Note: Descriptions are shown in the official language in which they were submitted.
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COLLAGEN FREE COSMETIC PREPARATIONS
Field of the Invention
The invention belongs to the field of cosmetics and concerns preparations,
especially face masks, which are free of animal collagen and which are
obtained
through cross-linking of chitosans in the presence of glucans.
Prior Art
Cosmetic fleeces are used as moisture masks for face and hands.
Normally these preparations are manufactured based on animal collagen, wherein
aqueous collagen suspensions are adjusted to a pH value in the acidic area and
thereafter the water is removed by freeze-drying. Because of the continuing
criticism of products from animals, there is a demand in the market for
products
which exclusively are manufactured with use of plant raw materials or marine
raw
materials. From the Japanese patent application JP-A2 Hei 6/048917 (Nagawa)
beauty packs with chitosan as active component as well as organic acids and.
collagen as further constituents are known. Object of the Japanese patent
application JP-A2 Hei 4/275207 (Nitta Gelatin) are moisture binding additives
to
skin cosmetic agents, which are mixtures in powder form of chitosan and
collagen. Object of the German patent application DE 19643066 Al (Henkel) is
further collagen free face masks, which are obtained through cross-linking of
chitosan with suitable diisocyanates or dialdehydes. These are however, with
regard to their dermatological compatibility until now not fully satisfactory.
The task of the invention was therefore to make available skin cosmetic
agents which on one side are free from animal collagen and on the other side
are
suited for manufacturing of moisture masks, especially for face and hands, and
which feature immunestimulation and machinability.
Object of the invention are collagen free cosmetic preparations which can
be obtained by cross-linking of swollen aqueous suspensions of chitosans and
&(1,3) glucans with diisocyanates or dialdehydes and subsequent removal of
water.
A further object of the invention concerns a method for manufacturing of
collagen free cosmetic preparations, by cross-linking of swollen aqueous
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suspensions of chitosans and (3-(1,3) glucans with diisocyanates or
dialdehydes
and subsequent removal of water.
Surprisingly it was found that addition of 13-(1,3) glucans to known
cross-linked chitosans delivers cosmetic preparations, especially face masks,
which have a significant better dermatological compatibility,
immunestimulating
effect and flexibility; at the same time the incorporation of different
auxiliary
substances becomes easier.
According to one aspect of the present invention, there is provided a
collagen-free cosmetic preparation, which is obtained by cross-linking of
swollen
aqueous suspensions of chitosans and 1i-(1,3) glucans with a diisocyanate
and/or
a dialdehyde.
According to another aspect of the present invention, there is
provided a collagen-free cosmetic preparation comprising a swollen aqueous
solution of chitosans and R-(1,3) glucans cross-linked with diisocyanates
and/or
dialdehydes.
According to still another aspect of the present invention, there is
provided a method for preparation of a collagen-free cosmetic preparation,
wherein swollen aqueous suspensions of chitosans and (3-(1,3) glucans are
cross-linked with a diisocyanate and/or a dialdehyde, whereafter the water is
removed.
Chitosans
Chitosans are biopolymers and belong to the group of hydrocolloids.
From a chemical point of view they are partial deacetylated chitins with
different
molecular weights, and contain the following - idealized - monomer module:
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2a
cH20H OH NHR
in
NH2
In contrast to most of the hydrocolloids, which are negatively charged in the
range of biological pH-values, chitosans are under these conditions cationic
biopolymers. The positively charged chitosans can interact with opposite
charged
surfaces and are therefore used in cosmetic hair and body care agents as well
as
in pharmaceutical preparations (see Ullmann's Encyclopedia of Industrial
Chemistry, 5th Ed., vol. A6, Weinheim, Verlag Chemie, 1986, p. 231-332). A
summary of these subjects are also published in for example B. Gesslein et
at.,
HAPPI 27 57 (1990), O. Skaugrud in Drug Cosm. Ind. 148, 24 (1991) and E.
Onsoyen et at. in Seifen-Ole-Fette-Wachse 117, 633 (1991). By the production
of
chitosan chitin is used as starting material, preferably the shell residues of
crust
animals, which are available in large amounts as cheap raw materials. The
chitin
is thereby, using a method which first was described by Hackmann et al.,
usually
first deprotonated by addition of bases, demineralized by addition of mineral
acids
and at last deacetylated by addition of strong bases, whereby the molecular
weights can be distributed over a broad spectrum. Corresponding methods are
for
example known from Makromol. Chem. 177, 3589 (1976) or the French patent
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application FR-Al 2701266. Preferably use is made of such types which are
described in the German patent applications DE-Al 4442987 and DE-Al
19537001 (Henkel), and which have an average molecular weight of 10 000 to
1 200 000, preferably 40 000 to 500 000, respectively 800 000 to 1 000 000
Daltons, a viscosity according to Brookfield (1 % by weight in glycolic acid)
below
5 000 mPas, a degree of deacetylation in the range of 80 to 88 % and a content
of
ashes of less than 0,3 % by weight.
9-(1,3) Glucans
The term glucans means homopolysaccharides based on glucose.
