U.S. patent application number 12/432581 was filed with the patent office on 2009-08-20 for method of quenching electronic excitation of chromophore-containing organic molecules in photoactive compositions.
This patent application is currently assigned to HALLSTAR INNOVATIONS CORP.. Invention is credited to CRAIG A. BONDA, Anna Pavlovic.
Application Number | 20090208435 12/432581 |
Document ID | / |
Family ID | 39596502 |
Filed Date | 2009-08-20 |
United States Patent
Application |
20090208435 |
Kind Code |
A1 |
BONDA; CRAIG A. ; et
al. |
August 20, 2009 |
METHOD OF QUENCHING ELECTRONIC EXCITATION OF CHROMOPHORE-CONTAINING
ORGANIC MOLECULES IN PHOTOACTIVE COMPOSITIONS
Abstract
The photostabilizing electronic excited state
energy--particularly singlet state energy from a UV-absorbing
molecule has been found to be readily transferred to (accepted by)
.alpha.-cyanodiphenylacrylate compounds of formulas (I) and (V)
having an alkoxy radical preferably in the four (para) position
(hereinafter methoxycrylenes) on one or both of the phenyl rings:
##STR00001## wherein at least one of R.sub.1 and R.sub.2 is a
straight or branched chain C.sub.1-C.sub.12 alkoxy radical,
preferably C.sub.1-C.sub.8, more preferably C.sub.1-C.sub.4, and
most preferably methoxy, and any non-alkoxy radical R.sub.1 or
R.sub.2 is hydrogen; and R.sub.3 is a straight or branched chain
C.sub.1-C.sub.24 alkyl radical, preferably C.sub.12-C.sub.24, more
preferably C.sub.20; ##STR00002## wherein A and B are the same or
different and are selected from the group consisting of oxygen,
amino and sulfur; R.sup.1 and R.sup.3 are the same or different and
are selected from the group consisting of C.sub.1-C.sub.30 alkyl,
C.sub.2-C.sub.30 alkylene, C.sub.2-C.sub.30 alkyne, C.sub.3-C.sub.8
cycloalkyl, C.sub.1-C.sub.30 substituted alkylene, C.sub.2-C.sub.30
substituted alkyne, aryl, substituted aryl, heteroaryl,
heterocycloalkyl, substituted heteroaryl and substituted
heterocycloalkyl; R.sup.2 is selected from the group consisting of
C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkylene, C.sub.2C.sub.30
alkyne, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.30 substituted
alkyl, C.sub.3-C.sub.8 substituted cycloalkyl, C.sub.1-C.sub.30
substituted alkylene, C.sub.2-C.sub.30 substituted alkyne; R.sup.4,
R.sup.5, R.sup.6 and R.sup.7 are the same or different and are
selected from the group consisting of C.sub.1-C.sub.30 alkoxy
straight chin on branched and a, b, c and d are each either 0 or 1,
and a, b, c and d add up to 1, 2, 3, or 4.
Inventors: |
BONDA; CRAIG A.; (Winfield,
IL) ; Pavlovic; Anna; (Elmwood Park, IL) |
Correspondence
Address: |
MARSHALL, GERSTEIN & BORUN LLP
233 SOUTH WACKER DRIVE, 6300 SEARS TOWER
CHICAGO
IL
60606-6357
US
|
Assignee: |
HALLSTAR INNOVATIONS CORP.
Chicago
IL
|
Family ID: |
39596502 |
Appl. No.: |
12/432581 |
Filed: |
April 29, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12022758 |
Jan 30, 2008 |
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12432581 |
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11891281 |
Aug 9, 2007 |
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12022758 |
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Current U.S.
