Note: Descriptions are shown in the official language in which they were submitted.
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1
PROCESS FOR THE PRODUCTION OF PERFUME BEADS
Field of the Invention
This invention relates to the production of perfume shaped bodies,
more particularly perfume beads, which may be incorporated in detergents
and laundry treatment and aftertreatment compositions and which provide
the treated laundry with a perfume-enhancing effect. The present invention
also relates to detergents containing the shaped bodies produced in
accordance with the invention and to the use of the shaped bodies
produced in accordance with the invention for improving the adsorption of
perfumes onto surfaces.
Background of the Invention
In the washing, treatment and aftertreatment of laundry, it is now
common practice to add small quantities of perfume to the detergents and
aftertreatment compositions in order to provide the wash liquor itself and
also the laundry treated with the wash liquor with a pleasant fragrance. In
addition, besides color and appearance, the perfuming of detergents and
aftertreatment compositions is an important aspect of the aesthetic product
impression and an important factor in the consumer deciding for or against
a certain product. For perfuming, the perfume may either be directly
incorporated in the detergent/composition or may be added to the wash
liquor in an additional step. The first method determines a certain product
characteristic whereas, in the second method, the consumer is able
individually to chose his/her perfume from the various perfume variants on
offer - comparable with the choice of an eau-de-toilette or an aftershave
lotion.
Accordingly, perfume shaped bodies and processes for perfuming
wash liquors are widely described in the prior art. Thus, DE 41 33 862
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(Henkel) discloses tablets containing carrier materials, perfumes and
optionally other typical detergent ingredients, sorbitol and in addition 20 to
70% by weight of an effervescent system of carbonate and acid being used
as the carrier material. These tablets, which may be added for example in
the after-rinse cycle or fabric softening cycle of a domestic washing
machine, contain about 3 to 15% by weight and preferably 5 to 10% by
weight of perfume. In view of their high disintegrator content, the tablets in
question are sensitive to atmospheric moisture and have to be stored in a
suitably protected form.
DE 39 11 363 (Baron Freytag von Loringhoven) describes a process
for the production of a perfume-enriched wash liquor and a perfume
addition medium suitable for this purpose. The addition medium present in
the form of capsules or tablets contains the perfume together with an
emulsifier in liquid form (capsules) or fixed to fillers and carriers
(tablets),
sodium aluminium silicates and cyclodextrins being mentioned as carriers.
The perfume content of the capsules or tablets is at least 1 g for a capsule
or tablet volume of more than 1 cm3. Tablets or capsules containing more
than 2.5 g of perfume for a volume of at least 5 cm3 are preferred. For
storage, tablets or capsules of the type in question have to be provided
with a gas- and water-tight covering layer to protect the ingredients. The
document in question does not provide any further particulars of the
production of physical properties of suitable tablets.
International patent application WO 94125563 (Henkel-Ecolab)
describes a process for the production of detersive shaped bodies using
the microwave technique which does not involve any high-pressure
tabletting. The tablets produced by this process are distinguished by an
extremely high dissolving rate or disintegration rate coupled with fracture
resistance without any need for a disintegrator. At the same time, they are
stable in storage and can be stored without any additional precautions.
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Tablets with a perfume oil content of 1 to 3% by weight typical of
detergents can also be produced by this process. In general, perfume oils
are readily volatile and, accordingly, could even evaporate on exposure to
microwave radiation. If, therefore, relatively high levels of readily volatile
liquid substances are to be used, a two-component system consisting of a
component produced by the microwave technique and a component
containing the sensitive liquid substances is described.
Particulate additives for perfuming wash liquors and for use in
detergents and processes for their production are described in International
patent applications WO 97!29176 and WO 97!29177 (Procter & Gamble).
According to the teaching of these documents, perfume is added to porous
carrier materials (for example sucrose in admixture with zeolite X) and,
finally, a coating material (carbohydrates) is applied and the required
particle size distribution is established.
Earlier German patent application 197 35 783.0 (Henkel) describes
highly concentrated perfume shaped bodies containing carrier material(s),
to 50% by weight of perfumes) and optionally other auxiliaries and
additives typical of detergents, at least 50% by weight of the shaped bodies
- after subtracting the quantity of perfume - consisting of fatty acids and
20 fatty acid salts. These perfume shaped bodies are suitable both for
perfuming detergents and for perfuming laundry in a washing machine.
A process for applying perfumes to laundry in a washing machine is
described in DE 195 30 999 (Henkel). In this process, a perfume-
containing shaped body produced by exposure to microwave radiation is
used in the final rinse cycle of a washing machine. According to the
teaching of this document, the preferably spherical shaped bodies with
diameters above 3 mm and bulk densities of up to 1100 g/I are produced
by introducing a mixture of predominantly water-soluble carrier materials,
hydrated substances, optionally surfactants and perfume into suitable
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molds and sintering the mixture by exposure to microwave radiation. The
perfume contents of the shaped bodies are between 8 and 40% by weight
and the carrier materials used include starches, silicas, silicates and
disilicates, phosphates, zeolites, alkali metal salts of polycarboxylic acids,
oxidation products of polyglucosans and polyaspartic acids. A crucial pre-
condition of the process described in this document for producing shaped
bodies is that at least partly bound water should be present in the mixture
sintered by microwaving to form shaped bodies, i.e. the starting materials
should be at least partly present in hydrated form.
The solutions proposed in the cited prior art require either additional
barrier layers or coating layers to fix the perfume to the carrier or are not
equally suitable for perfuming detergents and for direct use solely as a
perfume, for example in the final rinse cycle of a washing machine. Patent
application WO 99121953 describes a process for the production of
perfume shaped bodies, more particularly perfume beads, which contain up
to 15% by weight of perfume, but which nevertheless do not have to be
provided with a gas-tight and water-tight coating layer or pack for storage in
order to protect the ingredients or to prevent losses of perfume in storage.
The process in question is a process for the production of perfume shaped
bodies, more particularly perfume beads, with bulk densities above 700 g/I,
characterized in that a solid and substantially water-free premix of
a) 65 to 95% by weight of carrier(s),
b) 0 to 10% by weight of auxiliary(ies) and
c) 5 to 25% by weight of perfume
is subjected to granulation or press agglomeration. The perfume beads
thus produced may be incorporated as a compound in standard detergents
and also directly used for individually choosing perfume in domestic
washing processes and create a perfume-enhancing impression on the
treated laundry.
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A distinct improvement in the perfume impression of detergents and
the surface treated with them can be achieved with these perfume beads.
However, the yield of perfume applied to the treated surface, more
particularly textile fibers, in relation to the amount of perfume used is
still
5 very low. Accordingly, there is still a need for improved processes for
producing perfume beads which would improve the adsorption of the
perfumes onto surfaces and hence would guarantee a higher yield of
perfume.
