Note: Descriptions are shown in the official language in which they were submitted.
CA 02291869 1999-12-O1
Peroxide Preparations Containing Stabilized Perfumes
Field of the Invention
This invention relates generally to bleaching agents and
disinfectants and, more particularly, to peroxide preparations containing
perfumes in microencapsulated form.
Prior Art
In Mediterranean countries and also in the United States, cold water
is still predominantly used for washing laundry. The effect of this is that
conventional bleaching agents, for example perborates or percarbonates,
are hardly used because they do not develop any particular activity at
temperatures around 20°C. For this reason, liquid bleaches - generally
surface-active preparations containing up to 10% by weight of hydrogen
peroxide - are normally added to the wash liquor. Even in heavily diluted
form, peroxide liquors have an unpleasantly pungent odor so that perfumes
are added to them
Reference is also made in this connection to European patent
application EP 0397246 A1 from which perfume capsules with an average
size of less than 350 Nm, preferably no more than 150 Nm, and a water-
insoluble fragile shell and detergents containing these perfume capsules
are known.
Although a sufficiently large number of perfume oils which are stable
to peroxide and are not oxidized, even over prolonged periods, are known
from the prior art, substances with a citrus fragrance are not among them.
However, since it is precisely this fragrance which the consumer associates
with freshness and cleanness, there is a desire at the commercial level to
market peroxide bleaches with a citrus fragrance which are sufficiently
stable in storage, i.e. emit the fresh fragrance required at the latest in
use,
despite the known chemical instability of the perfumes. Accordingly, the
object of the present invention was to find a simple technical solution to the
problem described above.
CA 02291869 1999-12-O1
2
Description of the Invention
The present invention relates to peroxide preparations containing
perfumes which are characterized in that the perfumes are present in
microencapsulated form.
It has surprisingly been found that peroxide-containing textile
bleaching preparations can be formulated with perfumes when the
perfumes are used in microencapsulated form. The microcapsules are
chemically and physically, more particularly spatially, stable in the liquid
preparations according to the invention, i.e. the microcapsules do not
undergo decomposition or sedimentation in the preparations. In this way,
peroxide-containing preparations can be produced with a virtually free
choice of perfumes. In particular, even storage-stable preparations with a
citrus fragrance can now be obtained.
Peroxide compounds
Peroxide compounds in the context of the invention are understood
to be substances wich contain an O-O-group. Typical examples are
perborates, percarbonates, percarboxylic acids and, in particular, hydrogen
peroxide. The aqueous preparations according to the invention preferably
contain hydrogen peroxide in quantities of 1 to 10% by weight, preferably in
quantities of 5 to 8% by weight and more preferably in quantities of 6 to 7%
by weight, based on 100% active substance. The hydrogen peroxide is
used, for example, in the form of a 35% by aqueous solution.
Microcapsules
"Microcapsules" are understood to be aggregates which contain at
least one solid or liquid core surrounded by at least one continuous shell,
more particularly a shell of polymer(s). They are normally finely disperses
liquid or solid phases coated with film-forming polymers, in the production
of which the polymers are deposited onto the material to be encapsulated
after emulsification and coacervation or interfacial polymerization. The
microscopically small capsules, also known as nanocapsules, can be dried
CA 02291869 1999-12-O1
3
in the same way as powders. Besides single-core microcapsules, there
are also multiple-core aggregates, also known as microspheres, which
contain two or more cores distributed in the continuous shell material. In
addition, single-core or multiple-core microcapsules may be surrounded by
an additional second, third etc. shell. Single-core microcapsules with a
continuous shell are preferred. The shell may consist of natural,
semisynthetic or synthetic materials. Natural shell materials are, for
example, gum arabic, agar agar, agarose, maltodextrins, alginic acid and
salts thereof, for example sodium or calcium alginate, fats and fatty acids,
cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, poly-
saccharides, such as starch or dextran, sucrose and waxes. Semisynthetic
shell materials are inter alia chemically modified celluloses, more
particularly cellulose esters and ethers, for example cellulose acetate, ethyl
cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and
carboxymethyl cellulose, and starch derivatives, more particularly starch
ethers and esters. Synthetic shell materials are, for example, polymers,
such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl
pyrrolidone.