Depending on sterical linking there is a difference between 13-(1,3), f3-(1,4)
and 13-
(1,6) glucans. 13-(1,3) Glucans normally show a helical structure, whereas
glucans
with a (1,4) linkage generally have a linear structure. The f3-glucans of the
invention have a (1,3) structure, i.e. they are substantially free from
undesired
(1,6) linkages. Preferably such f3-(1,3) glucans are used where the side
chains
exclusively show (1,3) linkages. Especially the agents contain glucans which
are
obtained on the basis of yeasts from the family Saccharomyces, especially
Saccharomyces corevisiae. Glucans of this type are available in technical
amounts according to known methods. The international patent application WO
95/30022 (Biotec-Mackzymal) describes a method for producing such substances,
wherein glucans with f3-(1,3) and 13-(1,6) linkages are brought in contact
with
13-(1,6) glucanases in such a way, that practically all 9-(1,6) linkages are
loosened. Preferably used for the manufacture of these glucans are glucanases
based on Trichodermia harzianum. As to the manufacture and availability of the
glucans contained in these agents, reference is made to the above cited
publication. The glucans can be contained in the preparations in amounts of
0:1 to
5, preferably 0.2 to 5, and preferably 0.5 to I % by weight, based on the
preparations.
Cross-linking Agents
Diisocyanates which can be used for cross-linking of the chitosans,
preferably follow the formula (I),
O=CN-[X]-NC=O (I)
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wherein X represents a linear or branced naphthenic or aromatic hydrocarbon
residue with 1 to 12 carbon atoms. Prefreably hexametylene diisocynate is used
as cross-linking agent. As dialdehydes substances following the formula (II)
can
be used,
OHC-[Y]-CHO (II)
wherein Y represents a linear or branced naphthenic or aromatic hydrocarbon
residue with I to 12 carbon atoms. Prefreably glutaric dialdehyde is used as
cross-linking agent. The cross-linking agents can be used in amounts of 0.5 to
10,
preferably 1 to 8, and especially 2 to 5 % by weight.
Polyols
Polyols which according to the invention can be used as further
constituents in the cosmetic preparations, preferably have 2 to 15 carbon
atoms
and at least two hydroxyl groups. Typical examples are:
Glycerol;
= alkylene glycols, such as for example ethylene glycol, diethylene glycol,
propylene glycol, butylene glycol, hexylene glycol as well as polyethylene
glycols with an average molecular weight from 100 to 1 000 Daltons;
= oligoglycerol mixtures of technical quality with a self-condensation degree
of 1.5 to 10, such as e.g. technical quality diglycerol mixtures with a
diglycerol content of 40 to 50 % by weight;
= methyol compounds, such as especially trimethylol ethane, trimethylol
propane, trimethylol butane, pentaerythrite and dipentaerythrite;
= low alkyl glucosides, especially such with 1 to 8 carbons in the alkyl
residue, such as for example methyl and butyl glucoside;
= sugar alcohols with 5 to 12 carbon atoms, such as for example sorbitol or
mannit;
= sugars with 5 to 12 carbon atoms, such as for example glucose or
saccharose;
amino sugars, such as for example glucamine.
Usually the polyols are used in amounts from 1 to 10, preferably 2 to 8 %
by weight, based on the dry substance oft the chitosans. Preferably use is
made
of glycerol and polyetylene glycols.
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Manufacture of the Preparations
Normally aqueous solutions or suspensions of the chitosans with a content
of dry matter of 0.5 to 3, preferably 1.8 to 2.2 % by weight with a pH value
of 3.5
to 6, preferably 5.0 to 5.7 are prepared by addition of inorganic or organic
acids,
5 preferably hydrochloric acid, whereby the temperature should be chosen so
that
the swelling of the biopolymers is supported. Normally the temperature lies in
the
area from 20 to 50 and preferably 35 to 45 C. The suspensions made in this
way,
in addition to the dissolved biopolymers also contain swollen not dissolved
particles. The viscosity of the suspension which appears through the mentioned
conditions can be of influence on the mecanical properties later on. To the
suspensions then the glucans and possibly polyols and further cosmetic
components are added. For the mechanical properties of the fleeces it has
shown
to be of advantage to add to the suspension natural fibres, such as for
example
lignin, polyose, pektin and especially cellulose, but also synthetic fibres
such as
Is for example polyesters, polyamides or mixtures thereof in an amount of I to
50,
preferably 5 to 10 % by weight. It is especially recommended to add the fibres
before homogenising of the solution. Subsequently the suspension is
homogenised, cross-linked with the diisocyanates and/or dialdehydes, and the
water is removed. Preferably the removal of water takes place through freeze-
drying, and thereafter splitting into blocks or fine slices can take place.
Commercial Applicability
The preparations according to the invention are preferably used for
preparation of cosmetic face masks. They can further contain as additional
auxiliary and additional agents mild surfactants, oil bodies, emulsifiers,
hyperfatting agents, pearl gloss waxes, consistency substances, thickening
agents, polymers, silicone compounds, fats, waxes, stabilizing agents,
biogenic
active substances, deodorants, antitranspirants, agents against dandruff, film
forming agents, swelling agents, UV light protection agents, antioxidants,
hydrotropes, preservatives, insect repellents, self tanning agents,
solubilizing
agents, perfume oils, colouring agents and suchlike.
Typical examples of suitable mild, i.e. especially skin compatible
surfactants are fatty alcohol polyglycol ether sulphates, monoglyceride
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sulphates, mono- and/or dialkyl sulfosuccinates, fatty acid isethionates,
fatty acid
sarcosinates, fatty acid taurides, fatty acid glutamates, a-olefine
sulphonates,
ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides,
alkylamido
betaines and/or protein fatty acid condensates, the last mentioned preferably
based on wheat proteins.
