U.S. patent number RE29,871 [Application Number 05/776,935] was granted by the patent office on 1978-12-26 for fatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions.
This patent grant is currently assigned to L'Oreal. Invention is credited to Jean Boulogne, Christos Papantoniou.
United States Patent |
RE29,871 |
Papantoniou , et
al. |
December 26, 1978 |
Fatty compositions for use in cosmetic makeup compositions and said
cosmetic makeup compositions
Abstract
A fatty composition for use in producing cosmetic compositions
comprising a mixture of at least one cosmetic fatty body and at
least one non-toxic copolymer of the formula: ##STR1## wherein
R.sub.1 represents a saturated hydrocarbon chain, linear or
branched, having from 1-19 carbon atoms; R.sub.2 represents a
member selected from the group consisting of A. ##STR2## wherein
R.sub.4 has the same meaning as R.sub.1 but is different from
R.sub.1 in the same copolymer, B. --CH.sub.2 --R.sub.5, wherein
R.sub.5 represents a saturated hydrocarbon chain, linear or
branched, having from 5-25 carbon atoms, C. --O--R.sub.6, wherein
R.sub.6 is a saturated hydrocarbon chain having from 2 to 18 carbon
atoms, and D. ##STR3## wherein R.sub.7 is a saturated hydrocarbon
chain, linear or branched, having from 1-19 carbon atoms, and
R.sub.3 represents hydrogen when R.sub.2 represents (a), (b), or
(c) or R.sub.3 represents .Iadd.hydrogen or .Iaddend.methyl when
R.sub.2 represents (d). The copolymer must contain at least 15
weight percent of at least one monomer of unit 1a or of unit 1b in
which the saturated hydrocarbon chain, linear or branched, has at
least 7 carbon atoms. This fatty composition is employed to produce
a cosmetic makeup composition, such as lip rouge, in paste or stick
form, or mascara, and is present in said cosmetic composition in
amounts of 99.5-15 percent by weight of the total weight of the
cosmetic composition.
Inventors: |
Papantoniou; Christos (Commune
de Villevaude, FR), Boulogne; Jean (L'Hay-les-Roses,
FR) |
Assignee: |
L'Oreal (Paris,
FR)
|
Family
ID: |
26640133 |
Appl.
No.: |
05/776,935 |
Filed: |
March 11, 1977 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
477515 |
Jun 7, 1974 |
03937811 |
Feb 10, 1976 |
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Foreign Application Priority Data
Current U.S.
Class: |
424/64; 424/59;
424/63; 424/70.11; 424/70.7; 424/DIG.5; 514/547; 514/782; 514/785;
514/787; 514/939; 514/943; 516/46; 523/105; 526/208; 526/212;
526/318; 526/330; 526/331; 528/4; 528/96 |
Current CPC
Class: |
A61K
8/8135 (20130101); A61K 8/8152 (20130101); A61Q
1/06 (20130101); A61Q 1/10 (20130101) |
Current International
Class: |
A61K
8/72 (20060101); A61K 8/81 (20060101); A61Q
1/10 (20060101); A61Q 1/02 (20060101); A61Q
1/06 (20060101); A61K 007/025 () |
Field of
Search: |
;424/63,64,70,78,365,DIG.5 ;252/312,316 ;260/18R,37NP,37P |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Clarke; Vera C.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Claims
What is claimed is:
1. A fatty composition for use in producing a cosmetic composition
selected from the group consisting of a lip rouge and a mascara,
comprising a mixture of:
i. at least one cosmetic fatty body consisting essentially of about
6-100% by weight of at least one cosmetic wax and 0-94% of at least
one cosmetic oil, and
ii. a non-toxic, fat soluble copolymer having the formula:
##STR11## wherein R.sub.1 represents a saturated hydrocarbon chain,
linear or branched, having from 1 to 19 carbon atoms,
R.sub.2 represents a member selected friom the group consisting
of
a. ##STR12## wherein R.sub.4 has the same meaning as R.sub.1 but is
different from R.sub.1 in the same copolymer,
b. --CH.sub.2 --R.sub.5, wherein R.sub.5 represents a saturated
hydrocaron chain, linear or branched, having from 5 to 25 carbon
atoms,
c. --O--R.sub.6, wherein R.sub.6 represents a saturated hydrocarbon
chain, having from 2 to 18 carbon atoms, and
d. ##STR13## wherein R.sub.7 represents a saturated hydrocarbon
chain, linear or branched, having from 1 to 19 carbon atoms, and
R.sub.3 represents hydrogen when R.sub.2 represents radicals (a),
(b) or (c) or R.sub.3 represents .Iadd.hydrogen or .Iaddend.methyl
when R.sub.2 represents radical (d), the said copolymer including
at least 15% by weight of at least one monomer of unit Ia or unit
Ib, wherein said saturated hydrocarbon chain, linear or branched,
has at least 7 carbon atoms, said copolymer having a molecular
weight between 2,000 and 500,000 and being present in an amount of
about 2-35% by weight relative to the total weight of the fatty
composition.
2. The fatty composition according to claim 1 wherein said wax is
selected from the group consisting of ozokerite, lanolin, lanolin
alcohol, hydrogenated lanolin, acetylated lanolin, lanolin wax,
beeswax, candellila wax, microcrystalline wax, carnauba wax, cetyl
alcohol, stearyl alcohol, spermaceti, cocoa butter, a fatty acid of
lanolin, petrolatum, a mono-, di- and triglyceride solid at
25.degree. C, a fatty ester solid at 25.degree. C, a silicone wax,
stearyl monoethanolamide, rosin, glycol abietate, glycerol
abietate, a hydrogenated oil solid at 25.degree. C, a
sucroglyceride and an oleate, myristate, lanolate, stearate and
dihydroxystearate of calcium, magnesium, zirconium and
aluminum.
3. The fatty composition according to claim 1, wherein said oil is
selected from the group consisting of paraffin oil,
perhydrosqualene, sweet almond oil, avocado oil, calophyllum oil,
ricin oil, horse oil, hog oil, olive oil, a mineral oil having a
boiling point between 310.degree. -410.degree. C, a silicone oil,
linoleic alcohol, linolenic alcohol, oleyl alcohol, cereal germ
oil, isopropyl lanolate, isopropyl palmitate, isopropyl myristate,
butyl myristate, cetyl myristate, hexadecyl stearate, butyl
stearate, decyl oleate, an acetyl glyceride, an octanoate and
decanoate of glycol and glycerol, a ricinoleate of cetyl alcohol
and isostearyl alcohol, isocetyl lanolate, isopropyl adipate, hexyl
laurate and octyl dodecanol.