Although they may be produced in any shape, the microcapsules
are preferably substantially spherical. Their diameter along their largest
spatial dimension may be between 10 nm (visually not discernible as a
capsule) and 10 mm, depending on the perfume present in their interior
and the application envisaged. Visible microcapsules between 0.1 mm and
7 mm and, more particularly, between 0.4 mm and 5 mm are preferred.
Microcapsules invisible to the naked eye preferably have a diameter of 20
to 500 nm and more preferably 50 to 200 nm. The microcapsules may be
obtained by known processes, of which coacervation and interfacial
polymerization are the most important. Any commercially available
surfactant-stable microcapsules may be used as the microcapsules,
including for example the commercial products (the shell material is shown
CA 02291869 1999-12-O1
4
in brackets) Hallcrest Microcapsules (gelatin, gum arabic), Coletica
Thalaspheres (maritime collagen), Lipotex Millicapseln (alginic acid, agar
agar), Induchem Unispheres (lactose, microcrystalline cellulose,
hydroxypropylmethyl cellulose), Unicerin C30 (lactose, microcrystalline
cellulose, hydroxypropylmethyl cellulose), Kobo Glycospheres (modified
starch, fatty acid esters, phospholipids), Softspheres (modified agar agar)
and Kuhs Probiol Nanospheres (phospholipids).
The active substances are released from the microcapsules by
mechanical, thermal, chemical or enzymatic destruction of the shell,
normally during the use of the preparations containing the microcapsules.
In the case of the bleaching agents normally used in undiluted form, they
are preferably released by mechanical action, more particularly by mech-
anical forces to which the microcapsules are exposed during dosing, pump-
circulation or spinning in the washing machine. In one preferred
embodiment of the invention, the preparations contain the same
microcapsules or different microcapsules in quantities of 0.1 to 10% by
weight, more preferably in quantities of 0.2 to 8% by weight and most
preferably in quantities of 0.5 to 6% by weight.
Perfumes
The perfumes used in microencapsulated form in accordance with
the invention are preferably perfumes which would otherwise be unstable in
peroxide preparations.
Typical examples of suitable perfumes are mixtures of natural and
synthetic perfumes. Natural perfumes are extracts of blossoms (lily,
lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium,
patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit
peel
(bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamon,
costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood,
cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage,
thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and
CA 02291869 1999-12-O1
balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal
raw materials, for example civet and beaver, may also be used.
Typical synthetic perfumes are products of the ester, ether,
aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfumes of
5 the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl
cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl
ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl
glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl
salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes
include, for example, the linear alkanals containing 8 to 18 carbon atoms,
citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxy-
citronellal, lilial and bourgeonal. Examples of suitable ketones are the
ionones, a-isomethylionone and methyl cedryl ketone. Suitable alcohols
are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl
alcohol and terpineol. The hydrocarbons mainly include the terpenes and
balsams. However, it is preferred to use mixtures of different perfume
compounds which, together, produce an agreeable fragrance.
Other suitable perfumes are essential oils of relatively low volatility
which are mostly used as aroma components. Examples are sage oil,
camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-
blossom
oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil
and lavendin oil. The following are preferably used either individually or in
the form of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral,
phenylethyl
alcohol, a-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen
aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione,
sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate,
cyclovertal, lavendin oil, clary oil, ~i-damascone, geranium oil bourbon,
cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl,
iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose
oxide, romillate, irotyl and floramate.
