U.S. patent application number 14/722037 was filed with the patent office on 2015-09-10 for stabilization of cosmetic compositions.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Stephanie Acker, Bernd Herzog, Katja Quass.
Application Number | 20150250695 14/722037 |
Document ID | / |
Family ID | 39816676 |
Filed Date | 2015-09-10 |
United States Patent
Application |
20150250695 |
Kind Code |
A1 |
Herzog; Bernd ; et
al. |
September 10, 2015 |
STABILIZATION OF COSMETIC COMPOSITIONS
Abstract
Disclosed is the use of UV absorbers selected from (a.sub.1)
diphenylacrylates; (a.sub.2) hydroxyphenyl triazines of formula
(1), in which R.sub.1, R.sub.2 and R.sub.3 independently of one
another, are C.sub.1-C.sub.18alkyl; (a.sub.3) benzotriazole
derivatives of formula (2), wherein R.sub.4 is a random statistical
mixture of at least three isomeric branched secondary alkyl groups
each having 8 to 30 carbon atoms and having the formula (2a);
E.sub.1 is a straight-chain C.sub.1-C.sub.14alkyl; E.sub.2 is a
straight-chain C.sub.4-C.sub.15alkyl; wherein the total number of
carbon atoms in E.sub.1 plus E.sub.2 is from 7 to 29; and R.sub.5
is C.sub.1-C.sub.5alkyl; and (a.sub.4) dialkyl naphthalate; for
stabilizing cosmetic compositions comprising (b) symmetrical
triazine derivatives of formula (3), wherein A is a radical of
formula (3a); or (3b) R.sub.6 and R.sub.10 independently from each
other are hydrogen; C.sub.1-C.sub.18alkyl; or C.sub.6-C.sub.12aryl;
R.sub.7, R.sub.8 and R.sub.9 independently from each other are
hydrogen; or a radical of formula (3c), wherein, in formula (3a),
at least one of the radicals R.sub.7, R.sub.8 and R.sub.9 are a
radical of formula (3c); R.sub.11, R.sub.12, R.sub.13 and R.sub.14
independently from each other are hydrogen; hydroxy; halogen;
C.sub.1-C.sub.18alkyl; C.sub.1-C.sub.18alkoxy;
C.sub.6-C.sub.12aryl; biphenylyl; C.sub.6-C.sub.12aryloxy;
C.sub.1-C.sub.18alkylthio; carboxy; --COOM;
C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; M is an alkali metal ion; x is 1 or 2; and y is a number
from 2 to 10; and a UV-absorber selected from (c.sub.1) cinnamic
acid derivatives; and (C.sub.2) dibenzoylmethane derivatives.
##STR00001##
Inventors: |
Herzog; Bernd;
(Grenzach-Wyhlen, DE) ; Quass; Katja;
(Rheinfelden, DE) ; Acker; Stephanie; (Dietwiller,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
LUDWIGSHAFEN |
|
DE |
|
|
Assignee: |
BASF SE
LUDWIGSHAFEN
DE
|
Family ID: |
39816676 |
Appl. No.: |
14/722037 |
Filed: |
May 26, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12673596 |
Feb 16, 2010 |
9066872 |
|
|
PCT/EP08/61132 |
Aug 26, 2008 |
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14722037 |
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Current U.S.
Class: |
424/59 |
Current CPC
Class: |
A61K 8/4966 20130101;
A61K 8/494 20130101; A61K 8/40 20130101; A61Q 17/04 20130101; A61K
8/37 20130101; A61K 8/4973 20130101; A61K 2800/592 20130101; A61K
8/368 20130101; A61K 8/35 20130101 |
International
Class: |
A61K 8/49 20060101
A61K008/49; A61K 8/37 20060101 A61K008/37; A61K 8/368 20060101
A61K008/368; A61Q 17/04 20060101 A61Q017/04; A61K 8/40 20060101
A61K008/40 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 30, 2007 |
EP |
07115267.2 |
Feb 19, 2008 |
EP |
08151592.6 |
Claims
1.-19. (canceled)
20. A method of treating the combination of components b and
c.sub.1 in a cosmetic formulation in need of stabilization
comprising: adding UV absorbers, wherein the UV absorbers are
(a.sub.1) diphenylacrylates; and (a.sub.2) hydroxyphenyl triazines
of formula (1) shown below: ##STR00020## in which R.sub.1, R.sub.2
and R.sub.3 independently of one another, are
C.sub.1-C.sub.18alkyl; to a cosmetic composition comprising: (b)
symmetrical triazine derivatives of formula ##STR00021## wherein A
is a radical of formula ##STR00022## R.sub.6 and R.sub.10
independently from each other are hydrogen; C.sub.1-C.sub.18alkyl;
or C.sub.6-C.sub.12aryl; R.sub.7, R.sub.8 and R.sub.9 independently
from each other are hydrogen; or a radical of formula ##STR00023##
wherein, in formula (3a), at least one of the radicals R.sub.7,
R.sub.8 and R.sub.9 are a radical of formula (3c); R.sub.11,
R.sub.12, R.sub.13 and R.sub.14 independently from each other are
hydrogen; hydroxy; halogen; C.sub.1-C.sub.18alkyl;
C.sub.1-C.sub.18alkoxy; C.sub.6-C.sub.12aryl; biphenylyl;
C.sub.6-C.sub.12aryloxy; C.sub.1-C.sub.18alkylthio; carboxy;
--COOM; C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; or mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; M is an alkali metal ion; x is 1 or 2; and y is a number
from 2 to 10; and (c.sub.1) cinnamic acid derivatives.
21. The method of claim 20, wherein the (a.sub.1) diphenylacrylates
are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate or 3-(benzofuranyl)
2-cyanoacrylate.
22. The method of claim 20, wherein the (c.sub.1) cinnamic acid
derivatives correspond to formula (14) shown below: ##STR00024##
wherein R.sub.16 and R.sub.17 independently from each other are
hydrogen, hydroxy, C.sub.1-C.sub.5alkyl, or C.sub.1-C.sub.5alkoxy;
and R.sub.18 is C.sub.1-C.sub.5alkyl.
23. The method of claim 20, wherein the (c.sub.1) cinnamic acid
derivative is 2-ethylhexyl 4-methoxycinnamate.
24. A method of treating the combination of components b and
c.sub.1 in a cosmetic formulation in need of stabilization
comprising: adding UV absorbers, wherein the UV absorbers are
(a.sub.1) diphenylacrylates; and (a.sub.3) benzotriazole
derivatives of formula (2) shown below: ##STR00025## wherein
R.sub.4 is a random statistical mixture of at least three isomeric
branched secondary alkyl groups each having 8 to 30 carbon atoms
and having the formula ##STR00026## E.sub.1 is a straight-chain
C.sub.1-C.sub.14alkyl; E.sub.2 is a straight-chain
C.sub.4-C.sub.15alkyl; wherein the total number of carbon atoms in
E.sub.1 plus E.sub.2 is from 7 to 29; and R.sub.5 is
C.sub.1-C.sub.5alkyl; and to a cosmetic composition comprising: (b)
symmetrical triazine derivatives of formula ##STR00027## wherein A
is a radical of formula ##STR00028## R.sub.6 and R.sub.10
independently from each other are hydrogen; C.sub.1-C.sub.18alkyl;
or C.sub.6-C.sub.12aryl; R.sub.7, R.sub.8 and R.sub.9 independently
from each other are hydrogen; or a radical of formula ##STR00029##
wherein, in formula (3a), at least one of the radicals R.sub.7,
R.sub.8 and R.sub.9 are a radical of formula (3c); R.sub.11,
R.sub.12, R.sub.13 and R.sub.14 independently from each other are
hydrogen; hydroxy; halogen; C.sub.1-C.sub.18alkyl;
C.sub.1-C.sub.18alkoxy; C.sub.6-C.sub.12aryl; biphenylyl;
C.sub.6-C.sub.12aryloxy; C.sub.1-C.sub.18alkylthio; carboxy;
--COOM; C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; or mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; M is an alkali metal ion; x is 1 or 2; and y is a number
from 2 to 10; and (c.sub.1) cinnamic acid derivatives.
25. The method of claim 24, wherein the (a.sub.1) diphenylacrylates
are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate or 3-(benzofuranyl)
2-cyanoacrylate.
26. The method of claim 24, wherein the (c.sub.1) cinnamic acid
derivatives correspond to formula (14) shown below: ##STR00030##
wherein R.sub.16 and R.sub.17 independently from each other are
hydrogen, hydroxy, C.sub.1-C.sub.5alkyl, or C.sub.1-C.sub.5alkoxy;
and R.sub.18 is C.sub.1-C.sub.5alkyl.
27. The method of claim 24, wherein the (c.sub.1) cinnamic acid
derivative is 2-ethylhexyl 4-methoxycinnamate.
28. A method of treating the combination of components b and
c.sub.1 in a cosmetic formulation in need of stabilization
comprising: adding UV absorbers, wherein the UV absorbers are
(a.sub.1) diphenylacrylates; and (a.sub.4) dialkyl naphthalate; to
a cosmetic composition comprising: (b) symmetrical triazine
derivatives of formula ##STR00031## wherein A is a radical of
formula ##STR00032## R.sub.6 and R.sub.10 independently from each
other are hydrogen; C.sub.1-C.sub.18alkyl; or C.sub.6-C.sub.12aryl;
R.sub.7, R.sub.8 and R.sub.9 independently from each other are
hydrogen; or a radical of formula ##STR00033## wherein, in formula
(3a), at least one of the radicals R.sub.7, R.sub.8 and R.sub.9 are
a radical of formula (3c); R.sub.11, R.sub.12, R.sub.13 and
R.sub.14 independently from each other are hydrogen; hydroxy;
halogen; C.sub.1-C.sub.18alkyl; C.sub.1-C.sub.18alkoxy;
C.sub.6-C.sub.12aryl; biphenylyl; C.sub.6-C.sub.12aryloxy;
C.sub.1-C.sub.18alkylthio; carboxy; --COOM;
C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; or mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; M is an alkali metal ion; x is 1 or 2; and y is a number
from 2 to 10; and (c.sub.1) cinnamic acid derivatives.
29. The method of claim 28, wherein the (a.sub.1) diphenylacrylates
are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate or 3-(benzofuranyl)
2-cyanoacrylate.
30. The method of claim 28, wherein the (c.sub.1) cinnamic acid
derivatives correspond to formula (14) shown below: ##STR00034##
wherein R.sub.16 and R.sub.17 independently from each other are
hydrogen, hydroxy, C.sub.1-C.sub.5alkyl, or C.sub.1-C.sub.5alkoxy;
and R.sub.18 is C.sub.1-C.sub.5alkyl.
31. The method of claim 28, wherein the (c.sub.1) cinnamic acid
derivative is 2-ethylhexyl 4-methoxycinnamate.
32. A cosmetic composition comprising: (a.sub.1) diphenylacrylates;
(b) symmetrical triazine derivatives of formula ##STR00035##
wherein A is a radical of formula ##STR00036## R.sub.6 and R.sub.10
independently from each other are hydrogen; C.sub.1-C.sub.18alkyl;
or C.sub.6-C.sub.12aryl; R.sub.7, R.sub.8 and R.sub.9 independently
from each other are hydrogen; or a radical of formula ##STR00037##
wherein, in formula (3a), at least one of the radicals R.sub.7,
R.sub.8 and R.sub.9 are a radical of formula (3c); R.sub.11,
R.sub.12, R.sub.13 and R.sub.14 independently from each other are
hydrogen; hydroxy; halogen; C.sub.1-C.sub.18alkyl;
C.sub.1-C.sub.18alkoxy; C.sub.6-C.sub.12aryl; biphenylyl;
C.sub.6-C.sub.12aryloxy; C.sub.1-C.sub.18alkylthio; carboxy;
--COOM; C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; or mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; M is an alkali metal ion; x is 1 or 2; and y is a number
from 2 to 10; and (c.sub.1) cinnamic acid derivatives, wherein the
composition is stable.
33. The cosmetic composition of claim 32 comprising: 0.1 to 10%
b.w. of the diphenylacrylates (a.sub.1); 0.1 to 10. % b.w. of the
symmetrical triazine (b); and 0.1 to 10% b.w. of the cinnamic acid
derivative (c.sub.1).
34. The cosmetic composition of claim 32, wherein the (a.sub.1)
diphenylacrylates are 2-ethylhexyl 2-cyano-3,3-diphenylacrylate or
3-(benzofuranyl) 2-cyanoacrylate.