Class: |
424/60 ;
424/59 |
Current CPC
Class: |
A61K 2800/52 20130101;
A61Q 17/04 20130101; A61K 8/40 20130101 |
Class at
Publication: |
424/60 ;
424/59 |
International
Class: |
A61K 8/40 20060101
A61K008/40; A61Q 17/04 20060101 A61Q017/04 |
Claims
1.-100. (canceled)
101. A method of accepting electronic singlet state excited energy
from a photon-excited photoactive compound, thereby
photostabilizing said photoactive compound, comprising mixing said
photoactive compound with a compound of formula (V): ##STR00036##
wherein A and B are the same or different and are selected from the
group consisting of oxygen, amino and sulfur; R.sup.1 and R.sup.3
are the same or different and are selected from the group
consisting of C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkylene,
C.sub.2-C.sub.30 alkyne, C.sub.3-C.sub.8 cycloalkyl,
C.sub.1-C.sub.30 substituted alkylene, C.sub.2-C.sub.30 substituted
alkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,
substituted heteroaryl and substituted heterocycloalkyl; R.sup.2 is
selected from the group consisting of C.sub.1-C.sub.30 alkyl,
C.sub.2-C.sub.30 alkylene, C.sub.2C.sub.30 alkyne, C.sub.3-C.sub.8
cycloalkyl, C.sub.1-C.sub.30 substituted alkyl, C.sub.3-C.sub.8
substituted cycloalkyl, C.sub.1-C.sub.30 substituted alkylene,
C.sub.2-C.sub.30 substituted alkyne; R.sup.4, R.sup.5, R.sup.6 and
R.sup.7 are the same or different and are selected from the group
consisting of C.sub.1-C.sub.30 alkoxy straight chin or branched and
a, b, c and d are each either 0 or 1, and a, b, c and d add up to
1, 2, 3, or 4 and exposing the mixture to UV radiation in an amount
sufficient for the photoactive compound to reach an electronic
singlet excited state, whereby the compound of formula (V) accepts
the singlet excited state energy from the excited photoactive
compound, thereby returning the photoactive compound to its ground
state so that it is capable of absorbing additional UV
radiation.
102. The method of claim 101, wherein R.sup.4 is methoxy and
R.sup.5 is hydrogen.
103. The method of claim 101, wherein R.sup.6 is methoxy and
R.sup.7 is hydrogen.
104. The method of claim 101, wherein R.sup.4 is hydrogen and
R.sup.5 is methoxy.
105. The method of claim 101, wherein R.sup.6 is hydrogen and
R.sup.7 is methoxy.
106. The method of claim 101, wherein the compound of formula (V)
is present in an amount in the weight range of 0.1% to 30%, based
on the total weight of the composition.
107. The method of claim 106, wherein the compound of formula (V)
is present in an amount in the weight range of 0.5% to 20%, based
on the total weight of the composition.
108. The method of claim 107, wherein the compound of formula (V)
is present in an amount in the weight range of 0.1% to 10%, based
on the total weight of the composition.
109. The method of claim 108, wherein the compound of formula (V)
is present in an amount in the weight range of 3% to 10%, based on
the total weight of the composition.
110. The method of claim 101, wherein the photoactive compound is
selected from the group consisting of p-aminobenzoic acid and salts
and derivatives thereof; anthranilate and derivatives thereof;
dibenzoylmethane and derivatives thereof; salicylate and
derivatives thereof; cinnamic acid and derivatives thereof;
dihydroxycinnamic acid and derivatives thereof; camphor and salts
and derivatives thereof; trihydroxycinnamic acid and derivatives
thereof; dibenzalacetone naptholsulfonate and salts and derivatives
thereof; benzalacetophenone naphtholsulfonate and salts and
derivatives thereof; dihydroxy-naphthoic acid and salts thereof;
o-hydroxydiphenyldisulfonate and salts and derivatives thereof;
p-hydroxdydiphenyldisulfonate and salts and derivatives thereof;
coumarin and derivatives thereof; diazole derivatives; quinine
derivatives and salts thereof; quinoline derivatives;
hydroxyl-substituted benzophenone derivatives; naphthalate
derivatives; methoxy-substituted benzophenone derivatives; uric
acid derivatives; vilouric acid derivatives; tannic acid and
derivatives thereof; hydroquinone; benzophenone derivatives;
1,3,5-triazine derivatives; disodium phenyl dibenzimidazole and
salts thereof; terephthalyidene dicamphor sulfonic acid and salts
and derivatives thereof; methylene bis-benzotriazolyl
tetramethylbutylphenol and salts and derivatives thereof;
bis-ethylhexyloxyphenol methoxyphenyl triazine and salts,
diethylamino hydroxyl benzoyl and derivatives thereof;
phenylbenzimidazole sulfonic acid and salts thereof;
terephthalylidene dicamphor sulfonic acid and salts thereof; and
combinations of the foregoing.