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6
Besides the perfumes mentioned above, peroxide-stable perfumes
may of course also be used in microencapsulated form. Examples of such
perfumes are: citronellol (3,7-dimethyl-6-octen-1-ol), dimethyl octanol (3,7-
dimethyl-1-octanol), hydroxycitronellol (3,7-dimethyloctane-1,7-diol), mugol
(3,7-dimethyl-4,6-octatrien-3-ol), myrcenol (2-methyl-6-methylene-7-octen-
2-0l), terpinolene (p-mentho-1,4-(8)-diene), ethyl-2-methyl butyrate, phenyl
propyl alcohol, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl
cyclopental-2-benzopyran), tonalide (7-acetyl-1,1,3,4,4,6-hexamethyl tetra-
hydronaphthalene), rose oxide, linalol oxide, 2,6-dimethyl-3-octanol,
tetrahydroethyl linalool, tetrahydroethyl linalyl acetate, o-sec.-butyl
cyclohexyl acetate and isolone diphorenepoxide and also isoborneal,
dihydroterpineol, isobornyl acetate, dihydroterpenyl acetate). Other
suitable perfumes are the substances mentioned columns 3 and 4 of
European patent application EP 0622451 A1 (Procter & Gamble). The
microcapsules contain the perfumes in quantities of generally 1 to 95% by
weight, preferably 50 to 80% by weight and more preferably 60 to 70% by
weight, based on the capsule weight.
Sec~uesterinq acLents
If the preparations are used for treating fabrics, it is advisable to add
to them electrolytes which act as sequestrants for heavy metal ions and
which therefore counteract yellowing of the fabrics. Suitable sequestering
agents are, for example, silicates, phosphonic acids and phosphonates,
polyacrylic acid compounds, alkali metal carbonates, lignin sulfonates and
mixtures of the electrolytes mentioned. The total quantity of sequestrant
used is normally 0.1 to 2% by weight, preferably 0.3 to 1.5% by weight and
more preferably 0.5 to 1.0% by weight, based on the preparation.
Silicates in the context of the invention are understood to be salts
and esters of orthosilicic acid Si(OH)4 and self-condensation products
thereof. Accordingly, the following crystalline substances, for example,
may be used as silicates:
CA 02291869 1999-12-O1
7
(a) neosilicates (island silicates) such as, for example, phenakite, olivine
and zircon;
(b) sorosilicates (group silicates) such as, for example, thortveitite and
hemimorphite;
(c) cyclosilicates (ring silicates) such as, for example, benitoite, axinite,
beryl, milarite, osumilite or eudialyte;
(d) inosilicates (chain and band silicates) such as, for example,
metasilicates (for example diopside) or amphiboles (for example
tremolite);
(e) phyllosilicates (sheet and layer silicates) such as, for example, talc,
kaolinite and mica (for example muscovite);
(f) tectosilicates (framework silicates) such as, for example, feldspars and
zeolites and clathrasils or dodecasils (for example melanophlogite),
thaumasite and neptunite.
In contrast to the ordered crystalline silicates, silicate glasses such
as, for example, soda waterglass or potash waterglass are preferably used.
These silicate glasses may be of natural origin (for example
montmorillonite) or may have been produced by a synthetic route. In
another embodiment of the invention, alumosilicates may also be used.
Typical examples of alkali metal or alkaline earth metal silicates are sodium
and/or potassium silicates with a modulus of 1.0 to 3.0 and preferably 1.5
to 2Ø
Phosphonic acids in the context of the invention are understood to
be organic derivatives of the acid HP(O)(OH)2; phosphonates represent
the salts and esters of these phosphonic acids. The organic phosphonic
acids and phosphonates preferably used are known chemical compounds
which may be prepared, for example, by the Michaelis-Arbuzov reaction.