35. The cosmetic composition of claim 32, wherein the (c.sub.1)
cinnamic acid derivatives correspond to formula (14) shown below:
##STR00038## wherein R.sub.16 and R.sub.17 independently from each
other are hydrogen, hydroxy, C.sub.1-C.sub.5alkyl, or
C.sub.1-C.sub.5alkoxy; and R.sub.18 is C.sub.1-C.sub.5alkyl.
36. The cosmetic composition of claim 32, wherein the (c.sub.1)
cinnamic acid derivative is 2-ethylhexyl 4-methoxycinnamate.
37. The cosmetic composition of claim 32, further comprises one of
(a.sub.2), (a.sub.3), or (a.sub.4), wherein (a.sub.2), (a.sub.3),
or (a.sub.4) are defined hereinbelow: (a.sub.2) hydroxyphenyl
triazines of formula (1) shown below: ##STR00039## in which
R.sub.1, R.sub.2 and R.sub.3 independently of one another, are
C.sub.1-C.sub.18alkyl; (a.sub.3) benzotriazole derivatives of
formula (2) shown below: ##STR00040## wherein R.sub.4 is a random
statistical mixture of at least three isomeric branched secondary
alkyl groups each having 8 to 30 carbon atoms and having the
formula ##STR00041## E.sub.1 is a straight-chain
C.sub.1-C.sub.14alkyl; E.sub.2 is a straight-chain
C.sub.4-C.sub.15alkyl; wherein the total number of carbon atoms in
E.sub.1 plus E.sub.2 is from 7 to 29; and R.sub.5 is
C.sub.1-C.sub.5alkyl; or (a.sub.4) dialkyl naphthalate.
38. A method of using the cosmetic composition of claim 37
comprising enhancing the stability of the cosmetic composition by
combining the (a.sub.1), the (b), and the (c.sub.1) with one of the
(a.sub.2), the (a.sub.3), or the (a.sub.4).
Description
[0001] It is well known that ultraviolet radiation (light) is
harmful to human skin. Depending on the wavelength the UV radiation
causes different types of skin damage. UV-B radiation (about 290 to
about 320 nm) is responsible for sunburn and can cause skin cancer.
UV-A radiation (about 320 to about 400 nm) while producing tanning
of the skin, contributes also to sunburn and the induction of skin
cancers. Moreover, the harmful effects of the UV-B radiation may be
aggravated by UV-A radiation.
[0002] Therefore, an effective sunscreen formulation preferably
comprises both at least one UV-A and UV-B filter covering the full
range of about 290 nm to about 400 nm to prevent the human skin
from the harmful effects of sunlight.
[0003] The effects of UV-A are mainly mediated by free radicals,
e.g. reactive oxygen species inducing different types of
degradation to cellular DNA, lipids, and proteins. The visible
indications are often the result of long-term, cumulative effects.
This is why skin photoaging is associated with UV-A light. It is
also known that normal outdoor UV-A radiation can be effective
enough to cause the breakdown of the proteins collagen and elastin
leading to a loss of firmness and resilience of the skin. Therefore
the UVA protection of a daily skin care is of significant
relevance.
[0004] Numerous UV-B filters are registered for their use in
sunscreen preparations, which are mainly derivatives of the
3-benzylidenecamphor, ethylhexyl salicylates and cinnamic acid
esters, such as 2-ethylhexyl p-methoxycinnamate.
[0005] A new class of organic UV filters are micronized triazine
derivatives which are commonly used in admixture with cinnamic acid
derivatives and/or dibenzoyl methane derivatives.
[0006] Unfortunately, this UV filter combination employed in
sunscreen compositions suffers from relatively rapid
photodegradation with the consequence that the protection from sun
damage is lost.
[0007] One challenge of this invention is therefore to enhance the
stability of these specific UV filter combinations.
[0008] Surprisingly, it has been found that the use of
diphenylacrylates and specific triazine derivatives will enhance
the stability of cosmetic and dermatological formulations
comprising the combination of specific micronized triazine
derivatives and UV absorbers selected from cinnamic acid
derivatives and dibenzoyl methane derivatives.
[0009] Therefore, the present invention relates to the use of UV
absorbers selected from
(a.sub.1) diphenylacrylates; (a.sub.2) hydroxyphenyl triazines of
formula
##STR00002##
in which [0010] R.sub.1, R.sub.2 and R.sub.3 independently of one
another, are C.sub.1-C.sub.18alkyl; (a.sub.3) benzotriazole
derivatives of formula
##STR00003##
[0010] wherein [0011] R.sub.4 is a random statistical mixture of at
least three isomeric branched secondary alkyl groups each having 8
to 30 carbon atoms and having the formula
[0011] ##STR00004## [0012] E.sub.1 is a straight-chain
C.sub.1-C.sub.14alkyl; [0013] E.sub.2 is a straight-chain
C.sub.4-C.sub.15alkyl; wherein the total number of carbon atoms in
E.sub.1 plus E.sub.2 is from 7 to 29; and [0014] R.sub.5 is
C.sub.1-C.sub.5alkyl; and (a.sub.4) dialkyl naphthalate; for
stabilizing cosmetic compositions comprising
##STR00005##
[0014] (b) symmetrical triazine derivatives of formula wherein
##STR00006## [0015] A is a radical of formula [0016] R.sub.6 and
R.sub.10 independently from each other are hydrogen;
C.sub.1-C.sub.18alkyl; or C.sub.6-C.sub.12aryl; [0017] R.sub.7,
R.sub.8 and R.sub.9 independently from each other are hydrogen; or
a radical of formula
##STR00007##
[0017] wherein, in formula (3a), at least one of the radicals
R.sub.7, R.sub.8 and R.sub.9 are a radical of formula (3c); [0018]
R.sub.11, R.sub.12, R.sub.13 and R.sub.14 independently from each
other are hydrogen; hydroxy; halogen; C.sub.1-C.sub.18alkyl;
C.sub.1-C.sub.18alkoxy; C.sub.6-C.sub.12aryl; biphenylyl;
C.sub.6-C.sub.12aryloxy; C.sub.1-C.sub.18alkylthio; carboxy;
--COOM; C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; [0019] M is an alkali metal ion; [0020] x is 1 or 2; and
[0021] y is a number from 2 to 10; and a UV-absorber selected from
(c.sub.1) cinnamic acid derivatives; and (c.sub.2) dibenzoylmethane
derivatives.
[0022] C.sub.1-C.sub.18alkyl according to the definition for the
radicals of the compound of formula (1) are straight-chain or
branched alkyl radicals like methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec.butyl, tert.butyl, amyl, isoamyl or tert.amyl, hexyl,
2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl,
dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or
octadecyl.
[0023] C.sub.1-C.sub.18alkyl according to the definition for the
radicals of the compound of formula (1) may be substituted by
methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl,
chloropropyl, N,N-diethylaminopropyl, cyanoethyl, phenethyl,
benzyl, p-tert-butylphenethyl, p-tert-octylphenoxyethyl,
3-(2,4-di-tert-amylphenoxy)-propyl,
ethoxycarbonylmethyl-2-(2-hydroxyethoxyl)ethyl, or
2-furylethyl.
[0024] C.sub.1-C.sub.18alkyl according to the definition for the
radicals of the compound of formula (1) are for example methoxy,
ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.butoxy, tert.butoxy,
amyloxy, isoamyloxy or tert.amyloxy, hexyloxy, heptyloxy, octyloxy,
isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy,
tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy or
octadecyloxy.
[0025] C.sub.6-C.sub.10aryl according to the definition for the
radicals of the compound of formula (1) is for example naphthyl and
preferably phenyl.
[0026] Preferably the present invention relates to the use of UV
absorbers selected from
(a.sub.1) diphenylacrylates; (a.sub.2) hydroxyphenyl triazines of
formula
##STR00008##
in which [0027] R.sub.1, R.sub.2 and R.sub.3 independently of one
another, are C.sub.1-C.sub.18alkyl; (a.sub.3) benzotriazole
derivatives of formula
##STR00009##
[0027] wherein [0028] R.sub.4 is a random statistical mixture of at
least three isomeric branched secondary alkyl groups each having 8
to 30 carbon atoms and having the formula
[0028] ##STR00010## [0029] E.sub.1 is a straight-chain
C.sub.1-C.sub.14alkyl; [0030] E.sub.2 is a straight-chain
C.sub.4-C.sub.15alkyl; wherein the total number of carbon atoms in
E.sub.1 plus E.sub.2 is from 7 to 29; and [0031] R.sub.5 is
C.sub.1-C.sub.5alkyl; and (a.sub.4) dialkyl naphthalate; for
stabilizing cosmetic compositions comprising (b) symmetrical
triazine derivatives of formula
##STR00011##
[0031] wherein [0032] A is a radical of formula
[0032] ##STR00012## [0033] R.sub.6 and R.sub.10 independently from
each other are hydrogen; C.sub.1-C.sub.18alkyl; or
C.sub.6-C.sub.12aryl; [0034] R.sub.7, R.sub.8 and R.sub.9
independently from each other are hydrogen; or a radical of
formula
##STR00013##
[0034] wherein, in formula (3a) at least one of the radicals
R.sub.7, R.sub.3 and R.sub.9 are a radical of formula (3c); [0035]
R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 independently
from each other are hydrogen; hydroxy; halogen;
C.sub.1-C.sub.18alkyl; C.sub.1-C.sub.18alkoxy;
C.sub.6-C.sub.12aryl; biphenylyl; C.sub.6-C.sub.12aryloxy;
C.sub.1-C.sub.18alkylthio; carboxy; --COOM;
C.sub.1-C.sub.18-alkylcarboxyl; aminocarbonyl; mono- or
di-C.sub.1-C.sub.18alkylamino; C.sub.1-C.sub.10acylamino; or
--COOH; [0036] M is an alkali metal ion; [0037] x is 1 or 2; and
[0038] y is a number from 2 to 10; and (c.sub.1) cinnamic acid
derivatives.
[0039] Preferably the present invention relates to the use
(a.sub.1) diphenylacrylates; (a.sub.2) hydroxyphenyl triazines of
formula (1); (a.sub.3) benzotriazole derivatives of formula (2);
(a.sub.4) dialkyl naphthalate; for stabilizing of cosmetic
compositions comprising (b) symmetrical triazine derivatives of
formula (3) and a UV-absorber selected from (c.sub.2)
dibenzoylmethane derivatives.
[0040] The diphenylacrylates (a) are preferably selected from
2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl)
2-cyanoacrylate, and more preferably from 2-ethylhexyl
2-cyano-3,3-diphenylacrylate.
[0041] The symmetrical triazine derivatives (b) preferably
correspond to formula
##STR00014##
wherein
[0042] R.sub.6, R.sub.10, R.sub.11, R.sub.12 and R.sub.13 are
defined as in formula (1).
[0043] More preferably, in formula (1) R.sub.6 and R.sub.10 are
hydrogen and/or R.sub.11 and R.sub.13 are hydrogen.
[0044] In formula (3), preferably [0045] R.sub.12 is hydrogen;
hydroxy; C.sub.1-C.sub.5alkyl; C.sub.1-C.sub.5alkoxy; --COOM;
--COOH; or COOR.sub.15; [0046] M is an alkali metal ion; and [0047]
R.sub.15 is C.sub.1-C.sub.5alkyl.
[0048] Most preferred symmetrical triazine derivatives (b)
correspond to compounds of formula
##STR00015##
wherein R.sub.6, R.sub.7, R.sub.8, R.sub.14 and R.sub.15 are
defined as in formula (1).
[0049] In formula (5)
R.sub.6, R.sub.7, R.sub.8, R.sub.14 and R.sub.15 are preferably
hydrogen; or, independently from each other,
C.sub.1-C.sub.18alkyl.
[0050] Most preferred symmetrical triazine derivatives (b)
correspond to the compounds of formula
##STR00016##
[0051] Further examples of triazine derivatives, which are
preferably used in the present invention, are the compounds of
formula
##STR00017## ##STR00018##
[0052] The triazine derivatives (component (b)) according to
formula (3) are preferably used in the micronized state.
[0053] The triazine derivatives of formula (3) which have no alkyl
substituents or only lower-alkyl substituents are characterized by
a poor oil-solubility and a high melting point. They are therefore
suitable in particular as UV absorbers in the micronized state.
[0054] They may be prepared by any known process suitable for the
preparation of microparticles, for example wet-milling,
wet-kneading, spray-drying from a suitable solvent, by expansion
according to the RESS process (Rapid Expansion of Supercritical
Solutions) of supercritical fluids (e.g. CO.sub.2, by
reprecipitation from suitable solvents, including supercritical
fluids (GASR process=Gas Anti-Solvent Recrystallisation/PCA
process=Precipitation with Compressed Anti-solvents).
