Note: Descriptions are shown in the official language in which they were submitted.
CA 02317022 2000-09-07
FRAGRANT BEADS IN DETERGENT FORMS
Field of the Invention
The invention relates to a method for producing detergent forms, in particular
detergent tablets for use in normal domestic washing machines.
Background of the Invention
Compared with detergents :in powder or liquid form, detergent forms have a
number
of advantages: they are easy to dose and because of their high density require
less
1o packaging as well as reduced transport and storage capacities. A further
important
advantage of such products is consumer acceptance, which may be founded not
only
on the advantages of convenience outlined, but also on the aesthetic qualities
of the
forms. Thus in the dishwashing machine sector, tablets have displaced the
formerly
common products in powder form from large sections of the market.
However, as well as the aforementioned advantages, there are also
disadvantages
which also lie in the form itself. Thus, after manufacture, a form has to be
sufficiently
stable to allow itself to be packaged, transported and stored without breaking
or
abrasion. These stability requirements necessitate a certain hardness of the
forms,
which is again an obstacle to rapid dissolution of the form. This dichotomy
between
hardness and disintegration time is a central problem in the production of
forms,
regardless of the area in which these forms are to be used.
There are further .specific problems in the production of detergent forms.
Whereas
dishwashing deterf;ents in tablet form are relatively low in surfactants and
are
predominantly made up of soluble components, textile detergents, for example,
contain distinctly higher quantities of surfactants, resulting in solubility
problems, as
some surfactants tend to turn to gel and/or will only dissolve slowly. Also
the
requirements made of a textile detergent in the form of pressed forms are
distinctly
3o higher than those made of dishwashing detergent tablets. In the dishwasher
the tablet
is placed in a small. basket where it dissolves throughout the whole cleaning
process.
1
CA 02317022 2000-09-07
In domestic washing machines a textile detergent form must on the one hand be
doseable via the dispensing compartment, which means that within seconds it
must
disintegrate into such small particles that the particles can be washed in,
and on the
other hand, in the case of dosing into the drum, it must be ensured that the
forms will
dissolve completely and rapidly, to prevent, as far as possible, contact
between solid,
moist detergent and the washing, to avoid spotting problems.
Unlike dishwashing tables, detergent forms contain further constituents that
further
reinforce the dichotomy between hardness and disintegration time. Whilst
1o dishwashing tablets do not as a rule have fragrances, perfumes in
detergents have a
considerable significance: on the one hand the fragrance makes for a clearly
characteristic "unm.istakable" product, and on the other hand, in the case of
detergents
the perfuming of the textiles treated is an extremely important characteristic
in the
performance experienced by the consumer. However, perfumes are distinctly
hydrophobic substances, which make the dissolution of perfumed detergents
still
more difficult, as they make the powder mixture water repellent when sprayed
onto it.
In the state of the art relating to detergent forms there is only a small
number of
publications dealing with th:e incorporation in these forms of hydrophobic
substances
2o and substances with water-repellent effect.
Thus the earlier German patent application 197 39 384.5 (Henkel KGaA)
describes
detergent forms made from compacted detergents in the form of particles, which
contain surfactant(s), builders, a cellulose-based disintegration agent and
optional
further constituents of detergents, and in which the disintegration agents are
spatially
separated from substances with water-repellent effect in a separate region of
the form.
By separating the disintegration agent from substances that can prevent
moisture from
reaching the disintegration agent, the forms described in this publication
have
excellent dissolving properties.
2
CA 02317022 2000-09-07
This publication only describes how the disintegration effect of the
disintegration
agent used can best be utilized. It says nothing about the optimized
incorporation of
substances with water-repellent effect.
The earlier German patent application 197 39 383.7 (Henkel KGa,A) describes
detergent forms made from compacted detergents in the form of particles, which
again contain surfactant(s), builders, a cellulose-based disintegration agent
and
optional further constituents of detergents, and in which all the substances
with water-
repellent effect are applied to a carrier material. Substances with water-
repellent effect
to within the meaning of this application are, for example, also perfume oils,
although
nothing is said about application onto the earner materials in this
publication.
The present invention is based on the task of making available a method for
the
production of detergent forms, which, as the method's end product, supplies
forms
which are characterized in that they are hard and disintegrate quickly. The
method is
in particular, intended to c;nable perfume to be incorporated into the forms
by a
suitable method, wiithout having to accept the disadvantages of conventional
detergent
forms containing perfume. I should thus provide a possibility for producing
perfume
containing detergent forms, whose properties match or surpass those of perfume-
free
2o forms.
Summary of the Invention
The solution to this task succeeds, if highly dosed fragrant forms, in
particular
fragrant beads, are incorporated into the detergent forms, with the perfume
foams
being produced b;y granulation or pressure agglomeration (e.g. pellet
pressing,
extrusion etc.).
The object of the invention is a method for producing detergent forms, in
which
highly dosed fragrant compounds are produced by granulation or pressure
3o agglomeration, mi};ed with further detergent constituents in the form of
powder or
granules and this premixture; is compacted into foams using a known method.
3
CA 02317022 2000-09-07
For use in the method according to the invention, highly dosed fragrant
compounds
are suitable, which can be produced by granulation or pressure agglomeration.
For
this purpose, fragrant compounds are preferred, in particular fragrant beads,
with
apparent densities of more than 700 g/1. The production of "fragrant beads"
preferred
for use in the method according to the invention is described, for example, in
the
earlier German patent application 197 46 780.6 (Henkel KGaA). This application
discloses a method for producing fragrant shapes, in particular fragrant
beads, with
apparent densities of more than 700 g/l, in which a solid and essentially
anhydrous
to premixture of
a) 65 to 95% wt. % Garner substance(s),
b) 0 to 10 wt. °/~ auxiliary agents) and
c) 5 to 25 wt. °/~ perfume
is subjected to granulation or pressure agglomeration.
Detailed Description of the Invention
Preferred Garner substances are selected from the group of surfactants,
surfactant
compounds, di- a~ld polysaccharides, silicates, zeolites, carbonates, sulfates
and
citrates and are used in quantities of between 65 and 95 wt. %, preferably 70
to 90 wt.
% in each case relative to the weight of the fragrant forms produced.
In addition to the "fragrant beads" which can be produced by the method
described
above, in the method according to the present invention the incorporation of
fragrant
beads is preferred, as described in the earlier German patent application 197
46 781.4
(Henkel KGaA). In this publication a method is disclosed for producing
fragrance-
reinforced detergents and/or components for these with apparent densities of
more
than 600 gil, in which a solid and essentially anhydrous premixture of
detergent
compound and/or raw materials is produced, containing at least 0.1 wt. %
perfume
relative to the prem~,ixture, and this premixture is subjected to pressure
agglomeration.
3o Such fragrance-reinforced detergents or the aforementioned fragrant forms
can be
incorporated in the premixtures in the method according to the invention.
4
CA 02317022 2000-09-07
The production of the highly dosed fragrant forms succeeds by means of
granulation
or pressure agglomeration. :fn the case of granulation the fragrant form
premixture is
compacted and homogenizc;d by the rotary mixing tool and granulated to produce
fragrant forms, in I>articulan fragrant beads. This granulation produces
fragrant beads
with a broad grain spectrum (coarse and fine constituents), and for this
reason the
pressure agglomeration variant of the method is preferred to the granulation
variant.