111. The method of claim 110, wherein the photoactive compound
comprises a dibenzoylmethane derivative.
112. The method of claim 111, further including a cinnamate
ester.
113. The method of claim 112, wherein the cinnamate ester is an
ester of an alkoxycinnamate.
114. The method of claim 113, wherein the alkoxycinnamate ester is
a methoxycinnamate ester.
115. The method of claim 112, wherein the cinnamate ester is
selected from the group consisting of 2-ethylhexyl
p-methoxycinnamate, isoamyl p-methoxycinnamate, and a combination
thereof.
116. The method of claim 113 wherein the cinnamate ester is
2-ethylhexyl p-methoxycinnamate.
117. The method of claim 114, wherein the dibenzoylmethane
derivative comprises butylmethoxy dibenzoylmethane.
118. The method of claim 98, further including a naphthalene
dicarboxylic acid ester in an amount of 0.1 to 10 wt %.
119. The method of claim 118, wherein the naphthalene dicarboxylic
acid ester comprises a diethylhexyl 2,6-naphthalene dicarboxylic
acid ester.
120. The method of claim 101, further including a salicylate or a
derivative thereof in an amount of 0.1 to 10 wt %.
121. The method of claim 115, further including a salicylate or a
derivative thereof in an amount of 0.1 to 10 wt %.
122. The method of claim 101, further including a benzophenone or a
derivative thereof in an amount of 0.1 to 10 wt. %.
123. The method of claim 122, wherein the benzophenone comprises
benzophenone-3 in an amount of 0.1 to 10 wt. %.
124. The method of claim 114, further including
bis-ethylhexyloxyphenol methoxyphenyl triazine in an amount of 0.1
to 10 wt. %.
125. The method of claim 114, further including diethylhexyl
syringylidene malonate in an amount of 0.1 to 10 wt. %.
126. The method of claim 98, wherein the photoactive compound
comprises a 1,3,5-triazine derivative.
127. The method of claim 114, further including methylene
bis-benzotriazoyl tetramethylbutyl phenol in an amount of 0.1 to 10
wt. %.
128. The method of claim 114, further including diethylamino
hydroxybenzoyl hexylbenzoate in an amount of 0.1 to 10 wt. %.
129. The method of claim 114, further including disodium
phenyldibenzylimidazole sulfonic acid in an amount of 0.1 to 10 wt.
%.
130. The method of claim 114, further including
2-(methylbenzilidene)-camphor.
131. The method of claim 114, further including phenylbenzimidazole
sulfonic acid or salt thereof in an amount of 0.1 to 10 wt. %.
132. The method of claim 111, wherein the photoactive compound
comprises a dibenzoylmethane derivative selected from the group
consisting of 2-methyldibenzoylmethane; 4 methyldibenzoylmethane;
4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;
2,4-dimethydibenzoylmethane; 2-5-dimethydibenzoylmethane;
4,4-diispropyldibenzoylmethane; 4,4-dimethoxydibenzoylmethane;
4-tert-butyl-4-methoxdibenzoylmethane;
2-methyl-5-isopropy-4-methoxydibenzoylmethane;
2-methyl-5-tert-butyl-4-methoxydibenzoylmethane;
2,4-dimethyl-4-methoxydibenzoymethane;
2,6-dimethyl-4-tert-butyl-4-methoxydibenzolmthane, and combinations
thereof.
133. The method of claim 101 further including 0.1 to 10 wt. % of a
triplet quencher selected from the group consisting of octocrylene,
methyl benzylidene camphor, diethylhexyl 2,6-naphthalate,
diethylhexyl syringylidene malonate, and combinations thereof.
134. The method of claim 116 further comprising 0.1 to 10 wt. %
benzophenone-3.
135. The method of claim 116 further comprising 0.1 to 10 wt. %
octyl salicylate.
136. The method of claim 110, wherein the photoactive compound
comprises a derivative of cinnamic acid.
137. The method of claim 115, wherein the photoactive compound
comprises 2-ethylhexyl-p-methoxycinnamate.
138. The method of claim 114, wherein the photoactive compound
comprises isoamyl methoxycinnamate.
139. The method of claim 101, that includes an ester of
cyanodiphenyl propenoic acid.