They correspond, for example, to formula (I):
CA 02291869 1999-12-O1
8
O
(I)
R -P-OR
I
OR2
in which R' is an optionally substituted alkyl and/or alkenyl group
containing 1 to 22 carbon atoms, preferably 2 to 18 carbon atoms and
more preferably 6 to 12 carbon atoms and R2 is hydrogen, an alkali metal
and/or alkaline earth metal, ammonium, alkylammonium and/or alkanol-
ammonium or an optionally substituted alkyl and/or alkenyl group
containing 1 to 22, preferably 2 to 18 and more preferably 6 to 12 carbon
atoms. Typical examples are optionally hydroxy-, nitrilo- and/or amino-
substituted phosphonic acids such as, for example, ethyl phosphonic acid,
nitrilotris-(methylenephosphonic acid), 1-amino- and 1-hydroxyalkane-1,1-
diphosphonic acids. One preferred embodiment of the invention is
characterized by the use of amine oxide phosphonic acids corresponding
to formula (II):
O CH3 H
II
HO-P (CH2)m(CH)~-N O ( )
OR3 H
in which R3 is hydrogen, a (CH2)m(CHCH3)nNH20 group or an alkali metal,
m is a number of 1 to 4 and n has a value of 0 or 1. Amine oxide
phosphonic acids are builders or sequestrants which are marketed, for
example, by Bozetto (Italy) under the name of Sequion~. They are
CA 02291869 1999-12-O1
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produced by reacting aminophosphonic acids to form the amine oxide.
According to the invention, both mono- and diamine oxides in the form of
the phosphonic acids (or salts) corresponding to formula (II) may be used.
Amine oxide phosphonic acids in which R3 is hydrogen, m = 3 and n = 0
(amine oxide based on aminotrimethylene phosphonic acid) are preferably
used.
Polyacrylic acid compounds are understood to be homopolymers
of acrylic acid and methacrylic acid and esters thereof. Besides the acids,
esters of the acids with alcohols containing 1 to 4 carbon atoms may also
be polymerized. Polyacrylic acid compounds having a particularly
advantageous stabilizing effect are present as alkali metal salts and have
an average molecular weight in the range from 1,000 to 10,000 dalton and
more particularly in the range from 4,000 to 6,000 dalton.
Thickeners
The use of electrolytes is a very simple and inexpensive method of
adjusting viscosity. However, it has been found that the presence of
chloride ions besides peroxide can cause pitting on certain textile through
the formation of chlorine. In one preferred embodiment of the invention,
therefore, organic thickeners are used. Organic thickeners are, for
example, polysaccharides, more particularly xanthan gum, guar guar, agar
agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl
cellulose, also relatively high molecular weight polyethylene glycol
monoesters and diesters of fatty acids, polyacrylates (for example
Carbopols~ [Goodrich] or Synthalens~ [Sigma]), polyacrylamides,
polyvinyl alcohol and polyvinyl pyrrolidone, aluminas such as, for example,
Laponite~ of Southern Clay Products or Zeothix~ of Huber, surfactants
such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids
with polyols such as, for example, pentaerythritol or trimethylol propane,
narrow-range fatty alcohol ethoxylates or alkyl oligoglucosides, which may
be added to the preparations in quantities of 0.1 to 2% by weight.
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Surfactants
To support their cleaning performance, the preparations may
additionally contain peroxide-stable surfactants such as, for example, fatty
acid salts, alkyl sulfates, alkyl sulfonates, alkyl benzenesulfonates, xylene
5 sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines,
sugar esters and fatty acid-N-alkyl glucamides. However, alkyl ether
sulfates, amine oxides, alk(en)yl oligoglycosides and fatty alcohol
polyglycolethers are preferably used. The surfactants together generally
make up from 1 to 15% by weight and preferably from 5 to 10% by weight
10 of the preparations.
