Note: Descriptions are shown in the official language in which they were submitted.
CA 02299781 2000-02-28
PEROXIDE PREPARATIONS CONTAINING MICROENCAPSULATED
COLORANTS
Field of the Invention
This invention relates generally to bleaching agents and
disinfectants and, more particularly, to peroxide preparations containing
colorants in microencapsulated form.
Background of the Invention
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 peroxide -
are normally added to the wash liquor. These peroxide bleaching liquors
rarely contain colorants because colorants are readily oxidized and change
color in peroxide-containing environments.
Accordingly, the problem addressed by the present invention was to
formulate colorants in a stable manner in peroxide-containing preparations,
thereby improving their appearance.
Description of the Invention
The present invention relates to peroxide-containing preparations
which are characterized in that they contain colorants in microencapsulated
form.
It has surprisingly been found that colorants can be stably
formulated in peroxide-containing preparations, thereby improving their
appearance, providing they are incorporated in microencapsulated form.
The microcapsules are chemically and physically, more particularly
CA 02299781 2000-02-28
2
spatially, stable in the preparations according to the invention, i.e. the
microcapsules do not undergo decomposition or sedimentation in the
preparations. In this way, virtually any known colorants can be used in
peroxide-containing preparations.
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 0.5 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 precisely, they are normally finely dispersed 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 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,
CA 02299781 2000-02-28
3
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, polysaccharides, 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 substances 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 in diameter are
preferred. Microcapsules invisible to the naked eye have a diameter of
preferably 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 in brackets) Hallcrest Microcapsules (gelatin, gum
arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapseln
(alginic acid, agar agar), Induchem Unispheres (lactose, microcrystalline
cellulose, hydroxypropylmethyl cellulose), Unicerin C30 (lactose, micro-
crystalline 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
CA 02299781 2000-02-28
4
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.
Colorants
In the context of the present invention, colorants are understood to
be any inorganic and organic substances with a coloring effect [DIN 55944
(Nov. 1973)]. Both natural and synthetic colorants may be used. The
inorganic colorants are pigments and may even have a filler-like character
while the organic colorants encompass both pigments and dyes. The
colorants also include, for example, gloss, pearlescent and luminous
pigments. These colorants do not include fluorescent dyes, so-called
optical brighteners.
Dyes in the context of the invention are colorants which are soluble
in solvents and/or binders and which absorb in the visible light region. Both
natural dyes, for example flower and plant dyes, and synthetic dyes, for
example aromatic or heterocyclic, ionic or nonionic compounds, may be
used.
Suitable pigments are, for example, green chlorophthalocyanines
(Pigmosol~ Griin, Hostaphine~ Griin), yellow Solar Yellow BG 300
(Sandoz), blue chlorophthalocyanine (Hostaphine~ Blau) and Cosmenyl~
Blau.
An overview of the colorants available in Europe can be found in
CA 02299781 2000-02-28
"Textilbetrieb", Wiirzburg, 1978, pp. 51-71. The substances suitable and
approved as dyes which are listed, for example, in the publication
"Kosmetische Farbemittel" of the Farbstoff Kommission der Deutschen
Forschungsgemeinschaft, 3rd fully revised edition, Verlag Chemie,
5 Weinheim, 1991, pp. 81-106.
These colorants are used in microencapsulated form in the
preparations according to the invention. By this is meant not only the use
of a single colorant in microencapsulated form, for example a colorless
peroxide bleaching agent containing blue microcapsules, but also the use
of various colorants in microencapsulated form, for example a colorless
peroxide bleaching agent containing blue and green microcapsules. This is
not meant to imply a limit to the number of microencapsulated colorants
used at the same time; for example, the microcapsules may contain three,
four or five etc. different colorants.
In one particular embodiment of the invention, non-
microencapsulated colorants may also be added to the peroxide-containing
preparations besides microencapsulated colorants. These are understood,
for example, to include blue peroxide bleaching compositions containing
blue andlor red microcapsules. Colored peroxide bleaching compositions
containing many differently colored microencapsulated colorants are also
possible, for example a green peroxide bleaching composition containing
blue, green, red etc. microcapsules. It is possible in this way to obtain
mixtures in which the microcapsules and the compositions according to the
invention can contain both identical and different colorants.
The colorants are used in concentrations of preferably 0.05 to 0.4%
by weight and more preferably 0.1 to 0.3% by weight, based on the mixture
as a whole.