As oil bodies use can be made of for example Guerbet alcohols based on
fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear
C6-C22
fatty acids with linear C6-C22fatty alcohols, esters of branched C6-C13
carboxylic
acids with linear C6-C22 fatty alcohols, such as e.g. myristyl myristate,
myristyl
palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl
behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate,
cetyl
isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate,
stearyl
palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl
behenate,
stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl
stearate,
1s isostearyl isostearate, isostearyl oleate, isosteayl behenate, isostearyl
oleate,
oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl
oleate, oleyl
behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl
stearate,
behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl
myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl
oleate,
erucyl behenate and erucyl erucate. In additon esters of linear C6-C22 fatty
acids
with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic
acids with linear or branched C6-C22 fatty alcohols, especially dioctyl
malate,
esters of linear and/or branched fatty acids with polyvalent alcohols (such as
e.g.
propylene glycol, dimeric diol or trimeric triol) and/or Guerbet alcohols,
triglycerides based on C6-C10 fatty acids, liquid mixtures of mono-/di-
/triglycerides
based on C6-C18 fatty acids, esters of C6-C22 fatty alcohols and/or Guerbet
alcohols with aromatic carboxylic acids, especially benzoic acid, esters of C2-
C12
dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms
or
polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, plant oils,
branched
primary alcohols, substituted cyclohexanes, linear and branched C6-C22 fatty
alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear
and/or
branched C6-C22 alcohols (e.g. Finsolv TN), linear or branched, symmetrical
or
unsymmetrical dialkyl ethers with 6 to 22 carbon atoms in each alkyl group,
ring
opening products of epoxydated fatty acid esters with polyols, silicone oils
and/or
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aliphatic or naphthenic hydrocarbons, such as e.g. squalan, squalen or dialkyl
cyclohexanes, can be used
As emulsifiers for example nonionic surfactants from at least one of the
following groups may be used:
(1) Addition products of 2 to 30 moles ethylene oxide and/or 0 to 5 moles
propylene oxide on linear fatty alcohols with 8 to 22 C atoms, on fatty acids
with 12 to 22 C atoms and on alkyl phenols with 8 to 15 C atoms in the alkyl
group;
(2) C12118 fatty acid mono- and diesters of addition products of I to 30 moles
ethylene oxide and glycerol;
(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated
and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene
oxide addition products;
(4) alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl
group
and their ethoxylated analogues;
(5) addition products of 15 to 60 moles ethylene oxide on ricinus oil and/or
hardened ricinus oil;
(6) polyol and especially polyglycerol esters,
(7) addition products of 2 to 15 moles ethylene oxide on ricinus oil and/or
hardened ricinus oil;
(8) partial esters based on linear, branched, unsaturated or saturated 06/22
fatty
acids, ricinolic acid and 12-hydroxy stearic acid and glycerol, polyglycerol,
pentaerythrite, d ipentaeryth rite, sugar alcohols (e.g. sorbitol), alkyl
glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) as well
as polyglucosides (e.g. cellulose);
(9) mono-, di- and trialkylphosphates as well as mono-, di- and/or tri-PEG
alkyl
phosphates and their salts;
(10) wool wax alcohols;
(11) polysiloxane/polyalkyl/polyether copolymers or corresponding derivatives;
(12) mixed esters of pentaerythrite, fatty acids, citric acid and fatty
alcohol
according to DE 1165574 PS and/or mixed esters of fatty acids with 6 to 22
carbon atoms, methyl glucose and polyols, preferably glycerol or
polyglycerol,
(13) polyalkylene glycols, as well as
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(14) glycerol carbonate.
The addition products of ethylene oxide and/or of propylene oxide on fatty
alcohols, fatty acids, alkyl phenols, glycerol mono- and diesters as well as
sorbitan mono- and -diesters of fatty acids or on ricinus oil are known
products
which are commercially available. They are mixtures of homologous substances,
with an average degree of alkoxylation corresponding to the ratio of the
amounts
of the substances ethylene oxide and/or propylen oxide and substrate, with
which
the addition reaction is carried out. C12118 fatty acid mono- and diesters of
addition
products of ethylene oxide on glycerol are known from DE 2024051 PS as
revertive fatting agents for cosmetic preparations.
C8118 alkyl mono- and oligoglycosides, their manufacture and their use is
known from prior art. Their preparation can especially be carried out by
reaction of
glucose or oligosaccharides with primary alcohols having 8 to 18 C atoms. With
regard to the glycoside residue both monoglycosides, where a cyclic sugar
group
is glycosidic bond to the fatty alcohol, and oligomeric glycosides with a
degree of
oligomerization until preferably about 8, are suitable. The degree of
oligomerization is then a statistical mean value, based on a distribution of
homologous which is usual for such products of technical quality.
Typical examples of suitable polyglycerol esters are polyglyceryl-2-
dipolyhydroxy stearate (Dehymulus PGPH), polyglycerol-3-diisostearate
(Lameform TGI), polyglyceryl-4-isostearate (Isolan GI 34), polyglyceryl-3-
oleate,
diisostearoyl polygl yce ryl-3-d i isostea rate (Isolan PDI), polyglyceryl-3
metyyl
cellulose diisostearate (Tego Care 450), polyglyceryl-3 beeswax (Cera Bellina
),
polyglyceryl-4 caprate (Polyglycerol caprate T2010/90), polyglyceryl-3 cetyl
ether
(Chimexane NL), polyglyceryl-3 distearate (Cremophor GS 32) and polyglyceryl
polyricine oleate (Admul WOL 1403), polyglyceryl dimerate isostearate, as
well
as their mixtures.