In the pressure agglomeration method the fragrant form premixture is compacted
io under pressure, with the action of shearing forces, and plasticized, at the
same time
homogenized and then formed and ejected from the apparatus. The technically
important pressure agglomeration processes are extrusion, roller compacting
and
pelletization.
In a preferred embodiment: of the invention, the fragrant-form premixture is
fed,
preferably continuously, into a planet roller extruder or a 2-shaft extruder
or 2-worm
extruder or 2-worm press with parallel or reverse travelling worn guide, whose
housing and extender-grarmlator head can be heated to the pre-set extrusion
temperature. Under the shearing effect of the extruder worms, the premixture
is
2o compacted and plasticized under pressure which preferably amounts to at
least 25 bar,
with extremely high throughputs depending on the apparatus used, but which can
also
be lower; the premixture is then extruded in the form of fine strands through
the hole-
type nozzle plate in the extruder head and finally the extrudate is preferably
reduced
to approximately spherical/cylindrical granules by means of a rotary chopping
blade.
The diameter of the: hole in the nozzle plate and the length to which the
strands are cut
are pre-set to the; chosen granulate dimension. This embodiment successfully
produces granulate s of an essentially uniform, pre-determinable particle
size, with the
possibility of adju,;ting the absolute particle sizes to the intended use in
individual
cases. In general particle diameters of up to 0.8 cm maximum are preferred.
Important
3o embodiments here provide for the production of uniforn granulates measured
in
millimetres, for example in the range from 0.5 to 5 mm and in particular the
range
5
CA 02317022 2000-09-07
from approximately 0.8 to 3 millimetres. The length : diameter ratio of the
cut-off
primary granulates" in an important embodiment lies in the range of
approximately
1:1 to approximately 3:1. In addition it is preferable to feed the primary
granulate,
which is still plastic, to a further forming processing step, in which any
edges on the
raw extrudate are rounded off, so that, ultimately, spherical or approximately
spherical extrudate grains c;~n be achieved. If desired, in this step, small
quantities of
dry powder, for example zeolite powder such as zeolite NaA powder can also be
used.
This forming process can bc; carried out in marketable rounding devices. It
should be
borne in mind that in this step only small quantities of fine-grained
constituents are
1o produced. Alternatively ext:rusion/pressing can also be carried out in low-
pressure
extruders, in the Kahl press or in the Bextruder.
Just as in the extrusion process, it is also preferable in the other
production methods
for fragrant forms, to feed the primary granulates/compactates to a further
forming
processing step, in particular a rounding process, so that, ultimately,
spherical or
approximately spherical (bead-shaped) grains can be obtained.
In a further preferred embodiment of the present invention, the procedure for
producing the fragrant forms is carried out by means of roller compacting. In
this
2o embodiment the fragrance-containing solid premixture is dosed directly
between two
rollers which are either smooth, or have recesses of a definite shape, and
rolled out
between the two rollers under pressure in the form of a leaf shaped
compactate,
known as the "she:ll". The rollers exert high linear pressure on the fragrant
form
premixture, and can be further heated and/or cooled as required. If smooth
rollers are
used, smooth, unstzuctured, shell bands are obtained, whereas if structured
rollers are
used, correspondingly structured shells can be produced, in which, for
example,
specific forms of the subsequent fragrant forms can be pre-determined. The
shell band
is subsequently broken into smaller pieces by a chopping and crushing process,
and
can in this way be processed to produce granules, which can be further
finished by
3o further known surface-treatment methods, and in particular brought to an
approximately spherical shape.
6
CA 02317022 2000-09-07
In a further preferrc;d embodiment of the present invention, production of the
fragrant
forms is earned out by means of pelletization. In this embodiment the
fragrance-
containing solid premixture is applied to a perforated surface and, whilst
being
plasticized, is pressed through the holes by a body exerting pressure. With
usual
embodiments of pellet presses, the fragrant form premixture is compacted and
plasticized under pressure, pressed through a perforated surface in the form
of fine
strands by means of a rotary roller, and finally cut up into granules by means
of a
chopping device. F'or this purpose the most widely differing refinements of
pressure
1o rollers and perforated matrices are possible. So, for example, flat
perforated plates are
used as well as concave or convex ring matrices, through which the material is
pressed by means of one or more pressure rollers. In the case of the plate
equipment
the pressure rollers can also be conical in shape, in the case of the ring-
shaped
equipment, matricc;s and pressure rollers) can rotate in the same direction or
the
opposite direction.. A piece of apparatus suitable for carrying out the method
according to the invention, is described, for example, in the German
disclosure
publication DE 38 16 842 (Schliiter Gmb). The ring matrix press disclosed in
this
publication consists of a rotating ring matrix, penetrated by pressure
channels and at
least one pressure roller which is in operative connection with the internal
surface of
2o the matrix, and which presses the material fed into the matrix space
through the
pressure channels iinto a material discharge section. The ring matrix and
press roller
can be driven in the same: direction, so that reduced shearing strain and
hence a
smaller temperature increase of the premixture can be achieved. However in the
pelletization process it is of course possible to work with rollers which can
be heated
or cooled, to regulate the temperature of the premixture as desired.
In the production of the fragrant forms, it is preferable to carry out the
granulation or
pressure agglomeration essentially water-free. The expression "essentially
water-free"
is understood to rr~ean a state in which the content of liquid, i.e. not in
the form of
hydrate water and/'or constitution water is below 2 wt. %, preferably below 1
wt.
and especially evc,n below 0.5 wt. %, in each case relative to the fragrant
form
7
CA 02317022 2000-09-07
premixture. Water can correspondingly be present essentially only in a
chemically
and/or physically combined form or as a component of the raw
materials/compounds
present in solid form at temperatures below 45°C at a pressure of 1
bar, but cannot be
introduced into the fragrant: form premixture as a liquid, solution or
dispersion. By
carrying out the mEahod for producing the fragrant forms essentially water-
free - i.e.
water-free except for the water contents ("impurities") of the solid raw
materials used
- an ecologically valuable process is made available, as, by omitting a
subsequent
drying step, not only is energy saved but also emissions, such as occur in the
majority
of conventional drying methods, can be avoided. In addition, the omission of
l0 subsequent drying steps makes it possible to incorporate delicate or
volatile fragrant
substances into the premixture and thus to produce fragrant forms, in
particular
fragrant beads.
The fragrant forms., which in the method according to the invention are
prepared with
further components to produce a tablet premixture, may vary widely with regard
to
their perfume content. Fragrant forms, in particular fragrant beads are
preferred,
which contain 3 to 40 wt. %., and preferably 5 to 30 wt. % and in particular 8
to 20 wt.
perfume, relative; to the weight of the fragrant forms.
Individual odorous compounds can be used as perfume oils or fragrant
substances in
the process to produce fragrant forms, e.g. the synthetic products of the
ester, ether,
aldehyde, ketone, ;alcohol and carbohydrate types. Odorous compounds of the
ester
type include, for example, benzyl acetate, phenoxyethylisobutyrate, p-tert.-
butylcyclohexylace;tete, linalylacetate, dimethylbenzylcarbinylacetate
(DMBCA),
phenylethylacetate" benzylacetate, ethylmethylphenylglycinate, allylcyclohexyl-
propionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate,
floramate,
melusate and jasmecyclate. The ethers include, for example, benzylethylether
and
ambroxan; the alde;hydes include, for example, the linear alkanals with 8-18 C
atoms,
citral, citronellal, citronellyloxyacetaldeyhyde, cyclamenealdehyde, lilial
and
3o bourgeonal; the ketones include, for example, the jonons, oc-
isomethylionone and
methyl-cedrylketone; the alcohols include anethol, citronellol, eugenol,
geraniol,
8
CA 02317022 2000-09-07
linalool, phenylethylalcohol and terpineol; the hydrocarbons include mainly
the
terpenes, such as limes arid pines. However, it is preferable to use mixtures
of
different odorants, which together produce an attractive special fragrance.