Seq~uesterinq a ents
If the preparations are used for treating fabrics, it is advisable to add
CA 02299781 2000-02-28
6
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:
(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
CA 02299781 2000-02-28
7
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
Phosphoric 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 phosphoric acids. The organic phosphoric
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):
O
R'-P-OR2 (I)
OR2
in which R' is an optionally substituted alkyl andlor 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 phosphoric acids such as, for example, ethyl phosphoric 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 phosphoric acids corresponding
to formula (II):
CA 02299781 2000-02-28
O CH3 H
HO-P-(CH2)m(CH)n-N->O (ll)
OR3 H
in which R3 is hydrogen, a (CH2)m(CHCH3)"NH20 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
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.
Surfactants
To support their cleaning performance, the preparations may
additionally contain peroxide-stable surfactants, for example fatty acid
salts, alkyl sulfates, alkyl sulfonates, alkyl benzenesulfonates, xylene
sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines,
CA 02299781 2000-02-28
9
sugar esters and fatty acid-N-alkyl glucamides. Alkyl ether sulfates, amine
oxides, alk(en)yl oligoglycosides and fatty alcohol polglycol ethers are
preferably used. The surfactants together generally make up from 1 to
15% by weight and preferably from 5 to 10% by weight 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):
R40-(CH2CH20)~S03X (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~2,~4 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
suitable as surface-active ingredients in accordance with the present
invention correspond to formula (IV):
CA 02299781 2000-02-28
Rs
R5-N-~~ (IV)
5 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
10 containing 1 to 4 carbon atoms. Amine oxides corresponding to formula
(IV), in which R5 and R6 represent C~2,~4 or C~v~$ 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 C~2,~4
or C~2,~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 more preferably in quantities of 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 R8 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 ingredients, may be derived from aldoses or ketoses
containing 5 or 6 carbon atoms, preferably glucose. Accordingly, the
preferred alkyl andlor 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
CA 02299781 2000-02-28
11
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 andlor 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 Ra 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$_~a 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
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):
CA 02299781 2000-02-28
12
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
aldehydes 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 HLB value above
10 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.
Thickeners
The use of electrolytes is a very simple and inexpensive method of
CA 02299781 2000-02-28
13
10
adjusting viscosity. However, it has been found that the presence of
chloride ions alongside peroxide can cause pitting in certain textiles
through the formation of chlorine. For this reason, organic thickeners are
used in one preferred embodiment of the invention. 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.
Commercial Ap~~lications
The preparations according to the invention generally have a non
aqueous component of 5 to 35% by weight and 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. 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. In addition, the preparations may contain perfumes and
optical brighteners and also antioxidants or preservatives, for example 2,6-
CA 02299781 2000-02-28
14
di-tert.-butyl-4-methylphenol (BHT).
The optical brighteners which are used in microencapsulated form
in accordance with the present invention are preferably those which are
otherwise unstable in peroxide-containing preparations. Typical examples
of suitable optical brighteners are derivatives of diaminostilbene disulfonic
acid and alkali metal salts thereof. Suitable optical brighteners are, for
example, derivatives of 4,4'-diamino-2,2'-stilbene disulfonic acid (flavonic
acid), such as in particular the salts of 4,4'-bis-(2-anilino-4-morpholino-
1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of
similar structure which, instead of the morpholino group, contain a
diethanolamino group, a methylamino group, an anilino group or a 2-
methoxyethylamino group. Other brighteners which may be present are
those of the substituted diphenyl styryl type, for example alkali metal salts
of 4,4'-bis-(2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-2-sulfostyryl)-
diphenyl
or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl, methyl umbelliferone,
coumarin, dihydroquinolinone, 1,3-diaryl pyrazoline, naphthalic acid amide,
benzoxazole, benzisoxazole and benzimidazole systems linked by CH=CH
bonds, heterocycle-substituted pyrene derivatives and the like. Mixtures of
the brighteners mentioned above may also be used. The potassium salt of
4,4'-bis-(1,2,3-triazolyl)-(2)-stilbine-2,2-sulfonic acid marketed under the
name of Phorwite~ BHC 766 is preferred. The microcapsules generally
contain the optical brighteners in quantities of 1 to 95% by weight,
preferably in quantities of 10 to 60% by weight and more preferably in
quantities of 25 to 50% by weight, based on the weight of the capsules.