140. The method of claim 101, wherein the mixture includes methyl
benzylidene camphor.
141. The method of claim 101, wherein the composition includes a
compound selected from the group consisting of methylene
bis-benzotriazolyl tetramethylbutylphenol, salts and derivatives
thereof; bis-ethylhexyloxyphenol methoxyphenyl triazine, and salts
and derivatives thereof;
142. The method of claim 101, wherein the composition includes a
hydroxyl-substituted benzophenone derivative or a
methoxy-substituted benzophenone derivative, or a combination
thereof.
143. The method of claim 101, further comprising a diester or
polyester of naphthalene dicarboxylic acid selected from the group
consisting of compounds of formula (II) and (III), and combinations
thereof: ##STR00037## wherein R.sub.1 and R.sub.2 are the same or
different and selected from the group consisting of
C.sub.1-C.sub.22 alkyl groups, diols having the structure
HO--R.sub.4--OH, and polyglycols having the structure
HO--R.sub.3--(--O--R.sub.4--).sub.n--OH; wherein each R.sub.3 and
R.sub.4 is the same or different and selected from the group
consisting of C.sub.1-C.sub.6 straight or branched chain alkyl
groups; and wherein m and n are each in a range of 1 to 100.
144. The method of claim 143, comprising a diester of formula (III)
wherein R.sub.1 and R.sub.2 are 2-ethylhexyl.
145. The method of claim 101, wherein said mixture includes a
cosmetically acceptable carrier.
146. The method of claim 101, wherein said mixture includes an oil
phase having a dielectric constant of at least about 8.
147. The method of claim 101, wherein the photoactive compound is a
water-soluble UV-absorbing compound.
148. The method of claim 147, wherein the photoactive compound is a
sulfonated UV-absorbing compound.
149. The method of claim 148, wherein the sulfonated UV absorbing
compound is selected from the group consisting of
phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic acid and
its corresponding salts, 2-phenylbenzimidazole-5-sulfonic acid and
its corresponding salts, and mixtures thereof.
150. The method of claim 101, wherein the photoactive compound is a
hydroxybenzophenone of the following structural formula:
##STR00038## where R.sup.1 and R.sup.2 independent of one another
are hydrogen, C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.10-cycloalkyl
or C.sub.3-C.sub.10-cyloalkenyl, wherein the substituents R.sup.1
and R.sup.2 together with the nitrogen atom to which they are bound
can form a 5- or 6-ring, and R.sup.3 is a C.sub.1-C.sub.20-- alkyl
radical.
151. The method of claim 150, further including at least one
dialkyl naphthalate comprising the structural formula: ##STR00039##
where R.sup.1 and R.sup.2 are independently one of branched and
unbranched alkyl groups with 6 to 24 carbons atoms.
152. The method according to claim 150, comprising at least one
further UVA filter substance and/or a broadband filter comprising
at least one of dibenzoylmethane derivatives and
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]plenyl}-6-(4-methoxyphenyl)-1,3,5--
triazine.
153. The method according to claim 150, further comprising at least
one UV filter substance selected from the group consisting of UV-A
filters, UV-B filters, broad-band filters, triazines,
benzotriazoles, organic pigments, inorganic pigments, and mixtures
thereof.
154. The method of claim 101, wherein the photoactive compound
comprises a benzotriazole compound that has the structure
##STR00040## where R.sup.1 and R.sup.2 are, independently of one
another, selected from the group consisting of branched and
unbranched: (a) C.sub.1-C.sub.18-alkyl radicals; (b)
C.sub.5-C.sub.12-cycloalkyl or aryl radicals; wherein said R.sup.1
and R.sup.2 are optionally substituted by one or more
C.sub.1-C.sub.4-alkyl groups.
155. The method of claim 154, wherein the benzotriazole UV filter
compound has the structure ##STR00041##
156. The method of claim 154, wherein the benzotriazole compound
has the structure ##STR00042##
157. The method of claim 101, wherein the photoactive compound is a
particulate UV absorbing substance.
158. The method of claim 157, wherein at least one particulate UV
filter substance is micronized inorganic pigment.
159. The method as claimed in claim 158, wherein the micronized
inorganic pigment is a micronized metal oxide.