Alkyl ether sulfates are anionic surfactants which may be obtained
by sulfation of alkyl polyglycol ethers and subsequent neutralization. Alkyl
ether sulfates suitable for use in accordance with the invention correspond
to formula (III):
R4O-(CHZCH2O)"SO3X (III)
in which R4 is an alkyl group containing 12 to 18 and, more particularly, 12
to 14 carbon atoms, n is a number of 2 to 5 and, more particularly, 2 to 3
and X stands for sodium or potassium. Typical examples are the sodium
salts of sulfates of the C~v~a cocoalcohol +2, +2.3 and +3 EO adduct. The
alkyl ether sulfates may have a conventional or narrow homolog
distribution. The alkyl ether sulfates are preferably used in quantities of 1
to 8% by weight, preferably 1.5 to 6% by weight and more preferably 2 to
4% by weight, based on the preparation.
Amine oxides are also known compounds which are occasionally
classified as cationic surfactants, but generally as nonionic surfactants.
They are produced by oxidation of tertiary fatty amines, which normally
have either one long and two short alkyl chains or two short and one long
alkyl chain, in the presence of hydrogen peroxide. The amine oxides
CA 02291869 1999-12-O1
11
suitable as surface-active ingredients in accordance with the present
invention correspond to formula (IV):
Rs
R5-N->O ~ (IV)
R'
in which R5 is a linear or branched alkyl group containing 12 to 18 carbon
atoms and R6 and R' independently of one another have the same
meaning as R5 or represent an optionally hydroxysubstituted alkyl group
containing 1 to 4 carbon atoms. Amine oxides corresponding to formula
(IV) in which R5 and R6 represent C~2,~4 or C~2,~8 cocoalkyl groups and R'
represents a methyl group or a hydroxyethyl group, are preferably used.
Amine oxides corresponding to formula (IV), in which R5 represents a 02114
or C~z~8 cocoalkyl group and R6 and R' represent a methyl or hydroxyethyl
group, are also preferred. The amine oxides are preferably used in
quantities of 1.5 to 6% by weight and preferably 2 to 4% by weight, based
on the preparation.
Alkyl and alkenyl oligoglycosides are known nonionic surfactants
which correspond to formula (V):
R80-[G]p
(V)
in which R$ is an alkyl and/or alkenyl radical containing 4 to 22 carbon
atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number
of 1 to 10. The alkyl and/or alkenyl oligoglycosides, which are also suitable
as surface-active ingredient, may be derived from aldoses or ketoses
containing 5 or 6 carbon atoms, preferably glucose. Accordingly, the
CA 02291869 1999-12-O1
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preferred alkyl and/or alkenyl oligoglycosides are alkyl and/or alkenyl
oligoglucosides. The index p in general formula (V) indicates the degree
of oligomerization (DP), i.e. the distribution of mono- and oligoglycosides,
and is a number of 1 to 10. Whereas p in a given compound must always
be an integer and, above all, may assume a value of 1 to 6, the value p for
a certain alkyl oligoglycoside is an analytically determined calculated
quantity which is generally a broken number. Alkyl and/or alkenyl oligo-
glycosides having an average degree of oligomerization p of 1.1 to 3.0 are
preferably used. Alkyl and/or alkenyl oligoglycosides having a degree of
oligomerization of less than 1.7 and, more particularly, between 1.2 and 1.4
are preferred from the applicational point of view. The alkyl or alkenyl
radical Rs may be derived from primary alcohols containing 4 to 11 and
preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic
alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and the
technical mixtures thereof obtained, for example, in the hydrogenation of
technical fatty acid methyl esters or in the hydrogenation of aldehydes from
Roelen's oxosynthesis. Alkyl oligoglucosides having a chain length of C8 to
Coo (DP = 1 to 3), which are obtained as first runnings in the separation of
technical C&~8 coconut oil fatty alcohol by distillation and which may
contain less than 6% by weight of C~2 alcohol as an impurity, and also alkyl
oligoglucosides based on technical C9,» oxoalcohols (DP = 1 to 3) are
preferred. In addition, the alkyl or alkenyl radical R8 may also be derived
from primary alcohols containing 12 to 22 and preferably 12 to 14 carbon
atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol,
palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol,
elaidyl
alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl
alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof
which may be obtained as described above. Alkyl oligoglucosides based
on hydrogenated C~2,~4 cocoalcohol with a DP of 1 to 3 are preferred. The
glycosides are preferably used in quantities of 1.5 to 6% by weight and
CA 02291869 1999-12-O1
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more preferably in quantities of 2 to 4% by weight, based on the
preparation.