Ther perfumes used in microencapsulated form in accordance with
the invention are preferably perfumes which would otherwise be unstable in
peroxide-containing preparations. Typical examples of suitable perfumes
are mixtures of natural and synthetic perfumes. Natural perfumes include
the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang-ylang),
stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander,
CA 02299781 2000-02-28
caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg,
angelica, celery, cardamom, costus, iris, calmus), woods (pinewood,
sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses
(tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir,
5 pine, dwarf pine), resins and 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 perfume
10 compounds of 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
15 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,
CA 02299781 2000-02-28
16
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.
Besides the perfumes mentioned above, microencapsulated
peroxide-stable perfumes may of course also be used, including for
example 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), tetrahydromyrcenol (THM, 2,6-dimethyloctan-2-ol), 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 tetrahydronaphtha-
lene), 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 weight of
the capsule.
The preparations according to the invention are prepared by stirring.
The product obtained may optionally be decanted or filtered to remove
foreign bodies andlor agglomerates. In addition, the preparations have a
viscosity above 100 and preferably above 200 mPas, as measured at 20°C
in a Brookfield viscosimeter (spindle 1, 10 r.p.m.).
CA 02299781 2000-02-28
17
Examples
Pigments in microcapsule form and, optionally, pure pigments were
added to various hydrogen peroxide solutions. Examples 1 to 6 of the
preparations according to the invention are set out in Table 1.
Table 1
Composition of the bleaching agents
E ~ .~ ", r'~'~~ . ,
~. -..3 .~.-.,
., ,. , , .
~'~ .... ~ ~ . , ..
~r a .,, ~~~. d ':':
. , s
x ,_- E, $ '
r t~~ 2Y ~ ~
.. j. ~T , ' .~a :~3
, : x ~ rx ":
r ,,..... ~ ~!"a.,...~. ~ .a,
8 r";~.. . e. r.
", ~.. .F: E Y : Y ~5::
. r . ~ ,..,
a ~,. ~.. " ~.>.
,~ ~. '.; I
Sp,eP ': e.. . "~
;~ .co.~ >.
:!, . fi~;r ~,
Y ~f..3 , 3 . t,
-s' n.J
'g , y a.., e.... x:r.
"q.~ ' .
i ,> yea.9.rai.
~,.,
s .~ 1
:.. ,.. f ,
.,
s . , :: a~?:,,
S~a. ~ ';.::.. n. ~3
~ .. ,. ~ ...:
2''.'a ,t
-z , .
'': . ~. 3P.: , '::..
t 3 - ~.,.. : i 2
~,.~.a...~.~,..,.~, ,..
~ . ... GM. .
1' ~ r aW , ~ ~ ,: ~I
b I'~a G N yx~~,,Ea~~~~~::%
.. , ~' 3, . .
r.. ''~t ~ ,
r s..~ ..."'.3st~'~'z;.:~..'4~,~.:9~.:::r
3 . I
.~ <.ar
. .n b ~,
~rs.s.u~.,..
W
Hydrogen peroxide 7.5 7.5 7.5 7.5 7.5 7.5
Cu~a Cocoalcohol+6E08.5 - _ 8.5 _ _
C,v,a Cocoalcohol+4E00.75 - - 0.75 - -
C2"4 Cocoalcohol+2E00.75 2 2 0.75 2 2
sulfate, TEA salt
Arlipon~ FT - 0.7 0.7 - _ _
Xanthan Gum (Keltrol- - 0.7 - - 0.7
T,
Kelco)
BHT 0.01 0.01 0.01 0.01 0.01 0.01
EtOH 0.192 0.192 0.192 0.192 0.192 0.192
Pigmosol Blue 0.000350.000350.000350.000350.000350.00035
Polyacrylate'~ - 1.0 - - 1.0 -
Trilon~ M2~ 0.1 0.1 0.1 0.1 0.1 0.1
Microcapsules3~ 0.3 0.2 0.1 - - _
Solar
Yellow BG 300
Microcapsules3~ - 0.2 - 0.2 0.1 0.1
Cosmenyl~ Blau
Microcapsules3~ - - 0.1 - 0.1 0.1
Hostaphine~ Griin
Microcapsules3~ - - 0.1 - - 0.1
Hostaphine~ Blau
Solar Yellow BG - - - 0.2 - _
300
Cosmenyl~ Blau - - - - 0.1 -
Hostaphine~ Blau - - - - - 0.1
Water ~ to 100
CA 02299781 2000-02-28
18
~~ Carbopol 497 (Goodrich);
2~ Methylglycine diacetic acid trisodium salt (BASF)
3~ shell material: sodium alginate