Note: Descriptions are shown in the official language in which they were submitted.
CA 02232422 1998-03-16
WO 97/09961 PCTIEP96/03911
The Use of Cationic Biopolymers for the Production of Antidandruff
Formulations
Field of the Invention
This invention relates to the use of cationic biopolymers for the
production of antidandruff formulations and for destroying yeasts.
Prior Art
"Scales" is the colloquial terrn for those parts of the horny layer of the
skin which are shed during the constant renewal of the skin layers. On the
hair-covered head, scales are clearly visible as a result of amalgamation by
tallow and perspiration into relatively large aggregates. Cosmetically
unattractive squamation of the scalp, which can be caused by a number of
pathological yeasts and which is generally accompanied by more or less
intensive itching, has hitherto been tackled by treatment with antidandruff
shampoos containing, for example, selenium compounds, pyrithione salts or
glucocorticosteroids as ingredients (cf. S. Shuster in Br. J. Dermatol., 111,
235 (1984) and Cosmet. Toil.,103, 87 (1988).
Now, neither selenium nor pyrithione salts are among the more
dermatologicallycompatible ingredients of hair treatment formulations. More
specifically, this means that they have a certain sensitizing potential and,
because of this, can cause irritation in particularly sensitive users. On
account of the danger of side effects, glucocorticosteroids are only used in
cases where squamation has been aggravated by illness. Accordingly, the
problem addressed by the present invention was to provide new active
ingredients for antidandruff formulations which would act against yeasts,
would reduce scaling of the scalp and at the same time would show improved
dermatological compatibility.
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Description of the Invention
The present invention relates to the use of cationic biopolymers, more
particularly chitosans, for the production of antidandruff formulations.
It has surprisingly been found that, even in very small quantities, the
polymers reduce suspensions of various yeasts to germ contents below 1 0/g
in four hours. Accordingly, when the polymer solutions are applied to the
scalp, i.e. for example where they form part of a hair treatment formulation,
squamation can be significantly reduced. The invention includes the
observation that, in addition, cationic biopolymers and especially chitosans
show particularly high dermatological compatibility which makes them suitable
for use on the scalp.
Cationic biopolymers
Cationic biopolymers, such as chitosans for example, belong to the
group of hydrocolloids. Chemically, they are generally partly deacetylated
chitins - or derivatives thereof - varying in molecularweight which contain the
idealized monomer unit (I):
(I)
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In contrast to most hydrocolloids, which are negatively charged at biological
pH values, chitosans and their derivatives are cationic compounds under
these conditions. The positively charged biopolymers are capable of
interacting with oppositely charged surfaces and, accordingly, are used in
cosmetic hair-care and body-care formulations and also as thickeners in
amphoteric/cationic surfactant mixtures. Reviews on this subject have been
published, for example, by B. Gesslein et al. in HAPPI 27, 57 (1990), by O.
Skaugrud in Drug Cosm. Ind. 148, 24 (1991) and by E. Onsoyen et al. in
Seifen-Ole-Fette-Wachse 117, 633 (1991). Chitosans are produced from
chitin, preferablyfrom the shell remains of crustaceanswhich are available in
large quantities as inexpensive raw materials. Normally, the chitin is first
deproteinized by addition of bases, demineralized by addition of mineral acids
and, finally, deacetylated by addition of strong bases, the molecularweights
being spread over a broad range. Corresponding processes for the
production of - microcrystalline - chitosan are described, for example, in WO
91/05808 (Firextra Oy) and in EP-B1 0 382 150 (Hoechst). Besides cationic
biopolymers of the chitosan type, derivatives, especially hydroxypropyl
chitosans, may also be used as starting materials for the production of the
antidandruffformulations. The quantities used may be in the range from 0.01
to 3% by weight and are preferably in the range from 0.05 to 1% by weight
and more preferably in the range from 0.1 to 0.5% by weight, based on the
formulation.
Commercial Applications
The cationic biopolymers are not only particularly compatible with the
skin, they also kill off the yeasts responsible for the excessive formation of
head scales such as, for example, Candida albicans or Mallassezia fuffur
(which was previously known by the name of Pityrosporum ovale) both quickly
and reliably. Accordingly, they are particularly advantageous active
substances for the production of antidandruff formulations. Another claim
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relates to their use for the destruction of yeasts. This also includes occlusiveapplication on the skin or mucous membrane, for example for treating thrush.
Antidandruff formulations
The antidandruffformulations may contain surfactants compatible with
their other ingredients. Typical examples are fatty alcohol polyglycol ether
sulfates, monoglyceride sulfates, mono- and/or dialkyl sulfosuccinates, fatty
acid isethionates, fatty acid sarcosinates, fatty acid taurides, ether carboxylic
acids, alkyl oligoglucosides, fatty acid glucamides, alkyl amidobetaines and/or
vegetable protein fatty acid condensates.