Summary of the Invention
It has now been found that this need is satisfied by a production
process in which the premix contains 0.5 to 20% by weight of a substance
that improves the adsorption of the perfume onto surfaces
In a first embodiment, therefore, the present invention relates to a
process for the production of perfume shaped bodies, more particularly
perfume beads, with bulk densities above 700 g/I, in which a solid and
substantially water-free premix of a) 65 to 95% by weight of carrier(s), b) 0
to 10% by weight of auxiliary(ies) and c) 5 to 25% by weight of perfume is
subjected to granulation or press agglomeration, characterized in that the
premix contains 0.5 to 20% by weight of a substance which improves
adsorption of the perfume onto surfaces.
In the context of the present invention, the expression "substantially
water-free" is understood to apply to a state in which the content of liquid
water, i.e. water which is not present as water of hydration and/or water of
constitution, is below 2% by weight, preferably below 1 % by weight and,
more preferably, even below 0.5% by weight, based on the premix.
Accordingly, water can only be introduced into the process for producing
the premix in chemically andlor physically bound form or as a constituent of
the raw materials or compounds present as solids, but not as a liquid,
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solution or dispersion. The premix advantageously has a total water
content of not more than 15% by weight, i.e. the water is present in
chemically and/or physically bound form and not in liquid, free form. In a
particularly preferred embodiment, the content of water not bound to zeolite
and/or to silicates in the solid premix is no more than 10% by weight and
preferably no more than ?% by weight.
The function of the carrier materials is to absorb the generally liquid
components of the perfume without the particles sticking to one another. A
homogeneously plasticized mixture in which the perfume is incorporated in
the carrier in fine distribution is only obtained by the action of the mixing
tools during the granulation step or the relatively strong shear forces in the
press agglomeration step and optionally through the addition of an auxiliary
or auxiliaries. This procedure has clear advantages over the conventional
application of perfume to porous carrier materials, as will be explained in
more detail hereinafter.
Detailed Description of the Invention
Preferred carrier materials are selected from the group of
surfactants, surfactant compounds, di- and polysaccharides, silicates,
zeolites, carbonates, sulfates and citrates and are used in quantities of 65
to 94.5% by weight and preferably in quantities of 70 to 90% by weight,
based on the weight of the shaped body formed.
Any surfactants or surfactant compounds solid at temperatures of up
to 40°C may be used as surface-active carrier materials. In the context
of
the present invention, a "surfactant compound" is understood to be a
surfactant-containing preparation which, besides typical carrier materials
and auxiliaries, contains at least 20% by weight of an anionic, cationic or
nonionic surfactant, based on the surfactant compound. The carrier
materials typically used in surfactant compounds may advantageously be
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identical with the above-mentioned carrier materials used in the process
according to the invention, although other carrier materials than those
mentioned above may also be present as carriers in the surfactant
compounds.
In preferred processes, one or more anionic surfactant compounds
or anionic surfactants, more particularly soaps, is/are used as carrier
materials in quantities of 65 to 94.5% by weight and preferably 70 to 90%
by weight, based on the weight of the tablet formed. Examples of anionic
surfactant compounds are alkyl benzenesulfonate (ABS) compounds on
silicate or zeolite carriers with ABS contents of, for example, 10, 15, 20 or
30% by weight, fatty alcohol sulfate (FAS) compounds on silicate, zeolite or
sodium sulfate carriers with active substance contents of, for example, 50
to 70, 80 or 90% by weight and anionic-surfactant-containing compounds
based on sodium carbonate/sodium silicate with anionic surfactant contents
above 40% by weight. Pure anionic surfactants may also be used as
carriers in accordance with the present invention providing they are solid
and non-hygroscopic. Soaps are particularly preferred as pure anionic
surfactant carriers because, on the one hand, they remain solid up to high
temperatures and, on the other hand, do not present any problems through
the unwanted absorption of water. Any salts of fatty acids are used as
soaps in the carrier materials for the shaped bodies according to the
invention. Whereas, in principle, aluminium, alkaline earth metal and alkali
metal salts of the fatty acids, for example, may be used, preferred shaped
bodies are those in which the alkali metal salts and preferably the sodium
salts of the fatty acids are present. Suitable fatty acids, of which the salts
may be used as carrier material, are any acids obtained from vegetable or
animal oils and fats. The fatty acids may be saturated or mono- to poly-
unsaturated. It is of course possible to use not only "pure" fatty acids, but
also the technical fatty acid mixtures obtained in the hydrolysis of fats and
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oils, for example palm kernel oil, coconut oil, peanut oil or rapeseed oil or
bovine tallow, these mixtures being distinctly preferred from the economic
point of view.
Thus, individual species or mixtures of salts of the following acids,
for example, may be used in the carrier materials for the highly
concentrated perfume shaped bodies according to the invention: caprylic
acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid,
stearic acid, octadecan-12-oleic acid, arachic acid, behenic acid, lignoceric
acid, cerotic acid, melissic acid, 10-undecenoic acid, petroselic acid,
petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic
acid, a-
and (i-elaeostearic acid, gadoleic acid, erucic acid, brassidic acid. The
salts
of the fatty acids with an odd number of carbon atoms, for example the
salts of undecanoic acid, tridecanoic acid, pentadecanoic acid,
heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic
acid, pentacosanoic acid, heptacosanoic acid, may of course also be used.
In particularly preferred processes, one or more substances from the
group of sodium salts of saturated or unsaturated C&24 fatty acids,
preferably saturated or unsaturated C~2-~8 fatty acids and, more preferably,
saturated or unsaturated C~6 fatty acids is/are used as carrier materials) in
quantities of 75 to 94.5% by weight and preferably in quantities of 80 to
90% by weight, based on the weight of the shaped body formed.
Other suitable carrier materials are, for example, di- and
polysaccharides, a broad range of substances from sucrose and maltose
through oligosaccharides to the "traditional" polysaccharides, such as
cellulose and starch and derivatives thereof, being suitable. Among the
substances belonging to these sub-groups, the starches are particularly
preferred.
