will prevent unwanted adhesion. Such spacers are
described in WO 95/13225, published on the 18t" of May 1995. There may also
be a plurality of spacers and a plurality of strips of adhesive material. The
main
2o requirement is that the communication between the exterior and the interior
of
the package should be minimal, even after first opening of the packaging
system.
A cold seal may be used, and in particular a grid of cold seal, whereby the
cold
seal is adapted so as to facilitate opening of the packaging system.
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47
Examples
The following is a non-limiting example of a suitable perfume composition A
which is used in the following non-limiting detergent tablet examples 1 and 2
s according to the present invention:
Perfume Component % in Perfume
Composition
Geraniol 5.0
Citronellol 5.0
4 t-Butyl Cyclo Hexyl Acetate5.0
Phenyl Ethyl Alcohol 10.0
Hexahydro-4,7-Methano-Inden-5-yl6.0
Acetate commercially available
under the tradename Cyclacet
Citronellyl Acetate 2.5
Geranyl Acetate 2.5
Hexyl Cinnamic Aldehyde 4.5
Para Hydroxy Phenyl Butanone 3.0
PT Bucinal 24.0
Methyl lonone 10.0
Rosalva 2.0
Methyl Dihydro Jasmonate 7.0
Undecylenic Aldehyde 0.5
Methyl Iso Butenyl Tetra Hydro1.0
Pyran
Ortho t Butyl Cyclo Hexyl 6.0
Acetate
Hexyl Salicylate 6.0
Total 100.0
Abbreviations used in the following detergent Examples 1-6
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48
In the detergent compositions, the abbreviated component identifications have
the following meanings:
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
Nonionic agglomerate comprise 26% nonionic surfactant, 6% Lutensit K-HD 96,
40% Sodium acetate anhydrous, 20% carbonate and 8% zeolite.
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.
Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59% of
zeolite and 29.5% of water.
Binder spray-on system comprises 16% by weight of polymer of the following
2o kind:
CH3
CH3
(EO)za~N N-(EO)za
I (EO)za
(EO)za
68 % by weight of: PEG4000 and 16% by weight of: DIBS (Sodium di
isoalkylbenzene sulphonate or Sodium toluene sulphonate).
Abbreviations used in the following detergent Examples 7
In the detergent compositions, the abbreviated component identifications have
the following meanings:
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LAS : Sodium linear C11-13 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
CxyAS : Sodium C1x - C1y alkyl sulfate
C46SAS : Sodium C14 - C16 secondary (2,3) alkyl
sulfate
CxyEzS : Sodium C1x-C1y alkyl sulfate condensed
with z
moles. of ethylene oxide
CxyEz : C1 x-C1 y predominantly linear primary
alcohol
condensed with an average of z moles of ethylene
~o oxide
QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 ' C14
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~~C~B
15 SADE2S : Sodium C~4-C22 alkyl disulfate of formula
2-(R).C4
H~.-1,4-(S04-)2 where R = Cep-Cog, condensed
with z
moles of ethylene oxide
MES : x-sulpho methylester of C~8 fatty acid
APA : Cg - C10 amido propyl dimethyl amine
2o Soap : Sodium linear alkyl carboxylate derived from
an
80/20 mixture of tallow and coconut fatty acids
STS : Sodium toluene sulphonate
CFAA . : C12-C14 (coco) alkyl N-methyl glucamide
TFAA : C1 g-C1 g alkyl N-methyl glucamide
2s TPKFA : C1 g_C1 g topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
TSPP : Tetrasodium pyrophosphate
Zeolite A : Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12.27H20 having a primary particle
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size in the range from 0.1 to 10 micrometers (weight
expressed on an anhydrous basis)
NaSKS-6 : Crystalline layered silicate of formula 8- Na2Si205
Citric acid : Anhydrous citric acid
5 Borate : Sodium borate
Carbonate : Anydrous sodium carbonate with a particle size
between 200pm and 900Nm
Bicarbonate : Anhydrous sodium bicarbonate with a particle size
distribution between 400Nm and 1200Nm
Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1 )
Sulfate : Anhydrous sodium sulfate
Mg sulfate : Anhydrous magnesium sulfate
Citrate : Tri-sodium citrate dehydrate of activity
86.4% with a
particle size distribution between 425pm
and 850Nm
15 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
2o weight 4,500
CMC : Sodium carboxymethyl cellulose
Cellulose ether : Methyl cellulose ether with a degree of
polymerization of 650 available from Shin
Etsu
Chemicals
25 Protease : Proteolytic enzyme, having 3.3% by weight
of active
enzyme, sold by NOVO Industries A/S under
the
tradename Savinase
Protease I : Proteolytic enzyme, having 4% by weight of
active
enzyme, as described in WO 95/10591, sold
by
3o Genencor Int. Inc.