4. The fatty composition of claim 1, wherein said copolymer is
crosslinked with a crosslinking agent selected from the group
consisting of tetraallyloxyethane and divinylbenzene.
5. The composition according to claim 1 where, in the unit of
formula Ib, R.sub.2 represents ##STR14## which is derived from a
vinyl ester selected from the group consisting of vinyl acetate,
vinyl propionate, vinyl butanoate, vinyl octanoate, vinyl
decanoate, vinyl laurate, vinyl stearate, vinyl isostearate,
vinyl-2,2-dimethyloctanoate, vinyl dimethylpropionate and vinyl
cecanoate.
6. The composition according to claim 1 where, in the unit of
formula Ib, R.sub.2 represents the radical --CH.sub.2 --R.sub.5
which is derived from an .alpha.-olefin selected from the group
consisting of 1-octene, 1-dodecene, 1-octadecene, 1-eicosene, and a
mixture of .alpha.-olefins having from 22 to 28 carbon atoms.
7. The composition according to claim 1 where, in the unit of
formula Ib, R.sub.2 represents the radical --O--R.sub.6 which is
derived from an alkylvinylether selected from the group consisting
of ethylvinylether, n-butylvinylether, isobutylvinylether,
decylvinylether, dodecylvinylether, cetylvinylether and
octadecylvinylether.
8. The composition according to claim 1 where, in the unit of
formula Ib, R.sub.2 represents the radical ##STR15## which is
derived from an allyl or methallyl ester selected from the group
consisting of allyl or methallyl acetate, propionate,
dimethylpropionate, butyrate, hexanoate, octanoate,
2,2-dimethylpentanoate, decanoate, laurate, stearate and
eicosanoate.
9. Composition according to claim 1 wherein said copolymer is
constituted by 50 to 95 mole % of a unit of formula Ia and of 50 to
5 mole % of a unit of formula Ib, wherein R.sub.2 represents a
member selected from the group consisting of --CH.sub.2 --R.sub.5,
--O--R.sub.6 and ##STR16##
10. Composition according to claim 1 wherein said copolymer is
constituted by 10 to 90 mole % of a unit of formula Ia and 90 to 10
mole % of a unit of formula Ib in which R.sub.2 represents the
radical ##STR17##
11. A cosmetic composition selected from the group consisting of a
lip rouge and a mascara comprising the fatty composition of claim 1
in an amount between 99.5 and 15% by weight of the total weight of
the cosmetic composition and a dye in an amount of 6-15 weight
percent, the amount of said copolymer relative to the total weight
of said cosmetic composition being at least 1.5% by weight.
12. The cosmetic composition of claim 11, wherein said fatty
composition is present in an amount between 75 and 99.5% and the
quantity of the wax in said fatty composition does not exceed 85%
relative to the total weight of said fatty composition.
13. The cosmetic composition of claim 11, wherein water is also
present in an amount not exceeding 8-10% relative to the total
weight of said cosmetic composition.
14. The cosmetic composition of claim 11, wherein said fatty
composition is present in an amount between 15 and 40% by weight
and also contains water in an amount from 50-70% by weight of the
total weight of said cosmetic composition.
15. The composition according to claim 11 which is anhydrous.
16. A lip polish comprising the fatty composition of claim 1 in an
amount between 99.5 and 15% by weight of the total weight of the
cosmetic composition, and an amount of dye from none to an amount
sufficient to tint the lip polish, the amount of said copolymer
relative to the total weight of said cosmetic composition being at
least 1.5% by weight.
Description
The present invention relates to a new fatty composition usefully
employed in the production of cosmetic products and especially for
makeup products such as lip rouge in stick or paste form and
mascara. The present invention relates to cosmetic compositions
containing said fatty composition.
As is well known cosmetic compositions of the type as lip rouge in
stick or paste form, or mascara, are constituted principally by a
fatty base which is a mixture of one or more waxes and one or more
oils.
The oils and the waxes which can be used for the production of such
makeup composition are diverse, their choice depending principally
on the ultimate use of the compositions.
Up to now, one has exclusively visualized the use of certain waxes
or oils of animal, vegetable or mineral origin, or of certain
synthetic substances having properties analogous to those of
natural substances and thus being able to advantageously replace
them.
Although utilized currently in cosmetics, these waxes and oils,
which are of natural or synthetic origin, do not permit to confer
to lip rouges in stick or in paste form or to mascara totally
satisfactory characteristics notably in that which concerns on the
one hand the firmness of the sticks and on the other hand the
brightness, the improved adherence and the persistence of the film
deposited on the lips or on the eyebrows.
In effect it is necessary on the one hand that lip rouge in the
form of a stick exhibits good firmness so that during application
it does not break or fracture and on the other hand that lip rouge
in the form of the paste and mascara exhibit good adherence while
having sufficient brightness.
The applicants, after considerable research, have surprisingly
found that it was possible to produce excellent makeup products and
notably lip rouge in stick or in paste form, as well as mascara,
having the different characteristics mentioned above when there is
used as the fatty base a composition containing in admixture at
least one cosmetic fatty body and at least one copolymer of a
particular type having great affinity for the fatty body and being
non-toxic.