Such perfume oils can also contain natural odorant mixtures, such as those
which can
be obtained from vegetable sources, e.g. pine, citrus, jasmin, patchouli, rose
or ylang-
ylang oil. Also suitable are muscatel-sage oil, camomile oil, oil of cloves,
balm oil,
mint oil, cinnamon-leaf oil, linden blossom oil, juniper berry oil, vetiver
oil, olibanum
oil, galbanum oil and labdanum oil, as well as orange blossom oil, neroli oil,
orange
peel oil and sandalwood oil.
In addition to perfume, the fragrant foams to be used according to the
invention
contain carrier substances. It is preferable to use, relative to the weight of
the fragrant
forms, 65 to 95 wt.'%, preferably 70 to 90 wt.%, earner substances) from the
group of
the surfactants, surfactant compounds, di- and polysaccharides, silicates,
zeolites,
carbonates, sulfates and citrates. These compounds, or classes of compounds
are
further described below, as they may also be components of the tablet
premixture.
Apart from perfume and carrier substance(s), it may also be an advantage for
the
2o fragrant foams to contain further auxiliary substances, which facilitate
their
production or improve their subsequent properties. It is preferable here for
the
fragrant forms, in particular fragrant beads, relative to the weight of the
fragrant
forms, to contain one or more substances from the group of polyethylene
glycols, fat
alcoholalkoxylates and the. fatty acid alkoxylates in quantities of 1 to 10
wt.%,
preferably of 2 to 9~ wt.% and in particular of 5 to 7 wt.%.
The optional fatty acid alkoxylates to be used, can be described by the
general
Formula I:
9
CA 02317022 2000-09-07
R'-C:00-(C>=12-CH-O)k-H (I),
Rz
in which R' is selected from C~_17-alkyl or alkenyl, R2 = -H or -CH3, and k =
2 to 10.
Suitable fat alcoholalkoxylates are sufficient for Formula II:
R3-O-(CHZ-C;H-O)~-H (II),
Ra
in which R3 is selected from Cg_1g-alkyl or alkenyl, R4 = -H or -CH3, and 1 =
2 to 10.
In both cases the corresponding auxiliary materials can be easily produced by
ethoxylation or propoxylation of fatty acids or fat alcohols by a known
method, in
which technical mixtures of the individual species are preferred for economic
reasons.
Further suitable auxiliary substances include polyethylene glycols
(abbreviated to:
PEG), which can be described by the general Formula III:
H-((J-CHZ-CHZ)"-OH (III),
in which the degrf;e of polymerization n can vary from approx. 5 up to
>100,000,
corresponding to molecular masses of 200 to 5,000,000 gmol-'. Of these,
products
with molecular masses below 25,000 gmol-' are described as actual polyethylene
glycols, whilst higher molecular products are often referred to in the
literature as
polyethylene oxide; (abbreviated to PEOX). The preferred polyethylene glycols
can
have a linear or branched structure, with linear polyethylene glycols in
particular
being preferred, and be closed at the end of the group.
The polyethylene ;;lycols, which are especially preferred, include such with
relative
molecular masses between. 2000 and 12000, with molecular masses around 4000
being advantageous, whilst polyethylene glycols with relative molecular masses
below 3500 and above 5000 can be used, especially in combination with
polyethylene
glycols with a relative molecular mass of around 4000, and such combinations,
advantageously announting to more than 50 wt.% relative to the total quantity
of
CA 02317022 2000-09-07
polyethylene glycols, have polyethylene glycols with a relative molucular mass
between 3500 and 5000. However polyethylene glycols can also be used as
binding
agents, which exist in a liquid state at room temperature and a pressure of 1
bar; this
applies especially to polyethylene glycol with a relative molecular mass of
200, 400
and 600.
The fragrant forms, especially fragrant beads, are now prepared, in the method
according to the invention, with further constituents and/or compounds of
detergents,
to produce a tablf;t premixture, which is compacted into tablets using a known
method.
Important constituents which can be incorporated into the tablet premixture,
include
surfactants, suppor.ing substances, bleaching agents, bleach activators and
salts (such
as sulfates, carbonates, citrates etc., especially Na and K salts) as well as
further
common detergent constituents and compounds. These are described in more
detail
below.
In the detergent forms produced by the method according to the invention,
anionic,
non-ionic, cationic, and/or amphoteric surfactants or mixtures of these can be
used.
2o From the technical point o:f view, mixtures of anionic and non-ionic
surfactants are
preferred. The total. surfactant content of the forms produced by the method
according
to the invention is between 5 and 60 wt.% relative to the form weight, with
surfactant
contents of more than 15 wt.% being preferred.
As anionic surfactants, those of the sulfonate and sulfate type may for
example be
used. As surfactants of the: sulfonate type, the preferred possibilities
include C9_13-
alkylbenzolsulfonate, olefin sulfonates, i.e mixtures of alkene and
hydroxyalkansulfonates such as disulfonates, as obtained, for example, from
C12_ls
monoolefins with terminal or internal double bonding by sulfonization with
gaseous
3o sulfur trioxide and subsequently alkaline or acid hydrolysis of the
sulfonization
products. Also suil:able are alkane sulfonates, which are prepared, for
example, from
11
CA 02317022 2000-09-07
Ci2-is-alkanes by rr~eans of sulfochlorination or sulfoxidation followed by
hydrolysis
and/or neutralization. The asters of a-sulfo fatty acids (estersulfonates)
e.g. the a-
sulfonated methylesters of the hydrated cocoa, palm nut, or tallow fatty acids
are also
suitable.
Further suitable anionic surfactants include sulfonated fatty acid glycerine
esters. The
fatty acid glycerine esters shall be taken to include the mono-, di- and
triesters, as well
as mixtures of these, ass obtained in the production by esterification of a
monoglycerine wil:h 1 to 3 mol fatty acid or during the ester interchange of
1o triglycerides with 0.3 to 2 mol glycerine. Preferred sulfonated fatty acid
glycerine
esters are the sulfonation products of saturated fatty acids with 6 to 22
carbon atoms,
for example, caproic acid., caprylic acid, capric acid, myristic acid, lauric
acid,
palmitic acid, steariic acid or behenic acid.
As alk(en)ylsulfate;s, the alkali and especially the sodium salts of the
sulfuric acid
semi-ester of the C12-Cg fat alcohols, for example from coconut oil alcohol,
tallow fat
alcohol, lauryl, my~ristyl, cetyl or stearyl acohol, or the Cto -CZO
oxoalcohols and those
semi-esters of secondary alcohols of these chain lengths are preferred. Also
preferred
are alk(en)ylsulfate;s of the aforementioned chain length, which contain a
synthetic,
straight-chained alkyl residue produced on a petrochemical basis, and whose
disintegration behamiour is similar to that of the adequate compounds based on
fat
chemical raw materials. For reasons of detergent technology, the C12-Ci6 -
alkyl-
sulfates and C12-C'.,5-alkyl-sulfates and C14-Cis -alkyl-sulfates are
preferred. Other
suitable anioic surfactants include 2,3-alkylsulfates, which are produced, for
example,
in accordance with US patent specifications 3,234,258 or 5,075,041 and can be
obtained as a commercial product of the Shell Oil Company under the name DAN~.