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51
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
1o Lipase : Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries A/S under the
tradename Lipolase
Lipase II : Lipolytic enzyme, having 2.0% by weight of
active
enzyme, sold by NOVO Industries AlS under the
tradename Lipolase Ultra
Endolase : Endoglucanase enzyme, having 1.5% by weight
of
active enzyme, sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
2o PB1 : 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
NACA-OBS : (6-nonamidocaproyl) oxybenzene sulfonate
3o LOBS : Dodecanoyloxybenzene sulfonate in the form
of the
sodium salt
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52
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.
Photoactivated Sulfonated zinc phthlocyanine encapsulated
: in
bleach (1 ) dextrin soluble polymer
Photoactivated Sulfonated alumino phthlocyanine encapsulated
: in
bleach (2) dextrin soluble polymer
~5Brightener 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
20 (typically 4,000)
PEO : Polyethylene oxide, with an average molecular
weight of 50,000
TEPAE : Tetraethylenepentaamine ethoxylate
PVI : Polyvinyl imidasole, with an average molecular
25 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
3oPVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole,
with an average molecular weight of 20,000
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53
QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3)
bis((C2H50)-(C2H40))n, wherein n = from
20 to 30
PEI : Polyethyleneimine with an average molecular
weight
of 1800 and an average ethoxylation degree
of 7
ethyleneoxy residues per nitrogen
Clay I : Bentonite clay
Clay II : Smectite clay
Flocculating agent polyethylene oxide of average molecular
I : weight of
between 200,000 and 400,000
1o Flocculating agent : polyethylene oxide of average molecular
II weight
of between 400,000 and 1,000,000
Flocculating agent : polymer of acrylamide and/ or acrylic
III acid of
average molecular weight of 200,000 and
400,000
SRP I : Anionically end-capped polyester soil release
polymer
SRP II : Polysaccheride soil release polymer
SRP 1 : Nonionically end capped poly esters
SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate)
short
block polymer
2o 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
Speckle : Coloured carbonate salt or organic carboxylic
acid
salt
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54
Example 1
i) A detergent base powder of composition A was prepared as follows: all the
particulate material of base composition were mixed together in a mixing
drum or spray drum to form a homogenous particulate mixture, apart from the
binder spray-on system, the fluorescer or brightener, and the photobleach
Zinc Phthalocyanine sulphonate. The particulate mixture was thereafter
divided in two equal parts, one part for making a white layer, another part
for
making a green layer. The white layer material is obtained by spraying the
brightener or fluorescer together with half of the binder. The green layer
material is obtained by spraying the photobleach Zinc Phthalocyanine
sulphonate together with the rest of the binder. The layer where then
processed independently in a Loedige KM 600~.
ii) Using a Bonals~ rotary press both matrices were filled in two independent
force feeding flasks. Both layers are compressed together in the pre-
~ 5 compression and compression stations to form a dual layer tablet.
iii) In this particular example, the tablets have a square cross section of 45
mm
side, a height of 24 mm and a weight of 45 gr. The height of the green bottom
layer corresponded to 50% of the total height of the tablet. The tensile
strength of the uncoated tablets was 13 kpa.
2o iv) The tablet was thereafter coated with 2.5 g of coating formed from 89%
by
weight of adipic acid and 10% by weight of Bentonite clay from CSM, and 1
by weight of ethane 1-hydroxy diphosphonate.