The present invention has then for an object a new fatty
composition for use in the production of cosmetic products, this
new fatty composition being characterized by the fact that it
comprises in admixture at least one cosmetic fatty body and at
least one non-toxic copolymer having the following formula:
##STR4## wherein R.sub.1 represents a saturated hydrocarbon chain,
linear or branched, having from 1 to 19 carbon atoms; R.sub.2
represents a member selected from the group consisting of
a. ##STR5## wherein R.sub.4 has the same meaning as R.sub.1 but is
different from R.sub.1 in the same copolymer,
b. --CH.sub.2 --R.sub.5, wherein R.sub.5 represents a saturated
hydrocarbon chain, branched or linear, having from 5 to 25 carbon
atoms,
c. --O--R.sub.6, wherein R.sub.6 represents a saturated hydrocarbon
chain having from 2 to 18 carbon atoms, and
d. ##STR6## wherein R.sub.7 represents a saturated hydrocarbon
chain, linear or branched, having from 1 to 19 carbon atoms and
R.sub.3 represents hydrogen when R.sub.2 represents radicals (a),
(b) or (c) or R.sub.3 represents .Iadd.hydrogen or .Iaddend.methyl
when R.sub.2 represents radical (d), the said copolymer being able
to be constituted by at least 15% by weight of at least one monomer
derived from a unit Ia or from a unit Ib in which the hydrocarbon
chains, saturated or branched, have at least 7 carbon atoms.
According to the invention, the term "fatty body" means a wax or a
mixture of waxes or even a mixture of at least one wax and at least
one oil. Preferably, the fatty body according to the invention is
constituted by from 6 to 100% of at least one wax and from 0 to 94%
of at least one oil.
The presence in the fatty composition of at least one copolymer
such as defined above permits to impart to makeup products present
in the form of the stick a great resistance to breaking, excellent
brightness and good holding power for the film deposited on the
lips.
For the compositions present in the form of a paste, and notably
lip rouges or lip polishes, the presence of at least one copolymer
imparts to these compositions very good unctuousness, great
flexibility and excellent brightness of the film deposited on the
lips as well as good adherence and improvement in the holding power
of the brightness of the film.
For compositions present in the form of mascara, the presence of a
copolymer also improves the adherence of the film and increases the
resistance to water of the film deposited on the eyelashes.
Copolymers such as described above exhibit the characteristic of
being fat soluble, that is, they have a great affinity for the
waxes and the oils with which they are admixed. It is this
important property which achieves the excellent qualities of the
cosmetic compositions produced with the fatty composition of the
present invention.
This fat solubility of the copolymers is due to the presence of at
least 15% by weight of at least one monomer carrying a fatty chain
having from 7 to 25 carbon atoms.
According to the invention, the fatty body is present in an amount
between about 65 to 98%, preferably between 75 to 95%, and the
copolymer is present in amounts between 2 to 35%, preferably 5 to
25% relative to the total weight of the fatty composition.
It must be remarked that in the fatty composition according to the
invention, the copolymer such as defined above can be used alone or
in admixture with another copolymer of the same type or even in
admixture with a fat soluble homopolymer.
Representative of such homopolymers are those resulting from the
homopolymerization of vinyl esters having from 9 to 22 carbon atoms
or of alkyl acrylates or alkyl methacrylates, the alkyl radicals
having from 10 to 20 carbon atoms.
Preferably the homopolymer is selected from the group consisting of
polyvinyl stearate, polyvinyl stearate crosslinked with the aid of
divinylbenzene, diallylether or diallyl phthalate,
polystearylmethacrylate, polyvinylaurate, polylaurylmethacrylate,
polystearylacrylate, polylaurylacrylate, these polyacrylates and
polymethacrylates being able to be cross-linked with the aid of
ethylene glycol dimethacrylate or tetraethylene glycol
dimethacrylate.
As has been stated above, the fatty body can be constituted by one
or more waxes and in this case, they can be for example ozokerite,
lanolin, lanolin alcohol, hydrogenated lanolin, acetylated lanolin,
lanolin wax, beeswax, Candellila wax, microcrystalline wax,
Carnauba wax, cetyl alcohol, stearyl alcohol, spermaceti, cocoa
butter, fatty acids of lanolin, petrolatum, Vaseline, mono-, di-
and triglycerides which are solid at 25.degree. C, fatty esters
which are solid at 25.degree. C, silicone waxes such as
methyloctadecane-oxypolysiloxane and
poly(dimethylsiloxy)stearoxysiloxane, stearyl monoethanolamide,
rosin and its derivatives such as the abietates of glycol and
glycerol, hydrogenated oils solid at 25.degree. C, sucroglycerides,
and the oleates, myristates, lanolates, stearates and
dihydroxystearates of Ca, Mg, Zr and Al.
The fatty body can also be constituted by a mixture of at least one
wax and at least one oil and in this case the oil can be for
example, paraffin oil, Purcellin oil, perhydrosqualene, sweet
almond oil, avocado oil, calophyllum oil, ricin oil, horse oil, hog
oil, olive oil, mineral oil having a boiling point between
310.degree. and 410.degree. C, silicone oil such as
dimethylpolysiloxane, linoleic alcohol, linolenic alcohol, oleyl
alcohol, the oil of cereal germs as the oil of wheat germ,
isopropyl lanolate, isopropyl palmitate, isopropyl myristate, butyl
myristate, cetyl myristate, hexadecyl stearate, butyl stearate,
decyl oleate, acetyl glycerides, the octanoates and decanoates of
alcohols and polyalcohols such as those of glycol and glycerol,
ricin oleates of alcohol and polyalcohols such as those of cetyl,
isostearyl alcohol, isocetyl lanolate, isopropyl adipate, hexyl
laurate and octyl dodecanol.
As can be seen from formula I, the copolymers included in the fatty
composition result from the copolymerization of at least one vinyl
ester and at least one other monomer which can be an
.alpha.-olefin, an alkylvinylether or an allyl or methallyl
ester.
The .alpha.-olefins, the alkylvinylethers and the allyl or
methallyl esters not being homopolymerizable monomers as opposed to
vinyl esters, it follows that the copolymers which result from the
copolymerization of at least one vinyl ester and at least one
non-homopolymerizable monomer such as those mentioned above, are in
general constituted by 50 to 95 molar percent of at least one unit
Ia and from 50 to 5 molar percent of at least one unit Ib, wherein
R.sub.2 represents the radicals --CH.sub.2 --R.sub.5, --O--R.sub.6
or ##STR7##
The copolymers can also result from the copolymerization of at
least one vinyl ester and at least one other vinyl ester different
from the first.