The carriers typically used in detergents, such as silicates and
zeolites, are also suitable as carriers for the purposes of the invention. The
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finely crystalline, synthetic zeolite containing bound water used is
preferably zeolite A and/or zeolite P. Zeolite MAP, for example Doucil
A24O (a Crosfield product), for example, is used as zeolite P. However,
zeolite X and mixtures of A, X and/or P are also suitable, for example the
co-crystallizate of zeolites A and X marketed as Vegobond~AX (by Condea
Augusta S.p.A.). The zeolite may be used in the form of a spray-dried
powder or even in the form of an undried stabilized suspension still moist
from its production. Where the zeolite is used in the form of a suspension,
the suspension may contain small additions of nonionic surfactants as
stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated
C~2_~8 fatty alcohols containing 2 to 5 ethylene oxide groups, C~2_~4 fatty
alcohols containing 4 to 5 ethylene oxide groups or ethoxylated
isotridecanols. Suitable zeolites have a mean particle size of less than 10
p,m (volume distribution, as measured by the Coulter Counter Method) and
contain preferably 18 to 22% by weight and more preferably 20 to 22% by
weight of bound water. In preferred embodiments, zeolites are present in
the premix in quantities of 10 to 94.5% by weight and, in particularly
preferred embodiments, in quantities of 20 to 70% by weight and more
particularly 30 to 60% by weight.
Other suitable carriers are layer-form sodium silicates corresponding
to the general formula NaMSiXO~+~~YH2O, where M is sodium or hydrogen,
x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
being 2, 3 or 4. Crystalline layer silicates such as these are described, for
example, in European patent application EP-A-0 164 514. Preferred
crystalline layer silicates corresponding to the above formula are those in
which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium
disilicates Na2Si205~yH20 are particularly preferred.
Other preferred builders are amorphous sodium silicates with a
modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more
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preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash
cycle properties. The delay in dissolution in relation to conventional
amorphous sodium silicates can have been obtained in various ways, for
example by surface treatment, compounding, compacting or by overdrying.
5 In the context of the invention, the term "amorphous" is also understood to
encompass "X-ray amorphous". In other words, the silicates do not
produce any of the sharp X-ray reflexes typical of crystalline substances in
X-ray diffraction experiments, but at best one or more maxima of the
scattered X-radiation which have a width of several degrees of the
10 diffraction angle. Particularly good builder properties may even be
achieved where the silicate particles produce crooked or even sharp
diffraction maxima in electron diffraction experiments. This may be
interpreted to mean that the products have microcrystalline regions
between 10 and a few hundred nm in size, values of up to at most 50 nm
and, more particularly, up to at most 20 nm being preferred. So-called X
ray amorphous silicates such as these, which also dissolve with delay in
relation to conventional waterglasses, are described for example in
German patent application DE-A-44 00 024. Compacted amorphous sili
cates, compounded amorphous silicates and overdried X-ray-amorphous
silicates are particularly preferred.
Other suitable carrier materials are layer silicates of natural and
synthetic origin. Such layer silicates are known, for example, from patent
application DE-B-23 34 899, EP-A- 0 026 529 and DE-A-35 26 405. Their
suitability is not confined to a particular composition or structural formula.
However, smectites, especially bentonites, are preferred.
Suitable layer silicates which belong to the group of water-swellable
smectites are, for example, montmorillonite, hectorite or saponite. In
addition, small quantities of iron may be incorporated in the crystal lattice
of
the layer silicates in accordance with the above formulae. By virtue of their
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ion-exchanging properties, the layer silicates may additionally contain
hydrogen, alkali metal, alkaline earth metal ions, more particularly Na+ and
Ca++. The water of hydration content is generally between 8 and 20% by
weight, depending on the degree of swelling and the processing technique.
Useful layer silicates are known, for example, from US-A-3,966,629, EP-A-
0 026 529 and EP-A-0 028 432. Layer silicates substantially freed from
calcium ions and strongly coloring iron ions by an alkali treatment are
preferably used.
Useful organic carriers are, for example, polycarboxylic acids usable
in the form of their sodium salts, such as citric acid, adipic acid, succinic
acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids,
nitrilotriacetic acid (NTA), providing their use is not ecologically unsafe,
and
mixtures thereof. Preferred salts are the salts of the polycarboxylic acids,
such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid,
sugar acids and mixtures thereof.
The acids per se may also be used. Besides their efectiveness as a
carrier, the acids also typically have the property of an acidifying
component and, hence, also serve to establish a relatively low and mild pH
value in detergents. Citric acid, succinic acid, glutaric acid, adipic acid,
gluconic acid and mixtures thereof are particularly mentioned in this regard.
If they are used in the premix according to the invention and are not
subsequently added, these acids are preferably used in water-free form.
The premix may optionally contain auxiliaries which improve the
cohesion of the carrier particles mixed with the perfume and which, under
the granulation or press agglomeration conditions, envelop the solid
particles and bond them to one another in such a way that the final end
products are made up almost exactly of these numerous small individual
particles that are held together by the auxiliary which acts as a preferably
thin dividing wall between the individual particles.
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These auxiliaries on the one hand facilitate the plasticization of the
premix under the granulation or press agglomeration conditions and, on the
other hand, develop disintegration-promoting properties during the
dissolution of the perfume shaped bodies without the shaped bodies
sticking to one another in transit or in storage.
Suitable auxiliaries are those from the group of polyethylene glycols,
fatty alcohol ethoxylates and fatty acid alkoxylates which, in preferred
processes, are used in quantities of 0 to 10% by weight, preferably in
quantities of 2 to 9% by weight and more preferably in quantities of 5 to 7%
by weight, based on the weight of the press granules.
The fatty acid alkoxylates optionally used may be described by
general formula (I):
R'-COO-( i H2-CH-O)k-H (I)
R2
in which R' is selected from C~_~~ alkyl or alkenyl, R2 = -H or -CH3 and k = 2
to 10. Suitable fatty alcohol alkoxylates correspond to formula (II):
R3-O-(CH2- i H-O),-H (I I )
R4
in which R3 is selected from C&~8 alkyl or alkenyl, R4 = -H or -CH3 and I = 2
to 10. In both cases, the corresponding auxiliaries may readily be
produced in known manner by ethoxylation or propoxylation of fatty acids
or fatty alcohols, technical mixtures of the individual species being
preferred for economic reasons.
Other suitable auxiliaries are polyethylene glycols (PEGs) which
may be described by general formula (III):
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H-(O-CH2-CH2)"-OH (III)
in which the degree of polymerization n can vary from about 5 to >100,000,
corresponding to molecular weights of 200 to 5,000,000 g/mole-'. The
products with molecular weights below 25,000 g/mole-' are actual
polyethylene glycols whereas relatively high molecular weight products are
often referred to in the literature as polyethylene oxides (PEOXs). The
polyethylene glycols preferably used may have a linear or branched
structure, linear polyethylene glycols being particularly preferred.
Particularly preferred polyethylene glycols include those with relative
molecular weights of 2,000 to 12,000 and advantageously around 4,000,
polyethylene glycols with relative molecular weights below 3,500 and above
5,000 being usable in particular in combination with polyethylene glycols
having a relative molecular weight of around 4,000 and more than 50% by
weight of these combinations, based on the total quantity of polyethylene
glycols, advantageously containing polyethylene glycols having a relative
molecular weight of 3,500 to 5,000. However, other suitable binders are
polyethylene glycols which, basically, are present as liquids at room
temperature/1 bar pressure, above all polyethylene glycol with a relative
molecular weight of 200, 400 and 600.