The preparations according to the invention may contain as further
surfactants fatty alcohol polyglycol ethers corresponding to formula (VI):
acid salts corresponding to formula (VI):
R90(CH2CH20)"H (VI)
in which R9 is a linear or branched alkyl and/or alkenyl group containing 6
to 22 and preferably 12 to 18 carbon atoms and n is a number of 1 to 10.
Typical examples are products of the addition of on average 1 to 10 and
preferably 2 to 5 moles of ethylene oxide onto caproic alcohol, caprylic
alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl
alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl
alcohol,
isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol,
linolyl
alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl
alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the
technical mixtures thereof obtained, for example, in the high-pressure
hydrogenation of technical methyl esters based on fats and oils or
aldehyde from Roelen's oxosynthesis and as monomer fraction in the
dimerization of unsaturated fatty alcohols. Products of the addition of 2 to
5 moles of ethylene oxide onto technical fatty alcohols containing 12 to 18
carbon atoms such as, for example, cocofatty alcohol, palm oil fatty
alcohol, palm kernel oil fatty alcohol and tallow fatty alcohol are preferred.
The polyglycol ethers may have a conventional broad homolog distribution,
but also a narrow homolog distribution . Mixtures of fatty alcohol polyglycol
ethers with a linear and branched alkyl chain have proved to be
advantageous by virtue of their favorable thickening effect. In addition,
particularly high-performance preparations contain mixtures of various fatty
alcohol polyglycol ethers in which one component has an HOB value above
CA 02291869 1999-12-O1
14
and the other an HLB value below 10. The polyglycol ethers are used in
quantities of preferably 1 to 5% by weight and more preferably 2 to 4% by
weight, based on the preparation.
Commercial Aplalications
5 The preparations according to the invention are generally aqueous
with a non-aqueous component of, preferably, 5 to 35% by weight and,
more preferably, 8 to 15% by weight and are particularly suitable for the
treatment of flat textile materials such as, for example, yarns, fabric webs
and, in particular, textiles. They are normally used at low temperatures, i.e.
10 at cold-wash temperatures (ca. 15 to 25°C). Not only are the
preparations
distinguished by excellent stain removal, they also reliably prevent the
deposition of lime and metal traces on the fibers and thus also prevent
incrustation and yellowing. Although the actual use of the preparations is
directed to the removal of stains during washing, they are also suitable in
principle for other applications in which bleaching solutions are used, for
example for the cleaning and disinfection of hard surfaces. The prepar-
ations according to the invention may additionally contain optical
brighteners, dyes and pigments in total quantities of 0.01 to 0.5% by
weight, based on the preparation. The optical brightener used may be, for
example, the potassium salt of 4,4'-bis-(1,2,3-triazolyl)-(2)-stilbene-2,2-
sulfonic acid which is marketed under the name of Phorwite~ BHC 766.
Suitable pigments are inter alia green chlorophthalocyanines (Pigmosol~
Green, Hostaphine~ Green) or yellow Solar Yellow BG 300 (Sandoz). The
preparations may also contain typical auxiliaries and additives, for example
antioxidants, such as phenols and phenol derivatives, for example butyl
hydroxytoluene (BHT, 2,6-ditert.-butyl-4-methylphenol). The preparations
according to the invention are prepared by stirring. The product obtained
may optionally be decanted or filtered to remove foreign bodies and/or
agglomerates. In addition, the preparations have a viscosity above 100
and preferably above 200 mPas, as measured at 20°C in a Brookfield
CA 02291869 1999-12-O1
viscosimeter (spindle 1, 10 r.p.m.).