The formulations, which are preferably shampoos or conditioners, may
also contain oils, emulsifiers, superfatting agents, thickeners, cationic
polymers, silicone compounds, biogenic agents, film formers, preservatives,
dyes and fragrances as further auxiliaries and additives.
Suitable oils are, for example, Guerbet alcohols based on fatty
alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms, esters of
linear C6 20 fatty acids with linear C6.20 fatty alcohols, esters of branched C6 ,3
carboxylic acids with linear C6 20 fatty alcohols, esters of linear C6 ,8 fatty acids
with branched alcohols, more particularly 2-ethyl hexanol, esters of linear
and/or branched fatty acids with polyhydric alcohols (for example dimer diol
or trimer diol) and/or Guerbet alcohols, triglycerides based on C6 ,0 fatty acids,
vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbet
carbonates, dialkyl ethers and/or aliphatic or naphthenic hydrocarbons.
Nonionic, ampholytic and/or zwitterionic surface-active compounds
distinguished by a lipophilic, preferably linear, alkyl or alkenyl group and at
least one hydrophilic group may be used as emulsifiers or co-emulsifiers.
The hydrophilic group may be both an ionic group and a nonionic group.
Nonionic emulsifiers contain, for example, a polyol group, a polyalkylene
glycol ether group or a combination of a polyol and a polyglycol ether group
as the hydrophilic group.
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Preferred formulations are those containing nonionic surfactants from
at least one of the following groups as o/w emulsifiers: (a1) adducts of 2 to
30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide with linear
fatty alcohols containing 8 to 22 carbon atoms, with fatty acids containing 12
to 22 carbon atoms and with alkylphenols containing 8 to 15 carbon atoms in
the alkyl group; (a2) C,2"8 fatty acid monoesters and diesters of adducts of 1
to 30 moles of ethylene oxide with glycerol; (a3) glycerol monoesters and
diesters and sorbitan monoesters and diesters of saturated and unsaturated
fatty acids containing 6 to 22 carbon atoms and ethylene oxide adducts
thereof; (a4) alkyl mono- and -oligoglycosides containing 8 to 22 carbon
atoms in the alkyl radical and ethoxylated analogs thereof and (a5) adducts
of 15 to 60 moles of ethylene oxide with castor oil and/or hydrogenated castor
oil; (a6) polyol and in particular polyglycerol esters such as, for example,
polyglycerol polyricinoleateor polyglycerolpoly-12-hydroxystearate. Mixtures
of compounds from several of these classes are also suitable. The addition
products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty
acids, alkylphenols, glycerol monoesters and diesters and sorbitan mono-
esters and diesters of fatty acids or with castor oil are known commercially
available products. They are homolog mixtures of which the average degree
of alkoxylation corresponds to the ratio between the quantities of ethylene
oxide and/or propylene oxide and substrate with which the addition reaction
is carried out. C,2"8 fatty acid monoesters and diesters of adducts of ethylene
oxide with glycerol are known as refatting agents for cosmetic formulations
from DE-PS 20 24 051. C8"8 alkyl mono- and oligoglycosides, their production
and their use as surfactants are known, for example, from US 3,839,318, US
3,707,535, US 3,547,828, DE-OS 19 43 689, DE-OS 20 36 472 and DE-A1
30 01 064 and also from EP-A 0 077 167. They are produced in particularby
reacting glucose or oligosaccharides with primary C8"8 alcohols. So far as the
glycoside unit is concerned, both monoglycosides in which a cyclic sugar unit
is attached to the fatty alcohol by a ylycoside bond and oligomeric glycosides
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with a degree of oligomerization of preferably up to about 8 are suitable. The
degree of oligomerization is a statistical mean value on which the homolog
distribution typical of such technical products is based. In addition,
zwitterionic surfactants may be used as emulsifiers. Zwitterionic surfactants
are surface-active compounds which contain at least one quaternary
ammonium group and at least one carboxylate and one sulfonate group in the
molecule. Particularly suitable zwitterionic surfactants are the so-called
betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for
example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-
dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl
ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazo-
lines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacyl-
aminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide
derivative known under the CTFA name of Cocoamidopropyl Betaine is
particularly preferred. Ampholytic surfactants are also suitable emulsifiers.
Ampholytic surfactants are surface-active compounds which, in addition to
a C8"8 alkyl or acyl group, contain at least one free amino group and at least
one -COOH- or -SO3H- group in the molecule and which are capable of
forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl
glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipro-pionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-
alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids
containing around 8 to 18 carbon atoms in the alkyl group. Particularly
preferred ampholytic surfactants are N-cocoalkylaminopropionate,
cocoacylaminoethyl aminopropionate and C,2"8 acyl sarcosine.