According to the invention, a preferred process is characterized in
that one or more substances from the group of polyethylene glycols with
molecular weights of 2 to 15 kgmole ~ and preferably in the range from 4 to
10 kgmole' is/are used as auxiliaries in quantities of 0 to 10% by weight,
preferably 2 to 9% by weight and more preferably 5 to 7% by weight, based
on the weight of the shaped body formed.
The perfume oils or perfumes used in the process according to the
may be individual perfume compounds, for example synthetic products of
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the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
Examples of perfume compounds of the ester type are benzyl acetate,
phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate,
dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl
acetate, ethyl methyl phenyl glycinate, ally) cyclohexyl propionate, styrallyl
propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and
jasmecyclate. The ethers include, for example, benzyl ethyl ether and
Ambroxan; the aldehydes include, for example, linear alkanals containing 8
to 18 carbon atoms, citral, citronellal, citronellyloxy acetaldehyde, cyclamen
aldehyde, lilial and bourgeonal; the ketones include, for example, ionones,
a-isomethyl ionone and methyl cedryl ketone; the alcohols include anethol,
citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol
while the hydrocarbons include, above all, terpenes, such as limonene and
pinene. However, mixtures of different perfumes which together produce
an attractive perfume note are preferably used.
Perfume oils such as these may also contain natural perfume
mixtures obtainable from vegetable sources, for example pine, citrus,
jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary oil
camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime
blossom
oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum
oil
and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
The substances which improve adsorption of the perfume onto the
surface are preferably one or more substances from the group of paraffins,
quaternary ammonium compounds, soil-release polymers, more particularly
copolymeric polyesters and other polymers, such as in particular polyvinyl
pyrrolidone and block copolymers containing (-CH2CH20)n- blocks where n
> 2.
Paraffin in the context of the present invention is understood to be a
solid or liquid mixture of purified saturated aliphatic hydrocarbons which is
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colorless, odorless and tasteless, dissolves easily in ether and chloroform,
but not in water or 90% alcohol and does not fluoresce (i.e. does not
contain any aromatic compounds). Various paraffins may be used. Thickly
liquid paraffin (Paraffinum liquidum) is an oily liquid (D = 0.827-0.890,
5 viscosity: 110-230 mPas) while thinly liquid paraffin (Paraffinum
perliquidum) is an oily liquid with a density of 0.810 to 0.875 and a
viscosity
of 25 to 80 mPas. There is also hard paraffin (Paraffinum solidum) which is
a solid crystalline mass with a solidification temperature of 50 to
62°C.
Industrially, the liquid paraffins are often classed as mineral oils and are
10 collectively referred to as paraffin oil or as white oil. Semisolid
paraffins
with melting points of 45 to 65°C are known by such names as soft
paraffin
while semisolid paraffins with a density of 0.820 to 0.880, a melting point of
38 to 60°C and a boiling point of >300°C are known by such names
as
petrolatum; a well-known trademark for paraffins of this type is Vaseline.
15 Paraffin is water-repellent, can be melted together with fats, wax and
spermaceti to form uniform melts, is non-toxic, sluggish in reaction, fairly
resistant to sulfuric acid, bromine and cold nitric acid and, in contrast to
fats
and fatty oils, does not become rancid (i.e. it is non-saponifiable). To
distinguish it from those fats and fatty oils, paraffin is sometimes also
referred to incorrectly as "mineral fat". Paraffin is normally produced from
petroleum distillation residues, from bituminous shales, peats and the
products of the low temperature carbonization of lignite and, synthetically,
by medium-pressure synthesis from CO and H2 in the presence of catalysts
by a modified Fischer-Tropsch synthesis. Hard paraffin is separated by
cooling from the paste - also known as slack wax - accumulating in that
synthesis and in petroleum distillation, de-oiled and bleached; liquid
paraffin is obtained by distillation. From the perspective of production and
intended application, some paraffin fractions are also marketed as
microwax, ceresin, petrolatum and waxes. According to the invention, all
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16
the various forms of paraffin listed above may be used, although it can be
of advantage from the processing perspective to use certain paraffins.
Thus, the liquid parafFns and preferably the thickly liquid paraffins can have
advantages in terms of processing. However, if the perfume beads are
produced using high pressures or temperatures, it may even be preferred
to use hard paraffin which is liquid under the processing conditions, but
solid during the storage of the perfume beads.
Suitable quaternary ammonium compounds for the process
according to the invention are any of the usual surface-active quaternary
ammonium compounds, cationic surfactants with a fabric-softening effect
being particularly preferred.
Preferred quaternary ammonium compounds are those which
correspond to one of formulae I, II and III:
R'
R~_N(+>_(CH2)n_T_R2 (I)
(CH2)n-T-R2
R'
R'-N(+~-(CH2)n-CH-CH2 (II)
R' T T
R2 Rz
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17
R'
R3-N~+~-(CHZ)~-T-R2 (II I)
R4
in which each of the groups R' independently of one another is selected
from C~_6 alkyl, C~~ alkenyl or C~_s hydroxyalkyl groups; each of the groups
R2 independently of one another is selected from C&28 alkyl or C~.28 alkenyl
groups; R3 = R' or (CH2)~-T-R2; R4 = R' or R2 or (CH2)~-T-R2; T = -CH2-,
-O-CO- or -CO-O- and n is an integer of 0 to 5.
Soil-release polymers in the context of the present invention are
polymers which are capable of releasing soil. Polymers such as these are
also referred to in the literature as soil-repellent polymers. They are
normally polyesters which contain dicarboxylic acid units and alkylene
glycol units and/or polyalkylene glycol units.