The sulfuric acid monoesters of the straight-chained or branched C~_21
alcohols
ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C9_l l-
alcohols
3o with an average 3..'> mol ethylene oxide (EO), or C~2_,8 fat alcohols with
1 to 4 EO, are
12
CA 02317022 2000-09-07
also suitable. Because of their high foaming behaviour, these are only used in
detergents in relatively small quantities, for example in quantities of 1 to 5
wt.%.
Further suitable anionic surfactants also include the salts of alkyl sulfonic
succinic
acid, which are also known as sulfosuccinates or sulfosuccinic acid esters,
and
represent the mono~esters and/or diesters of the sulfonic succinic acid with
alcohols,
preferably fat alcohols and especially ethoxylated fat alcohols. Preferred
sulfosuccinates contain Cg_1g fat acid residues or mixtures of these.
Especially
preferred sulfosuccinates contain a fat alcohol residue derived from
ethoxylated fat
to alcohols, that in themselves represent non-ionic surfactants (see
description below).
Again, sulfosuccinates, whose fat alcohol residues derive from ethoxylated fat
alcohols with concentrated homologen distribution, are especially preferred.
It is also
possible to use alk(en)yl su.ccinic acid with, preferably, 8 to 18 carbon
atoms in the
alk(en)yl chain or its salts.
As further anionic surfactants, soaps are especially suitable. These include
saturated
fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic
acid, stearic
acid, hydrated erucic acid or behenic acid, and especially soap mixtures
derived from
natural fatty acids, e.g. coconut, palm nut or tallow fatty acids.
The anionic surfactants including the soaps can exist in the form of their
sodium,
potassium or ammonium salts, and as soluble salts with organic bases, such as
mono-,
di- or triethanolamine. The anionic surfactants are preferably available in
the form of
the sodium or potassium salts, and especially in the form of the sodium salts.
As non-ionic surfactants it is preferable to use alcoxylated, preferably
ethoxylated,
especially primary alcohols, with preferably 8 to 18 C atoms, and on average 1
to 12
mol ethylene oxide; (EO) per mol alcohol, in which the alcohol residue can be
linear,
or preferably metlhyl-branched in 2 positions, or can contain linear and
methyl-
3o branched residues in the mixture, such as those which are usually present
in
oxoalcohol residues. However alcohol ethoxylates with linear residues from
alcohols
13
CA 02317022 2000-09-07
of native origin with 12 to 18 C atoms, e.g. from coconut, palm, tallow fat or
oleyl
alcohol, and on average 2 to 8 EO per mol alcohol are preferred. The preferred
ethoxylated alcoholls include, for example Clz-i4- alcohols with 3 EO or 4 EO,
C9_n-
alcohols with 7 EO, C13-is-avlcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cclz-ia-
alcohols
with3 EO, 5 EO or 7 EO, and mixtures of these, such as mixtures of Clz-~a-
alcohol
with 3 EO and Clz-.is-alcohol with 5 EO. The ethoxylation grades indicated
represent
average values, which, for a special product, may be a whole number or a
fraction.
Preferred alcohol ethoxylates have a concentrated homologen distribution
(narrow
range ethoxylates, ~NRE). In addition to these non-ionic surfactants, fat
alcohols with
1o more than 12 EO can also be used. Examples of these are tallow fat alcohols
with 14
EO, 25 EO, 30 EO or 40 EC>.
In addition, alkylg:lycosides with the general formula RO(G) can be used as
further
non-ionic surfactants, in vrhich R signifies a primary straight-chained or
methyl-
i 5 branched aliphatic :residue - especially methyl-branched in two positions -
with 8 to
22, preferably 12 to 18 C atoms, and G is the symbol which stands for a
glycose unit
with 5 or 6 C atoms, preferably for glucose. The degree of oligomerization x,
which
indicates the distribution of monoglycosides and oligoglycosides, may be any
number
between 1 and 10, but preferably from 1.2 to 1.4.
A further class of non-ionic; surfactant whose use is preferred, either as a
single non-
ionic surfactant o~r in combination with other non-ionic surfactants,
comprises
alcoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid
esters,
preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid
methyl
esters, such as those described, for example, in the Japanese patent
application JP
58/217598 or preferably those manufactured by the method described in
International
Patent Application WO-A-90/13533.
Non-ionic surfactants of the aminoxide type, for example N-coconut-alkyl-N,N-
3o dimethylaminoxidc; and N-tallow-alkyl-N,N-dihydroxyethylaminoxide, and the
fatty
acid alcanolamides may also be suitable. The quantity of these non-ionic
surfactants
14
CA 02317022 2000-09-07
preferably amounts to no more than that of the ethoxylated fat alcohols,
especially not
more than half of this.
Further suitable surfactants are polyhydroxy fatty acid amides with the
formula (IV),
Rs
R-CO-N-[Z] (IV)
in which RCO star.~ds for an aliphatic acyl residue with 6 to 22 carbon atoms,
Rs for
l0 hydrogen, an alkyl or hydroxyalkyl residue with 1 to 4 carbon atoms and [Z]
for a
linear or branched polyhydroxyalkyl residue with 3 to 10 carbon atoms and 3 to
10
hydroxyl groups. The polyhydroxy fatty acid amides are known substances, which
can usually be obtained by reductive amination of a reducing sugar with
ammonia, an
alkyl amine or an alkanolamine and subsequent acylation with a fatty acid, a
fatty acid
alkyl ester or a fatty acid chloride.
The polyhydroxy fatty acid amide group also contains combinations of the
formula
(V),
2o R6-O-R'
R-CO-N-[Z] (V)
in which R stands for a linear or branched alkyl or alkenyl residue with 7 to
12 carbon
atoms, R6 for a linc;ar, branched or cyclical alkyl residue or an aryl residue
with 2 to 8
carbon atoms and lE~~ for a linear, branched or cyclical alkyl residue or an
aryl residue
or an oxy-alkyl residue with 1 to 8 carbon atoms, where C1_4-alkyl or phenyl
residues
are preferred; and [Z] for a linear polyhydroxyalkyl residue, whose alkyl
chain is
replaced by at least two hydroxyl groups or alkoxylated, preferably
ethoxylated or
3o propoxylated derivatives of this residue.
CA 02317022 2000-09-07
[Z] is preferably obtained by reductive amination of a reduced sugar, for
example
glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-
alkoxy or N-
aryloxy-substituted compounds can then for example be transferred, according
to the
theory of the international application WO-A-95/07331 by conversion with fatty
acid
methyl esters in the presence of an alkoxide as a catalyst, into the desired
polyhydroxy fatty acid amide.
Within the framework of the present invention, it is preferred to introduce
anionic and
non-ionic surfactar.~ts via the method into the detergent forms, which can
result in
technical application advantages from the specific relative proportions, in
which the
individual surfactant classes are used.
Thus for example tlhe especially preferred detergent forms are those in which
the ratio
of anionic surfactants) to non-ionic surfactants) is between 10:1 and 1:10,
preferably between 7.5:1 and 1:5 and especially between 5:1 and 1:2, where the
surfactants can be introduced into the forms in the method according to the
invention
by means of the fragrant forms or by means of the preparation components in
the
tablet premixture.