[0055] As milling apparatus for the preparation of the sparingly
soluble micronized organic compounds there may be used, for
example, a jet mill, ball mill, vibratory mill or hammer mill,
preferably a high-speed mixing mill. Even more preferable mills are
modern ball mills; manufacturers of these types of mill are, for
example, Netzsch (LMZ mill), Drais (DCP-Viscoflow or Cosmo), Buhler
AG (centrifugal mills) or Bachhofer.
[0056] Examples of kneading apparatus for the preparation of the
micronized organic UV absorbers are typical sigma-blade batch
kneaders but also serial batch kneaders (IKA-Werke) or continuous
kneaders (Continua from Werner and Pfleiderer).
[0057] The grinding of the sparingly soluble organic compounds used
in the present invention is preferably carried out with a grinding
aid.
[0058] The dispersing agent is used as a low molecular weight
grinding aid for all the above micronization processes.
[0059] Useful anionic, non-ionic or amphoteric surfactants are
disclosed below in the sections entitled "specific dispersing
agents".
[0060] Preferred useful grinding aids for an aqueous dispersion are
anionic surfactants with a HLB (Hydrophile-Lipophile Balance) value
higher than 8, more preferably higher than 10.
[0061] Any conventionally usable anionic, non-ionic or amphoteric
surfactants can be used as dispersing agents. Such surfactant
systems may comprise for example: carboxylic acids and their salts:
alkaline soap of sodium, potassium and ammonium, metallic soap of
calcium or magnesium, organic basis soap such as Lauric, myristic,
palmitic, stearic and oleic acid etc., alkyl phosphates or
phosphoric acid esters, acid phosphate, diethanolamine phosphate,
potassium cetyl phosphate, ethoxylated carboxylic acids or
polyethyleneglycol esters, PEG-n acylates. Fatty alcohol
polyglycolether such as laureth-n, myreth-n, ceteareth-n,
steareth-n, oleth-n. fatty acid polyglycolether such as PEG-n
stearate, PEG-n oleate, PEG-n cocoate, monoglycerides and polyol
esters, C.sub.12-C.sub.22 fatty acid mono- and di-esters of
addition products of from 1 to 100 mol of ethylene oxide with
polyols, fatty acid and polyglycerol ester such as monostearate
glycerol, diisostearoyl polyglyceryl-3-diisostearates,
polyglyceryl-3-diisostearates, triglyceryl diisostearates,
polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates.
Mixtures of compounds from a plurality of those substance classes
are also suitable. Fatty acid polyglycolesters such as monostearate
diethylene glycol, fatty acid and polyethylene glycol esters, fatty
acid and saccharose esters such as sucro esters, glycerol and
saccharose esters such as sucro glycerides. Sorbitol and sorbitan,
sorbitan mono- and di-esters of saturated and unsaturated fatty
acids having from 6 to 22 carbon atoms and ethylene oxide addition
products, polysorbate-n series, sorbitan esters such as
sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan,
PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan, glucose
derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated
analogues with glucose being preferred as the sugar component, O/W
emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan
stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl
alcohol/cetearyl glucoside, W/O emulsifiers such as methyl glucose
dioleate/methyl glucose isostearate. Sulfates and sulfonated
derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl
lauryl sulfonate, linear sulfonated paraffins, sulfonated
tetrapropylene sulfonate, sodium lauryl sulfates, ammonium and
ethanolamine lauryl sulfates, lauryl ether sulfates, sodium laureth
sulfates [Texapon N70] or sodium myreth sulfates [Texapon K14S],
sulfosuccinates, acetyl isothionates, alkanolamide sulfates,
taurines, methyl taurines, imidazole sulfates. Zwitterionic or
amphoteric surfactants that carry at least one quaternary ammonium
group and at least one carboxylate and/or sulfonate group in the
molecule. Zwitterionic surfactants that are especially suitable are
betaines, such as N-alkyl-N,N-dimethylammonium glycinates,
cocoalkyldimethylammonium glycinate,
N-acylaminopropyl-N,N-dimethylammonium glycinates,
cocoacylaminopropyldimethylammonium glycinate and
2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from
8 to 18 carbon atoms in the alkyl or acyl group and also
cocoacylaminoethylhydroxyethylcarboxymethylglycinate,
N-alkylbetaine, N-alkylaminobetaines.
[0062] Examples of suitable mild surfactants as dispersing agents,
that is to say surfactants especially well tolerated by the skin,
include fatty alcohol polyglycol ether sulfates, monoglyceride
sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid
isethionates, fatty acid sarcosinates, fatty acid taurides, fatty
acid glutamates, a-olefin sulfonates, ethercarboxylic acids, alkyl
oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or
protein fatty acid condensation products, the latter preferably
being based on wheat proteins. Non ionic surfactants such as PEG-6
beeswax (and) PEG-6 stearate (and) polyglyceryl-2-isostearate
[Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165],
PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and)
polyglyceryl-3 ricinoleate.[Arlacel 1689], sorbitan stearate and
sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23
[Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax],
cetearyl alcohol and colysorbate 60 and PEG-150 and
stearate-20[Polawax GP 200, Polawax NF], cetearyl alcohol and
cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and
ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and
PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40
castor oil and sodium cetearyl sulfate [Emulgade F], stearyl
alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl
alcohol and szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F],
glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol
ceteth-3 acetate.[Hetester PCS], propylene glycol isoceth-3 acetate
[Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12
[Lanbritol Wax N 21], PEG-6 stearate and PEG-32 stearate [Tefose
1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000],
PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20
[Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C,
X].
[0063] Anionic emulsifiers such as PEG-2 stearate SE, glyceryl
stearate SE [Monelgine, Cutina KD], propylene glycol stearate
[Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N,
Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate
[Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2
stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate
[Teginacid Special]. Cationic acid bases such as cetearyl alcohol
and cetrimonium bromide.
[0064] Most preferred dispersing agents are sodium alkyl sulfates
or sodium alkyl ether sulfates, such as sodium laureth sulfate
[Texapon N70 from Cognis] or sodium myreth sulfate [Texapon K14 S
from Cognis].
[0065] The specific dispersing agents may be used in an amount of,
for example, from 1 to 30% by weight, especially from 2 to 20% by
weight and preferably from 3 to 10% by weight, based on the total
weight of the composition.
[0066] Useful solvents are water, brine, (poly-)ethylene glycol,
glycerol or cosmetically acceptable oils. Other useful solvents are
disclosed below in the sections entitled "Esters of fatty acids",
"Natural and synthetic triglycerides, including glyceryl esters and
derivatives", "Pearlescent waxes", "Hydrocarbon oils" and
"Silicones or siloxanes".
[0067] The micronized sparingly soluble organic compounds so
obtained usually have an average particle size from 0.02 to 2
micrometres, preferably from 0.03 to 1.5 micrometres and more
especially from 0.05 to 1.0 micrometres.
[0068] The micronized UV absorbers according to component (b) of
the present invention are used as aqueous dispersions, which
comprise [0069] 30-60, preferably 35 to 55 parts of the sparingly
soluble organic micronized substance according to component (b);
[0070] 2-20, preferably 2 to 20 parts of the dispersing agent;
[0071] 0.1-1 part, preferably 0.1 to 0.5 parts of a thickening
agent (for example xanthan gum); and [0072] 20-68 parts of
water.
[0073] The compounds according to component (b) have also a
stabilizing effect for UV absorbers selected from ethyl hexyl
triazine and dioctyl butamido triazone.
[0074] The cinnamic acid derivatives (c.sub.1) preferably
correspond to the formula
##STR00019##
in which [0075] R.sub.16 and R.sub.17 independently from each
other; are hydrogen; hydroxy; or C.sub.1-C.sub.5alkyl; or
C.sub.1-C.sub.5alkoxy; and [0076] R.sub.16 is
C.sub.1-C.sub.5alkyl.
[0077] Most preferred cinnamic acid derivative (c.sub.1) is
2-ethylhexyl 4-methoxycinnamate.
[0078] The dibenzoylmethane derivative (c.sub.2) is preferably
selected from 4-(tert-butyl)-4'-methoxydibenzoylmethane.
[0079] The present invention also relates to a cosmetic composition
comprising [0080] 0.1 to 10% b.w. of a diphenylacrylate UV filter
(a); [0081] 0.1 to 10. % b.w. of a triazine UV filter (b); and
[0082] 0.1 to 10% b.w. of a cinnamic acid derivative UV filter
(c.sub.1) and/or a dibenzoylmethane derivative (c.sub.2); [0083]
wherein the UV filters (a), (b), (c.sub.1) and (c.sub.2) are
defined as in claim 1.
[0084] Preferably, cosmetic composition comprise [0085] 0.1 to 10%
b.w. of a diphenylacrylate UV filter (a); [0086] 0.1 to 10. % b.w.
of a triazine UV filter (b); and [0087] 0.1 to 10% b.w. of a
cinnamic acid derivative UV filter (c.sub.1); [0088] wherein the UV
filters (a), (b) and (c.sub.1) are defined as in claim 1.
[0089] Preferably, cosmetic composition comprise [0090] 0.1 to 10%
b.w. of a diphenylacrylate UV filter (a); [0091] 0.1 to 10. % b.w.
of a triazine UV filter (b); and [0092] 0.1 to 10% b.w. of a
dibenzoylmethane derivative (c.sub.2); [0093] wherein the UV
filters (a), (b) and (c.sub.2) are defined as in claim 1.
[0094] The cosmetic formulations or pharmaceutical compositions
according to the present invention may additionally contain one or
more than one further UV filter as listed in Tables 1 and 2.
TABLE-US-00001 TABLE 1 Suitable UV filter substances which can be
additionally used with the UV absorbers according to the present
invention p-aminobenzoic acid derivatives, for example
4-dimethylaminobenzoic acid 2-ethylhexyl ester; salicylic acid
derivatives, for example salicylic acid 2-ethylhexyl ester;
benzophenone derivatives, for example
2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;
3-imidazol-4-yl acrylic acid and esters; benzofuran derivatives,
especially 2-(p-amino phenyl)benzofuran derivatives, described in
EP-A-582 189, US-A-5 338 539, US-A-5 518 713 and EP-A-613 893;
polymeric UV absorbers, for example the benzylidene malonate
derivatives described in EP-A-709 080; camphor derivatives, for
example 3-(4'-methyl)benzylidene-bornan-2-one, 3-benzylidene-
bornan-2-one, N-[2(and
4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4'-
trimethylammonium)-benzylidene-bornan-2-one methyl sulfate,
3,3'-(1,4-phenylenedi-
methine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic
acid) and salts, 3- (4'-sulfo)benzylidene-bornan-2-one and salts;
camphorbenzalkonium methosulfate; benzotriazole compounds, for
example 2,2'-methylene-bis(6-(2H-benzotriazol-2-yl)-4-
(1,1,3,3-tetramethylbutyl)-phenol; trianilino-s-triazine
derivatives, for example
2,4,6-trianiline-(p-carbo-2'-ethyl-1'-oxy)-1,3,5- triazine and the
UV absorbers disclosed in US-A-5 332 568, EP-A-517 104, EP-A-507
691, WO 93/17002 and EP-A-570 838; 2-phenylbenzimidazole-5-sulfonic
acid and salts thereof; menthyl o-aminobenzoates; inorganic
particulate sunscreens coated or not such as titanium dioxide, zinc
oxide, iron oxides, mica, MnO, Fe.sub.2O.sub.3, Ce.sub.2O.sub.3,
Al.sub.2O.sub.3, ZrO.sub.2. (surface coatings:
polymethylmethacrylate, methicone (methylhydrogenpolysiloxane as
described in CAS 9004-73-3), dimethicone, isopropyl titanium
triisostearate (as described in CAS 61417-49-0), metal soaps as
magnesium stearate (as described in CAS 4086-70-8),
perfluoroalcohol phosphate as C9-15 fluoroalcohol phosphate (as
described in CAS 74499-44-8; JP 5-86984 , JP 4-330007)). The
primary particle size is an average of 5 nm-35 nm and the particle
size in dispersion is in the range of 100 nm-300 nm.
aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP
1133980 and EP 1046391 phenyl-benzimidazole derivatives as
disclosed in EP 1167358
TABLE-US-00002 TABLE 2 Suitable UV filter substances and adjuvants
which can be additionally used with the UV absorbers according to
the present invention No. Chemical Name CAS No. 1
(+/-)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo-
36861-47-9 [2.2.1]heptan-2-one; p-methyl benzylidene camphor 2
1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one;
15087-24-8 benzylidene camphor 3
(2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone 1641-17-4 4
2,4-dihydroxybenzophenone 131-56-6 5
2,2',4,4'-tetrahydroxybenzophenone 131-55-5 6 2-Hydroxy-4-methoxy
benzophenone; 131-57-7 7 2-Hydroxy-4-methoxy
benzophenone-5-sulfonic acid 4065-45-6 8
2,2'-dihydroxy-4,4'-dimethoxybenzophenone 131-54-4 9
2,2'-Dihydroxy-4-methoxybenzophenone 131-53-3 10
Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its
56039-58-8 salts; Mexoryl SL 12 Methyl
N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]- 52793-97-2
hept-2-ylidene)methyl]anilinium sulphate; Mexoryl SO 22
3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate; homosalate 118-56-9
27 Menthyl-o-aminobenzoate 134-09-8 28 Menthyl salicylate 89-46-3
30 2- ethylhexyl 4- (dimethylamino)benzoate 21245-02-3 32 2-
ethylhexyl salicylate 118-60-5 33 Benzoic
acid,4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)tris-, tris(2-
88122-99-0 ethylhexyl)ester;
2,4,6-Trianilino-(p-carbo-2'-ethylhexyl-1'-oxi)- 1,3,5-triazine;
Octyl Triazone 34 4- aminobenzoic acid 150-13-0 35 Benzoic acid,
4-amino-, ethyl ester, polymer with oxirane 113010-52-9 38
2-phenyl-1H-benzimidazole-5-sulphonic acid; 27503-81-7
phenylbenzimidazolsulfonic acid 39 2-Propenamide,
N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2- 147897-12-9
ylidene)methyl]phenyl]methyl]-, homopolymer 40 Triethanolamine
salicylate 2174-16-5 41
3,3'-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo- 90457-82-2
bicyclo[2.2.1]heptane-1 methanesulfonic acid]; Cibafast H 42
Titanium Dioxide 13463-67-7 44 Zinc oxide 1314-13-2 45
2,2'-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-
103597-45-1 tetramethylbutyl)-phenol]; Tinosorb M 47
1H-Benzimidazole-4,6-disulfonic acid, 2,2'-(1,4-phenylene)bis-,
180898-37-7 disodium salt 48 Benzoic acid,
4,4'-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]- 154702-15-5
phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethyl-
hexyl)ester; diethylhexyl butamido triazone; Uvasorb HEB 49 Phenol,
2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3[1,3,3,3-
155633-54-8
tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-;
drometrizole trisiloxane; Mexoryl XL 50
Dimethicodiethylbenzalmalonate; Polysilicone 15; Parsol SLX
207574-74-1 51 Benzenesulfonic acid,
3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-,
monosodium salt; Tinogard HS 52 Benzoic acid,
2-[4-(diethylamino)-2-hydroxybenzoyl]-, hexyl 302776-68-7 ester;
Uvinul A Plus 53 1-Dodecanaminium,
N-[3-[[4-(dimethylamino)benzoyl]amino]- 156679-41-3
propyl]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1);
Escalol HP610 54 1-Propanaminium,
N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2- 177190-98-6 propenyl)amino]-,
chloride 55 1H-Benzimidazole-4,6-disulfonic acid,
2,2'-(1,4-phenylene)bis- 170864-82-1 56 1,3,5-Triazine,
2,4,6-tris(4-methoxyphenyl)- 7753-12-0 57 1,3,5-Triazine,
2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]- 208114-14-1 58
1-Propanaminiurn, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-
340964-15-0
dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-
N-methyl-, methyl sulfate (salt) 59 2-Propenoic acid,
3-(1H-imidazol-4-yl)- 104-98-3 60 Benzoic acid, 2-hydroxy-,
[4-(1-methylethyl)phenyl]methyl ester 94134-93-7 61
1,2,3-Propanetriol, 1-(4-aminobenzoate); glyceryl PABA 136-44-7 62
Benzene acetic acid, 3,4-dimethoxy-a-oxo- 4732-70-1 63 2-Propenoic
acid, 2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5 64 Anthralinic
acid, p-menth-3-yl ester 134-09-8 65
2,2'-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid
349580-12-7, mono sodium salt or Disodium phenyl dibenzimidazole
tetrasulfonate or Neoheliopan AP 66 1,3,5-Triazine-2,4,6-triamine,
N,N'-bis[4-[5-(1,1-dimethylpropyl)- 288254-16-0
2-benzoxazolyl]phenyl]-N''-(2-ethylhexyl)- or Uvasorb K2A 68
sterols (cholesterol, lanosterol, phytosterols), as described in
WO0341675 69 mycosporines and/or mycosporine-like amino acids as
described in WO2002039974, e.g. Helioguard 365 from Milbelle AG,
isolated mycosporine like amino acids from the red alga porphyra
umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into
liposomes,) 70 alpha-lipoic-acid as described in DE 10229995 71
synthetic organic polymers as described in EP 1371358, [0033]-
[0041] 72 phyllosilicates as described in EP 1371357 [0034]-[0037]
73 silica compounds as described in EP1371356, [0033]-[0041] 74
inorganic particles as described in DE10138496 [0043]-[0055] 75
latex particles as described in DE10138496 [0027]-[0040] 76
1H-Benzimidazole-4,6-disulfonic acid, 2,2'-(1,4-phenylene)bis-,
180898-37-7 disodium salt ; Bisimidazylate; Neo Heliopan APC
[0095] The cosmetic or pharmaceutical preparations can be prepared
by physically mixing the UV absorbers (a), (b) and (c) and
optionally further UV absorbers with the adjuvant using customary
methods, for example by simply stirring together the individual
components.
[0096] Cosmetic or pharmaceutical preparations contain from
0.05-40% by weight, based on the total weight of the composition,
of the UV absorber mixture of the present invention.
[0097] The UV absorber mixture according to the present invention
is useful to protect skin, hair and/or natural or artificial hair
color.
[0098] The cosmetic or pharmaceutical preparations may be, for
example, creams, gels, lotions, alcoholic and aqueous/alcoholic
solutions, emulsions, wax/fat compositions, stick preparations,
powders or ointments. In addition to the above mentioned UV
filters, the cosmetic or pharmaceutical preparations may contain
further adjuvants as described below.
[0099] As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O
and W/O/W emulsions or microemulsions) the preparations contain,
for example, from 0.1 to 30% by weight, preferably from 0.1 to 15%
by weight and especially from 0.5 to 10% by weight, based on the
total weight of the composition, of one or more UV absorbers, from
1 to 60% by weight, especially from 5 to 50% by weight and
preferably from 10 to 35% by weight, based on the total weight of
the composition, of at least one oil component, from 0 to 30% by
weight, especially from 1 to 30% by weight and preferably from 4 to
20% by weight, based on the total weight of the composition, of at
least one emulsifier, from 10 to 90% by weight, especially from 30
to 90% by weight, based on the total weight of the composition, of
water, and from 0 to 88.9% by weight, especially from 1 to 50% by
weight, of further cosmetically acceptable adjuvants.
[0100] The cosmetic or pharmaceutical compositions/preparations
according to the invention may also contain one or one more
additional compounds as described below.
[0101] Fatty Alcohols
[0102] Guerbet alcohols based on fatty alcohols having from 6 to
18, preferably from 8 to 10 carbon atoms including cetyl alcohol,
stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol,
benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc.
[0103] Esters of Fatty Acids
[0104] Esters of linear C.sub.6-C.sub.24 fatty acids with linear
C.sub.3-C.sub.24 alcohols, esters of branched
C.sub.6-C.sub.13carboxylic acids with linear C.sub.6-C.sub.24 fatty
alcohols, esters of linear C.sub.6-C.sub.24 fatty acids with
branched alcohols, especially 2-ethylhexanol, esters of
hydroxycarboxylic acids with linear or branched C.sub.6-C.sub.22
fatty alcohols, especially dioctyl malates, esters of linear and/or
branched fatty acids with polyhydric alcohols (for example
propylene glycol, dimer diol or trimer triol) and/or Guerbet
alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic
acid, capric acid, lauric acid, isotridecanoic acid, myristic acid,
palmitic acid, palmitoleic acid, stearic acid, isostearic acid,
oleic acid, elaidic acid, petroselinic acid, linoleic acid,
linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid,
behenic acid and erucic acid and technical-grade mixtures thereof
(obtained, for example, in the pressure removal of natural fats and
oils, in the reduction of aldehydes from Roelen's oxosynthesis or
in the dimerisation of unsaturated fatty acids) with alcohols, for
example, isopropyl alcohol, caproic alcohol, capryl alcohol,
2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl
alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol,
stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl
alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol,
elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl
alcohol, erucyl alcohol and brassidyl alcohol and technical-grade
mixtures thereof (obtained, for example, in the high-pressure
hydrogenation of technical-grade methyl esters based on fats and
oils or aldehydes from Roelen's oxosynthesis and as monomer
fractions in the dimerisation of unsaturated fatty alcohols).
[0105] Examples of such ester oils are isopropylmyristate,
isopropylpalmitate, isopropylstearate, isopropyl isostearate,
isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate,
isooctylstearate, iso-nonylstearate, isononyl isononanoate,
2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate,
2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate,
erucylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate,
cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate,
myristyl behenate, myristyl oleate, myristyl stearate, myristyl
palmitate, myristyl lactate, propylene glycol dicaprylate/caprate,
stearyl heptanoate, diisostearyl malate, octyl hydroxystearate,
etc.
[0106] Other Adjuvants
[0107] alpha glucosylrutin (CAS No. 130603-71-3), 2-butyloctyl
o-hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No.
1406-18-4), vitamin E acetate (CAS No. 58-95-7), diethylhexyl
2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate,
di(2-ethylhexyl)-succinate and diisotridecyl acetate, and also diol
esters, such as ethylene glycol dioleate, ethylene glycol
diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene
glycol diisostearate, propylene glycol dipelargonate, butanediol
diisostearate and neopentyl glycol dicaprylate. Esters of
C.sub.6-C.sub.24 fatty alcohols and/or Guerbet alcohols with
aromatic carboxylic acids, saturated and/or unsaturated, especially
benzoic acid, esters of C.sub.2-C.sub.12dicarboxylic acids with
linear or branched alcohols having from 1 to 22 carbon atoms or
polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy
groups, or iminodisuccinic acid and imiondisuccinic acid salts [CAS
7408-20-0] or latex particles, aloe vera, chamomile, ginko biloba,
ginseng, coenzyme Q10, laminaria ochroleuca extract, magnolia
oborata extract, melalenca alternifolia leaf oil, rubus idaeus seed
oil, vaccinium macrocarpon seed oil, pumpkin seed extract, pumpkin
seed oil, grape seed extract, carnosine, alpha-arbutin,
madecassoside, termino-laside, tetrahydrocurcuminoids (THC),
mycosporines, mycosporine like amino acids from the red alga
porphyra umbilicalis, mycosporine-like amino acids (as described in
WO2002039974), cis-9-octadecenedioic acid, lipoic acid, laurimino
dipropiomic acid tocopheryl phosphates (LDTP), microcrystalline
cellulose (MCC), polycarbonates as described in WO 0341676, sterols
(cholesterol, lanosterol, phytosterols), as described in WO0341675
and linear poly-alpha-glucans as described in U.S. Pat. No.
6,616,935
[0108] Natural or Synthetic Triglycerides Including Glyceryl Esters
and Derivatives
[0109] Di- or tri-glycerides, based on C.sub.6-C.sub.18 fatty
acids, modified by reaction with other alcohols (caprylic/capric
triglyceride, wheat germ glycerides, etc.). Fatty acid esters of
polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate,
polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated
vegetable oil, sweet almond oil, wheat germ oil, sesame oil,
hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil,
hydrogenated castor oil, shea butter, cocoa butter, soybean oil,
mink oil, sunflower oil, safflower oil, macadamia nut oil, olive
oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago
oil, etc.
[0110] Waxes including esters of long-chain acids and alcohols as
well as compounds having wax-like properties, e.g., carnauba wax,
beeswax (white or yellow), lanolin wax, candellila wax, ozokerite,
japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl
esters wax, synthetic beeswax, etc. Also, hydrophilic waxes as
Cetearyl Alcohol or partial glycerides.
[0111] Pearlescent Waxes:
[0112] Alkylene glycol esters, especially ethylene glycol
distearate; fatty acid alkanolamides, especially coco fatty acid
diethanolamide; partial glycerides, especially stearic acid
monoglyceride; esters of polyvalent, unsubstituted or
hydroxy-substituted carboxylic acids with fatty alcohols having
from 6 to 22 carbon atoms, especially long-chained esters of
tartaric acid; fatty substances, for example fatty alcohols, fatty
ketones, fatty aldehydes, fatty ethers and fatty carbonates, which
in total have at least 24 carbon atoms, especially laurone and
distearyl ether; fatty acids, such as stearic acid, hydroxystearic
acid or behenic acid, ring-opening products of olefin epoxides
having from 12 to 22 carbon atoms with fatty alcohols having from
12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon
atoms and from 2 to 10 hydroxy groups, and mixtures thereof.