Suitable w/o emulsifiiers are: (b1) adducts of 2 to 15 moles of
ethylene oxide with castor oil andlor hydrogenated castor oil; (b2) partial
esters based on linear, branched, unsaturated or saturated C,2,22 fatty acids,
ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, penta-
erythritol, dipentaerythritol, sugar alcohols (for example sorbitol) and polyglu-
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cosides (for example cellulose); (b3) trialkyl phosphates; (b4) wool wax
alcohols; (b5) polysiloxane/polyalkyl polyether copolymers and corresponding
derivatives; (b6) mixed esters of pentaerythritol, fatty acids, citric acid and
fatty alcohol according to DE-PS 11 65 574 and (b7) polyalkylene glycols.
Superfatting agents may be selected from such substances as, for
example, polyethoxylated lanolin derivatives, lecithin derivatives, polyol fattyacid esters, monoglycerides and lFatty acid alkanolamides, the fatty acid
alkanolamides also serving as foam stabilizers. Suitable thickeners are, for
example, polysaccharides, more especially xanthan gum, guar-guar, agar-
agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl
cellulose, also relatively high molecular weight polyethylene glycol mono-
esters and diesters of fatty acids, polyacrylates, polyvinyl alcohol and
polyvinyl pyrrolidone, surfactants such as, for example, narrow-range fatty
alcohol ethoxylates or alkyl oligoglucosides and electrolytes, such as sodium
chloride and ammonium chloride.
Suitable cationic polymers are, for example, cationic cellulose
derivatives, cationic starch, copolymers of diallyl ammonium salts and
acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole polymers such as,
for example, Luviquat(É~ (BASF AG, Ludwigshafen, FRG), condensation
products of polyglycols and amines quaternized collagen polypeptides such
as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lame-
quat(~)L, Grunau GmbH), polyethyleneimine, cationic silicone polymers such
as, for example, Amidomethicone or Dow Corning, Dow Corning Co., USA,
copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine
(Cartaretine(~), Sandoz AG, CH), polyaminopolyamides as described, for
example, in FR-A 2 252 840 and crosslinked water-soluble polymers thereof,
cationic chitin derivatives such as, for example, quaternized chitosan, option-
ally in microcrystalline distribution, cationic guar gum such as, for example,
Jaguar~g)CBS, Jaguar(E~)C-17, Jaguartl~)C-16 of Celanese, USA, quaternized
ammonium salt polymers such as, for example, Mirapol~ A-15, Mirapol g) AD-
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1, Mirapol~)AZ-1 of Miranol, USA.
Suitable silicone compounds are, for example, dimethyl polysilox-
anes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty-acid-,
alcohol-, polyether-, epoxy-, fluorine- and/or alkyl-modified silicone com-
pounds. In the context of the invention, biogenic agents are, for example,
plant extracts and vitamin complexes. Conventional film formers are, for
example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl
pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylicacid series, quaternary cellulose derivatives, collagen, hyaluronic acid or salts
thereof and similar compounds. Suitable preservatives are, for example,
phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.
Suitable pea.lescers are, for example, glycol distearic acid esters, such as
ethylene glycol distearate, and also fatty acid monoglycol esters. The dyes
used may be selected from any of the substances which are licensed and
suitable for cosmetic purposes, as listed for example in the publication "Kos-
metische Farbemittel" of the Farl,storrkommission der Deutschen For-
schungsgemeinschaft, published by Verlag Chemie, Weinheim, 1984,
pages 81-106. These dyes are normally used in concentrations of 0.001 to
0.1 % by weight, based on the mixh~re as a whole.
In all, the auxiliaries and additives may make up 1 to 50 and preferably
5 to 40% by weight of the formulations.
The following Examples are intended to illustrate the invention without
limiting it in any way.
Examples
A quantitative suspension test was carried out with the corresponding
test germs to determine germicidal activity. A cationic biopolymer (Hydagen~
CMF, Henkel KGaA, Dusseldorf/FRG) in the form of a 1 % by weight solution
in demineralized water containing an addition of 0.7% by weight of benzoic
acid (Examples 1 and 2) or 0.4% by weight of glycolic acid (Examples 3 and
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4) was used for this test. The test germs used were the yeasts Candida
albicans ATCC 10231 and Malassezia fuffur (= Pityrosporum ovale). 0.1 ml
of the yeast suspensions was added to and thoroughly mixed with 10 g of the
test samples. After an incubation period of 4 h to 7 d, the germ content in the
mixtures was determined. The results are set out in Table 1 below.
Table 1
Germ destruction with cationic biopolymers
Example Test germ; Germ ccnte.,t after contact time
germ counVml
4h 1d 3d 7d
Candida albicans < 10 < 10 < 10 < 10
4.8* 108
2 Malassezia furfur ~ 10 < 10 < 10 < 10
1 8*107
3 Candida albicans < 10 < 10 < 10 < 10
4.8 * 1 o8
4 Malassezia furfur 2*104 < 10 < 10 < 10
1.8* 107