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Composition
A
(%)
Anionic agglomerates 1 9.1
Anionic agglomerates 2 22.5
Nonionic agglomerates 9.1
Cationic agglomerates 4.6
Layered silicate 9.7
Sodium percarbonate 12.2
Bleach activator agglomerates 6.1
Sodium carbonate 7.67
EDDS/Sulphate particle 0.5
Tetrasodium salt of Hydroxyethane 0.6
Diphosphonic acid
Soil Release Polymer 0.3
Fluorescer 0.2
Zinc Phthalocyanine sulphonate 0.03
Soap powder 1.2
Suds suppressor 2.8
Citric acid 5.5
Protease 1
Lipase 0.35
Cellulase 0.2
Amylase 1.1
Binder spray-on system 4.75
Perfume spray-on 0.5
Example 2
i) A detergent base powder of composition A was prepared as follows: all the
5 particulate material of base composition were mixed together in a mixing
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56
drum or spray drum to form a homogenous particulate mixture, apart from the
binder spray-on system, the fluorescer or brightener, and the photobleach
Zinc Phthalocyanine sulphonate. The particulate mixture was thereafter
divided in two equal parts, one part for making a white layer, another part
for
making a green layer. The white layer material is obtained by spraying the
brightener or fluorescer together with half of the binder. The green layer
material is obtained by spraying the photobleach Zinc Phthalocyanine
sulphonate together with the rest of the binder. The layer where then
processed independently in a Loedige KM 600°.
ii) Using a Bonals~ rotary press both matrices were filled in two independent
force feeding flasks. Both layers are compressed together in the pre-
compression and compression stations to form a dual layer tablet.
iii) In this particular example, the tablets have a square cross section of 45
mm
side, a height of 24 mm and a weight of 45 gr. The height of the green bottom
~ 5 layer corresponded to 50% of the total height of the tablet. The tensile
strength of the uncoated tablets was 13 kpa.
iv) The tablet was thereafter coated with 2.5 g of coating formed from 89% by
weight of adipic acid and 10% by weight of Bentonite clay from CSM, and
0.5% by weight of ethane 1-hydroxy diphosphonate and 0.5% by weight of
2o diethylene triamine yenta (methylene phosphonate).
Example 3
i) A detergent base powder of composition A was prepared as follows: all the
particulate material of base composition were mixed together in a mixing
25 drum or spray drum to form a homogenous particulate mixture, apart from the
binder spray-on system, the fluorescer or brightener, and the photobleach
Zinc Phthalocyanine sulphonate. The particulate mixture was thereafter
divided in two equal parts, one part for making a white layer, another part
for
making a green layer. The white layer material is obtained by spraying the
3o brightener or fluorescer together with half of the binder. The green layer
material is obtained by spraying the photobleach Zinc Phthalocyanine
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WO 00/55294 PCTNS00/05985
57
sulphonate together with the rest of the binder. The layer where then
processed independently in a Loedige KM 600~.
ii) Using a Bonals° rotary press both matrices were filled in two
independent
force feeding flasks. Both layers are compressed together in the pre-
compression and compression stations to form a dual layer tablet.
iii) In this particular example, the tablets have a square cross section of 45
mm
side, a height of 24 mm and a weight of 45 gr. The height of the green bottom
layer corresponded to 50% of the total height of the tablet. The tensile
strength of the uncoated tablets was 13 kpa.
iv) The tablet was thereafter coated with 2.5 g of coating formed from 89% by
weight of adipic acid and 10% by weight of Bentonite clay from CSM, and
0.5% by weight of ethane 1-hydroxy diphosphonate and 0.5% by weight of
diethylene triamine penta (methylene phosphonate).