[0113] Hydrocarbon Oils:
[0114] Mineral oil (light or heavy), petrolatum (yellow or white),
microcrystalline wax, paraffinic and isoparaffinic compounds,
hydrogenated isoparaffinic molecules as polydecenes and polybutene,
hydrogenated polyisobutene, squalane, isohexadecane, isododecane
and others from plant and animal kingdom.
[0115] Silicones or Siloxanes (Orqanosubstituted Polysiloxanes)
[0116] Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic
silicones, and also amino-, fatty acid-, alcohol-, polyether-,
epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone
compounds, which at room temperature may be in either liquid or
resinous form. Linear polysiloxanes, dimethicone (Dow Corning 200
fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids,
cyclopentasiloxanes volatiles (Dow Corning 345 fluid),
phenyltrimethicone (Dow Corning 556 fluid). Also suitable are
simethicones, which are mixtures of dimethicones having an average
chain length of from 200 to 300 dimethylsiloxane units with
hydrogenated silicates. A detailed survey by Todd et al. of
suitable volatile silicones may in addition be found in Cosm. Toil.
91, 27 (1976).
[0117] Fluorinated or Perfluorinated Oils
[0118] Perfluorhexane, dimethylcyclohexane, ethylcyclopentane,
polyperfluoromethylisopropyl ether.
[0119] Emulsifiers
[0120] Any conventionally usable emulsifier can be used for the
compositions. Emulsifier systems may comprise for example:
carboxylic acids and their salts: alkaline soap of sodium,
potassium and ammonium, metallic soap of calcium or magnesium,
organic basis soap such as Lauric, palmitic, stearic and oleic acid
etc. Alkyl phosphates or phosphoric acid esters, acid phosphate,
diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated
carboxylic acids or polyethyleneglycol esters, PEG-n acylates.
Linear fatty alcohols having from 8 to 22 carbon atoms, branched
from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene
oxide with fatty acids having from 12 to 22 carbon atoms and with
alkylphenols having from 8 to 15 carbon atoms in the alkyl group.
Fatty alcohol polyglycolether such as laureth-n, ceteareth-n,
steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n
stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol
esters. C12-C22 fatty acid mono- and di-esters of addition products
of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and
polyglycerol ester such as monostearate glycerol, diisostearoyl
polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates,
triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or
polyglyceryl dimerates. Mixtures of compounds from a plurality of
those substance classes are also suitable. Fatty acid
polyglycolesters such as monostearate diethylene glycol, fatty acid
and polyethylene glycol esters, fatty acid and saccharose esters
such as sucro esters, glycerol and saccharose esters such as sucro
glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of
saturated and unsaturated fatty acids having from 6 to 22 carbon
atoms and ethylene oxide addition products. Polysorbate-n series,
sorbitan esters such as sesquiisostearate, sorbitan,
PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate,
PEG-17-dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono
and oligo-glycosides and ethoxylated analogues with glucose being
preferred as the sugar component. O/W emulsifiers such as methyl
gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate,
methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside.
W/O emulsifiers such as methyl glucose dioleate/methyl glucose
isostearate. Sulfates and sulfonated derivatives,
dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate,
linear sulfonated paraffins, sulfonated tetrapropylene sulfonate,
sodium lauryl sulfates, ammonium and ethanolamine lauryl sulfates,
lauryl ether sulfates, sodium laureth sulfates, sulfosuccinates,
acetyl isothionates, alkanolamide sulfates, taurines, methyl
taurines, imidazole sulfates. Amine derivatives, amine salts,
ethoxylated amines, oxide amine with chains containing an
heterocycle such as alkyl imidazolines, pyridine derivatives,
isoquinoteines, cetyl pyridinium chloride, cetyl pyridinium
bromide, quaternary ammonium such as cetyltrimethylbroide ammonium
bromide (CTBA), stearylalkonium. Amide derivatives, alkanolamides
such as acylamide DEA, ethoxylated amides such as PEG-n acylamide,
oxydeamide. Polysiloxane/polyalkyl/polyether copolymers and
derivatives, dimethicone, copolyols, silicone polyethylene oxide
copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers
(Meroxapols), Polaxamers or
poly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene).
Zwitterionic surfactants that carry at least one quaternary
ammonium group and at least one carboxylate and/or sulfonate group
in the molecule. Zwitterionic surfactants that are especially
suitable are betaines, such as N-alkyl-N,N-dimethylammonium
glycinates, cocoalkyldimethylammonium glycinate,
N-acylaminopropyl-N,N-dimethylammonium glycinates,
cocoacylaminopropyldimethylammonium glycinate and
2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from
8 to 18 carbon atoms in the alkyl or acyl group and also
cocoacylaminoethylhydroxyethylcarboxymethylglycinate,
N-alkylbetaine, N-alkylaminobetaines. Alkylimidazolines,
alkylopeptides, lipoaminoacides, self emulsifying bases and the
compounds as described in K. F. DePolo, A short textbook of
cosmetology, Chapter 8, Table 8-7, p 250-251.
[0121] Nonionic emulsifiers such as PEG-6 beeswax (and) PEG-6
stearate (and) polyglyceryl-2-isostearate [Apifac], glyceryl
stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl
stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3
ricinoleate.[Arlacel 1689], sorbitan stearate and sucrose cocoate
[arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945],
cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol
and colysorbate 60 and PEG-150 and stearate-20[Polawax GP 200,
Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade
PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000N1,
Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F
Special], cetearyl alcohol and PEG-40 castor oil and sodium
cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and
steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and
steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75
stearate [Gelot 64], propylene glycol ceteth-3 acetate.[Hetester
PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl
alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG-6
stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and
ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and
ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561],
glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
[0122] Anionic emulsifiers such as PEG-2 stearate SE, glyceryl
stearate SE [Monelgine, Cutina KD], propylene glycol stearate
[Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N,
Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate
[Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2
stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate
[Teginacid Special]. Cationic acid bases such as cetearyl alcohol
and cetrimonium bromide.
[0123] The emulsifiers may be used in an amount of, for example,
from 1 to 30% by weight, especially from 4 to 20% by weight and
preferably from 5 to 10% by weight, based on the total weight of
the composition.
[0124] When formulated in O/W emulsions, the preferably amount of
such emulsifier system could represent 5% to 20% of the oil
phase.
[0125] Adjuvants and Additives
[0126] The cosmetic/pharmaceutical preparations, for example
creams, gels, lotions, alcoholic and aqueous/alcoholic solutions,
emulsions, wax/fat compositions, stick preparations, powders or
ointments, may in addition contain, as further adjuvants and
additives, mild surfactants, super-fatting agents, consistency
regulators, thickeners, polymers, stabilisers, biogenic active
ingredients, deodorising active ingredients, anti-dandruff agents,
film formers, swelling agents, further UV light-protective factors,
antioxidants, hydrotropic agents, preservatives, insect repellents,
self-tanning agents, solubilisers, perfume oils, colourants,
bacteria-inhibiting agents and the like.
[0127] Super-Fatting Agents
[0128] Substances suitable for use as super-fatting agents are, for
example, lanolin and lecithin and also polyethoxylated or acrylated
lanolin and lecithin derivatives, polyol fatty acid esters,
monoglycerides and fatty acid alkanolamides, the latter
simultaneously acting as foam stabilisers.
[0129] Surfactants
[0130] Examples of suitable mild surfactants, that is to say
surfactants especially well tolerated by the skin, include fatty
alcohol polyglycol ether sulfates, monoglyceride sulfates, mono-
and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty
acid sarcosinates, fatty acid taurides, fatty acid glutamates,
a-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides,
fatty acid glucamides, alkylamidobetaines and/or protein fatty acid
condensation products, the latter preferably being based on wheat
proteins.
[0131] Consistency Regulators/Thickeners and Rheology Modifiers
[0132] Silicium dioxide, magnesium silicates, aluminium silicates,
polysaccharides or derivatives thereof for example hyaluronic acid,
xanthan gum, guar-guar, agar-agar, alginates, carraghenan, gellan,
pectines, or modified cellulose such as hydroxycellulose,
hydroxypropylmethylcellulose. In addition polyacrylates or
homopolymer of reticulated acrylic acids and polyacrylamides,
carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez
10) or Salcare range such as Salcare SC80(steareth-10 allyl
ether/acrylates copolymer), Salcare SC81(acrylates copolymer),
Salcare SC91 and Salcare AST(sodium acrylates copolymer/-PPG-1
trideceth-6), sepigel 305(polyacrylamide/laureth-7), Simulgel NS
and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl
taurate copolymer), Stabilen 30 (acrylates/vinyl isodecanoate
crosspolymer), Pemulen TR-1(acrylates/C10-30 alkyl acrylate
crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28
(acrylates/beheneth-25 methacrylate copolymer), etc.
[0133] Polymers
[0134] Suitable cationic polymers are, for example, cationic
cellulose derivatives, for example a quaternized hydroxymethyl
cellulose obtainable under the name Polymer JR 400 from Amerchol,
cationic starches, copolymers of diallylammonium salts and
acrylamides, quartemised vinylpyrrolidone/vinyl imidazole polymers,
for example Luviquat.RTM. (BASF), condensation products of
polyglycols and amines, quaternised collagen polypeptides, for
example lauryldimonium hydroxypropyl hydrolyzed collagen
(Lamequat.RTM. L/Grunau), quaternised wheat polypeptides,
polyethyleneimine, cationic silicone polymers, for example
amidomethicones, copolymers of adipic acid and
dimethylaminohydroxypropyldiethylenetriamine (Cartaretin/Sandoz),
copolymers of acrylic acid with dimethyldiallylammonium chloride
(Merquat 550/Chemviron), polyaminopolyamides, as described, for
example, in FR-A-2 252 840, and the crosslinked water-soluble
polymers thereof, cationic chitin derivatives, for example of
quaternised chitosan, optionally distributed as microcrystals;
condensation products of dihaloalkyls, for example dibromobutane,
with bisdialkylamines, for example bisdimethylamino-1,3-propane,
cationic guar gum, for example Jaguar C-17, Jaguar C-16 from
Celanese, quaternised ammonium salt polymers, for example Mirapol
A-15, Mirapol AD-1, Mirapol AZ-1 from Miranol. As anionic,
zwitterionic, amphoteric and non-ionic polymers there come into
consideration, for example, vinyl acetate/crotonic acid copolymers,
vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl
maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic
anhydride copolymers and esters thereof, uncrosslinked polyacrylic
acids and polyacrylic acids crosslinked with polyols,
acrylamidopropyl-trimethylammonium chloride/acrylate copolymers,
octyl acrylamide/methyl methacrylatetert-butylaminoethyl
methacrylate/2-hydroxypropyl methacrylate copolymers,
polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,
vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam
terpolymers and also optionally derivatised cellulose ethers and
silicones. Furthermore the polymers as described in EP 1093796
(pages 3-8, paragraphs 17-68) may be used.
[0135] Biogenic Active Ingredients
[0136] Biogenic active ingredients are to be understood as meaning,
for example, tocopherol, tocopherol acetate, tocopherol palmitate,
ascorbic acid, deoxyribonucleic acid, retinol, bisabolol,
allantoin, phytantriol, panthenol, AHA acids, amino acids,
ceramides, pseudoceramides, essential oils, plant extracts and
vitamin complexes.
[0137] Deodorising Active Ingredients
[0138] As deodorising active ingredients there come into
consideration, for example, antiperspirants, for example aluminium
chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the
trade mark Locron.RTM. of Hoechst AG, Frankfurt (FRG), there is
available commercially, for example, an aluminium chlorohydrate
corresponding to formula Al.sub.2(OH).sub.5Cl.times.2.5H.sub.2O,
the use of which is especially preferred (see J. Pharm. Pharmacol.
26, 531 (1975)). Besides the chlorohydrates, it is also possible to
use aluminium hydroxyacetates and acidic aluminium/zirconium salts.