Zwitterionic surfactants can also be used as emulsifiers. The term
zwitterionic surfactants is intended to mean such surface active compounds
which
in their molecule have at least a quaternary ammonium group and at least one
carboxylate and one sulphonate group. Especially suitable zwitterionic
surfactants
are the so-called betaines such as the N-alkyl-N,N-dimethyl ammonium
glycinates, for example the coco alkyldimethyl ammonium glycinate,
N-acylaminopropyl-N,N-dimethyl ammonium glycinate, for example the coco
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acylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxylmethyl
hydroxyethyl imidazoline with in each case 8 to 18 C atoms in the alkyl or
acyl -
groups, as well as the coco acylaminoethyl hydroxyethyl carboxymethyl
glycinate.
Especially preferred is that under the CTFA term cocamidopropyl betaine known
fatty acid amide derivative. Also suitable emulsifiers are ampholytic
surfactants.
Ampholytic surfactants are such surface active compounds which in addition to
a
C8118 alkyl or acyl group in the molecule at least contain a free amino group
and at
least one -COOH or -SO3H group and which can form inner salts. Examples of
suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids,
N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids,
N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyltaurines, N-
alkylsarcosines,
2-alkylaminopropionic acids and alkylamino acetic acids with in each case
about 8
to 18 C atoms in the alkyl group. Especially preferable ampholytic surfactants
are
the N-coco alkylamino propionate, the coco acylamino ethylamino propionate and
the C12/18 acylsarcosine. In addition to the ampholytic, also quaternary
emulsifiers
can be used, of which ester salts of the type of esterquats, preferably
methylquaternised di-fatty acid triethanolamine ester salts, are especially
preferable.
As hyperfatting agents substances such as for example lanolin and
lecithin as well as polyethoxylated or acylated lanolin and lecithin
derivatives,
polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be
used,
whereby the last mentioned at the same time act as foam stabilisers.
As exemplary pearl gloss waxes the following should be mentioned:
Alkylene glycolester, especially ethylene glycol distearate; fatty acid
alkanolamides, especially coco fatty acid diethanolamide; partial glycerides,
especially stearic acid monoglyceride; esters of polyvalent, possibly
hydroxysubstituted carboxylic acids with fatty alcohols with 6 to 22 carbon
atoms,
especially long chain esters of tartaric acid; fat substances, such as for
example
fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty
carbonates,
wherein the sum of carbon atoms is at least 24, especially lauron and
distearyl
ethers; fatty acids such as stearic acid, hydroxystearic acid or behenic acid,
ring
opening products of olefine epoxides with 12 to 22 carbon atoms with fatty
alcohols with 12 to 22 carbon atoms and/or polyols with 2 to 15 carbon atoms
and
2 to 10 hydroxyl groups as well as their mixtures.
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As consistency givers preferably use is made of fatty alcohols or hydroxy
fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and
additionally
partial glycerides, fatty acids or hydroxy fatty acids. A combination of these
substances with alkyl oligoglucosides and/or fatty acid-N-methyl glucamides
with
5 the same chain length and/or polyglycerol-poly-12-hydroxy stearates is
preferred.
Suitable thickening agents are for example types of AerosilTM (hydrophilic
silicic acids), polysaccharides, especially xanthan gum, guar-guar, agar-agar,
alginates and methyl celluloses, carboxymethyl celluloses and hydroxyethyl
cellulose, as well as higher molecular polyethylene glycol mono- and diesters
of
10 fatty acids, polyacrylates, (e.g. Carbopols from Goodrich or Synthalenes
from
Sigma), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone,
surfactants
such as for example ethoxylated fatty acid glycerides, ester of fatty acids
with
polyols such as for example pentaerythrite or trimethylolpropane, fatty
alcohol
ethoxytates with narrow distribution of homologous, or alkyl oligoglucosides
as
well as electrolytes such as sodium chloride and ammonium chloride.
Suitable cationic polymers are for example cationic cellulose derivatives,
such as e.g. a quaternized hydroxyethyl cellulose, which is available under
the
name of Polymer JR 400 from Amerchol, cationic starch, copolymers of diallyl
ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazol
polymers, such as e.g. Luviquat (BASF), condensation products of polyglycols
and amines, quaternized collagen polypeptides, such as for example lauryl
dimonium hydroxypropyl hydrolyzed collagen (Lamequat L / Gri nau), quaternized
wheat polypeptides, polyethylene imine, cationic silicone polymers, such as
e.g.
amidomethicones, copolymers of adipic acid and dimethylamino hydroxypropyl
diethylenetriamine (Cartaretine / Sandoz), copolymers of acrylic acid with
dimethyl diallylammonium chloride (Merquat 550 /Chemviron), polyamino
polyamides, such as e.g. described in FR 2252840 A, as well as their cross-
linked
water soluble polymers, cationic chitin derivatives such as for example
quaternized chitosan, possibly microcrystalline distributed, condensation
products
3o of dihalogen alkyls, such as e.g. dibromobutane with bisdialkylamines, such
as
e.g. bis-dimethylamino-1,3-propane, cationic guar-gum, such as e.g. Jaguar
CBS, Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt
polymers, such as e.g. Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 from
Miranol.