For example, DE-0S 16 17 141 describes a washing process using
polyethylene terephthalate/polyoxyethylene glycol copolymers. DE-OS 22
00 911 relates to detergents containing nonionic surfactant and a
copolymer of polyoxyethylene glycol and polyethylene terephthalate. DE-
OS 22 53 063 mentions acidic textile finishes which contain a copolymer of
a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and
optionally an alkylene or cycloalkylene glycol. Polymers of ethylene
terephthalate and polyethylene oxide terephthalate, in which the
polyethylene glycol units have molecular weights of 750 to 5,000 and the
molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is
from 50:50 to 90:10, and their use in detergents is described in DE-PS 28
57 292. According to DE-OS 33 24 258, polymers of ethylene
terephthalate and polyethylene oxide terephthalate with molecular weights
CA 02317168 2000-08-31
18
of 15,000 to 50,000, the polyethylene glycol units having molecular weights
of 1,000 to 10,000 and the molar ratio of ethylene terephthalate to poly-
ethylene oxide terephthalate being from 2:1 to 6:1, may be used in deter-
gents. European patent EP 066 944 relates to textile treatment
compositions which contain a copolyester of ethylene glycol, polyethylene
glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid
in certain molar ratios. European patent EP 0 185 427 describes methyl- or
ethyl-terminated polyesters containing ethylene and/or propylene
terephthalate units and polyethylene oxide terephthalate units and
detergents which contain such a soil-release polymer. European patent EP
0 241 984 relates to a polyester which, besides oxyethylene groups and
terephthalic acid units, also contains substituted ethylene units and glycerol
units. European patent EP 0 241 985 describes polyesters which, besides
oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-
butylene and/or 3-methoxy-1,2-propylene groups and glycerol units and
which are terminated by C» alkyl groups. European patent EP 0 253 567
relates to soil-release polymers of ethylene terephthalate and polyethylene
oxide terephthalate with a molecular weight of 900 to 9,000, the poly-
ethylene glycol units having molecular weights of 300 to 3,000 and the
molar ratio of ethylene terephthalate to polyethylene oxide terephthalate
being from 0.6 to 0.95:1. European patent application EP 0 272 033
describes at least partly C~~ alkyl- or acyl-terminated polyesters containing
polypropylene terephthalate and polyoxyethylene terephthalate units.
European patent EP 0 274 907 describes sulfoethyl-terminated tere-
phthalate-containing soil-release polyesters. According to European patent
application EP 0 357 280, soil-release polyesters containing terephthalate,
alkylene glycol and poly-C2.~-glycol units are produced by sulfonation of
unsaturated terminal groups. International patent application WO 95132232
relates to soil-release polyesters corresponding to the following general
CA 02317168 2000-08-31
19
formula:
X-(O-(CHR-)a)b[O-OC-Ph-CO-(O-(CHR-)o)p]y0-Y (I)
in which
a is a number of 2 to 8,
b is a number of 1 to 300,
o is a number of 2 to 8,
p is a number of 1 to 300 and
y is a number of 1 to 500,
Ph is an o-, m- or p-phenylene group which can carry to 1 to 4
substituents selected from alkyl groups containing 1 to 22 carbon
atoms, sulfonic acid groups, carboxyl groups and mixtures thereof,
R is selected from hydrogen, a C~.22 alkyl group and mixtures thereof
and
X and
Y independently of one another are selected from hydrogen, alkyl and
aryl monocarboxylic acid units containing 5 to 32 carbon atoms, hydroxy-
monocarboxylic acid units containing 2 to 22 carbon atoms and having a
degree of oligomerization of 1 to 100 and dicarboxylic acid semiester units
of which the second carboxylic acid group is esterified with an alcohol A-
(OCHZCHZ)d-OH, where A is an alkyl or alkenyl group containing 8 to 22
carbon atoms, Z is hydrogen or an alkyl group containing 1 to 2 carbon
atoms and d is a number of 1 to 40, with the proviso that X and Y cannot
both be hydrogen where R is hydrogen or an alkyl group containing 1
carbon atom, a and/or o = 2 and b and/or p = 1. International patent
application WO 97131085 describes soil repellents for cotton fabrics which
have to contain several functional units: a first unit, which may be cationic
for example, is capable of adsorption onto the cotton surface by
CA 02317168 2000-08-31
electrostatic interaction, and a second unit which is hydrophobic is
responsible for the active substance remaining at the water/cotton
interface. Although the active substances disclosed in the document in
question are not exclusively polymers in the context of the chemical
5 definition of a polymer, they are intended to be included among the soil-
release polymers in the context of the present application by virtue of their
corresponding function.
However, not only these preferred polyesters, but also any polymers
capable of releasing soil are soil-release polymers in the context of the
10 present invention.
Chemically, polyvinyl pyrrolidone is [poly(1-vinyl-2-pyrrolidinone, a
polymer corresponding to the following general formula:
15 '.~'~- ~ "-
N
n
20 Polyvinyl pyrrolidones are produced by radical bulk, solution or suspension
polymerization of 1-vinyl pyrroiidone using radical formers (peroxides, azo
compounds) as initiators. Ionic polymerization of the monomer only gives
products of low molecular weight.
Commercially available polyvinyl pyrrolidones have molecular
weights of about 2,500 to 750,000 g/mole which are characterized by
indication of the K values.
Other polymers suitable for use as adsorption aids in accordance
with the invention are block copolymers containing blocks (-CHZ-CH20)~-
with n >2, i.e. polyoxyethylene units. These block copolymers may be both
CA 02317168 2000-08-31
21
the polyesters already described in the foregoing and modified poly-
ethylene glycols.
In the use according to the invention, the compound suitable for use
as adsorption aids in accordance with the invention lead to an improvement
in the perfume impression left behind in the laundry by the perfume beads.
In other words, perfume beads produced in accordance with the invention
create just as good a perfume impression as conventional perfume beads
for less perfume. Any saving of perfume signifies a considerable cost
advantage because perfume oils are among the expensive ingredients of
detergents.
In the process according to the invention, after the individual
constituents have been combined, the substantially water-free premix is
subjected to granulation or press agglomeration. In granulation, the premix
is compacted and homogenized by the rotating mixing tools and granulated
to form perfume shaped bodies, more particularly perfume beads. The
granulation of the substantially water-free premix gives perfume beads with
a broader particle size distribution (coarse and fine fractions) so that the
press agglomeration variant is preferred to the granulation variant.
In the press agglomeration process, the premix is compacted and
plasticized under pressure and under the effect of shear forces,
homogenized and then discharged from the machines via a forming/
shaping stage. Technically the most important press agglomeration
processes are extrusion, roller compacting, pelleting and tabletting.
Preferred press agglomeration processes for the purposes of the present
invention are extrusion, roller compacting and pelleting.