Examples
On the one hand perfume capsules and on the other hand the pure
perfume were added to various hydrogen peroxide solutions which were
5 then introduced into dark bottles and stored at 25°C. Quantities of
100 ml
of the solutions were visually evaluated immediately after their preparation
and after storage for 1 week and 4 weeks, subsequently poured into glass
beakers and then treated for 1 minute with a magnetic stirrer on a low-
speed setting. The odor impression was then subjectively evaluated. The
10 results are set out in Table 1. Examples 1 to 3 correspond to the invention
while Examples C1 to C3 are intended for comparison.
CA 02291869 1999-12-O1
16
Table 1
Odor impression
a r r,~ ~, ':> ' =::~'s
,~ -,, 08 r ~3 ,'a s ~ , ,
'. a, ".,, ,~ - 'r r,
~f n,. g'k e., ~ .
x ~: PH.. 4f". , ~' :~ ': .,.j
A / ,.. ,;M:~~;.," ~~f ; r : ,n
.. ~..,. , ~o~"....' ~ t.. f
~.. f~ ;., ~ a: ~
'i" 93 ~ . ,.'
~ ~ ~a~
f n
~~' if
x :ro
~
3y, , ". 1~ d , . < , ,
.~I~".~~',v . c, ,. ;. , ': ~
~; ':. P~f; .:, , ~ . -<' ..
.",~ ~ ~4 ,5 " . - ! ~.~~~,s,'
, ~ i ., ."'.
. .-> n .. :
.
Hydrogen peroxide7.5 7.5 7.5 7.5 7.5 7.5
Cocofatty alcohol0.75 2.0 2.0 0.75 2.0 2.0
+2E0 sulfate
TEA
salt
C~u~4 cocofatty8.5 - - 8.5 - -
alcohol+6E0
C,v~4 cocofatty0.75 - - 0.75 - -
alcohol+4E0
C,z~4 cocofatty- 0.7 0.7 - - -
alcohol+2.5E0
(NRE)
Xanthan gum - - 0.7 - - 0.7
Polyacrylate - 1.0 - - 1.0 -
Trilon~M 0.1 0.1 0.1 0.1 0.1 0.1
Microcapsules 0.3 0.3 0.3 - - -
(Lipotec)4~
Citrus fragrance- - - 0.3 0.3 0.3
(Vercitron)
EtOH 0.19 0.19 0.19 0.19 0.19 0.19
13HT 0.01 0.01 0.01 0.01 0.01 0.01
Dye <0.001 <0.001 <0.001 <0.001 <0.001 <0.001
Water to 100
Odor impression
-after productioncitrus-citrus-citrus-citrus-citrus-citrus-like
like like like like like
-after 1 week citrus-citrus-citrus-pungentpungentpungent
like like like
-after4 weeks citrus-citrus-citrus-pungentpungentpungent
like like like
Optical impressionhomo- homo- homo- clear clear clear
geneousgeneousgeneous
'~ Keltrol~ T (Kelco); 2~ Carbopol 497 (Goodrich); 3~ methylglycine diacetic
acid trisodium salt (BASF); 4~ filling, 90% by weight citrus fragrance
(Vercitron), shell material: sodium alginate; 5~ Pigmosol~ Blue 6900 =
water-dispersible copper phthalocyanine preparation = Pigment Blue 15 =
C.I. 74160 (BASF)
The preparations according to the invention containing the
microencapsulated perfume are homogeneous even after storage for 4
CA 02291869 1999-12-O1
17
weeks, i.e. the capsules have not sedimented. Whereas the comparison
formulations, despite their 30% higher perfume content, lose their citrus
fragrance and instead assume a pungent odor after only 1 week due to
chemical decomposition, an adequate quantity of citrus fragrance is
released, even after storage, when the preparations according to the
invention are exposed to a mechanical load. Accordingly, the
microencapsulation is suitable for preventing chemical decomposition of
the sensitive perfumes.