160. The method as claimed in claim 159, wherein the micronized
metal oxide is an oxide of a metal selected from the group
consisting of titanium, zinc, iron, zirconium, silicon, manganese,
aluminum, cerium, and mixtures thereof.
161. The method as claimed in claim 159, wherein the micronized
metal oxide further comprises barium sulfate.
162. The method as claimed in claim 159, wherein the micronized
metal oxide has a primary particle size of less than 300 nm.
163. The method as claimed in claim 162, wherein the micronized
metal oxide has a primary particle size of 10 to 150 nm.
164. The method as claimed in claim 159, wherein the micronized
metal oxide is a surface treated metal oxide.
165. The method as claimed in claim 101, wherein the particulate UV
absorbing substance is present in an amount of 0.01 to 20 weight %
based on the total weight of the composition.
166. The method as claimed in claim 154, further comprising at
least one additional UV filter substance selected from the group
consisting of triazines, benzotriazoles, organic, inorganic
pigments, and mixtures thereof.
167. The method as claimed in claim 154, further comprising at
least one UV-A filter substance or broad-band filter substance.
168. The method of claim 167, wherein said at least one UV-A filter
substance or broad-band filter substance includes at least one
dibenzoylmethane derivative.
169. The method of claim 168, wherein the dibenzoylmethane
derivative is selected from the group consisting of
4-(tert-butyl)-4'-methoxydibenzoylmethane,
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5--
triazine, and mixtures thereof.
170. The method of claim 101, wherein the photoactive compound
comprises: (a) an asymmetrically substituted triazine UV filter
compound; and (b) one or more dialkyl naphthalates having the
structural formula ##STR00043## wherein R.sup.1 and R.sup.2 are,
independently of one another, branched or unbranched alkyl groups
having 6 to 24 carbon atoms.
171. The method of claim 170, wherein the dialkyl naphthalate is
diethylhexyl naphthalate.
172. The method of claim 170, wherein the asymmetrically
substituted triazine compound is selected from the group consisting
of:
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5--
triazine;
2,4-bis{[4-(3-sulfonato-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6--
(4-methoxyphenyl)-1,3,5-triazine sodium salt;
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-me-
thoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[(4-2-methoxyethoxycarbo-
nyl)-phenylamino]-1,3,5-triazine;
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[(4-e-
thoxycarbonyl)phenylamino]-1,3,5-triazine;
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)-1,-
3,5-triazine;
2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-met-
hoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(2-methylpropenyloxy)-2-hydroxyl]phenyl}-6-(4-methoxyphenyl)-1-
,3,5-triazine;
2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethylsiloxy-2-methylpropyloxy)-2-h-
ydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; and
dioctylbutylamidotriazone.
173. The method of claim 101, wherein the composition includes an
oxidation-sensitive or UV-sensitive ingredient selected from the
group consisting of coenzyme Q10, vitamin A and derivatives
thereof, vitamin E and derivatives thereof, lipoic acid and
derivatives thereof and carotenoids.
174. The method as claimed in claim 173, wherein the at least one
oxidation-sensitive or UV-sensitive active ingredient includes
vitamin E or derivatives thereof.
175. The method as claimed in claim 101, further comprising at
least one UV filter substance selected from the group consisting of
triazines, benzotriazoles, UV filters liquid at room temperature,
organic pigments and inorganic pigments.
176. The method as claimed in claim 101, further comprising at
least one UV-A filter substance or broadband filter selected from
the group consisting of
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxy-phenyl)-1,3,5-
-triazine,
phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetras-ulfonic acid
bis-sodium salt,
benzene-1,4-di(2-oxo-3-bornylidenemethyl-10-sulfonic acid,
2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-te-trameth-
-yl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol, and mixtures
thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention is directed to a method of quenching
electronic excited state(s) of chromophore-containing UV-absorbing
organic molecules in photoactive compositions. More particularly,
it has been found that .alpha.-cyano-.beta.,.beta.
diphenylacrylates (crylenes) having an alkoxy radical, preferably
on one of the phenyl rings (alternatively on both phenyl rings),
quenches the excited state of the chromophore by accepting the
excited state energy (singlet and sometimes also the triplet
state), thereby returning the UV-absorbing molecule back to its
ground state so that the chromophore can absorb more photons, e.g.,
from ultraviolet (UV) light, thereby photostabilizing UV-absorbing
chromophore-containing organic molecules, particularly butyl
methoxydibenzoylmethane (Avobenzone), octyl methoxycinnamate
(Octinoxate), and octyl salicylate (Octisalate) in photoactive
compositions.