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As exemplary anionic, zwitterionic, amphoteric and non-ionic
polymers the following can be used: Vinyl acetate/crotonic acid copolymers,
vinyl
pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl
acrylate copolymers, methyl vinylether/maleic acid anhydride copolymers and
their esters, non-cross-linked and with polyols cross-linked polyacrylic
acids,
acrylamido propyltrimethyl ammonium chloride/acrylate copolymers,
octylacrylamide/methyl methacrylate/ tert.-butylaminoethyl methacrylate/2-
hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl
pyrrolidone/
vinylacetate copolymers, vinyl pyrrolidone/ dimethylamino
ethylmethacrylate/vinyl
caprolactam terpolymers as well as possibly derivatized cellulose ethers and
silicones.
Suitable silicon compounds are for example dimethyl polysiloxane,
methylphenyl polysiloxane, cyclic silicones as well as amino, fatty acid,
alcohol,
polyether, epoxy, fluorine, glykoside and/or alkyl modified silicone
compounds,
which at room temperature can be in the liquid as well as in the resin state.
Further suitable are simethicones, which are mixtures of dimethicones with an
average chain length of 200 to 300 dimethyl siloxane units and hydrogenated
silicates. A detailed survey of suitable volatile silicones can also be found
in Todd
et al., Cosm.Toil. 91, 27 (1976).
Typical exemplary fats are glycerides, and as waxes natural waxes,
among others, can be used, such as e.g. candelilla wax, carnauba wax, Japan
wax, espartogras wax, cork wax, guaruma wax, rice seed oil wax, sugar cane
wax, ouricury wax, montan wax, beeswax, schellac wax, spermaceti, lanolin
(wool
wax), bOrzel fat, ceresin, ozokerit (terrestrial wax), petrolatum, paraffin
waxes,
micro waxes; chemically modified waxes (hard waxes), such as e.g. montanester
waxes, sasot waxes, hydrogenated yoyoba waxes as well as synthetic waxes,
such as e.g. polyalkylene waxes and polyethylene glycol waxes.
As stabilizers metal salts of fatty acids, such as e.g. magnesium,
aluminium and/or zinc stearate or ricinoleate can be used.
As biogenic active substances should be understood for example
tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, desoxy
ribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA
acids,
amino acids, ceramides, pseudoceramides, essential oils, extracts of plants
and
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marine organisms, vitamin complexes and biotechnological substances, such as
e.g. 9-glucans or other yeast components.
Cosmetic deodorants act against body odours, mask them or eliminate
them. Body odours develop through the effect of skin bacterias on apocrinic
sweat, whereby unpleasant smelling degradation products are formed. According
to this deodorants contain active substances which acts as germ inhibitors,
enzyme inhibitors, odour inhibitors or odour masking agents.
As germ inhibiting agents principally all substances with specific effects
against gram-positive bacteria, such as e.g 4-hydroxy benzoic acid and its
salts
and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl) urea. 2,4,4'-trichloro-
2'-
hydroxy diphenylether, (Triclosan), 4-chloro-3,5-dimethyl phenol, 2,2'-
methylen
bis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methyl ethyl) phenol, 2-benzyl-4-
chiorophenol, 3-(4-chlorophenoxy)-1,2-propanediol, 3-iodo-2-propinyl butyl
carbamate, chlorohexidin, 3,4,4'-trichlorocarbanilide (TCC), antibacterial
odour
substances, thymol, menthol, mint oil, farnesol, phenoxy ethanol, glycerol
monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid n-octylamide
or salicylic acid n-decylamide.
As enzyme inhibitors are for example esterase inhibitors suited. These
are preferably trialkyl citrates such as wie trimethyl citrate, tripropyl
citrate,
triisopropyl citrate, tributyl citrate and especially triethyl citrate
(Hydageen CAT,
Henkel KGaA, Dusseldorf/FRG). The substances inhibit the enzyme activity and
thereby reduce the odour formation. Further substances which can be used as
esterase inhibitors are sterol sulphates or phosphates, such as for example
lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulphate or
phosphate, dicarbonic acids and their esters, such as for example glutaric
acid,
glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid,
adipic acid
monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid
diethyl
ester, hydroxycarboxylic acids and their esters such as for example citric
acid,
malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.
As odour absorbers such substances are suited which take up oudour
forming compounds and are able to hold them extensively. They reduce the
partial pressure of each component and thereby also reduce their spreading
rate.
It is in this connection important that the perfumes are not affected. Odour
absorber have no effect on bacterias. They contain e.g. as main component a
CA 02371543 2009-06-02
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13
complex zinc salt of ricinolic acid or special, to a high degree odour neutral
scent
substances which are known by the skilled person an "Fixateure", such as e.g.
extracts of labdanum or styrax or certain abietinic acid derivatives. As odour
masking substances odouriferous substances or parfume oils are used, which in
addition to their function as odour masking substances give the deodorants
their
special scent. As perfume oils mixtures of natural and synthetic scent
substances
should be mentioned. Natural scent substances are extracts of flowers, stems
and
blades, fruits, fruit shells, roots, wood, herbs and grass, needles and twigs,
as well
as resins and balsams. Raw materials from animals are also possible, such as
for
example zibet and castoreum. Typical synthetic odour compounds are products
from types of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons.