In this case, as indicated above, the vinyl esters are
homopolymerizable and the copolymers of this type are generally
constituted by 10 to 90 molar percent of at least one unit Ia and
from 90 to 10 molar percent of at least one unit Ib wherein R.sub.2
represents the radical ##STR8##
Representative vinyl esters leading to unit of formula Ia, or to
the unit of formula Ib in which R.sub.2 = ##STR9## include vinyl
acetate, vinyl propionate, vinyl butanoate, vinyl octanoate, vinyl
decanoate, vinyl laurate, vinyl stearate, vinyl isostearate,
vinyl-2,2-dimethyloctanoate, vinyl dimethylpropionate, and vinyl
cecanoate.
Representative .alpha.-olefins leading to the unit of formula Ib
wherein R.sub.2 = CH.sub.2 --R.sub.5, include 1-octene, 1-dodecene,
1-octadecene, 1-eicosene, and mixtures of .alpha.-olefins having
from 22 to 28 carbon atoms.
Representative alkylvinylethers leading to the unit of formula Ib
wherein R.sub.2 = --O--R.sub.6, including ethylvinylether,
n-butylvinylether, isobutylvinylether, decylvinylether,
dodecylvinylether, cetylvinylether and octadecylvinylether.
Representative allyl or methallyl esters leading to the unit of
formula Ib wherein R.sub.2 = ##STR10## include allyl and methallyl
acetates, propionates, dimethylpropionates, butyrates, hexanoates,
octanoates, decanoates, laurates, 2,2 -dimethylpentanoates,
stearates and eicosanoates.
The copolymers such as have been described above can also be
cross-linked with the aid of certain types of cross-linking agents
which have for their purpose the sensible increase in their
molecular weight.
This cross-linking is effected during the copolymerization and the
cross-linking agents can be either of the vinyl type or the allyl
or methallyl types.
Representative cross-linking agents include tetraallyloxyethane,
divinylbenzene, divinyloctanedioate, divinyldodecanedioate, and
divinyloctadecanedioate.
The copolymers employed in the present invention are, for the most
part, known and have a molecular weight between about 2,000 and
500,000 and preferably between 4,000 and 200,000.
Representative copolymers usefully employed in the fatty
composition according to the invention, include the following:
vinyl acetate/allyl stearate, vinyl acetate/vinyl laurate, vinyl
acetate/vinyl stearate, vinyl acetate/octadecene, vinyl
acetate/octadecylvinylether, vinyl propionate/allyl laurate, vinyl
propionate/vinyl laurate, vinyl stearate/1 -octadecene, vinyl
acetate/1-dodecene, vinyl stearate/ethylvinylether, vinyl
propionate/cetylvinylether, vinyl stearate/allyl acetate,
vinyl-2,2-dimethyloctanoate/vinyl laurate,
allyl-2,2-dimethylpentanoate/vinyl laurate, vinyl
dimethylpropionate/vinyl stearate, allyldimethylpropionate/vinyl
stearate, vinyl propionate/vinyl stearate cross-linked with 0.2% of
divinylbenzene, vinyldimethylpropionate/vinyl laurate cross-linked
with 0.2% of divinylbenzene, vinyl acetate/octadecylvinylether
cross-linked with 0.2% of tetraallyloxyethane, vinyl acetate/allyl
stearate cross-linked with 0.2% of divinylbenzene, vinyl
acetate/1-octadecene cross-linked with 0.2% of divinylbenzene and
allyl propionate/allyl stearate cross-linked with 0.2%
divinylbenzene.
The copolymers cross-linked or not, usefully employed in the
present invention can be obtained according to conventional
methods, i.e. by polymerization in mass, in suspension, in solution
or in emulsion.
Preferably the polymerization is effected in solution in an organic
solvent or in suspension in water.
As catalysts, one can use, for example benzoyl peroxide, lauroyl
peroxide, or azobisisobutyronitrile.
The temperature of polymerization is generally between 50.degree.
to 130.degree. C.
The present invention also has for an object cosmetic compositions,
solid or semi-solid, containing as the fatty composition, the
composition such as defined above.
According to the invention, the amount of fatty composition in the
cosmetic composition, is generally between about 99.5 to 15% by
weight with respect to the total weight of the cosmetic
composition, it being understood that the amount of the copolymer
relative to the total weight of the cosmetic composition cannot be
lower than 1.5% by weight thereof.
The compositions according to the invention can be present either
in the form of a lip rouge in stick or in paste form or in the form
of a mascara.
When the compositions according to the invention are present in the
form of sticks, they can be either lip rouges, or lip polishes. The
difference between these two forms of the invention resides in the
fact that the lip polishes do not contain or contain only a very
small amount of dyes which serve only to tint the stick but which
do not permit it to impart to the lips any significant amount of
coloration.
In this particular form of the invention the fatty composition is
preferably present in an amount between 75 to 99.5% with respect to
the total weight of the stick.
The various components which can be introduced into these sticks
are those conventionally used for this type of formulation. Among
those one can mention, in particular, are dyes, soluble or
insoluble, which are generally present in an amount between about 6
to 15%, solvents for certain dyes insoluble in the fatty body, and
particularly eoisne derivatives, pearlescent agents in an amount of
2 to 20%, perfumes, anti-solar agents, antioxidants and
perservatives.
Among the different dyes for lip rouges, one can mention in
particular: the eosines and other halogenated derivatives of
fluorescein (bromo-acids) and principally those known under the
name of D and C Red No. 21, D and C Red No. 27, D and C Orange No.
5, inorganic pigments such as the oxides of iron, chromium,
ultramarines (polysulfides of amino silicates) titanium dioxide,
these compounds being employed in amounts of about 1 to 6%, organic
pigments such as: D and C Red No. 36 and D and C Orange No. 17.
Finally in the list of dyes one can also include lakes such as the
calcium lakes of D and C Red Nos. 7, 21 and 27, barium lakes of D
and C Red Nos. 6 and 9, aluminum lakes of D and C Red No. 21 and D
and C Yellow Nos. 5 and 6, and the zirconium lakes of D and C Red
No. 21 and of D and C Orange No. 5.
Among the solvents for the dyes insoluble in the oils, one can
mention glycols, esters of tetrahydrofurfuryl, polyethyleneglycols
and monoalkanolamides.
Among the pearlescent agents one can mention particularly: bismuth
oxychloride, mica-titanium and the crystals of guanine.
Among the antioxidant agents, one can mention particularly those of
the phenolic type such as the propyl, octyl and dodecyl esters of
gallic acid, butylated hydroxy anisole, butylated hydroxy toluene
and nordihydroguaiaretic acid.