Esterase inhibitors may be added as further deodorising active
ingredients. Such inhibitors are preferably trialkyl citrates, such
as trimethyl citrate, tripropyl citrate, triisopropyl citrate,
tributyl citrate and especially triethyl citrate (Hydagen CAT,
Henkel), which inhibit enzyme activity and hence reduce odour
formation. Further substances that come into consideration as
esterase inhibitors are sterol sulfates or phosphates, for example
lanosterol, cholesterol, campesterol, stigmasterol and sitosterol
sulfate or phosphate, dicarboxylic acids and esters thereof, 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 and
hydroxycarboxylic acids and esters thereof, for example citric
acid, malic acid, tartaric acid or tartaric acid diethyl ester.
Antibacterial active ingredients that influence the germ flora and
kill or inhibit the growth of sweat-decomposing bacteria can
likewise be present in the preparations (especially in stick
preparations). Examples include chitosan, phenoxyethanol and
chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol
(Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved
especially effective.
[0139] Anti-Dandruff Agents
[0140] As anti-dandruff agents there may be used, for example,
climbazole, octopirox and zinc pyrithione. Customary film formers
include, for example, chitosan, microcrystalline chitosan,
quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl
acetate copolymers, polymers of quaternary cellulose derivatives
containing a high proportion of acrylic acid, collagen, hyaluronic
acid and salts thereof and similar compounds.
[0141] Antioxidants
[0142] In addition to the primary light-protective substances it is
also possible to use secondary light-protective substances of the
antioxidant kind that interrupt the photochemical reaction chain
triggered when UV radiation penetrates the skin or hair. Typical
examples of such antioxidants are amino acids (e.g. glycine,
histidine, tyrosine, tryptophan) and derivatives thereof,
imidazoles (e.g. urocanic acid) and derivatives thereof, peptides,
such as D,L-carnosine, D-carnosine, L-carnosine and derivatives
thereof (e.g. anserine), carotinoids, carotenes, lycopene and
derivatives thereof, chlorogenic acid and derivatives thereof,
lipoic acid and derivatives thereof (e.g. dihydrolipoic acid),
aurothioglycose, propylthiouracil and other thiols (e.g.
thioredoxin, glutathione, cysteine, cystine, cystamine and the
glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl,
palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters
thereof) and also salts thereof, dilauryl thiodipropionate,
distearyl thiodipropionate, thiodipropionic acid and derivatives
thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides
and salts) and also sulfoximine compounds (e.g. buthionine
sulfoximines, homocysteine sulfoximine, buthionine sulfones,
penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating
agents (e.g. hydroxy fatty acids, palmitic acid phytic acid,
lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic
acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin,
EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids
and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic
acid), folic acid and derivatives thereof, ubiquinone and ubiquinol
and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl
palmitate, magnesium ascorbyl phosphate, ascorbyl acetate),
tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and
derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate
of benzoin resin, rutinic acid and derivatives thereof,
glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine,
butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic
acid, trihydroxybutyrophenone, uric acid and derivatives thereof,
mannose and derivatives thereof, superoxide dismutase,
N-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionyl]sulfanilic acid
(and salts thereof, for example the disodium salts), zinc and
derivatives thereof (e.g. ZnO, ZnSO.sub.4), selenium and
derivatives thereof (e.g. selenium methionine), stilbene and
derivatives thereof (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
those mentioned active ingredients. HALS (="Hindered Amine Light
Stabilizers") compounds may also be mentioned.
[0143] Further synthetic and natural antioxidants are listed e.g.
in WO 0025731: Structures 1-3 (page 2), structure 4 (page 6),
structures 5-6 (page 7) and compounds 7-33 (page 8-14).
[0144] The amount of antioxidants present is usually from 0.001 to
30% by weight, preferably from 0.01 to 3% by weight, based on the
weight of the UV absorber of formula (1).
[0145] Hydrotropic Agents
[0146] To improve the flow behaviour it is also possible to employ
hydrotropic agents, for example ethoxylated or non ethoxylated
mono-alcohols, diols or polyols with a low number of carbon atoms
or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol,
propyleneglycol, glycerine, ethylene glycol, ethylene glycol
monoethylether, ethylene glycol monobutylether, propylene glycol
monomethylether, propylene glycol monoethylether, propylene glycol
monobutylether, diethylene glycol monomethylether; diethylene
glycol monoethylether, diethylene glycol monobutylether and similar
products). The polyols that come into consideration for that
purpose have preferably from 2 to 15 carbon atoms and at least two
hydroxy groups. The polyols may also contain further functional
groups, especially amino groups, and/or may be modified with
nitrogen. Typical examples are as follows: glycerol, alkylene
glycols, for example ethylene glycol, diethylene glycol, propylene
glycol, butylene glycol, hexylene glycol and also polyethylene
glycols having an average molecular weight of from 100 to 1000
Dalton; technical oligoglycerol mixtures having an intrinsic degree
of condensation of from 1.5 to 10, for example technical diglycerol
mixtures having a diglycerol content of from 40 to 50% by weight;
methylol compounds, such as, especially, trimethylolethane,
trimethylolpropane, trimethylolbutane, pentaerythritol and
dipentaerythritol; lower alkyl-glucosides, especially those having
from 1 to 8 carbon atoms in the alkyl radical, for example methyl
and butyl glucoside; sugar alcohols having from 5 to 12 carbon
atoms, for example sorbitol or mannitol; sugars having from 5 to 12
carbon atoms, for example glucose or saccharose; amino sugars, for
example glucamine; dialcohol amines, such as diethanolamine or
2-amino-1,3-propanediol.
[0147] Preservatives
[0148] Suitable preservatives include, for example, Methyl-,
Ethyl-, Propyl-, Butyl-parabens, Benzalkonium chloride,
2-Bromo-2-nitro-propane-1,3-diol, Dehydroacetic acid, Diazolidinyl
Urea, 2-Dichloro-benzyl alcohol, DMDM hydantoin, Formaldehyde
solution, Methyldibromoglutanitrile, Phenoxyethanol, Sodium
Hydroxymethylglycinate, Imidazolidinyl Urea, Triclosan and further
substance classes listed in the following reference: K. F.
DePolo--A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3,
7-4 and 7-5, p 210-219.
[0149] Bacteria-Inhibiting Agents
[0150] Typical examples of bacteria-inhibiting agents are
preservatives that have a specific action against gram-positive
bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether,
chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC
(3,4,4'-trichlorocarbanilide). A large number of aromatic
substances and ethereal oils also have antimicrobial properties.
Typical examples are the active ingredients eugenol, menthol and
thymol in clove oil, mint oil and thyme oil. A natural deodorising
agent of interest is the terpene alcohol farnesol
(3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in
lime blossom oil. Glycerol monolaurate has also proved to be a
bacteriostatic agent. The amount of the additional
bacteria-inhibiting agents present is usually from 0.1 to 2% by
weight, based on the solids content of the preparations.
[0151] Perfume Oils
[0152] There may be mentioned as perfume oils mixtures of natural
and/or synthetic aromatic substances. Natural aromatic substances
are, for example, extracts from blossom (lilies, lavender, roses,
jasmine, neroli, ylang-ylang), from stems and leaves (geranium,
patchouli, petitgrain), from fruit (aniseed, coriander, carraway,
juniper), from fruit peel (bergamot, lemons, oranges), from roots
(mace, angelica, celery, cardamom, costus, iris, calmus), from wood
(pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from
herbs and grasses (tarragon, lemon grass, sage, thyme), from
needles and twigs (spruce, pine, Scots pine, mountain pine), from
resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum,
opoponax). Animal raw materials also come into consideration, for
example civet and castoreum. Typical synthetic aromatic substances
are, for example, products of the ester, ether, aldehyde, ketone,
alcohol or hydrocarbon type. Aromatic substance compounds of the
ester type are, for example, benzyl acetate, phenoxyethyl
isobutyrate, p-tert-butylcyclohexyl acetate, Malyl acetate,
dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl
benzoate, benzyl formate, ethylmethylphenyl glycinate,
allylcyclohexyl propionate, styrallyl propionate and benzyl
salicylate. The ethers include, for example, benzyl ethyl ether;
the aldehydes include, for example, the linear alkanals having from
8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl
oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, filial and
bourgeonal; the ketones include, for example, the ionones,
isomethylionone and methyl cedryl ketone; the alcohols include, for
example, anethol, citronellol, eugenol, isoeugenol, geraniol,
linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons
include mainly the terpenes and balsams. It is preferable, however,
to use mixtures of various aromatic substances that together
produce an attractive scent. Ethereal oils of relatively low
volatility, which are chiefly used as aroma components, are also
suitable as perfume oils, e.g. sage oil, camomile oil, clove oil,
melissa oil, oil of cinnamon leaves, lime blossom oil, juniper
berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil
and lavandin oil. Preference is given to the use of bergamot oil,
dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol,
hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde,
linalool, boisambrene forte, ambroxan, indole, hedione, sandelice,
lemon oil, tangerine oil, orange oil, allyl amyl glycolate,
cyclovertal, lavandin oil, muscatel sage oil, damascone, bourbon
geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super,
Fixolide NP, evernyl, iraldein gamma, phenyl acetic acid, geranyl
acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat
alone or in admixture with one another.
[0153] Colorants
[0154] There may be used as colorants the substances that are
suitable and permitted for cosmetic purposes, as compiled, for
example, in the publication "Kosmetische Farbemittel" of the
Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag
Chemie, Weinheim, 1984, pages 81 to 106. The colorants are usually
used in concentrations of from 0.001 to 0.1% by weight, based on
the total mixture.
[0155] Other Adjuvants
[0156] It is furthermore possible for the cosmetic preparations to
contain, as adjuvants, anti-foams, such as silicones, structurants,
such as maleic acid, solubilizers, such as ethylene glycol,
propylene glycol, glycerol or diethylene glycol, opacifiers, such
as latex, styrene/PVP or styrene/acrylamide copolymers, complexing
agents, such as EDTA, NTA, alaninediacetic acid or phosphonic
acids, propellants, such as propane/butane mixtures, N.sub.2O,
dimethyl ether, CO.sub.2, N.sub.2 or air, so-called coupler and
developer components as oxidation dye precursors, reducing agents,
such as thioglycolic acid and derivatives thereof, thiolactic acid,
cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or
oxidising agents, such as hydrogen peroxide, potassium bromate or
sodium bromate.
[0157] Suitable insect repellents are, for example,
N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535;
suitable self-tanning agents are, for example, dihydroxyacetone
and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone
precursors as described in WO 01/85124 and/or erythrulose.
[0158] Polymeric Beads or Hollow Spheres as SPF Enhancers
[0159] The combination of the UV-absorbers and UV-absorber
combinations, listed above, with SPF enhancers, such as non-active
ingredients like Styrene/acrylates copolymer, silica beads,
spheroidal magnesium silicate, crosslinked Polymethylmethacrylates
(PMMA; Micopearl M305 Seppic), can maximize better the UV
protection of the sun products. Holosphere additives
(Sunspheres.RTM. ISP, Silica Shells Kobo.) deflect radiation and
the effective path length of the photon is therefore
increased.(EP0893119). Some beads, as mentioned previously, provide
a soft feel during spreading. Moreover, the optical activity of
such beads, e.g. Micropearl M305, cans modulate skin shine by
eliminating reflection phenomena and indirectly may scatter the UV
light.