BACKGROUND
[0002] The absorption of ultraviolet light by a
chromophore-containing organic molecule causes the excitation of an
electron in the chromophore moiety from an initially occupied, low
energy orbital to a higher energy, previously unoccupied orbital.
The energy of the absorbed photon is used to energize an electron
and cause it to "jump" to a higher energy orbital, see Turro,
Modern Molecular Photochemistry, 1991. Two excited electronic
states derive from the electronic orbital configuration produced by
UV light absorption. In one state, the electron spins are paired
(antiparallel) and in the other state the electron spins are
unpaired (parallel). The state with paired spins has no resultant
spin magnetic moment, but the state with unpaired spins possesses a
net spin magnetic moment. A state with paired spins remains a
single state in the presence of a magnetic field, and is termed a
singlet state. A state with unpaired spins interacts with a
magnetic field and splits into three quantized states, and is
termed a triplet state.
[0003] In the electronically excited state, the
chromophore-containing organic molecule is prone to degrade via a
number of known pathways and, therefore, can absorb little or no
additional UV light. To photostabilize an electronically excited
chromophore-containing organic molecule in order to provide
sufficient UV protection, it must be returned to the ground state
before it undergoes a photochemical reaction destructive to its UV
absorbing capability. There are known photostabilizing sunscreen
additives, such as Octocrylene, methylbenzilydene camphor, and the
esters or polyesters of naphthalene dicarboxylic acid of this
assignee's U.S. Pat. Nos. 6,113,931; 6,284,916; 6,518,451; and
6,551,605, all hereby incorporated by reference, that are capable
of quenching excited triplet state energy. Surprisingly, it has
been found that alkoxy crylenes, particularly methoxy crylenes,
return chromophore-containing organic molecules, particularly butyl
methoxydibenzoylmethane (Avobenzone), octyl methoxycinnamate
(Octinoxate), and octyl salicylate (Octisalate), from both an
electronically excited singlet state and excited triplet state back
to their ground state, thereby photostabilizing the UV-absorbing
organic molecules.
[0004] Deflandre U.S. Pat. No. 5,576,354 generally discloses a
cosmetic sunscreen composition containing at least 1% by weight of
an .alpha.-cyano-.beta.,.beta.-diphenylacrylate that will
photostabilize a dibenzoylmethane derivative, e.g., Parsol 1789
(Avobenzone), so long as the composition contains a fatty phase,
e.g., glycerol stearates, isopropyl myristate or the like, and so
long as the mole ratio of the
.alpha.-cyano-.beta.,.beta.-diphenylacrylate to the
dibenzoylmethane derivative is at least 0.8. The compounds
preferred in the '354 patent and disclosed in the examples are
octocrylene, which contains no alkoxy radical(s) (UVINULN 539);
.beta.,.beta.-bis(4-methoxyphenyl)acrylates (containing no cyano
radical); and the .alpha.-cyano-.beta.,.beta.-diphenylacrylates,
which contain no alkoxy radical(s).
[0005] As stated in this assignees pending application Ser. Nos.
10/241,388; 10/361,223; and 10/7865,793, an
.alpha.-cyano-.beta.,.beta.-diphenylacrylate compound (e.g.,
octocrylene) is known to quench (accept) the excited triplet state
energy of an excited photoactive compound by dissipating the energy
kinetically in the form of rapid isomerizations. This process is
shown below:
##STR00003##
wherein the .alpha.-cyano-.beta.,.beta.-diphenylacrylate compound
(octocrylene shown above as structure A), accepts the triplet
excited state energy from a photoactive compound and forms a
diradical (shown above as structure A*) at the .alpha. and .beta.
positions of the acrylate, which converts the double bond into a
single bond and allows for the free rotation of the phenyl groups.
This rotation occurs rapidly and efficiently to dissipate any
excited triplet state energy accepted by the
.alpha.-cyano-.beta.,.beta.-diphenylacrylate compound from the
photoactive compound.