When the compositions are present in the form of pastes, they can
also be lip rouges or lip polishes and contain then the same
ingredients as the sticks. In this form of the invention, the fatty
composition is also present in amounts essentially identical to
that of the sticks.
However, in this latter case, the amount of wax is considerably
lower and it is recommended preferably not to exceed 85% wax with
respect to the total weight of the fatty composition.
These compositions which are in the form of sticks or pastes are
preferably anhydrous although in certain cases they can contain
certain quantities of water not exceeding generally 8 to 10% with
respect to the total weight of the cosmetic composition.
When the cosmetic compositions according to the invention are
present in the form of mascara, they are in a semi-solid form and
can be either anhydrous or aqueous.
In this particular form of the invention, the amount of the fatty
composition is preferably between 15 to 40% with respect to the
total weight of the mascara.
When the mascara is anhydrous it contains in addition to the fatty
composition a volatile component in an amount generally between
about 35 to 50% with respect to the total weight of the mascara.
Among the volatile components one can mention in particular are
isoparaffin, oil of turpentine, isopropyl alcohol, ethyl alcohol,
white spirits and the like.
When to the contrary the mascara is aqueous in form (generally in
the form of an oil-in-water emulsion) it contains preferably from
50 to 70% by weight of water with respect to the total weight of
the mascara, from 8 to 20% of an emulsifying agent such as the
oleostearate of amino propanediol, the stearate or oleate of amino
propanediol, of morpholine, or mono-, di- or triethanolamine, or
mono-, di or tri-isopropanolamine, polyoxyethylenated fatty ethers
or esters, or polyglycerols of fatty ethers or esters, etc. and a
substance to improve the adherence and the drawing of the mascara,
such as for example, derivatives of cellulose including hydroxy
cellulose or even of gum arabic.
The mascaras which are either anhydrous or aqueous also contain
dyeing agents and in particular certain pigments such as carbon
black or black iron oxide, chromium oxides, yellow and red iron
oxides and additionally certain metallic powders such as those of
silver or aluminum.
The mascaras according to the invention can also contain other
components conventionally employed such as perfumes, antioxidants
and preservatives.
As has been indicated above the compositions which are present in
the form of sticks, pastes or mascaras must not contain a quantity
of copolymer lower than 1.5% by weight relative to the total weight
of these types of compositions.
In that which concerns the maximum concentration of the copolymers
in the cosmetic compositions, this is generally a function of the
relative amounts of the fatty composition and is about 35% and
preferably about 25% for sticks and pastes and about 15%,
preferably about 10% for the mascara.
The following examples are given to illustrate the invention.
EXAMPLES OF PREPARING COPOLYMERS
Example 1
60% vinyl acetate/40% allyl stearate (molar ratio of 85% vinyl
acetate/15% allyl stearate).
Into a one liter round bottomed flask provided with a mechanical
agitator, nitrogen lead-in tube and a condenser, there are
introduced 60 grams of vinyl acetate, 40 grams of allyl stearate
and 3.5 grams of benzoyl peroxide in solution in 100 grams of
toluene. The solution is heated with agitation for 18 hours at
100.degree. C. After distillation of 75 grams of toluene under
reduced pressure, 120 grams of methanol previously heated to
50.degree. C are introduced therein. Vinyl methanol acetate
azeotrope (boiling point equal 63.8.degree. C) is distilled up to
the recovery of about 100 grams of the mixture and then 120 grams
of methanol heated to 50.degree. C are again introduced. About 120
grams of the mixture are again distilled off. Then there are added
500 grams of methanol and the mixture is heated with agitation for
10 minutes at the boiling point of methanol. The polymer passes
into solution which remains cloudy. The reaction mixture is then
left to cool with agitation at 20.degree. C and the polymer
precipitates in the form of a paste. The remaining methanol is
removed and the polymer is reprecipitated with methanol. After the
elimination of the methanol, 400 grams of ethanol are introduced
and the resulting mixture is heated with agitation for 10 minutes
at the boiling point of ethanol. Thereafter the mixture is
permitted to cool to 20.degree. C with agitation. After removal of
the ethanol containing the allyl stearate which has not reacted,
the polymer is reprecipitated a last time with methanol. The
polymer which precipitates is isolated and dried under reduced
pressure without heating.
Yield: 40%
Viscosity: 0.83 cp M.sub.n = 10,000.
Example 2
Preparation of 35% vinyl acetate/65% allyl stearate (molar ratio of
vinyl acetate 67%/allyl stearate 33%).
Into a 500 milliliter round bottomed flask provided with a
condenser, a nitrogen lead-in tube and an agitation means, there
are introduced 35 grams of vinyl acetate, 65 grams of allyl
stearate and 3.4 grams of benzoyl peroxide in solution in 100 grams
of benzene. The solution is heated to reflux, with agitation for 19
hours. Then 3.4 grams of benzoyl peroxide in solution in 10 grams
of benzene are introduced therein and the polymerization is
continued for 14 additional hours. Finally 1.7 grams of benzoyl
peroxide in solution in 5 grams of benzene are introduced in the
reaction mixture and the polymerization is continued for 9 hours.
The mixture is then left to cool, after which the solution is
dumped into two liters of methanol. The polymer precipitates in the
form of a white powder which is dried at 50.degree. C under reduced
pressure.
Yield: 96%
Viscosity: 1.10 cp.
Examples 3 to 23
By operating in a similar manner other copolymers have been
obtained. These are listed in Table A below.