In one preferred embodiment of the invention, the premix is
delivered, preferably continuously, to a planetary roll extruder or to a twin-
screw extruder with co-rotating or contra-rotating screws, of which the
barrel and the extrusion/granulation head can be heated to the prede-
CA 02317168 2000-08-31
22
termined extrusion temperature. Under the shearing effect of the extruder
screws, the premix is compacted under a pressure of preferably at least 25
bar or - with extremely high throughputs - even lower, depending on the
apparatus used, plasticized, extruded in the form of fine strands through
the multiple-bore extrusion die in the extruder head and, finally, size-
reduced by means of a rotating cutting blade, preferably into substantially
spherical or cylindrical granules. The bore diameter of the multiple-bore
extrusion die and the length to which the strands are cut are adapted to the
selected granule size. In this embodiment, granules are produced in a
substantially uniformly predeterminable particle size, the absolute particle
sizes being adaptable to the particular application envisaged. In general,
particle diameters of up to at most 0.8 cm are preferred. Important
embodiments provide for the production of uniform granules in the
millimeter range, for example in the range from 0.5 to 5 mm and more
particularly in the range from about 0.8 to 3 mm. In one important
embodiment, the length-to-diameter ratio of the primary granules is in the
range from about 1:1 to about 3:1. In another preferred embodiment, the
still plastic primary granules are subjected to another shaping process step
in which edges present on the crude extrudate are rounded off so that,
ultimately, spherical or substantially spherical extrudate granules can be
obtained. If desired, small quantities of drying powder, for example zeolite
powder, such as zeolite NaA powder, may be used in this step. This
shaping step may be carried out in commercially available spheronizers. It
is important in this regard to ensure that only small quantities of fines are
formed in this stage. According to the present invention, there is no need
for drying because the process according to the invention is carried out in
the substantial absence of water, i.e. without the addition of free non-bound
water.
CA 02317168 2000-08-31
23
Alternatively, extrusion/compression steps may also be carried out in
low-pressure extruders, in a Kahl press or in a so-called Bextruder.
As in the extrusion process, it is also preferred in the other
production processes to subject the primary granules/compactates formed
to another shaping process step, more particularly spheronizing, so that,
ultimately, spherical or substantially spherical (bead-like) granules can be
obtained.
By virtue of the fact that the process according to the invention is
carried out in the substantial absence of water, i.e. except for the water
present as "impurity" in the solid raw materials used, an ecologically
valuable process is also provided because elimination of the need for a
subsequent drying step not only saves energy, emissions which occur
predominantly in conventional drying techniques can also be avoided. In
addition, the absence of subsequent drying steps enables the perfumes to
be incorporated in the premix and thus provides for the production of the
perfume shaped bodies, more particularly perfume beads, according to the
invention.
In another preferred embodiment of the present invention, the
process according to the invention is carried out by roller compacting. In
this variant, the perfume-containing, solid and substantially water-free
premix is introduced between two rollers - either smooth or provided with
depressions of defined shape - and rolled under pressure between the two
rollers to form a sheet-like compactate. The rollers exert a high linear
pressure on the premix and may be additionally heated or cooled as
required. Where smooth rollers are used, smooth untextured compactate
sheets are obtained. By contrast, where textured rollers are used,
correspondingly textured compactates, in which for example certain shapes
can be imposed in advance on the subsequent perfume shaped bodies,
can be produced. The sheet-like compactate is then broken up into smaller
CA 02317168 2000-08-31
24
pieces by a chopping and size-reducing process and can thus be
processed to granules which can be further refined and, more particularly,
converted into a substantially spherical shape by further surface treatment
processes known per se.
In another preferred embodiment of the present invention, the
process according to the invention is carried out by pelleting. In this
process, the perfume-containing, solid and substantially water-free premix
is applied to a perforated surface and is forced through the perforations
and at the same time plasticized by a pressure roller. In conventional pellet
presses, the premix is compacted under pressure, plasticized, forced
through a perforated surface in the form of fine strands by means of a
rotating roller and, finally, is size-reduced to granules by a cutting unit.
The
pressure roller and the perforated die may assume many different forms.
For example, flat perforated plates are used, as are concave or convex ring
dies through which the material is pressed by one or more pressure rollers.
In perforated-plate presses, the pressure rollers may also be conical in
shape. In ring die presses, the dies and pressure rollers may rotate in the
same direction or in opposite directions. A press suitable for carrying out
the process according to the invention is described, for example, in DE-OS
38 16 842 (Schliiter GmbH). The ring die press disclosed in this document
consists of a rotating ring die permeated by pressure bores and at least
one pressure roller operatively connected to the inner surface thereof which
presses the material delivered to the die space through the pressure bores
into a discharge unit. The ring die and pressure roller are designed to be
driven in the same direction which reduces the shear load applied to the
premix and hence the increase in temperature which it undergoes.
However, the pelleting process may of course also be carried out with
heatable or coolable rollers to enable the premix to be adjusted to a
required temperature.
CA 02317168 2000-08-31
Another press agglomeration process which may be used in
accordance with the invention is tabletting. In view of the size of the
shaped bodies produced, it may be appropriate in the tabletting variant to
add conventional disintegration aids, for example cellulose and cellulose
5 derivatives or crosslinked PVP, in addition to the binder described above to
facilitate the disintegration of the shaped bodies in the wash liquor.
The perfume shaped bodies produced in accordance with the
invention may be additionally sprayed with perfume in a subsequent step.
The conventional perfuming variant, i.e. powdering and spraying with
10 perfume, can also be carried out with the perfume shaped bodies produced
in accordance with the invention.
Advantageously, at least 30% by weight, preferably at least 40% by
weight and more preferably at least 50% by weight of the total perfume
present in the perfume shaped bodies produced in accordance with the
15 invention are introduced into the detergent by the production process
according to the invention, i.e. incorporated in the granules or press
agglomerates, while the remaining 70% by weight, preferably 60% by
weight and more preferably 50% by weight of the total perfume present
may be sprayed onto or otherwise applied to the granules or press
20 agglomerates which may optionally be surface-treated.
By dividing the total perfume content of the detergents into perfume
present in the granules or press agglomerates and perfume adhering to the
granules or press agglomerates, it is possible to achieve a number of
product features which are only possible through the process according to
25 the invention. For example, the total perfume content of the detergents can
be divided into two portions x and y, portion x consisting of firmly adhering
perfume oils, i.e. less volatile perfume oils, and portion y consisting of
more
volatile perfume oils.
Now, it is possible to produce detergents where the percentage of
CA 02317168 2000-08-31
26
perfume introduced into the detergent through the granules or press
agglomerates is mainly made up of firmly adhering perfumes. In this way,
firmly adhering perfumes which are intended to perfume the treated
articles, more especially textiles, are "retained" in the product and thus
develop their effect primarily on the treated laundry. By contrast, the more
readily volatile perfumes contribute towards more intensive perfuming of
the detergents per se. In this way, it is also possible to produce detergents
which, as detergents, have a perfume that differs from the perfume of the
treated articles. There are virtually no limits in this regard to the
creativity
of perfumists because almost limitless possibilities for perfuming the
detergents and - through the detergents - the articles treated with them
exist on the one hand through the choice of the perfumes and on the other
hand through the choice of the method used to incorporate them in the
detergents.
The principle described above can of course also be reversed by
incorporating the more readily volatile perfumes in the granules or press
agglomerates and spraying the less volatile firmly adhering perfumes onto
the detergents. In this way, the loss of the more readily volatile perfumes
from the pack in storage and in transit is minimized while the perfume
characteristic of the detergents is determined by the more firmly adhering
perfumes. The adsorption aids present in the perfume shaped bodies
ensure that the perfume components are uniformly adsorbed.