2o Within the framework of the present invention, methods according to the
invention
are preferred in which the highly dosed fragrant forms are mixed with at least
one
surfactant granulate.
From the technical point of view, it may be advantageous if certain surfactant
classes
are not contained in some phases of the detergent forms or throughout the
form, i.e. in
all the phases. Within the context of the invention, phase shall be understood
to mean
any spatial separation, for example the multiphase nature of multi-phase or
toroidal-
core or encased tablets. Individual phases are also however produced in that
the
fragrant forms, especially fragrant beads, are compacted in the method
according to
3o the invention, so that the fragrant forms make up one phase, whilst the
other phase is
made up of the further particles of the tablet premixture. A further important
16
CA 02317022 2000-09-07
embodiment of the invention therefore provides that at least one phase of the
forms is
free from non-ionic. surfactants. This variant can be especially easily
produced by the
method according to the invention, if non-ionic surfactants are completely
left out of
the fragrant forms or from the other components of the tablet premixture.
Conversely however, it is possible to achieve a positive effect by means of
the
specific surfactants contained in individual phases or in the whole form, i.e.
in all
phases. The introduction of the alkylpolyglycosides described above has proved
advantageous here, so that detergent forms are preferred, in which at least
one phase
of the forms contains alkylpolyglycosides, which in turn can be achieved by
the
introduction of APG into the tablet premixture.
As with the non-ionic surfactants, the omission of anionic surfactants from
individual
or all phases can reault in detergent forms which are better suited to
specific areas of
use. Thus within the framework of the invention, detergent forms are also
possible, in
which at least one phase of the forms is free from anionic surfactants, which
can be
achieved particularly easily, similarly to the aforementioned method according
to the
invention, if anionic surfactants are left out of either the fragrant forms or
the other
components of the tablet premixture.
In the preferred embodiment of the invention, the tablet premixture to be
compacted
contains one or more detc;rgent constituents, in particular from the group of
the
supporting substaJices, bleaching agents, bleach activators, enzymes, dyes and
disintegration agents. These; are described below.
In addition to the active detergent substances, supporting substances are the
most
important constituents of detergents. Via the method according to the
invention, all
supporting substaazces normally used in detergents can be introduced into the
detergent forms, especially zeolites, silicates, carbonates, organic co-
builders and -
3o where there are no ecological prejudices against their use - also
phosphates.
17
CA 02317022 2000-09-07
Suitable crystalline, stratified sodium silicates possess the general formula
NaMSiX02X+i ~H20, where M means sodium or hydrogen, x is a number from 1.9 to
4
and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such
crystalline, stratified silicates are for example described in the European
Patent
Application EP-A- 0 164 514. Preferred crystalline stratified silicates of the
formula
given are those in v~rhich M stands for sodium and x has the values 2 or 3. In
particular
both ~3 ad b-sodium disilicates NazSi205 ~ yHZO are preferred, where ~i-sodium
disilicate, for example, can be obtained by the method described in the
International
Patent Application WO-A-gl/08171.
It is also possible to use amorphous sodium silicates with a module Na20 :
Si02 of
1:2 to 1:3.3, preferably from 1:2 to 1:2.8, and especially from 1:2 to 1:2.6,
whose
dissolving delayed, and which have secondary detergent properties. The delayed
dissolving compared with conventional amorphous sodium silicates can be
produced
in different ways., for example by means of surface treatment, compounding,
compacting/comprc;ssion, o:r by overdrying. Within the framework of this
invention,
the term "amorphous" will also be understood to mean "X-ray amorphous". This
means that, during X-ray experiments, the silicates do not provide any sharp X-
ray
reflexes, such as l:hose typical of crystalline substances, but at best one or
more
2o maxima of the scattered X-radiation, which have a breadth of several
graduations of
the angle of deflection. However it may very well lead to particularly good
builder
properties, if the siilicate particles in electron deflection experiments
provide blurred
or even sharp deflection maxima. This should be interpreted to mean that the
products
have micro-crystalline ranges of the magnitude of 10 to a few hundred mn, with
values up to a maximum of 50 nm and especially up to a maximum of 20 nm being
preferred. Such "X-ray amorphous" silicates, which also have delayed
dissolving
compared with thc; conventional water glasses, are described, for example, in
the
German patent application DE-A-44 00 024. Especially preferred are
compressed/compa~cted amorphous silicates, compounded amorphous silicates and
overdried X-ray amorphous silicates.
18
CA 02317022 2000-09-07
The fine crystalline, synthetic and bonded water-containing zeolite used is
preferably
zeolite A and/or P. Zeolite MAP~ (commercial product of the company Crosfield)
is
especially preferred as zeolite P. Also suitable however are zeolite X and
mixtures of
A, X and/or P. A co-crystallizate of zeolite X and zeolite A (c. 80 wt.%
zeolite X), for
example, is commercially .available as per the invention. This is marketed by
the
company CONDEA Augusta S.p.A. under the trade name VEGOBOND AX~ and
can be described by the formula:
nNa20 ~ (1-n)K20 ' A12O3 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20
to The zeolite can be used both as a supporting substance in a granular
compound, and
also for a type of "powdering" of the whole mixture to be compacted, with both
methods normally being used to incorporate the zeolite into the premixture.
Suitable
zeolites have an average vparticle size of less than 10 ~.m (volume
distribution;
measurement method: Coulter Counter) and preferably contain 18 to 22 wt.%, in
particular 20 to 22 wt.% of bonded water.
It is of course also possible to use the generally known phosphates as builder
substances, if such use should not be avoided for ecological reasons. The
sodium salts
of the orthophosphates, the pyrophosphates, and especially the
tripolyphosphates are
particularly suitable.
2o Useful organic supporting substances include, for example, the polycarbonic
acids, in
the form of their sodium salts, such as citric acid, adipic acid, succinic
acid, glutaric
acid, tartaric acid, saccharic acids, carbamic acids, nitrilotriacetic acid
(NTA),
providing there is no objection to such use on ecological grounds, and
mixtures of
' these. Preferred salts are the salts of the polycarbonic acids such as
citric acid, adipic
acid, succinic acid, glutaric acid, tartaric acid, saccharic acids and
mixtures of these.
To facilitate the disintegration of highly compressed forms, it is possible to
incorporate disintegration agents, known as "tablet explosives", to shorten
the
disintegration times. The terms "tablet explosives" or disintegration
accelerators,
19
CA 02317022 2000-09-07
according to Rompp (9th edition, Volume 6, page 4440) and Voigt "Lehrbuch der
pharmazeutischen Technohgy" [Textbook of Pharmaceutical Technology] (6th
edition, 1987, page 182-184) are understood to mean auxiliary agents which
assist the
rapid integration of tablets in water or gastric juice, and the release of the
pharmaceuticals in resorbable form.
These substances, which are also described as "explosives" because of their
effect,
increase their volume on contact with water. On the one hand the substance's
own
volume is increased (expanding), and on the other hand, the release of gases
produces
pressure which causes the 'tablets to disintegrate into smaller particles.
Well-known
l0 disintegration agents include, for example, carbonate/citric acid systems,
and other
organic acids can also be used. Expanding disintegration agents are, for
example,
synthetic polymers. such as polyvinylpyrrolidon (PVP) or natural polymers
and/or
modified natural substances such as cellulose and starch and their
derivatives,
alginates or casein derivatives.
Preferred detergent forms contain 0.5 to 10 wt.%, preferably 1 to 5 wt.% and
especially 2 to 4 wt.% of a disintegration agent, in each case relative to the
weight of
the form.