TABLE A
__________________________________________________________________________
EXAMPLES OF PREPARATION Precipitating Viscosity Nature and % agent
(cp) Example Copolymer prepared Mole % Weight % Solvent of catalyst
(b) (a)
__________________________________________________________________________
3 Vinyl acetate 53 30 Isopropanol AIBN 2% methanol 0.81 Vinyl
laurate 47 70 (c) 4 Vinyl acetate 70 40 Methanol AIBN 1% Methanol
1.95 Vinyl stearate 30 60 5 Vinyl propionate 43 25 Isopropanol AIBN
3% Methanol 0.74 Vinyl laurate 57 75 6 Vinyl stearate 77 80
Isopropanol AIBN 3% Octane 0.70 1-octadecene 7 Vinyl acetate 66 50
Isopropanol AIBN 2% Evaporate to 0.70 Dodecene 34 50 dryness 8
Vinyl acetate 81 60 Isopropanol AIBN 2% Water 0.76 1-octadecene 9
Vinyl stearate 50 80 Methanol AIBN 3% Evaporate to 1.10 Ethyl vinyl
ether 50 20 dryness 10 Vinyl propionate 94 85 Isopropanol AIBN 2%
Water 0.79 Cetyl vinyl ether 6 15 11 Vinyl acetate 77 50
Isopropanol AIBN 3% Water 0.70 Octadecyl vinyl ether 23 50 12 Vinyl
propionate 90 80 Methanol AIBN 3% Water 1.11 Allyl laurate 10 20 13
Vinyl stearate 53 80 Methanol AIBN 4% Methanol 0.89 Allyl acetate
47 20 14 Vinyl-2,2-dimethyl octanoate 72 70 Methanol AIBN 4%
Methanol 1.01 Vinyl laurate 28 30 15 Allyl-2,2-dimethyl pentanoate
25 20 Methanol AIBN 3% Methanol 0.69 Vinyl laurate 75 80 16 Vinyl
dimethyl propionate 38 20 Methanol AIBN 1% Methanol 1.27 Vinyl
stearate 17 Allyl dimethyl propanoate 48 30 Methanol AIBN 4%
Methanol 0.70 Vinyl stearate 52 70 18 Vinyl propionate 57 30
Acetone AIBN 3% Evaporation 0.97 Vinyl stearate cross-linked
dryness with 0.2% of divinylbenzene 43 70 19 Vinyl dimethyl
propanoate 24 15 Isopropanol AIBN 2% Methanol 0.76 Vinyl laurate
cross-linked with 0.2% of divinylbenzene 76 85 20 Vinyl acetate 77
50 Benzene AIBN 3% Ethanol 0.61 Octadecyl vinyl ether cross- linked
with 0.2% of tetra- allyloxyethane 23 50 21 Vinyl acetate 62 30
Isopropanol AIBN 2% Methanol 0.68 Allyl stearate cross-linked with
0.2% of divinylbenzene 38 70 22 Vinyl acetate 75 50 Isopropanol
AIBN 2% Evaporation 0.6 1-octadecene cross-linked dryness with 0.2%
of divinylbenzene 25 50 23 Allyl propionate 23 10 Acetone AIBN 2%
Evaporation 0.74 Vinyl stearate cross-linked 77 90 dryness with
0.2% of divinylbenzene
__________________________________________________________________________
Remarks: All the copolymers of Examples 3-23 have been prepared by
heatin in solution at 80.degree. C for 24 hours. (a)The viscosities
have been measured in a 5% solution in toluene at 34.6.degree. C.
(b)After the termination of the polymerization reaction, the
mixture is poured into one of the solvents indicated above to
precipitate the copolymer. (c)AIBN = azobisisobutyronitrile.
EXAMPLES OF COMPOSITIONS ACCORDING TO THE INVENTION
Example I
One prepares in accordance with the invention a lip rouge in the
form of a stick having the following composition:
______________________________________ Fatty composition A 89.9
grams Butylated hydroxy toluene - antioxidant 0.1 g
Trimethyl-benzylidene-heptanone-anti-solar 1 g agent Perfume 1 g
Dyes: Titanium oxide 4.5 g D and C Red No. 36 1 g Aluminum lake of
F.D.C. Yellow 6 1 g Aluminum lake of D and C Red No. 27 1.5 g
______________________________________
Fatty composition A is an admixture of the following
______________________________________ Ozokerite 16 g Lanolin 28 g
Oleyl alcohol 10 g Cetyl ricinoleate 20 g Triglycerides of octanoic
acid 20 g Oil of wheat germ 1 g Copolymer according to Example 1 5
g ______________________________________
Example II
One prepares in accordance with the invention a pearlescent lip
rouge in the form of a stick having the following composition:
______________________________________ Fatty Composition B 79.9 g
Butylated hydroxy toluene - antioxidant 0.1 g
Trimethyl-benzylidene-heptanone-anti-solar agent 1 g Dyes: Titanium
oxide 1 g Aluminum lake of D and C Red No. 27 1.5 g Black iron
oxide 1 g Yellow iron oxide 0.5 g Mica-titanium 15 g
______________________________________
Fatty composition B is an admixture of the following
components:
______________________________________ Candellila wax 9 g
Microcrystalline wax 4 g Mineral oil 13 g Cetyl ricinoleate 15 g
Lanolin 15 g Lanolin - liquid 25 g Isopropyl lanolate 14 g
Copolymer according to Example 3 5 g
______________________________________
Example III
One prepares according to the invention a transparent lip polish in
the form of a stick having the following composition:
______________________________________ Fatty composition C 96.9 g
Butylated hydroxy anisole - antioxidant 0.1 g Perfume 1 g Dyes:
Zirconium lake of D and C Red No. 21 0.5 g D and C Red No. 36 1 g
Aluminum lake of F.D.C. Yellow No. 5 0.5 g
______________________________________
Fatty composition C is an admixture of the following
components:
______________________________________ Ozokerite 12.5 g Carnauba
wax 2 g Candellila wax 2 g Hydrogenated lanolin 5 g Ricin oil 38.5
g Oleyl alcohol 15 g Isopropyl lanolate 10 g Lanolin - liquid 5 g
Copolymer of Example 1 10 g
______________________________________
Example IV
One prepares in accordance with the invention a lip rouge in the
form of a stick having the following composition:
______________________________________ Fatty composition D 89.9 g
Butylated hydroxy toluene - antioxidant 0.1 g
Trimethyl-benzylidene-heptanone-anti-solar agent 1 g Perfume 1 g
Dyes: Titanium oxide 4.5 g D & C Red No. 36 1 g Aluminum lake
of F.D.C. Yellow 6 1 g Aluminum lake of D and C Red No. 27 1.5 g
______________________________________
Fatty composition D is identical to fatty composition C except that
the 10 grams of the copolymer of Example 1 are replaced by the
following mixture:
______________________________________ Copolymer according to
Example 2 6 g Polyvinylstearate 4 g
______________________________________
Example V
One prepares according to the invention a lip rouge in the form of
a stick having the following composition:
______________________________________ Fatty composition E 89.8 g
Butylated hydroxy toluene - antioxidant 0.1 g
Trimethyl-benzylidene-heptanone-anti-solar agent 1 g Perfume 1 g
Dyes: Titanium oxide 2.2 g Aluminum lake of D and C Red No. 27 3.6
g Black iron oxide 0.4 g D and C Red No. 36 0.9 g Aluminum lake of
D & C Yellow No. 6 1 g
______________________________________
Fatty composition E is an admixture of the following
components:
______________________________________ Microcrystalline wax 9 g
Lanolin 30 g Oleyl alcohol 9 g Cetyl ricinoleate 20 g Triglycerides
of octanoic acid 16 g Isopropyl lanolate 10 g Oil of wheat germ 1 g
Copolymer of Example 4 5 g
______________________________________
In fatty composition E the copolymer according to Example 4 can
advantageously be replaced by the same quantity of one of the
copolymers prepared according to Examples 5, 6, 7 or 9.