Example 4
i) A detergent base powder of composition A was prepared as follows: all the
particulate material of base composition was mixed together in a mixing drum
or spray drum to form a homogenous particulate mixture. The binder system
was then sprayed on. The powder where then processed in a Loedige KM
600°.
ii) Using a Instron~ Laboratory bench press, detergent powder was filled in
the
die. The powder had been compressed with a force so that the tensile
strength of the tablet was 10kpa.
iii) In this particular example, the tablets have a diameter of 54 mm side, a
height
of 24 mm and a weight of 45 gr.
iv) The tablet was thereafter coated with 2.5 g of coating formed from 90% by
weight of Adipic acid and 10% by weight of bentonite clay from CSM.
The tablet was thereafter coated with 2.5 g of coating formed from 77% by
weight
of Adipic acid, 18.5% by weight of bentonite clay from and 1 % by weight of
3o CoasoITM and 2.5 % by weight of NaOH (1 M), and 1 % by weight of ethane 1-
hydroxy diphosphonate.
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58
Example 5
i) A detergent base powder of composition A was prepared as follows: all the
particulate material of base composition were mixed together in a mixing
drum or spray drum to form a homogenous particulate mixture. The binder
system was then sprayed on. The powder where then processed in a Loedige
KM 600°.
ii) Using a Instron~ Laboratory bench press, detergent powder was filled in
the
die. The powder had been compressed with a force so that the tensile
strength of the tablet was 10kpa.
iii) In this particular example, the tablets have a diameter of 54 mm side, a
height
of 24 mm and a weight of 45 gr.
The tablet was thereafter coated with 2.5 g of coating formed from 88% by
weight
of Adipic acid, 10% by weight of bentonite clay from and 1 % of CoasoIT'~, and
1
~5 by weight of ethane 1-hydroxy diphosphonate.
Example 6
i) A detergent base powder of composition A was prepared as follows: all the
2o particulate material of base composition were mixed together in a mixing
drum or spray drum to form a homogenous particulate mixture. The binder
system was then sprayed on. The powder where then processed in a Loedige
KM 600~.
ii) Using a Instron~ Laboratory bench press, detergent powder was filled in
the
25 die. The powder had been compressed with a force so that the tensile
strength of the tablet was 10kpa.
iii) In this particular example, the tablets have a diameter of 54 mm side, a
height
of 24 mm and a weight of 45 gr.
iv) The tablet was thereafter coated with 2.5 g of coating formed from 86% by
3o weight of Adipic acid, 10% by weight of bentonite clay from and 1 % by
weight
of CoasoITM and.2 % by weight of Solka-FIocT""1016, and 0.5% by weight of
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59
ethane 1-hydroxy diphosphonate and 0.5% by weight of diethylene triamine
penta (methylene phosphonate).
Example 7