As preferred disintegration agents, within the framework of the invention,
disintegration agents based on cellulose are used, so that preferred detergent
forms
2o contain such a cellulose-based disintegration agent in quantities of 0.5 to
10 wt.%,
preferably 1 to 5 wt.% and especially 2 to 4 wt.%. Pure cellulose has the
formal gross
compound (C6H,oO5)" and, formally represents a ~i-1.4-polyacetal of
cellobiose,
which in turn is made up of two glucose molecules. Suitable celluloses consist
of c.
500 to 5000 glucose units, and consequently have average molecular masses of
50,000 to 500,000. Cellulose-based disintegration agents which can be used
within
the framework of the invention also include cellulose derivatives, which can
be
obtained from cellulose by polymeric reactions. Such chemically modified
celluloses
include, for example, products of esterification or etherification processes,
in which
hydroxy-hydrogen atoms are substituted. But celluloses, in which the hydroxy
groups
CA 02317022 2000-09-07
are replaced by functional groups which are not bonded via an oxygen atom, can
also
be used as cellulose derivatives. The group of cellulose derivatives includes,
for
example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters
and
ethers and amino ce;lluloses.
The aforementioned cellulose derivatives are preferably not used alone as
cellulose-
based disintegration agents, but mixed with cellulose. These mixtures
cellulose
derivative content is preferably below 50 wt.% and especially below 20 wt.%,
relative
to the cellulose-based disintegration agent. It is particularly preferable to
use pure
cellulose, which is free frorr~ cellulose derivatives as a disintegration
agent.
to Micro-crystalline cellulose can be used as a further cellulose-based
disintegration
agent or as a part of this component. These micro-crystalline celluloses are
obtained
by partial hydrolysis of celluloses under such conditions that only the
amorphous
areas (ca. 30% o f the total cellulose mass) of the celluloses are attacked
and
completely dissolved, leaving the crystalline areas (c. 70%) undamaged.
Subsequent
disaggregation of the micro-fine celluloses produced by the hydrolysis
provides the
micro-crystalline c;elluloses, with primary particle sizes of c. 5 ~,m which
are
compatible, for example, with granulates with an average particle size of 200
~,m.
Within the framework of the invention, detergent forms are preferred, which
contain
an additional cellulose-based disintegration agent in the forms.
2o In addition to the aforementioned components, surfactant, builders and
disintegration
agents, further usual constituents from the group of bleaching agents, bleach
activators, enzymea, fluorescence agents, dyes, foam inhibitors, silicon oils,
anti-
redeposition agents, optical brighteners, gray inhibitors, dye-transfer
inhibitors and
corrosion inhibitors can be incorporated into the detergent forms via the
method
according to the invention.
Amongst the compound used as bleaching agents, and supplying H202 in water,
sodium perborate tetrahydrate and sodium perborate monohydrate are
particularly
important. Further useful bleaching agents include, for example, sodium
percarbonate,
21
CA 02317022 2000-09-07
peroxypyrophospha.tes, citrate perhydrates and per acid salts providing Hz02,
and per
acids such as perb~enzoate, peroxophthalates, diperazelaine acid, phthaloimino
per
acid or diperdodecandi acid.
To achieve an improved bleaching effect when washing at temperatures of
60°C and
below, bleach activators can. be incorporated as the sole component or as a
constituent
of component b). Compounds which under perhydrolysis conditions produce
aliphatic
peroxocarbonic acids, preferably with 1 to 10 C atoms, in particular 2 to 4 C
atoms
and/or possibly substituted perbenzoic acid, can be used as bleaching
activators.
Suitable substances are those which support the O and/or N-acryl groups of the
to aforementioned C-atom number and/or possibly substituted benzoyl groups.
Repeatedly acylated alkylene diamines are preferred, especially
tetraacetylethylene
diamine (TAED), acylate;d triazin derivatives, in particular 1,5-diacetyl-2,4-
dioxohexahydo-1,3,5-triazin (DADHT), acylated glycoluriles, especially
tetraacetylglycoluril (TAGU),. N-acylimides, especially N-nonanoylsuccinimide
(NOSI), acylated phenol sulfonates, especially n-Nonanoyl or
isononanoylbenzolsulfanate (n- and iso-NOBS respectively), carbonic acid
anhydrides, especially phthalic acid anyhydride, acylated polyvalent alcohols,
especially triacetine, ethylene glycol diacetate and 2,5-diacetoxy-2,5-
dihydrofuran.
In addition to the conventional bleach activators or instead of these, "bleach
catalysts"
can also be incor~~orated unto the forms. These substances are bleach-
reinforcing
transitional metallic salts or transitional metallic complexes such as for
example Mn,
Fe, Co, Ru - or Mo-salene complexes or - carbonyl complexes. Mn, Fe, Co, Ru,
Mo,
Ti, V and Cu complexes with N-containing tripod-ligands such as Co, Fe, Cu and
Ru-
ammine complexes can also be used as bleach catalysts.
Possible enzymes include those from the class of proteases, lipases, amylases,
cellulases, or mixtures of these. Enzymatic substances produced from bacterial
strains
or fungi such as Bacillus subtilis, Bacillus licheniformus and Streptomyces
griseus are
especially suitable. It is preferable to use proteases of the subtilisin type
and
especially proteases produced from Bacillus lentus. For this purpose, enzyme
3o mixtures, for example, of protease and amylase, or protease and lipase, or
protease
22
CA 02317022 2000-09-07
and cellulase, or of cellulase and lipase, or of protease, amylase and lipase,
or
protease, lipase and cellulase, but in particular cellulase-containing
mixtures are of
special interest. Peroxidases or oxidases have also proved suitable in some
cases. The
enzymes can be .adsorbed by carrier substances and/or embedded in encasing
substances, to protc;ct them from premature degradation. The proportion of
enzymes,
enzyme mixtures or enzyme granulates in the forms according to the invention
can for
example be approximately 0.1 to 5 wt.%, preferably 0.1 to approximately 2
wt.%.
In addition the detergent farms can also contain components which have a
positive
effect on the ability to wash oil and grease out of textiles (known as "soil
repellents")
This effect is especially cle~cr, if a textile becomes dirty, haaving already
been washed
several times with a detergent according to the invention containing these oil
and
grease-dissolving components. The oil and grease-dissolving components
include, for
example, non-ionic; cellulose ethers such as methyl cellulose and
methylhydroxy-
propyl cellulose vvith a proportion of methoxyl groups of 15 to 30 wt.% and
hydroxypropoxyl groups of 1 to 15 wt.%, in each case relative to the non-ionic
cellulose ethers, anal the polymers of the phthalic acids and/or terephthalic
acid or of
their derivatives, known from the state of the art, in particular polymers of
ethylenterephthalates and/or polyethylene glycolterephthalates or anionic
and/or non-
ionic modified derivatives of these. Of these, the sulfonated derivatives of
the phthalic
acid and terephthalic acid polymers are especially preferred.
The forms may also contain, as optical brighteners, derivatives of
diaminostilbene
disulfonic acid or its alkali metallic salts. For example, salts of the 4,4'-
bis(2-anilino-
4-morpholino-1,3,.'>-trazinyl-6-amino)stilbene-2,2'-disulfonic acid or
similarly formed
compounds which instead of the morpholino group, carry a diethanolamino group,
a
methyl amino group, an anilino group or a 2-methoxyethylamino group are
suitable.