[0160] Cosmetic or Pharmaceutical Preparations
[0161] Cosmetic or pharmaceutical formulations are contained in a
wide variety of cosmetic preparations. There come into
consideration, for example, especially the following preparations:
[0162] skin-care preparations, e.g. skin-washing and cleansing
preparations in the form of tablet-form or liquid soaps, soapless
detergents or washing pastes, [0163] bath preparations, e.g. liquid
(foam baths, milks, shower preparations) or solid bath
preparations, e.g. bath cubes and bath salts; [0164] skin-care
preparations, e.g. skin emulsions, multi-emulsions or skin oils;
[0165] cosmetic personal care preparations, e.g. facial make-up in
the form of day creams or powder creams, face powder (loose or
pressed), rouge or cream make-up, eye-care preparations, e.g. eye
shadow preparations, mascara, eyeliner, eye creams or eye-fix
creams; lip-care preparations, e.g. lipsticks, lip gloss, lip
contour pencils, nail-care preparations, such as nail varnish, nail
varnish removers, nail hardeners or cuticle removers; [0166]
foot-care preparations, e.g. foot baths, foot powders, foot creams
or foot balsams, special deodorants and antiperspirants or
callus-removing preparations; [0167] light-protective preparations,
such as sun milks, lotions, creams or oils, sun blocks or
tropicals, pre-tanning preparations or after-sun preparations;
[0168] skin-tanning preparations, e.g. self-tanning creams; [0169]
depigmenting preparations, e.g. preparations for bleaching the skin
or skin-lightening preparations; [0170] insect-repellents, e.g.
insect-repellent oils, lotions, sprays or sticks; [0171]
deodorants, such as deodorant sprays, pump-action sprays, deodorant
gels, sticks or roll-ons; [0172] antiperspirants, e.g.
antiperspirant sticks, creams or roll-ons; [0173] preparations for
cleansing and caring for blemished skin, e.g. synthetic detergents
(solid or liquid), peeling or scrub preparations or peeling masks;
[0174] hair-removal preparations in chemical form (depilation),
e.g. hair-removing powders, liquid hair-removing preparations,
cream- or paste-form hair-removing preparations, hair-removing
preparations in gel form or aerosol foams; [0175] shaving
preparations, e.g. shaving soap, foaming shaving creams,
non-foaming shaving creams, foams and gels, preshave preparations
for dry shaving, aftershaves or aftershave lotions; [0176]
fragrance preparations, e.g. fragrances (eau de Cologne, eau de
toilette, eau de perfume, perfume de toilette, perfume), perfume
oils or perfume creams; [0177] cosmetic hair-treatment
preparations, e.g. hair-washing preparations in the form of
shampoos and conditioners, hair-care preparations, e.g.
pre-treatment preparations, hair tonics, styling creams, styling
gels, pomades, hair rinses, treatment packs, intensive hair
treatments, hair-structuring preparations, e.g. hair-waving
preparations for permanent waves (hot wave, mild wave, cold wave),
hair-straightening preparations, liquid hair-setting preparations,
hair foams, hairsprays, bleaching preparations, e.g. hydrogen
peroxide solutions, lightening shampoos, bleaching creams,
bleaching powders, bleaching pastes or oils, temporary,
semi-permanent or permanent hair colorants, preparations containing
self-oxidising dyes, or natural hair colorants, such as henna or
camomile.
[0178] Presentation Forms
[0179] The final formulations listed may exist in a wide variety of
presentation forms, for example: [0180] in the form of liquid
preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all
kinds of microemulsions, [0181] in the form of a gel, [0182] in the
form of an oil, a cream, milk or lotion, [0183] in the form of a
powder, a lacquer, a tablet or make-up, [0184] in the form of a
stick, [0185] in the form of a spray (spray with propellant gas or
pump-action spray) or an aerosol, [0186] in the form of a foam, or
[0187] in the form of a paste.
[0188] Of special importance as cosmetic preparations for the skin
are light-protective preparations, such as sun milks, lotions,
creams, oils, sun blocks or tropicals, pretanning preparations or
after-sun preparations, also skin-tanning preparations, for example
self-tanning creams. Of particular interest are sun protection
creams, sun protection lotions, sun protection milk and sun
protection preparations in the form of a spray.
[0189] Of special importance as cosmetic preparations for the hair
are the above-mentioned preparations for hair treatment, especially
hair-washing preparations in the form of shampoos, hair
conditioners, hair-care preparations, e.g. pre-treatment
preparations, hair tonics, styling creams, styling gels, pomades,
hair rinses, treatment packs, intensive hair treatments,
hair-straightening preparations, liquid hair-setting preparations,
hair foams and hairsprays. Of special interest are hair-washing
preparations in the form of shampoos.
[0190] A shampoo has, for example, the following composition: from
0.01 to 5% by weight of the aqueous dispersion as defined in claim
1, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of
cocamidopropyl betaine, 3.0% by weight of sodium chloride, and
water ad 100%.
[0191] For example, especially the following hair-cosmetic
formulations may be used: [0192] a.sub.1) spontaneously emulsifying
stock formulation, consisting of the UV absorber according to the
invention, PEG-6-C.sub.10oxoalcohol and sorbitan sesquioleate, to
which water and any desired quaternary ammonium compound, for
example 4% minkamidopropyl dimethyl-2-hydroxyethylammonium chloride
or Quaternium 80 is added; [0193] a.sub.2) spontaneously
emulsifying stock formulation consisting of the UV absorber
according to the invention, tributyl citrate and PEG-20-sorbitan
monooleate, to which water and any desired quaternary ammonium
compound, for example 4% minkamidopropyl
dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;
[0194] b) quat-doped solutions of the UV absorber according to the
invention in butyl triglycol and tributyl citrate; [0195] c)
mixtures or solutions of the UV absorber according to the invention
with n-alkylpyrrolidone.
[0196] Other typical ingredients in such formulations are
preservatives, bactericides and bacteriostatic agents, perfumes,
dyes, pigments, thickening agents, moisturizing agents, humectants,
fats, oils, waxes or other typical ingredients of cosmetic and
personal care formulations such as alcohols, poly-alcohols,
polymers, electrolytes, organic solvents, silicon derivatives,
emollients, emulsifiers or emulsifying surfactants, surfactants,
dispersing agents, antioxidants, anti-irritants and
anti-inflammatory agents etc.
[0197] Examples of cosmetic and pharmaceutical preparations
(X=preferred combinations)
TABLE-US-00003 O/W systems: Ingredients 1 2 3 4 5 6 7 8 Potassium
Cetyl Phosphate 2%-5% X Cetearyl Alcohol/Dicetyl Phosphate/ X
Ceteth-10 Phosphate 2%-6% Sodium Stearyl Phtalamate 1%-2% X
Cetearyl Alcohol/Behentrimonium X Methosulfate 1%-5% Quaternium-32
1%-5% X Dimethicone copolyol/Caprylic/Capric X Triglyceride (1%-4%)
Steareth-2/Steareth-21 2%-5% X Polyglyceryl Methyl Glucose X
Distearate 1%-4% Lipophilic emollient/dispersant oil X X X X X X X
X 15%-20% Fatty Alcohols and/or Waxes 1%-5% X X X X X X X X
Thickeners (water swellable X X X X X X X X thickeners) 0.5%-1.5%
Preservatives 0.5%-1% X X X X X X X X Chelating agents (such as
EDTA) X X X X X X X X 0%-0.2% Antioxidants 0.05%-0.2% X X X X X X X
X Water deionizer Qs 100% X X X X X X X X Perfume oils 0.1%-0.4% X
X X X X X X X Cosmetic composition according to the X X X X X X X X
present invention 0.1%-20% UV-absorber as described in Table X X X
X X X X X 1 and 2 0%-30%
TABLE-US-00004 W/O systems Ingredients 1 2 3 4 5 Polyglyceryl-2
Dipolyhydroxystearate 2%-4% X X X X X PEG-30 Dipolyhydroxystearate
2%-4% X Rapeseed Oil Sorbitol Esters 1%-5% X PEG-45/Dodecyl Glycol
Copolymer 1%-5% X Sorbitan Oleate/Polycerol-3 ricinoleate 1%-5% X
Lipophilic emollient/dispersant oil 10%-20% X X X X X Fatty
Alcohols and/or Waxes 10%-15% X X X X X Electrolytes (NaCl,
MgSO.sub.4) 0.5%-1% X X X X X Polyol phase (Propylene glycol,
glycerin) 1%-8% X X X X X Preservatives 0.3%-0.8% X X X X X Perfume
oils 0.1%-0.4% X X X X X Chelating agents (such as EDTA) 0%-0.2% X
X X X X Antioxidants 0.05%-0.2% X X X X X Water deionized Qs 100% X
X X X X Cosmetic composition according to the present invention
0.1%-20% X X X X X UV-absorber as described in Table 1 and 2
0%-30%. X X X X X
TABLE-US-00005 W/Silicone systems Ingredients 1 2 3 4 Dimethicone
Copolyol/Cyclomethicone 5%-10% X X Laurylmethicone Copolyol 5%-10%
X X Cyclopentasiloxane 15%-25% X X Dimethicone 15%-25% X X
Dimethicone/Vinyldimethicone X X X X Crosspolymer 1%-10%
Humectant/polyols (Propylene glycol, X X X X glycerin. . .) 2%-8%
Chelating agents (such as EDTA) 0%-0.2% X X X X Antioxidants
0.05%-0.2% X X X X Preservatives 0.3%-0.8% X X X X Perfume oils
0.1%-0.4% X X X X Water deionized Qs 100% X X X X Cosmetic
composition according to X X X X the present invention 0.1%-20%
UV-absorber as described in Table 1 and 2 0%-30% X X X X
TABLE-US-00006 Multiple emulsions Ingredients 1 2 3 4 5 6 7 8 9 10
11 12 PEG-30 X X X Dipolyhydroxy- stearate (2%-6%) Cetyl
Dimethicone X X Copolyol 1% - 3% PEG-30 X X Dipolyhydroxy-
stearate/Steareth- 2/Steareth-21 4%-6% Polyglyceryl-2 X X
Dipolyhydroxy- stearate 1%-3% Polyglyceryl-6 X X X Ricinoleate
1%-3% Oil phase 15%-30% Fatty acid esters X X X X X X X Natural and
X X X X X X X synthetic Triglycerides Hydrocarbon oils X X X X X X
X Silicone oils X X X X X X X Preservatives X X X X X X X X X X X X
0.3%-0.8% Water Deioniz. qs X X X X X X X X X X X X 100% Sorbitan
Stearate/ X X X Sucrose Cocoate 3%-7% Sucrose Laurate X X X 3%-7%
Poloxamer 407 X X X 3%-7% Polyoxyethylene X X X (20) Sorbate
Monoleate 3%-5% Primary emulsion X X X X X X X X X X X X W1/O 50%
Thickeners (water X X X X X X X X X X X X swellable) polymers
0.3%-1% Water deionized X X X X X X X X X X X X Qs 100% Perfume
oils X X X X X X X X X X X X 0.1%-0.4% Cosmetic compo- X X X X X X
X X X X X X sition according to the present invention 0.1%-20%
UV-absorber as X X X X X X X X X X X X described in Table 1 and 2
0%-30%
TABLE-US-00007 O1/W/O2 emulsions Ingredients 1 2 3 4 5 6 7 8
Primary emulsion O1/W PEG-60 Hydrogenated X X X X Castor Oil 25%
Steareth-25 25% X X X X Oil phase 75% Fatty acid esters X X Natural
and synthetic X X Triglycerides Hydrocarbon oils X X Silicone oils
X X Preservatives 0.3%-0.8% X X X X X X X X Water deionized Qs 100%
X X X X X X X X Non ionic multifunctional W/O X X X X X X X X
emulsifier 2%-5% Waxes 1%-5% X X X X X X X X Oil phase 20%-30% X X
X X X X X X Silicone oils Primary emulsion O1/W 15% X X X X X X X X
Electrolytes (NaCl, MgSO.sub.4) X X X X X X X X 0.1%-0.5% Water
deionized Qs 100% X X X X X X X X Perfume oils 0.1%-0.4% X X X X X
X X X Cosmetic composition X X X X X X X X according to the present
invention 0.1%-20% UV-absorber as described in X X X X X X X X
Table 1 and 2 0%-30%
TABLE-US-00008 Microemulsions Ingredients 1 2 3 4 5 6 7 8 9 10
PEG-8 Caprylic/Capric X X X X X Glycerides 10%-25% PPG-5-ceteth-20
10%-25% X X X X X Polyglyceryl-6 Isostearate X X 5%-15%
Polyglyceryl-3 Diisostearate X X 5%-15% Polyglyceryl-6 Dioleate X X
5%-15% PPG-10 Cetyl Ether 5%-15% X X Ethoxydiglycol 5%-15% X X Oil
phase 10%-80% X X X X X X X X X X Isostearyl Benzoate X X X X X X X
X X X Isostearyl Isostearate X X X X X X X X X X PEG-7 Glyceryl
Cocoate X X X X X X X X X X Cyclomethicone X X X X X X X X X X
Polyalcohols/Humectants X X X X X X X X X X 1%-10% Preservatives
0.3-0.8% X X X X X X X X X X Perfume oils 0.1%-0.4% X X X X X X X X
X X Water Deioniz. qs 100% X X X X X X X X X X Cosmetic composition
X X X X X X X X X X according to the present invention 0.1%-20%
UV-absorber as described in X X X X X X X X X X Table 1 and 2
0%-30%
TABLE-US-00009 O/W Spray emulsions Ingredients 1 2 3 4 5 6 Alkyl
Phosphates 0.1%-5% X X X Glucosidic derivatives 0.1%-5% X X X
Solubilisants Ethoxylated Glyceryl ethers 0.1%-1% X X Polysorbates
0.1%-1% X X Ethoxylated Oleyl ethers 0.1%-1% X X PVP/VA Copolymer
1%-10% X X X PVM/MA Copolymer 1%-10% X X X Oil phase 5%-20% X X X X
X X Natural oils (Meadowfoam, X X X X X X Jojoba, Macadamia...)