The following are detergent compositions according to the invention which may
be used as is or in place of Composition A, above described, in any one of
Examples 1-6.
In the following examples all levels are quoted as % by weight of the
composition:
B C D E
Blown powder
Clay I or II 7.0 10.0 6.0 2.0
Flocculating agent 0.3 1.0 1.0 0.5
I or II
LAS 16.0 5.0 11.0 6.0
TAS - 5.0 - 2.0
Zeolite A - 20.0 - 10.0
STPP 24.0 - 14.0 -
Sulfate - 2.0 - -
MA/AA - 2.0 1.0 1.0
Silicate 4.0 7.0 3.0 -
CMC 1.0 - 0.5 0.6
Brightener 0.2 0.2 0.2 0.2
Sodium carbonate 10.0 10.0 20.0 -
DTPMP 0.4 0.4 0.2 -
Spray on
Brightener 0.02 - - 0.02
C45E7 or E9 - - 2.0 1.0
C45E3 or E4 - - 2.0 4.0
Perfume 0.5 - 0.5 0.2
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WO 00/55294 PCT/US00/05985
Silicone antifoam 0.3 - - -
Dry additives
QEA - - - 1.0
HEDP/ EDDS 0.3 - - -
Sulfate 2.0 - - -
Carbonate 20.0 13.0 15.0 24.0
Citric acid 2.5 - - 2.0
QAS - - 0.5 0.5
SKS-6 3.5 - - 5.0
Percarbonate - - - 9.0
PB4 - - 5.0
NOBS - - - 1.3
TAED - - 2.0 1.5
Protease 1.0 1.0 1.0 1.0
Lipase - 0.4 - 0.2
Amylase 0.2 0.2 0.2 0.4
Brightener 0.05 - - 0.05
Perfume 1.0 0.2 0.5 0.3
Speckle 1.2 0.5 2.0 -
Misc/minor to 100%
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61
The following are compositions suitable for use herein
G H I J I K L
Sodium C11-C13 12.0 16.0 23.0 19.0 18.0 20.0 16.0
alkylbenzenesulfonate
Sodium C14-C15 alcohol 4.5 - - - 4.0
sulfate
C14-C15 alcohol - - - - -
ethoxylate (0.5) sulfate
C,4-C,5 alcohol ethoxylate- - 2.0 - 1.0 1.0 1.0
(3) sulfate
Sodium C14-C15 alcohol2.0 2.0 - 1.3 - - 5.0
ethoxylate
C9-C,4 alkyl dimethyl - - 1.0 0.5 2.0
hydroxy ethyl quaternary
ammonium salt
Tallow fatty acid - - - - 1.0
Tallow alcohol ethoxylate- - - - - - -
(50)
Sodium tripolyphosphate23.0 25.0 14.0 22,0 20.0 10.0 20.0
/
Zeolite
Sodium carbonate 25.0 22.0 35.0 20.0 28.0 41.0 30.0
Sodium Polyacrylate 0.5 0.5 0.5 0.5 - - -
(45%)
Sodium - - 1.0 1.0 1.0 2.0 0.5
polyacrylate/maleate
polymer
Sodium silicate (1:6 3.0 6.0 9.0 8.0 9.0 6.0 8.0
ratio
Na0/Si02)(46%)
Sodium sulfate - - - - - 2.0 3.0
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62
Sodium perborate/ 5.0 5.0 10.0 - 3.0 1.0 -
percarbonate
Poly(ethyleneglycol),1.5 1.5 1.0 1.0 - - 0.5
MW
-4000 (50%)
Sodium carboxy methyl1.0 1.0 1.0 - 0.5 0.5 0.5
cellulose
Citric acid - - - - - - -
NOBS/ DOBS - 1.0 - - 1.0 0.7 -
TAED 1.5 1.0 2.5 - 3.0 0.7 -
SRP 1.5 1.5 1.0 1.0 - 1.0
Clay I or II 5.0 6.0 12.0 7.0 10.0 4.0 3.0
Flocculating agent 0.2 0.2 3.0 2.0 0.1 1.0 0.5
I or III
Humectant 0.5 1.0 0.5 1.0 0.5 0.5 -
Wax 0.5 0.5 1.0 - - 0.5 0.5
Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0
Magnesium sulphate - - - - - 0.5 1.5
Chelant - - - - 0.8 0.6 1.0
Enzymes, including - - - - 2.0 1.5 2.0
amylase, cellulase,
protease and lipase
Speckle 2.5 4.1 4.2 4.4 5.6 5.0 5.2
minors, e.g. perfume,2.0 1.0 1.0 1.0 2.5 1.5 1.0
PVP, PVPVI/PVNO,
brightener, photo-bleach,
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63
The following are detergent compositions suitable for use herein