Moreover, brighteners of the substituted diphenylstyryle type may be present,
e.g. the
alkali salts of the 4,4'-bis( 2-sulfostyryl)-diphenyls, 4,4'-bis(4-chlorine-3-
sulfostyryl)-
diphenyls, or 4-(4-chlorstyryl)-4'-(2-sulfostyryl)diphenyls. Mixtures of the
aforementioned bri.ghteners can also be used.
23
CA 02317022 2000-09-07
To improve the aesthetic impression of the means according to the invention,
they can
be colored with suitable dyes. Preferred dyes, whose selection will present no
difficulty to the expert, possess high storage stability and lack of
sensitivity to the
other constituents of the means and to light, and no marked substantivity
towards
textile fibers, so as not to color these.
For aesthetic reasons it may be desirable to produce forms in which only
individual
phases or layers are colored. With the method according to the invention this
can be
achieved without problems in the most widely differing variations. Thus at
least two
phases are already present i:n the form - due to the incorporation of the
fragrant forms
- of which only one may be coloured, or both may be differently coloured, so
as to
achieve "mottled" forms.
The coloring of the; individual phases can be achieved conventionally by the
addition
of dyes or dye solutions to the fragrant forms/granulates or powders of the
tablet
premixture. However it is preferable to use powder agents which are colored
right
through, and which cover the surface of the particle and thus optically
suggest a grain
which is colored throughout. On the one hand this saves dye, and on the other
hand it
avoids problems with incorporation of too much dye into the forms and
consequently
into the washing mixture.
The production o:f detergent forms is achieved in the method according to the
2o invention in a known way by compression of the tablet premixture containing
the
fragrant forms. Fo:r production, the premixture is compressed in a "matrix"
between
two dies into a solid compressed form. This procedure, which hereinafter is
referred
to as "tableting", is divided into four sections: dosing, compressing (elastic
deformation), plastic deformation and ejection.
The tableting procedure is carried out in commercial tablet presses, which may
in
principle be fitted with single or double dies. In the latter case, it is not
only the upper
die that is used to build up pressure. During the compression process the
lower die
also moves towards the upper die, whilst the upper die presses downwards. For
small
production quantities, eccentric tablet presses are preferably used, in which
the die or
24
CA 02317022 2000-09-07
dies are fixed to an eccentric disc, which in turn is mounted onto an axis
with a
specific rotating speed. The movement of this compressing die is comparable to
the
operation of a conventional four-stroke engine. The compression may take place
with
one upper and one lower die, but there may also be several dies fixed to an
eccentric
disc, so that the number of matrix bores is correspondingly increased. The
throughputs of eccentric presses vary according to type from a few hundred to
a
maximum of 3000 tablets per hour.
For larger throughputs, rotary tablet presses are selected, in which a fairly
large
number of matrices are arranged in a circle around a "matrix table". The
number of
to matrices, depending on the model, varies between 6 and 55, and larger
matrices are
also commercially .available. Each matrix on the matrix table has an upper and
a lower
die, and again the pressure may be actively built up by only the upper or the
lower
die, but also by both dies. The matrix table and the dies move around a shared
vertical
axis, the dies being guided. by rail-type curved tracks into the positions for
filling,
compressing, plastic deformation and ejection. At points where particularly
critical
lifting or lowering of the dies is required (filling, compressing, ejection),
these curved
tracks are supported by additional depression parts, pull-down rails and
lifting tracks.
The filling of the matrices is achieved via a fixed feed mechanism, known as
the
"filling shoe" which is connected to a container for the premixture. The
pressure on
2o the premixture in c;ach cast; is individually adjustable via the
compression paths for
upper and lower die, the pressure build-up being achieved by rolling the die
stamp
heads past adjustable pressure rollers.
Rotary presses can also be provided with two or more filling shoes to increase
the
throughput. To produce forms with two or more layers, several filling shoes
are
arranged one behind the other, without the lightly compacted first layer being
ejected
before further filling. Suitable process management also makes it possible to
produce
encased or spot tablets, which have an onion-peel type structure, so that in
the case of
the spot tablets, the top side of the core or the core layers is not covered
and thus
remains visible. Rotary tablet presses can be equipped with single or multiple
tools, so
3o that, for example, an outer circle with 50 and an inner circle with 30
bores can be used
CA 02317022 2000-09-07
for compacting simultaneously. The throughputs of modern rotary tablet presses
amount to more than a million forms per hour.
Within the framework of the invention, suitable tableting machines are
available, for
example, from the following companies: Apparatebau Holzwarth GbR, Asperg,
Wilhelm Fette GrnbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne,
KOMAGE, Kell a~n See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau
AG, Bern (CH) and Courtoy N.V., Halle (BE/LL~. Especially suitable is for
example
the hydraulic double press F(PF 630 produced by LAEIS, D.
The forms can be produced in a predetermined three-dimensional shape and
to predetermined size" and may comprise several phases, i.e. layers,
enclosures or cores
and rings. Practically any shape that can reasonably be handled is possible,
for
example the construction as tablets, sticks or bar shapes, cubes, cuboids and
corresponding form elements with flat side surfaces and in particular
cylindrical
shapes with a circular or oval cross-section. This last refinement includes
the form of
the tablet as compact cylindrical pieces with a height: diameter ratio of more
than 1.
The portioned pressings can be formed in each case as individual elements
separate
from one another, corresponding to the predetermined dosing quantity of the
detergent. However it is also possible to produce pressings which combine a
number
of such mass units in one pressing, particularly such having predetermined
breaking
points to allow the; portioned smaller units to separate easily. For the use
of textile
detergents in machines of the type usual in Europe with mechanisms arranged
horizontally, the production of the portioned pressings as tablets, in
cylindrical or
cuboid form may be appropriate, with a diameter: height ratio of approximately
0.5
2 to 2 : 0.5 being preferred. Commercial hydraulic presses, eccentric presses
or rotary
presses are suitable; devices particularly for the production of such
pressings.
The shape of another embodiment of the forms is adapted in its dimensions to
the
dispensers of commercial domestic washing machines, so that the forms can be
dosed
without any dosing aid directly into the dispensers, where they dissolve
during the
26
CA 02317022 2000-09-07
dispensing process. Needless to say, it is also possible to use the detergent
forms via a
dosing aid, without any problem.
A further preferred form that can be produced has a plate or tablet-like
structure with
alternating thick long, and thin short segments, so that individual segments
of this
"bar" can be broken off at the assigned breaking points, which represent the
short, thin
segments, and introduced into the machine. This principle of "bar-shaped" form
detergents can also be implemented in other geometrical forms, for example
triangles
standing up vertically, which are only longitudinally connected together at
one of
their sides. For optical reasons, this offers the possibility of constructing
the base of
to the triangle which connects the individual segments with each other, as one
phase,
whilst the tip of the triangle forms the second phase. In this embodiment
different
coloring of the two phases is particularly attractive.
After the compacting process, the detergent forms axe highly stable. The
breaking
strength of cylindrical forms can be determined from the measured variable of
the
diametral breaking strain. This can be determined by
Q = ~cDt
where v stands for the diam.etral breaking strain (diametral fracture stress,
DFS) in Pa,
P is the force in N, which leads to the pressure exerted on the forms, which
causes the
2o fracture in the forms, D is. the form diameter in meters, and t is the
height of the
forms.