Odour compounds from types of esters are e.g. benzyl acetate, p-tert.-
butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl
benzoate,
benzyl formate, allylcyclohexyl propionate, styrallyl propionate and benzyl
salicylate. Bennylethyl ether belongs for example to the ethers, to the
aldehydes
e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal,
citronellyl
oxyacetaldehyde, cyclamen aldehyde, hydroxy citronellal, lilial and
bourgeonal, to
the ketones e.g. the ionones and methylcedryl ketone, to the alcohols anethol,
citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and
terpineol; to the hydrocarbons mainly the terpenes and balsams belong.
However,
mixtures of different odour substances are preferred, which together give a
pleasant smell. Also etheral oils with low volatility, which often are used as
aroma
components, are suited as perfume oils, e.g. sage oil, camomile oil, carnation
oil,
melissa oil, mint oil, cinnamon leaf oil, limeflower oil, juniper berry oil,
vetiver oil,
oliban oil, galbanum oil, labdanum oil and lavandin oil. Preferably used are
bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl
alcohol,
a-hexylcinnamon aldehyde, geraniol, benzyl aceton, cyclamen aldehyde,
linalool,
boisambrene forte, ambroxane, indol, hedione, sandelice, lemon oil, mandarin
oil,
orange oil, allylamyl glycolate, cyclovertal, lavandine oil, muskateller sage
oil,
1. -damascone, geranium oil bourbon, cyclohexyl salicylate, vertofix coeur,
iso-E-
super, FixolideTM NP, Evernyl, iraidein gamma, phenylacetic acid, geranyl
acetate,
benzyl acetate, rose oxide, romillate, irotyl and floramate, alone or in
mixtures.
Antitranspirants (antiperspirants) reduce the formation of sweat through
influence on the activity of the eccrine sweat glands, and therefore
counteract
CA 02371543 2001-10-24
14
axillary wetness and body odour. Aqueous or water free formulations of
antitranspirants typically contain the following ingredients:
(a) astringent active substances,
(b) oil components,
(c) nonionic emulsifiers,
(d) co-emulsifiers,
(e) consistency substances,
(f) auxiliaries such as e.g. thickening agents or complexing agents and/or
(g) non-aqueous solvents such as e.g. ethanol, propylen glycol and/or
glycerol.
As astringent antitranspirant active substances above all salts of
aluminium, zirkonium or zinc are suited. Such suitable antihydrotic active
agents
are e.g. aluminium chloride, aluminium chlorohydrate, aluminium
dichlorohydrate,
aluminium sesquichlorohydrate and their complexes, e.g. with propylene glycol-
1,2. Aluminium hydroxy allantoinat, aluminium chloride tartrate, aluminium-
zirkonium trichlorohydrate, aluminium-zirkonium tetrachloro hydrate, Aluminium-
zirkonium pentachloro hydrate and their complexes, e.g. with amino acids such
as
glycine. In addition antitranspirants can contain small amounts of common oil
solube and water soluble auxiliaries. Such oil solube auxiliaries can e.g. be:
= Inflammation inhibiting, skin protecting, or fragrant etheral oils,
= synthetic skin protecting active agents and/or
= oil soluble perfums.
Common water soluble additives are e.g. preservatives, water soluble
scents, agents for adjustment of pH, e.g. buffer mixtures, water soluble
thickeners, e.g. water soluble natural and synthetic polymers such as e.g.
xanthan
gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular
polyethylene
oxides.
As anti dandruff agents climbazol, octopirox and zinc pyrethion can be
used.
Useable film formation agents are for example chitosan, microcrystalline
chitosan, quaternary chitosan, polyvinyl pyrrolidone, vinyl
pyrrolidone/vinylacetate
copolymers, polymers of the acrylic acids, quaternary derivatives of
cellulose,
collagen, hyaluronic acid or its salts and similar compounds.
As swelling agents for aqueous phases montmorillonite, clay mineral
substances, pemulen, as well as alkylmodified Carbopol types (Goodrich) can be
CA 02371543 2001-10-24
used. Further suitable polymers or swelling agents can be found in the survey
of
R. Lochhead in Cosm. Toil. 108, 95 (1993).
UV light protection factors are e.g organic substances (light protection
filters) which at room temperature are in liquid or crystalline form, and
which are
5 capable of absorbing ultraviolet radiation and to set free the received
energy in
the form of radiation with long wavelength, e.g. in the form of heat. UVB
filters can
be soluble in oils or in water. As oil soluble substances the following are
mentioned as examples:
= 3-Benzyliden camphor, respectively 3-benzylidene norcamphor and the
10 derivatives thereof, e.g. 3-(4-methylbenzylidene) camphor as described in
EP-B1 0693471;
= 4-aminobenzoic acid derivatives, preferably 4-(dimethylamino) benzoic acid
2-ethylhexyl ester, 4-(dimethylamino) benzoic acid 2-octyl ester and
4-(dimethylamino) benzoic acid amyl ester;
15 esters of cinnamonic acid, preferably 4-methoxy cinnamonic acid
2-ethylhexyl ester, 4-methoxy cinnamonic acid propyl ester, 4-methoxy
cinnamonic acid isoamyl ester, 2-cyano-3,3-phenyl cinnamonic acid
2-ethythexylester (octocrylene);
= esters of salicylic acid, preferably salicylic acid 2-ethylhexylester,
salicylic
acid 4-isopropyl benzylester, salicylic acid homomenthylester;
= derivatives of benzophenone, preferably 2-hydroxy-4-methoxy
benzophenone, 2-hydroxy-4-methoxy-4'-methyl benzophenone,
2,2'-dihydroxy-4-methoxy benzophenone;
= esters of benzalmalonic acid, preferably 4-methoxy benzmalonic acid
2-ethylhexyl ester,
= triazine derivatives, such as e.g. 2,4,6-trianilino-(p-carbo-2'-ethyl-l'-
hexyloxy)-1,3,5-triazine and octyl triazone, as described in EP Al 0818450,
or dioctyl butamido triazone (Uvasorb HEB);
= propane-l,3-diones, such as e.g.1-(4-tert.-butyl phenyl)-3-(4'-methoxy-
phenyl)-propane-1,3-lion;
= ketotricyclo(5,2,1,0)-decane derivatives, as described in EP 069521 131.