Example VI
One prepares according to the invention a lip rouge in the form of
a stick having the following composition:
______________________________________ Fatty Composition E' 82.5 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dyes:
Titanium oxide 1.8 g D and C Orange No. 5 0.3 g Aluminum lake of D
and C Yellow No. 6 8.8 g D and C Red No. 6 5.5 g
______________________________________
Fatty composition E' is identical to fatty composition E except
that the 5 grams of the copolymer according to Example 4 have been
replaced by the same quantity of the copolymer according to Example
10.
Example VII
One prepares in accordance with the invention a pearlescent lip
rouge in the form of a stick having the following composition:
______________________________________ Fatty composition E" 78.85 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dyes:
Zirconium lake of D and C Red. No. 21 0.8 g Black iron oxide 0.05 g
D and C Orange No. 5 0.2 g D and C Red No. 36 0.8 g Aluminum lake
of D and C Yellow No. 6 3.2 g Mica-titanium 15 g
______________________________________
Fatty composition E" is identical to fatty composition E except
that the 5 grams of copolymer according to Example 4 have been
replaced by the same quantity of the copolymer according to Example
11.
Example VIII
One prepares according to the invention a lip rouge in the form of
a stick having the following composition:
______________________________________ Fatty composition F 89.62 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dyes: D
and C Red No. 30 5 g Calcium lake of D and C Red No. 7 0.8 g D and
C Red No. 36 0.5 g Titanium oxide 2.6 g Black iron oxide 0.38 g
______________________________________
Fatty composition F is an admixture of the following
components:
______________________________________ Ozokerite 13 g Lanolin -
liquid 8 g Oleyl alcohol 15 g Carnauba wax 3 g Ricin oil 44 g
Isopropyl lanolate 12 g Copolymer of Example 20 5 g
______________________________________
Example IX
One prepares in accordance with the invention a lip polish in the
form of a paste having the following composition:
______________________________________ Fatty composition G 97.9 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dyes:
Titanium oxide 0.2 g Zirconium lake of D and C Red No. 21 0.3 g
Aluminum lake of F.D.C. Yellow No. 6 0.2 g D and C Red No. 36 0.3 g
______________________________________
Fatty composition G is an admixture of the following
components:
______________________________________ Lanolin 30 g Lanolin-liquid
30 g Vaseline 10 g Mineral oil 9 g Microcrystalline wax 1 g
Copolymer of Example 17 20 g
______________________________________
In this fatty composition G the copolymer according to Example 17
can advantageously be replaced by a copolymer prepared according to
Examples 19 and 22.
Example X
One prepares in accordance with the invention a pearlescent lip
polish in the form of a paste having the following composition:
______________________________________ Fatty Composition H 80.9 g
Butylated hydroxy anisole - antioxidant 0.1 g Perfume 1 g Dyes:
Aluminum lake of D and C Red No. 27 0.5 g D and C Red No. 36 0.5 g
Aluminum Lake of F.D.C. Yellow No. 5 0.5 g Bismuth oxychloride 16.5
g ______________________________________
Fatty composition H is an admixture of the following
______________________________________ Lanolin 30 g Lanolin wax 4 g
Oleyl alcohol 13 g Cetyl ricinoleate 10 g Mineral oil 3 g Ricin oil
20 g Copolymer of Example 13 20 g
______________________________________
In fatty composition H the copolymer according to Example 13 can
advantageously be replaced by the same quantity of a copolymer
prepared according to Examples 12, 15 and 16.
Example XI
One prepares in accordance with the invention a lip polish in the
form of a paste having the following composition:
______________________________________ Fatty composition I 97.04 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dyes:
Zirconium lake of D and C Red No. 21 0.4 g Calcium lake of D and C
Red No. 7 0.12 g Black iron oxide 0.14 g Aluminum lake of D and C
Yellow No. 6 1.2 g ______________________________________
Fatty composition I is an admixture of the following
components:
______________________________________ Microcrystalline wax 1.5 g
Ozokerite 2.5 g Lanolin 15 g Mineral oil 37 g Bentonite - cationic
4 g Copolymer of Example 23 10 g
______________________________________
Example XII
One prepares in accordance with the invention a slightly
pearlescent lip polish in the form of a paste having the following
composition:
______________________________________ Fatty composition J 93.95 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dye:
Zirconium lake of D and C Red No. 21 0.2 g D and C Red No. 21 0.05
g Calcium lake of D and C Red No. 7 0.2 g Aluminum lake of D and C
Yellow No. 6 0.5 g Mica-titanium 4 g
______________________________________
Fatty composition J is an admixture of the following
components:
______________________________________ Microcrystalline wax 2.5 g
Ozokerite 3 g Lanolin - liquid 28 g Mineral oil 11 g Lanolin 23 g
Solidified mineral oil 15 g Bentonite - cationic 7.5 g Copolymer of
Example 18 10 g ______________________________________
In this fatty composition the copolymer according to Example 18 can
advantageously be replaced by the same quantity of the copolymer
prepared according to Examples 14, 20 or 21.