The premixture to 'be compacted into the detergent forms can contain the
highly dosed
fragrant forms in varying quantities. Within the framework of the invention it
is
preferred, that the proportion of highly dosed fragrant forms in the
premixture to be
compacted is 1 to 15 wt.%, preferably 2 to 12 wt.% and especially 5 to 10
wt.%, each
relative to the premixture.
27
CA 02317022 2000-09-07
A further object o:P the invention is the use of highly dosed fragrant
compounds,
especially fragrant beads, with apparent densities of more than 700 g/1, which
are
produced by granulation or pressure agglomeration, in detergent forms.
The incorporation of the perfume in this concentrated and, due to its method
of
production, extremely homogenous form, has a positive influence on the
physical
properties of the forms. The tendency of the perfume, under the pressure
exerted
during the compression of the tablets, to migrate throughout the form, is
eliminated
and the perfume oil, with water-repellent effect, is thus concentrated in
small sections
of the tablet. Thus the detergent forms produced by the method according to
the
invention have properties that are just as positive as those of completely
perfume-free
forms.
In comparison with perfume-containing forms, not only are the physical
properties of
the forms, but also the olfactory characteristics of the means and the
textiles treated
with the means distinctly unproved. As noted with the "fragrant beads" in the
earlier
German patent application 197 46 781.4, the detergent forms of the present
invention,
and the textiles treated with the washing liquor prepared from these, also
produce a
noticeably better impression with regard to fragrance.
Examples
According to the theory of t:he earlier German patent application 197 46
780.6,
fragrant beads were produced, by mixing a spray-dried surfactant granulate
(carrier
substance) is mixed with further auxiliary substances and perfume, introducing
it into
a two-shaft extruder manufactured by the company Lihotzky, then plastifying it
and
extruding it under pressure.
Table 1 shows the. composition of the spray-dried surfactant granulate, and
Table 2
the composition of the fragrant bead premixture.
28
CA 02317022 2000-09-07
Table 1: spray-dried surfactant granulate [wt.%]
Na-C9_13-alkylbenzolsulfonate 26.17
Sodium carbonate 4.00
Zeolite 4A 55.63
Salts from solution 0.70
Water 13.00
Sodium hydroxide 0.50
Table 2 : fragrant bead premixture [wt.%]
C12_~g fat alcohol 5.0
Zeolite X 10.0
PEG 4000 4.0
Surfactant granulatf; 68.0
(Table 1)
Perfume oil 10.0
The plasticized premixture left the extruder under a pressure of 85 bar via a
perforated
plate with exit bores of 0.5 or 0.7 or 0.85 or 1.2 mm in diameter.
The extruded strands were cut off with a rotating chopping blade with a length
diameter ratio of c. 1, and rounded off in a Marumerizer~.
Parallel to the fragrant beads a further surfactant granulate was produced by
granulation, which had the composition shown in Table 3:
29
CA 02317022 2000-09-07
Table 3: Surfactant granulate [wt.%]
C9-i 3-alkylbenzolsulfonate 18.6
Ciz-is-fat alcohol sulfate 5.4
Ci2-is-fat alcohol with 7 EO 5.7
Soap 1.6
Sodium carbonate 16.6
Sodium silicate 5.4
Zeolith A (anhydrous active 29.9
substance)
Optical brightener 0.3
Na-ydroxyethane-1,1-diphosphonate0.8
Acrylic acid-malefic acid-copolymer5.4
Water, salts 10.3
The tablet premixtu~res E1, <~s well as V1 and V2 were now produced, by mixing
the
surfactant granulate; described in Table 3 with further detergent
constituents. The
premixture E1 according to the invention also contained the fragrant beads
described
in Table 2, whilst the perfiune in comparative example V 1 was sprayed
directly onto
the premixture in a suitable quantity. For comparison, a perfume-free
premixture V2
was also produced.
The premixtures were compacted to produce detergent tablets in a Korsch tablet
press.
The compacting prc;ssure w:~s adjusted so that in each case three series of
forms were
obtained (E1, E1', E1", and similarly for V1 and V2), differing in hardness.
The
composition of the; premixtures to be compacted (and hence of the forms to be
produced from these) is shown by Table 4.
CA 02317022 2000-09-07
Table 4: Premixture/detergent forms [wt.%]
E1 V1 V2
Surfactant granulate; (Table :3) 56.8 61.3 61.8
Sodium perborate-monohydrate 17.8 17.8 17.8
Tetraacetylethylene diamine 7.3 7.3 7.3
Paraffin-silicon-defoamer 15% on 3.5 3.5 3.5
soda
Enzymes 2.5 2.5 2.5
Terephthalic acid-el:hylene glycol-PEG-esters1.1 1.1 1.1
Fragrant beads (Table 2) 5.0 - -
Perfume oil 0.5 -
Cellulose-based disintegration 5.0 5.0 5.0
agents
Zeolite A (powder) 1.0 1.0 1.0
The hardness of the: tablets was measured by deforming the tablets to
fracture, with
the force being exerted on the side surfaces of the tablet; the maximum force
resisted
by the tablet was deaermined.
To determine the disintegration of the tablet, the tablet was placed in a
beaker of
water (600 ml water, temperature 30°C) and the time taken for the
tablet to
disintegrate completely was measured. Table S shows the experimental data
Table 5: Detergent tablets [physical data]
Tablet E:l E1' El" Vl Vl' Vl" V2 V2' V2"
Tablet 40 531V 63 41 SO 62 41 51 60
N N N N N N N N
hardness
Tablet l Osecl4sc~c21 l4sec 22sec53sec9sec l6sec21
sec sec
disintegration
The data in Table 5 show that the incorporation of the perfume via highly
dosed
fragrant forms brings clear advantages: on the one hand the tablet's
disintegration time
31
CA 02317022 2000-09-07
is not so strongly dependent: on the tablet hardness as in the case of tablets
in which
the perfume is sprayed onto the premixture (Compare E1 to V1), and, on the
other
hand, the forms according to the invention, in spite of the use of perfume,
achieve the
good disintegration times of perfume-free tablets, or even exceed these
(Compare E1
V2).
The olfactory imprf;ssions of the forms produced according to the invention
are also
superior to those oaf conventionally produced tablets. For this purpose the
forms E1
and V 1 were compa~xed.
The composition oiF the perfume oil contained in the forms or the fragrant
beads is
shown by Table 6. The scenting of the products and of the textiles treated
(cotton) was
assessed as a subjective olfactory impression by perfumers, with the numerical
values
in the assessment table (Table 7) indicating the number of perfumers who
classified
the products in question and,~or the textiles to be treated with the means in
question, as
"more strongly fra~~ant". Thus, of the 7 perfumers, 6 assessed the detergent
forms
according to the invention as better. The results of the smelling tests are
summarized
in Table 7.
32
CA 02317022 2000-09-07
Table 6: Composition of the. perfume oil [wt.%]
Phenylethyl alcohol 52.0
Dimethylbenzylcarbinylacetate2.5
Iraldeine range 5.0
Phenyl acetic acid 0.5
Geranylacetate 2.0
Benzylacetate 30.
Rose oxide L 10% in DPG 2.5
Romilate 20.
Irotyl 0.5
Cyclohexylsalicylal:e 20.0
Floramate 10.0
Table 7: Frasrance enhancement (intensity preference)
Perfumers
(intensity
preference)
Product Damp washingDry washing
E1 (5% perfume oil in 1 2 2
fragrant
beads)
Vl (0.5% perfume; oil, 6 5 5
spxayed
on)
33