As,water soluble substances the following can be mentioned:
= 2-Phenylbenzimidazol-5-sulphonic acid and the alkali, alkaline earth,
ammonium, alkylammonium, alkanolammonium and glucammonium salts;
CA 02371543 2009-06-02
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= suiphonic acid derivatives of benzophenones, preferably 2-hydroxy-
4-methoxybenzophenon-5-suiphonic acid and their salts;
= sulphonic acid derivatives of 3-benzyliden camphor, such as e.g.
4-(2-oxo-3-bornylidenemethyl)-benzene suiphonic acid and
2-methyl-5-(2-oxo-bornylidene) sulphonic acid and their salts.
As typical UV-A filters especially derivatives of benzoyl methane come in
question, such as e.g. 1-(4'-tert.-butylphenyl)-3-(4'-methoxyphenyl)propane-
1,3-
dion, 4-tert.butyl-4'-methoxydibenzoyl-methane (ParsolTM 1789), or 1-phenyl-3-
(4'-
isopropylphenyl-propane-1,3-dion, as also enamine compounds, as described in
DE 19712033 (BASF). The UV-A and UV-B filters can of course also be used in
mixtures. In addition to the mentioned soluble substances also insoluble light
protection pigments can be used for this purpose, i.e. fine disperse metal
oxides
or salts. Examples of suitable metal oxides are especially zinc oxide and
titanium
dioxide and in addition other oxides of iron, zirconium, silicon, manganese,
aluminium and cerium, as well as their mixtures. As salts silicates (talc),
barium
sulphate or zinc stearate can be used. The oxides and salts are used in the
form
of the pigments for skin caring and skin protecting emulsions and decorative
cosmetics. The particles should have an average diameter of less than 100 nm,
preferably between 5 and 50 nm and especially between 15 and 30 nm. They can
have a spherical shape, but particles can also be used which have an
ellipsoidal
form or else have a shape which differs from the spherical shape. The pigment
can also be present in a surface treated form, i.e. made hydrophilic or
hydrophobic. Typical examples are coated titanium dioxides, such as e.g.
Titandioxid T 805 (Degussa) or Eusolex T2000 (Merck). As hydrophobic coating
agents preferably silicones and especially trialkoxy octyl silane or
Simethicone
can be used. In sun protecting agents preferably so-called micro or nano
pigments are used. In sun protecting agents preferably so-called micro or nano
pigments are used. Preferably micronized zinc oxide is used.
Further suitable UV light protection factors can be found in the survey by
P.Finkel in SOFW-Joumal 122, 543 (1996). In addition to the primary light
protection substances also secondary light protection substances of the
antioxidant type find use, which interrupt the photochemichal reaction chain,
which is initiated when UV radiation penetrates the skin. Typical examples of
such
are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their
derivatives,
CA 02371543 2001-10-24
17
imidazoles (e.g. urocaninic acid) and their derivatives, peptides such as
D,L-camosine, D-camosine, L-camosine and their derivatives (e.g. anserine),
carotinoides, carotine (e.g. a-carotin, R-carotin, lycopin) and their
derivatives,
chlorogenic acid and its derivatives, liponic acid and its derivatives (e.g.
dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
thiore-
doxin, glutathion, cystein, cystin, cystamine and their glycosyl, n-acetyl,
methyl,
ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, y-linoleyl,
cholesteryl and
glyceryl esters) as well as their salts, dilauryl thiodipropionate, distearyl
thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers,
peptides, lipides, nucleotides, nucleosides and salts) as well as sulfoximine
compounds (e.g. buthionin sulfoximines, homocystein sulfoximines, butionin
sulfones, penta-, hexa-, hepta-thionin sufoximine) in very small compatible
doses
(e.g. pmol to Nmol/kg), further (metal) chelating agents (e.g. a-hydroxy fatty
acids,
palmitic acid, phytinic acid, lactoferrine), a-hydroxy acids (e.g. citric
acid, lactic
acid, malic acid), humin acid, bile acid, bile extracts, bilirubin,
bifiverdin, EDTA,
EGTA and their derivatives, unsaturated fatty acids and their derivatives
(e.g.
y-linolenic acid, linolic acid, oleic acid), folic acid and their derivatives,
ubichinon
and ubichinol and their derivatives, vitamin C and derivatives (e.g. ascorbyl
palmitate, Mg-ascorbyl phosphate, ascorbyl acetate), tocopherols and
derivatives
(e.g. vitamin E acetate), vitamin A and derivatives (vitamin A patmitate) as
well as
koniferyl benzoate of benzoe resin, rutinic acid and their derivatives, a-
glycosylrutin, ferula acid, furfuryliden glucitol, carosine, butylhydroxy
toluene,
butylhydroxy anisol, nordihydro guajak resin acid, nordihydro guajaret acid,
trihydroxy butyrophenon, uric acid and their derivatives, mannose and its
derivatives, super oxide dismutase, zinc and its derivatives (e.g. ZnO,
ZnSO4),
selen and its derivatives (e.g. selen-methionin), stilbenes and their
derivatives
(e.g. stilbene oxide, trans-stilbene oxide), and the derivatives suitable
according
to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides,
peptides
and lipids) of these mentioned active substances.