The general description of the perfumes suitable for use in
accordance with the invention (see above) represented the various classes
of perfumes in general terms. In order to be noticeable, a perfume has to
be volatile, its molecular weight being an important factor along with the
nature of the functional groups and the structure of the chemical
compound. Thus, most perfumes have molecular weights of up to about
200 dalton, molecular weights of 300 dalton and higher being more the
CA 02317168 2000-08-31
27
exception. In view of the differences in volatility of perfumes, the odor of a
perfume or fragrance composed of several perfumes changes during the
evaporation process, the odor impressions being divided into the top note,
the middle note or body and the end note or dry out. Since odor perception
is also based to a large extent on odor intensity, the top note of a perfume
or fragrance does not consist solely of readily volatile compounds whereas
the end note or dry out consists largely of less volatile, i.e. firmly
adhering,
perfumes. In the composition of perfumes, more readily volatile perfumes
may be fixed, for example, to certain "fixatives", which prevents them from
vaporizing too rapidly. The above-described embodiment of the present
invention, in which the more readily volatile perfumes or fragrances are
incorporated in the press agglomerate, is one such method of fixing a
perfume. Accordingly, in the following classification of perfumes into
"readily volatile" and "firmly adhering" perfumes, nothing is said about the
odor impression or about whether the corresponding perfume is perceived
as a top note or middle note.
Firmly adhering perfumes suitable for use in accordance with the
present invention are, for example, the essential oils, such as angelica root
oil, aniseed oil, arnica flowers oil, basil oil, bay oil, bergamot oil,
champax
blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil,
fennel
oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac
wood oil, Indian wood oil, helichrysum oil, ho oil, ginger oil, iris oil,
cajeput
oil, sweet flag oil, camomile oil, camphor oil, canaga oil, cardamom oil,
cassia oil, Scotch fir oil, copaiba balsam oil, coriander oil, spearmint oil,
caraway oil, cumin oil, lavender oil, lemon grass oil, limette oil, mandarin
oil, melissa oil, amber seed oil, myrrh oil, clove oil, neroli oil, niaouli
oil,
olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru
balsam oil, petit grain oil, pepper oil, peppermint oil, pimento oil, pine
oil,
rose oil, rosemary oil, sandalwood oil, celery seed oil, lavender spike oil,
CA 02317168 2000-08-31
28
Japanese anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver
oil, juniper bevy oil, wormwood oil, wintergreen oil, ylang-ylang oil, ysop
oil,
cinnamon oil, cinnamon leaf oil, citronella oil, citrus oil and cypress oil.
However, relatively high-boiling or solid perfumes of natural or
synthetic origin may also be used in accordance with the invention as firmly
adhering perfumes or perfume mixtures. These compounds include those
mentioned in the following and mixtures thereof: ambrettolide, a-amyl
cinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl
anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl
benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate,
benzyl formate, benzyl valerate, bomeol, bornyl acetate, a-bromostyrene,
n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether,
eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
formate, heliotropin, methyl heptyne carboxylate, heptaldehyde,
hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl
alcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafrol,
jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-
methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid
methyl ester, p-methyl acetophenone, methyl chavicol, p-methyl quinoline,
methyl-~i-naphthyl ketone, methyl-n-nonyl acetaldehyde, methyl-n-nonyl
ketone, muskone, ~i-naphthol ethyl ether, ~i-naphthol methyl ether, nerol,
nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-
oxyacetophenone, pentadecanolide, ~3-phenyl ethyl alcohol, phenyl
acetaldehyde dimethyl acetal, phenyl acetic acid, pulegone, safrol, isoamyl
salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate,
santalol,
scatol, terpineol, thymene, thymol, ~y-undecalactone, vanillin, veratrum
aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl
cinnamate, benzyl cinnamate.
The more readily volatile perfumes include, in particular, the
CA 02317168 2000-08-31
29
relatively low-boiling perfumes of natural or synthetic origin which may be
used either individually or in the form of mixtures. Examples of more
readily volatile perfumes are alkyl isothiocyanates (alkyl mustard oils),
butanedione, limonene, linalool, linalyl acetate and propionate, menthol,
menthone, methyl-n-heptenone, phellandrene, phenyl acetaldehyde,
terpinyl acetate, citral, citronellal.
In addition to the above-mentioned constituents of the substantially
water-free premix, other ingredients may be introduced into the process
according to the invention in small quantities of 1 to 10% by weight,
preferably 1 to 5% by weight and more preferably 1 to 2% by weight, based
on the premix. These substances may be used to color the perfume beads
or to provide them with certain performance properties. However, it is also
possible to add detergent ingredients of which the incorporation is normally
attended by process-related disadvantages. Thus, substances normally
used in small quantities, such as optical brighteners, phosphonates, dye
transfer inhibitors, etc., are subsequently incorporated. By introducing
these substances into the process according to the invention, perfume
shaped bodies, more particularly perfume beads, which contain other
active substances and which may therefore be introduced into detergents
as a perfume and active compound, are obtained. Moeover, an additional
process step in the production of detergents is saved in this way.
In other embodiments, the present invention relates to the use of
perfume shaped bodies, more particularly perfume beads, with bulk
densities above 700 g/l produced by the process according to the invention
by granulation or press agglomeration of a solid and substantially water-
free premix of
a) 65 to 94.5% by weight of carrier(s),
b) 0 to 10% by weight of auxiliary(ies),
c) 5 to 25% by weight of perfume and
CA 02317168 2000-08-31
d) 0.5 to 20% by weight of a substance which improves adsorption of the
perfume onto surfaces
for perfuming detergents.
In another embodiment, therefore, the present invention relates to
5 detergents containing perfume shaped bodies, more particularly perfume
beads, produced in accordance with the invention in quantities of more
than 0.5% by weight, preferably in quantities of more than 1 % by weight
and more preferably in quantities of more than 2% by weight, based on the
detergent.
10 The perfume shaped bodies, more particularly perfume beads,
produced in accordance with the invention may be incorporated in standard
detergents where they are used as described above for perfuming the
detergents. However, the perfume shaped bodies, more particularly
perfume beads, produced in accordance with the invention may also be
15 offered separately as part of a building block system whereby the
consumer acquires a perfume-free basic detergent and can then add
various perfume shaped bodies, more particularly perfume beads, in order
in this way to be able to choose from the range of perfume variants,
depending on the nature of the treated laundry.