Example XIII
One prepares in accordance with the invention a lip polish in the
form of a paste having the following composition:
______________________________________ Fatty composition K 97.570 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Dyes:
Black iron oxide 0.035 g D and C Red No. 6 0.37 g D and C Red No.
36 0.175 g Yellow iron oxide 0.75 g
______________________________________
Fatty composition K is an admixture of the following
components:
______________________________________ Microcrystalline wax 1.5 g
Ozokerite 2 g Lanolin - liquid 28 g Mineral oil 11 g Lanolin 20 g
Solidified mineral oil 15 g Bentonite - cationic 7.5 g Copolymer
according to Example 17 15 g
______________________________________
In fatty composition K the copolymer according to Example 17 can be
replaced by mixture of copolymers prepared according to Examples 8
and 11 (10 grams of copolymer according to Example 8 and 5 grams of
the copolymer according to Example 11).
Example XIV
One prepares according to the invention a lip rouge in the form of
a paste having the following composition:
______________________________________ Fatty composition L 85.9 g
Butylated hydroxy toluene - antioxidant 0.1 g Bentonite - cationic
5 g Perfume 1 g Dye: Titanium oxide 1 g Aluminum lake of D and C
Red No. 27 3 g Calcium lake of D and C Red No. 7 4 g
______________________________________
Fatty composition L is an admixture of the following
components:
______________________________________ Lanolin 18 g Isopropyl
lanolate 18 g Mineral oil 4 g Oleyl alcohol 10 g Hydrogenated
lanolin 8 g Cetyl ricinoleate 8 g Ricin oil 18 g Copolymer of
Example 1 20 g ______________________________________
Example XV
One prepares in accordance with the invention a lip rouge in the
form of a paste having the following composition:
______________________________________ Fatty composition M 83.9 g
Butylated hydroxy anisole - antioxidant 0.1 g Perfume 1 g Bentonite
- cationic 3 g Dyes: Titanium oxide 1 g Aluminum lake of D and C
Red No. 27 3 g D and C Red No. 30 3 g Calcium lake of D and C Red
No. 7 5 g ______________________________________
Fatty composition M is identical to fatty composition G except that
20 grams of the copolymer of the latter are replaced by a mixture
of:
______________________________________ Copolymer of Example 1 10 g
Copolymer of Example 6 5 g Polyvinylstearate cross-linked with the
aid of divinylbenzene 5 g
______________________________________
Example XVI
One prepares according to the invention a lip rouge in the form of
a paste having the following composition:
______________________________________ Fatty composition N 76.9 g
Butylated hydroxy toluene - antioxidant 0.1 g Perfume 1 g Bentonite
- cationic 4 g Dyes: Calcium lake of D and C Red No. 7 1.5 g D and
C Red No. 30 3 g Aluminum lake of F.D.C. Red No. 5 1.5 g
Mica-titanium 12 g ______________________________________
Fatty composition N is an admixture of the following
components:
______________________________________ Microcrystalline wax 1 g
Candellila wax 2 g Lanolin wax 5 g Ricin oil 8 g Cetyl ricinoleate
8 g Mineral oil 20 g Isopropyl lanolate 11 g Triglycerides of
decanoic acid 15 g Copolymer of Example 21 30 g
______________________________________
In this fatty composition the copolymer according to Example 21 can
advantageously be replaced by the copolymer according to Example
23.
Example XVII
One prepares in accordance with the invention a mascara having the
following composition:
______________________________________ Fatty composition O 18 g
Oleostearate of aminopropanediol 12 g Hydroxyethylcellulose 1 g
Demineralized water 58.8 g Black iron oxide 10 g Methyl
para-hydroxy benzoate 0.2 g
______________________________________
Fatty composition O is an admixture of the following
components:
______________________________________ Carnauba wax 99 g Copolymer
of Example 1 11 g ______________________________________
Example XVIII
One prepares in accordance with the invention a mascara having the
following composition:
______________________________________ Fatty composition P 18 g
Oleostearate of aminopropanediol 12 g Hydroxyethylcellulose 1 g
Demineralized water 58.8 g Yellow iron oxide 6 g Black iron oxide 4
g Methyl para-hydroxy benzoate 0.2 g
______________________________________
Fatty composition P is an admixture of the following
components:
______________________________________ Carnauba wax 89 g Copolymer
of Example 2 11 g ______________________________________
In this fatty composition the copolymer of Example 2 can
advantageously be replaced by the same quantity of a copolymer
according to Examples 3, 5, 7, 8 and 18.
Example XIX
One prepares in accordance with the invention a mascara having the
following composition:
______________________________________ Fatty composition O 18 g
Oleostearate of aminopropanediol 12 g Hydroxyethylcellulose 1 g
Demineralized water 58.8 g Polysulfide of aminosilicate 8 g Black
iron oxide 2 g Methyl para-hydroxy benzoate 0.2 g
______________________________________
Fatty composition Q is an admixture of the following
components:
______________________________________ Carnauba wax 89 g Copolymer
of Example 12 11 g ______________________________________
In this fatty composition the copolymer of Example 12 can
advantageously be replaced by the same quantity of the copolymer
prepared according to Examples 20, 21 and 23.
Example XX
One prepares according to the invention an anhydrous mascara by
admixing the following components:
______________________________________ Fatty composition R 39 g
Isoparaffin 56.8 g Black iron oxide 4 g Methyl para-hydroxy
benzoate 0.2 g ______________________________________
Fatty composition R is an admixture of the following
components:
______________________________________ Beeswax 62.5 g Lanolin
alcohol 12.5 g Acetylated lanolin 10 g Copolymer of Example 14 15 g
______________________________________
Example XXI
One prepares in accordance with the invention an anhydrous mascara
by admixing the following components:
______________________________________ Fatty composition S 39 g
Isoparaffin 56.8 g Black iron oxide 4 g Methyl para-hydroxy
benzoate 0.2 g ______________________________________
Fatty composition S is an admixture of the following
components:
______________________________________ Beeswax 62.5 g Lanolin
alcohol 12.5 g Acetylated lanolin 10 g Copolymer of Example 9 15 g
______________________________________
In this fatty composition the copolymer of Example 9 can
advantageously be replaced by an equal quantity of the copolymer
prepared according to Examples 5, 6, 7, 15 and 19 or a mixture of
these copolymers.
* * * * *