Fatty acids esters X X X X X X Mineral oils X X X X X X Silicone
oils X X X X X X Alcohol 0%-50% X X X X X X Thickeners 0.1%-0.5% X
X X X X X Polyacrylates X X X X X X Aluminum/Magnesium Silicates X
X X X X X Gums X X X X X X Neutralizing agents 0%-1% X X X X X X
Polyalcohols/Humectants 1%-5% X X X X X X Chelating agents (such as
EDTA) 0%-0.2% X X X X X X Antioxidants 0.05%-0.2% X X X X X X Water
Deioniz. qs 100% X X X X X X Perfume oils 0.1%-0.5% X X X X X X
Preservatives 0.4%-1% X X X X X X Cosmetic composition according to
X X X X X X the present invention 0.1%-20% UV-absorber as described
in X X X X X X Table 1 and 2 0%-30%
TABLE-US-00010 G-Aqueous Ingredients 1 2 3 4 5 6 7 8 9 10 11 12
Thickeners Natural X X X X Thickener 1%-5% Semi-synthetic X X X X
Thickener 1%-5% Synthetic X X X X Thickener 0.3%-1.3% Neutralizing
X X X X X X X X X X X X Agents 0.5%-1.5% Polyols- X X X X X X X X X
X X X Humectants 5%-50% Polyquaternium X X X X X X series 1%-5%
PVM/MA X X X X X X Copolymer 1%-5% Preservatives X X X X X X X X X
X X X 0.5%-1% Chelating X X X X X X X X X X X X Agents (as EDTA)
<0.1% Water Deioniz. X X X X X X X X X X X X qs 100% Perfume
oils X X X X X X X X X X X X 0.05%-0.4% Ethoxylated X X X Glyceryl
ethers 0.1%-5% Polysorbates X X X 0.1%-5% Ethoxylated X X X X X X
Oleyl ethers 0.1%-5% Cosmetic X X X X X X X X X X X X composition
according to the present invention 0.1%-20% UV-absorber as X X X X
X X X X X X X X described in Table 1 and 2 0%-30%
TABLE-US-00011 Oleogels Ingredients 1 2 3 4 5 6 7 8 9 10
Hydrogenated X X Lecithin 1%-10% Silica Dimethyl X X Silylate
1%-10% Silica 1%-5% X X C.sub.24-28 Alkyl X X Dimethicone 1%-5%
Aluminum or X X Magnesium Stearate 1%-5% Polyols-Humectants X X X X
X X X X X X 5%-70% Oil phase 20%-90% Dicaprylyl Ether X X X Phenyl
Trimethicone X X Hydrogenated X Polyisobutene Isopropyl Isostearate
X X Oleogel basis X X (Mineral oil and hydrogenated
Butylene/Ethylene or Ethylene/Propylene Styrene Copolymer) Silicone
wax X X X X X X X X X X 1%-10% Dimethiconol X X X X X X X X X X
Behenate Dimethiconol X X X X X X X X X X Stearate Perfume oils X X
X X X X X X X X 0.1%-0.5% Antioxidants X X X X X X X X X X
0.05%-0.2% Cosmetic X X X X X X X X X X composition according to
the present invention 0.1%-20% UV-absorber as X X X X X X X X X X
described in Table 1and 2 0%-30%)
TABLE-US-00012 Light/dry cosmetic oils Ingredients 1 2 3 4
Hydrocarbon oils 30%-70% X X Fatty acid esters branched or not
10%-50% X X Silicones/Siloxanes 0%-10% X X Perfluorinated oils and
Perfluoroethers 0%-10% X X Viscosifying agents 0%-10% X X X X
Esters of long chain acids and alcohols 0%-2% X X X X Antioxidants
0.1%-1% X X X X Solubilisants/dispersing agents 0%-5% X X X X
Perfume oils 0.1%-0.5% X X X X Cosmetic composition according to
the X X X X present invention 0.1%-20% UV-absorber as described in
Table 1 and 2 0%-30% X X X X
TABLE-US-00013 Foaming/mousse products Ingredients 1 SD Alcohol 40
0%-8% X Propellant 8%-15% X Nonionic Emulsifier/Surfactant 0.5%-3%
X Corrosion Inhibitor 0%-1% X Perfume oils 0.1%-0.5% X
Preservatives 0.1%-1% X Miscellaneous 0%-1% X Cosmetic composition
according to the present invention 0.1%-20% X UV-absorber as
described in Table 1 and 2 0%-30% X
TABLE-US-00014 Stick products Ingredients 1 Waxes 15%-30% X Natural
and silicone oils 20%-75% X Lanoline derivatives 5%->50% X
Esters of lanolin X Acetylated lanolin X Lanolin oil X Colorants
and pigments 10%-15% X Antioxidants 0.1%-0.8% X Perfume oils
0.1%-2% X Preservatives 0.1%-0.7% X Cosmetic composition according
to the present invention 0.1%-20% X UV-absorber as described in
Table 1 and 2 0%-30% X
TABLE-US-00015 Liquid and compact Ingredients 1 2 Liquid foundation
Powder phase 10%-15% X Oil phase 30%-40%; 75% (only for anhydrous
form) X Thickener/suspending agents 1%-5% X Film forming polymers
1%-2% X Antioxidants 0.1%-1% X Perfume oils 0.1%-0.5% X
Preservatives 0.1%-0.8% X Water deionized Qs 100% X Compact powder
Powder phase 15%-50% X Oil phase 15%-50% X Polyol phase 5%-15% X
Antioxidants 0.1%-1% X Perfume oils 0.1%-0.5% X Preservatives
0.1%-0.8% X For the two product forms Cosmetic composition
according to the present invention 0.1%-20% X X UV-absorber as
described in Table 1 and 2 0%-30% X X
TABLE-US-00016 Conditioning Shampoos Ingredients 1 Primary
surfactants (listed previously) 5%-10% X Secondary surfactants
(listed previously) 5%-15% X Foam Stabilizers (listed previously)
0%-5% X Water deionized 40%-70% X Actives 0-10% X Conditioners x
Refatting agents x Moisturizing agents x Thickeners/Rheology
modifiers 0%-3% X Humectants 0%-2% X PH adjusting agents 0%-1% X
Preservatives 0.05%-1% X Perfume oils 0.1%-1% X Antioxidants
0.05%-0.20% X Chelating Agents (EDTA) 0%-0.2% X Opascifying agents
0%-2% X Cosmetic composition according to the present invention
0.1%-20% X UV-absorber as described in Table 1 and 2 0%-30% X
[0198] The cosmetic preparation according to the invention is
distinguished by excellent protection of human skin against the
damaging effect of sunlight.
[0199] The following examples illustrate the invention.
EXAMPLE 1
Formulations F1-F3
TABLE-US-00017 [0200] Ingredients F1 F2 F3 INCI NAME [% b.w.] [%
b.w.] [% b.w.] Water deionized 75.80 73.50 70.50 disodium EDTA 0.20
0.20 0.20 Glycerin 2.00 2.00 Xanthane gum 0.50 0.50 0.50 Ethylhexyl
Methoxycinnamate 2.00 2.00 2.00 Octocrylene 5.00 Glyceryl stearate
& PEG-100 stearate 4.00 4.00 4.00 Cetearyl alcohol 2.500 2.500
2.50 Phenethyl Benzoate C12-15 alkyl benzoate 8.00 8.00 8.00 Octyl
Palmitate 5.00 5.00 5.00 Tris-Biphenyl Triazine 2.00 2.00 Decyl
Glucoside 0.3 0.3 SPF in vitro 3.8 .+-. 0.4 8.6 .+-. 0.9 12.8 .+-.
1.3 UVA/UVB-ratio 0.21 0.46 0.44
EXAMPLE 2
Photodegradation of UV Absorber Combinations
[0201] For the determination of photodegradation the so-called
"plate-test" is employed: 2 .mu.l/cm.sup.2 of the formulations are
spread on quartz plates (sand-blasted surface of 2.8 cm.sup.2), and
rinsed off the plates after 0, 5, and 10 MED of UV irradiation
using an Atlas CPS+ solar simulator.
[0202] Tested formulation comprising components (a), (b) and
(C):
TABLE-US-00018 Component (a) 2-ethylhexyl
2-cyano-3,3-diphenylacrylate (OCR) Component (b)
1,3,5-Triazine,2,4,6-tris([1,1'-biphenyl]-4-yl) (TBT) Component (c)
Ethylhexyl Methoxycinnamate (OMC)
[0203] Results
[0204] The results are listed in Table 3.
[0205] The substances tagged with an asterix (*) are those the
recovery percentages refer to.
[0206] The experimental error in terms of the standard deviation is
in the range of .+-.3%.
TABLE-US-00019 TABLE 3 Recovery of UV absorbers in the presence and
absence of C-801 Compo- Compo- Compo- Formu- nent nent nent 0 5 10
lation (a) (b) (c) MED MED MED 2-1 5* 100% 101% 102% 2-2 5* 2 100%
103% 102% 2-3 5 2* 100% 104% 102% 2-4 5* 2 2 100% 103% 103% 2-5 5
2* 2 100% 101% 102% 2-6 2* 100% 83% 63% 2-7 2 2* 100% 22% 17% 2-8
2* 2 100% 102% 103% 2-9 5 2 2* 100% 71% 54%
[0207] 1,3,5-Triazine,2,4,6-tris([1,1'-biphenyl]-4-yl) (TBT)
(component (b)) itself shows no degradation within the range of
experimental error under all conditions. The same is observed with
Octocrylene (OCR).
[0208] The results further show that in the combination of
Ethylhexyl Methoxycinnamate (OCR) and
1,3,5-Triazine,2,4,6-tris([1,1'-biphenyl]-4-yl) (TBT), the
Ethylhexyl Methoxycinnamate can be stabilized by addition of
Octocrylene.
EXAMPLE 3
[0209] The so-called "plate-test" is employed: 2 .mu.l/cm.sup.2 of
the formulations are spread on quartz plates (sand-blasted surface
of 2.8 cm.sup.2), and rinsed off the plates after 0, 5, and 10 MED
of UV irradiation using an Atlas CPS+ solar simulator.
[0210] Formulations of BMDBM (Butyl Methoxy Dibenzoylmethane)
alone, BMDBM in combination with OCR (Octocrylene), and
formulations of BMDBM with Tris-Biphenyl Triazine (TBT) in
combination with either BEMT (Bis-Ethylhexyloxyphenol Methoxyphenyl
Triazine), or Benzotriazolyl Dodecyl p-Cresol (BDC,) are
investigated.
[0211] The concentration of 1 Tris-Biphenyl Triazine (TBT) is kept
to 4%, corresponding to 2% of active.
[0212] Results
[0213] The results are listed in Table 4.
[0214] The percentages refer to the recovery of BMDBM.
[0215] The experimental error in terms of the confidence interval
at 95% level of significance is in the range of .+-.2% in relation
to the original amount of BMDBM (with each condition four plates
were investigated).
[0216] The active of Tris-Biphenyl Triazine (TBT) itself shows no
degradation within the range of experimental error under all
conditions.
[0217] The same is observed with BEMT, BDC and OCR.
TABLE-US-00020 TABLE 4 Recovery of UV absorbers in the presence and
absence of TBT UV-Absorber/ Formulation UV Absorber mixture 0 MED 5
MED 10 MED 3-1 2% BMDBM 100% 36% 11% 3-2 2% BMDBM + 4% TBT 100% 15%
5% 3-3 2% BMDBM + 5% OCR 100% 85% 80% 3-4 2% BMDBM + 5% OCR + 100%
85% 73% 4% TBT 3-5 2% BMDBM + 10% OCR 100% 95% 91% 3-6 2% BMDBM +
10% OCR + 100% 94% 87% 4% TBT 3-7 2% BMDBM + 1.5% BEMT + 100% 47%
28% 4% TBT 3-8 2% BMDBM + 3% BEMT + 100% 66% 47% 4% TBT 3-9 2%
BMDBM + 1.5% BEMT + 100% 68% 46% 1% BDC + 4% TBT 3-10 2% BMDBM + 3%
BEMT + 100% 76% 59% 1% BDC + 4% TBT BMDBM Butyl Methoxy
Dibenzoylmethane TBT Tris-Biphenyl Triazine OCR Octocrylene BDC
Benzotriazolyl Dodecyl p-Cresol BEMT Bis-Ethylhexyloxyphenol
Methoxyphenyl Triazine
CONCLUSION
[0218] The data show that the presence of TBT leads to accelerated
photodegradation of BMDBM. This effect can be almost completely
reversed by addition of Octocrylene and also by BEMT or BDC, when
realistic concentrations are employed.
* * * * *