20 In all these embodiments, the perfume beads are ultimately used for
perfuming surfaces, more particularly fibers and, in one particularly
preferred embodiment, for perfuming textile fibers. Accordingly, the
present invention also relates to the use of substances which improve the
adsorption of perfumes onto surfaces for improving the perfume impression
25 on laundry in the practical application of perfume shaped bodies, more
particularly perfume beads, which bulk densities above 700 g/I produced by
granulation of press agglomeration from a solid and substantial water-free
premix containing
a) 65 to 94.5% by weight of carrier(s),
CA 02317168 2000-08-31
31
b) 0 to 10% by weight of auxiliaries and
c) 5 to 25% by weight of perfume.
The above-described substances from the group of paraffins, quaternary
ammonium compounds, soil release polymers, more particularly
copolymeric polyesters, and other polymers such as, in particular, polyvinyl
pyrrolidone and block copolymers containing (-CH2-CH2-O)~- blocks where
n >2.
In another preferred embodiment, the present invention relates to a
process for applying perfumes to laundry in a washing machine by adding
perfume-containing shaped bodies, more particularly perfume beads, in the
rinse cycle, characterized in that shaped bodies with bulk densities above
700 g/I produced by the process according to the invention by granulation
or press agglomeration of a solid and substantially water-premix of
a) 65 to 94.5% by weight of carrier(s),
b) 0 to 10% by weight of auxiliary(ies),
c) 5 to 25% by weight of perfume and
d) 0.5 to 20% by weight of a substance which improves adsorption of the
perfume onto surfaces
are added to the wet laundry in the wash or rinse cycle of an automatic
washing process.
Examples
Free-flowing premixes were prepared by mixing the formulation
ingredients listed below in a Lt~dige mixer and were then compacted and
plasticized in an extruder.
CA 02317168 2000-08-31
32
Table 1:
Perfume beads premix (composition in % by weight)
E1 E2 E3 E4 E5 E6 E7 E8 C1
Dehyquart - - 2.5 -
AU57
[%
by
wei
ht]
Dehyquart - 2.5 1.0 - - - 2.5 - -
Au48
[%
by
wei
ht]
Repelofex 5.0 - - - - 2.5 2.5 -
SRP4
[%
by
wei
ht]
Sokalan - - - 3.5 - - - -
HP22
[%
by
wei
ht]
- - - - - 1.3 - - - -
Paraffin
[%
by
wei
ht]
PEG/vinyl - - - - - - 2.5 -
acetate
graft
copolymer
[%
by
wei
ht]
Spray 79.081.5 83.080.5 82.781.5 79.079.084.0
dried
granules
[%
by
wei
ht]
Perfume 10.010.0 10.010.0 10.010.0 10.010.010.0
oil
[%
by
wei
ht]
PEG 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
4000
[%
by
wei
ht]
Bulk density[ /I] 760 740 730 780 710 770 760 750 770
Dehyquart AU 57/AU 48: N-methyl-N,N-bis-(acyloxyethyl)-N-(2-
hydroxyethyl)-ammonium methosulfate;
products of Henkel KGaA
Repelotex SRP 4: terephthalic acid/ethylene glycol/polyethylene
glycol ester; a product of Rhodia
Sokalan HP 22: modified polyalkylene glycol; a product of BASF
PEG: polyethylene glycol
Composition of the spray dried granules (surfactant compounds
produced by spray drying): 26.2% by weight Na-Cg~3-alkyl
benzenesulfonate, 4.0% by weight sodium carbonate, 55.6% by weight
zeolite 4A, 0.7% by weight salts from solution, 13.0% by weight water and
0.5% by weight sodium hydroxide.
CA 02317168 2000-08-31
33
After leaving the mixer, the free-flowing premixes had a bulk density
of about 400 g/I and were introduced into a Lihotzky twin-screw extruder in
which they were plasticized and extruded under pressure.
The plasticized premixes left the extruder under a pressure of 85 bar
through a multiple-bore die with bore diameters of 0.5 mm. The extruded
strands were cut to a length-to-diameter ratio of about 1 by a rotating blade
and rounded in a Marumerizer~. After the fine particles (< 0.4 mm) and the
coarse particles (> 2.0 mm) had been removed by sieving, the extrudates
had the bulk densities shown in Table 1.
The perfume beads E1 to E8 produced in accordance with the
invention were mixed with perfume-free extrudates to form detergents and
compared with extrudates of similar composition where the particular
perfume oils had been conventionally sprayed onto the extruded and
rounded particles that had been powdered with fine-particle zeolite (C2)
and with similarly produced detergents which contained perfume beads
with no adsorption aid (C1 ). The perfume oil content was kept constant in
the various formulations.
The composition of the perfume oils used in the individual perfume
beads is shown in Table 2. The perfuming of the product and of treated
textiles (cotton) was evaluated by several perfumists as a subjective odor
impression. The figures in the evaluation Table (Table 3) indicate the order
of the intensities perceived by the perfumists. A relatively high figure
signifies a relatively weak perfume impression.
CA 02317168 2000-08-31
34
Table 2:
Composition of the perfume oils [% by weight]
Perfume % by
wei ht
Bergamot oil 15.0
Dihydromyrcenol 20.0
Citrus oil messina 7.5
Mandarin oil 2.5
Orange oil sweet 5.0
Allyl amyl lycolate 2.0
Cyclovertal 0.5
Lavandin oil grosso 2.5
Clary oil 1.0
Lilial 2.0
[3-Damascone 0.1
Geranium oil bourbon 3.0
Hedione 5.0
Cyclohexyl salicylate 4.0
Vertofix Coeur 10.0
Iso-E-super 5.0
Ambroxan 1.6
Ethylene brassylate 10.0
Evernyl 1.0
CA 02317168 2000-08-31
35
Table 3:
Perfume enhancement (intensity preference averaged over the number of
perfumists)
Intensity preference
Product Damp laundry Dry laundry
E1 2 3 1
E2 1 1 2
E3 3 2 4
E4 4 4 3
C2 5 5 5
C1 3 3 3
E5 1 2 2
E6 2 1 1
C1 2 3 3
E7 1 1 2
E8 3 2 1
In a first series of tests, Examples E1 to E4 according to the
invention were compared with Comparison Example C2. Both with the
perfume beads themselves and on damp and dry laundry, the perfume
impression of the Comparison Examples was found to be the weakest. All
Examples according to the invention fared better. In a second series of
tests, perfume beads with no adsorption aid (C1 ) were compared with
Examples E5 and E6 according to the invention. In this case, too, the
Examples according to the invention all fared better in regard to perfume
impression than the perfume beads with no adsorption aid. In the third
series of tests also, the Examples according to the invention were found to
CA 02317168 2000-08-31
36
perfume the laundry far more strongly than was possible with the perfume
beads with no adsorption aid. Accordingly, the Examples show that the
perfume impression is improved for the same amount of perfume where
perfume beads according to the invention are used.