As preservatives for example phenoxyethanol, formaldehyde solution,
parabene, pentanediol or sorbic acid as well as those mentioned in enclosure
6,
parts A and B of the cosmetic regulations, are further classes of substances.
As
insect repellents N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent
3535 come into question, as self tanning agent dihydroxy acetone is suited.
CA 02371543 2009-06-02
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As perfume oils mixtures of natural and synthetic scent substances should
be mentioned. Natural odour substances are extracts of flowers (lilies,
lavender,
roses, jasmin, neroli, ylang-ylang), stems and blades (geranium, patchouli,
petitgrain), fruits (anis, coriander, caraway, juniper), fruit shells
(bergamot, lemon,
orange), roots (macis, angelica, celery, kardamon, costus, iris, calmus), wood
(stone pine, sandel, guajac, cedar, rosewood), herbs and grass (tarragon,
lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, traipsed),
resins
and balsams (galbanum, elemi, benzoe, myrrh, olibanum, opoponax). Raw
materials from animals are also possible, such as for example zibet and
castoreum. Typical synthetic odour compounds are products from types of
esters,
ethers, aldehydes, ketones, alcohols and hydrocarbons. Odour compounds from
types of esters are e.g. benzyl acetate, phenoxyethyl isobutyrate, p-tert.-
butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate,
phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl
glycinate,
allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
Benzylethyl
ether belongs for example to the ethers, to the aldehydes e.g. the linear
alkanales
with 8 to 18 carbon atoms, citral, citronellal, citronellyl oxyacetaldehyde,
cyclamen
aldehyde, hydroxy citronellal, lilial and bourgeonal, to the ketones e.g. the
ionones, a-isomethyl ionon and methylcedryl ketone, to the alcohols anethol,
citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and
terpineol; to the hydrocarbons mainly the terpenes and balsams belong.
However,
mixtures of different odour substances are preferred, which together give a
pleasant smell. Also etheral oils with low volatility, which often are used as
aroma
components, are suited as perfume oils, e.g. sage oil, chamomile oil,
carnation oil,
melissa oil, mint oil, cinnamon leaf oil, limeflower oil, juniper berry oil,
vetiver oil,
oliban oil, galbanum oil, labolanum oil and lavandin'oil. Preferably used are
bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl
alcohol,
a-hexylcinnamon aldehyde, geraniol, benzyl acetone, cyclamen aldehyde,
linalool,
boisambrene forte, ambroxane, indol, hedione, sandelice, lemon oil, mandarin
oil,
orange oil, allylamyl glycolate, cyclovertal, lavandine oil, muskateller sage
oil,
I,-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, iso-
E-
super, FixolideTM NP, Evemyl, iraidein gamma, phenylacetic acid, geranyl
acetate,
benzyl acetate, rose oxide, romillate, irotyl and floramate, alone or in
mixtures.
CA 02371543 2001-10-24
19
As colouring agents such substances which are suited and approved for
cosmetic purposes can be used, such as for example those mentioned in the
publication "Kosmetische Farbemittel" (cosmetic dyes) of the
"Farbstoffkommission der Deutschen Forschungsgemeinschaft", published by
Verlag Chemie, Weinheim, 1984, p. 81-106. These dyes are generally used in
concentrations from 0.001 to 0.1 % by weight, based on the whole mixture.
The full amount of auxiliary and additional agents can be 1 to 50, preferably
5 to 40 % by weight, based on the agents.
Examples
Example I
Into a 2 liter apparatus with a stirrer 1960 ml of water was added and
warned up to 40 C, and 40 g chitosan (Hydagen CMPF, Henkel KGaA,
Dusseldorf / FRG) was added. The pH value of the mixture was adjusted to 5.5
by
addition of hydrochloric acid. Thereafter 2 g (5 % by weight based on dry
substance) glycine and 0.5 g betaglucan (Higcareen GS) was added and the
mixture was homogenised with an Ultraturrax. Thereafter 0.8 g (2 % by weight
based on dry substance) hexamethylene diisocyanate was carefully stirred in.
After the cross-linking the suspension was frozen into a block and
subsequently
lyophilized. By splitting of the blocks after water removal to the desired
thickness,
water soluble fleeces were obtained, which by moistening behaved like sponges.
Example 2
Into a 2 liter apparatus with a stirrer 1960 ml of water was added and
warned up to 40 C, and 40 g chitosan (Hydagen CMPF, Henkel KGaA,
Dusseldorf / FRG) was added. The pH value of the mixture was adjusted to 5.5
by
addition of hydrochloric acid. Thereafter 2 g (5 % by weight based on dry
substance) glycine, 1 g betaglucan (Higcareen GS) and 2 g (5 % by weight
based on dry substance) cellulose fibers were added and the mixture was
homogenised with an Ultraturrax. Thereafter 0.8 g (2 % by weight based on dry
substance) hexamethylene diisocyanate was carefully stirred in. After the
cross-
linking the suspension was frozen into a block and subsequently lyophilized.
By
splitting of the blocks after water removal to the desired thickness, water
soluble
fleeces were obtained, which by moistening behaved like sponges.