M N O
Sodium C11-C13 23.0 13.0 20.0 18.0
alkylbenzenesulfonate
Sodium C14-C15 alcohol sulfate - 4.0 -
Clay I or II 5.0 10.0 14.0 6.0
Flocculating agent I or II 0.2 0.3 0.1 0.9
Wax 0.5 0.5 1.0 -
Humectant (glycerol/ silica) 0.5 2.0 1.5 -
C,4-C,5 alcohol ethoxylate sulfate- - 2.0
Sodium C14-C15 alcohol ethoxylate2.5 3.5 - -
(
Cg-C,4 alkyl dimethyl hydroxy - - 0.5
ethyl
quaternary ammonium salt
Tallow fatty acid 0.5 - - -
Tallow alcohol ethoxylate (50) - - 1.3
Sodium tripolyphosphate - 41.0 - 20.0
Zeolite A, hydrate (0.1-10 micron26.3 - 21.3 -
size)
Sodium carbonate 24.0 22.0 35.0 27.0
Sodium Polyacrylate (45%) 2.4 - 2.7 -
Sodium polyacrylate/maleate - - 1.0 2.5
polymer
Sodium silicate (1.6 or 2 or 4.0 7.0 2.0 6.0
2.2 ratio
NaO/Si02)(46%)
Sodium sulfate - 6.0 2.0 -
Sodium perborate/ percarbonate 8.0 4.0 - 12.0
Poly(ethyleneglycol), MW --40001.7 0.4 1.0 -
50%)
Sodium carboxy methyl cellulose1.0 - - 0.3
Citric acid - - 3.0 -
NOBS/ DOBS 1.2 - - 1.0
TAD 0.6 1.5 - 3.0
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Perfume 0.5 1.0 0.3 0.4
Soil release polymer - 1.5 1.0 1.0
Moisture 7.5 3.1 6.1 7.3
Magnesium sulphate - - - 1.0
Chelant - - - 0.5
speckle 1.0 0.5 0.2 2.7
Enzymes, including amylase, - 1.0 - 1.5
cellulase, protease and lipase
minors, e.g. brightener, photo-bleach1.0 1.0 1.0 1.0
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The following are detergent compositions suitable for use herein
Q R S T U
Blown Powder _ _
STPP/ Zeolite A 9.0 15.0 15.0 9.0 9.0
Flocculating agent II 0.5 0.2 0.9 1.5 -
or III
LAS 7.5 23.0 3.0 7.5 7.5
QAS 2.5 1.5 - - -
DTPMP 0.4 0.2 0.4 0.4 0.4
HEDP or EDDS - 0.4 0.2 - -
CMC 0.1 0.4 0.4 0.1 0.1
Sodium carbonate 5.0 20.0 20.0 10.0
Brightener 0.05 - - 0.05 0.05
Clay I or II - 10.0 - - -
STS 0.5 - - 0.5 0.5
MA/AA 1.5 2.0 2.0 1.5 1.5
Agglomerates
Suds suppresser (silicon)1.0 1.0 - 2.0 0.5
Agglomerate
Clay 9.0 - - 4.0 10.0
Wax 0.5 - - 0.5 1.5
Glycerol 0.5 - - 0.5 0.5
Agglomerate
LAS - 5.0 5.0 - -
TAS - 2.0 1.0 - -
Silicate - 3.0 4.0 - -
Zeolite A - 8.0 8.0 -
Carbonate - 8.0 4.0 - -
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Spray On
Perfume 0.3 - - 0.3 0.3
C45E7 or E9 2.0 - - 2.0 2.0
C25E3 or E4 2.0 - - 2.0 2.0
Dry additives
Citrate or citric acid 2.5 - 2.0 2.5 2.5
Clay I or II - 5.0 5.0 - -
Flocculating agent I or - - - 0.2
II
Bicarbonate - 3.0 - - -
Carbonate 15.0 - - 25.0 31.0
TAED 1.0 2.0 5.0 1.0 -
Sodium perborate or 6.0 7.0 10.0 6.0 -
percarbonate
SRP I, II or III 0.2 0.1 0.2 0.5 0.3
CMC or nonionic cellulose1.0 1.5 0.5 - -
ether
Protease 0.3 1.0 1.0 0.3 0.3
Lipase - 0.4 0.4 - -
Amylase 0.2 0.6 0.6 0.2 0.2
Cellulase 0.2 0.6 0.6 0.2 0.2
Silicone antifoam - 5.0 5.0 - -
Perfume (starch) 0.2 0.3 1.0 0.2 0.2
Speckle 0.5 0.5 0.1 - 1.0
SKS-6 (silicate 2R) 3.5 - - - 3.5
Photobleach 0.1 - - 0.1 0.1
Soap 0.5 2.5 - 0.5 0.5
Sodium sulfate - 3.0 - - -
Misc/minors to 100% 100.0 100.0100.0 100.0 100.0
Density (g/litre) 850 850 850 850 850