[0006] While octocrylene is able to quench (accept) the triplet
excited state energy from a photoactive compound, thereby
photostabilizing, to some degree, dibenzoylmethane derivatives, as
shown in examples 1, 4, 6 and 8 of Deflandre et al. U.S. Pat. No.
5,576,354, hereby incorporated by reference, there exists a need in
the photoactive composition art to find one or more compounds that
quench (accept) the singlet excited state energy and preferably
also the triplet excited state energy from photoactive compounds,
which octocrylene does not.
[0007] Quite surprisingly, it has been found that the alkoxy
substituted .alpha.-cyano-.beta.,.beta.-diphenylacrylates (alkoxy
crylenes) will quench the electronically excited singlet state
energy of UV-absorbing organic molecules, such as the
dibenzoylmethane derivatives of U.S. Pat. No. 5,576,354, even at
very low loadings compared to the quantity of UV-absorbing
compounds.
SUMMARY
[0008] The photostabilizing electronic excited state
energy--particularly singlet state energy from a UV-absorbing
molecule--has been found to be readily transferred to (accepted by)
.alpha.-cyanodiphenylacrylate compounds having an alkoxy radical in
the four (para) position (hereinafter "alkoxycrylenes") on one or
both of the phenyl rings having the formula (I):
##STR00004##
, wherein one or both of R.sub.1 and R.sub.2 is a straight or
branched chain C.sub.1-C.sub.30 alkoxy radical, preferably
C.sub.1-C.sub.8, more preferably methoxy, and any non-alkoxy
radical R.sub.1 or R.sub.2 is hydrogen; and R.sub.3 is a straight
or branched chain C.sub.1-C.sub.30 alkyl radical, preferably
C.sub.2-C.sub.20.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a graph showing the photostability of the
sunscreen compositions of Examples 1-3 (when irradiated with 35 MED
of UV radiation) provided by 4.5% octyldocedyl methoxy crylene
(C2OMC); and 2.75% Octocrylene (OC) compared to the photostability
prior to UV irradiation and compared to the composition with no
photostabilizer;
[0010] FIG. 2 is a graph showing the photostability of the
sunscreen composition of Example 4 before and after irradiation
with 35 MED of UV radiation;
[0011] FIG. 3 is a graph showing the photostability of the
sunscreen composition of Example 5 before and after irradiation
with 35 MED of UV radiation; and
[0012] FIG. 4 is a graph showing the photostability of the
sunscreen composition of Example 6 before and after irradiation
with 35 MED of UV radiation; and
[0013] FIG. 5 is a graph showing the sunscreen composition of
Example 7 before and after irradiation with 35 MED of UV
radiation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] Ranges may be expressed herein as from "about" or
"approximately" one particular value and/or to "about" or
"approximately" another particular value. When such a range is
expressed, another embodiment includes from the one particular
value and/or to the other particular value. Similarly, when values
are expressed as approximations, by use of the antecedent "about,"
it will be understood that the particular value forms another
embodiment.
[0015] The term "alkoxy" herein refers to a radical extending from
the para position of one or both of the phenyl rings having the
formula O--R, wherein R is an alkyl radical, straight chain or
branched having 1 to 30 carbon atoms, preferably wherein
R.dbd.C.sub.1 to C.sub.8, more preferably C.sub.2-C.sub.20, and
most preferably --O--CH.sub.3 (methoxy). The oxygen atom of the
alkoxy radical is covalently bonded to the para carbon atom of one
or both of the phenyl rings, preferably only one of the phenyls,
preferably having the formula (II) or (III):
##STR00005##
wherein R.sub.3 is as previously defined.
[0016] The term "crylene" as used herein refers to a chromophoric
moiety that includes an .alpha.-cyano-.beta.,.beta.-diphenyl
propanoic acid ester.
[0017] The term "cyano" as used herein refers to a --C.ident.N
group, also designated "--CN."
[0018] Photoactive compositions, e.g., sunscreen compositions,
generally include UV-A and UV-B photoactive compounds in a
cosmetically acceptable carrier, optionally including additives,
such as emollients, stabilizers, emulsifiers, and combinations
thereof. These additives can be used in preparing a UV filter
composition in an emulsion (oil-in-water or water-in-oil) from a
composition that includes one or more photoactive compounds and a
solvent or a solvent combination that includes one or more organic
solvents and water. When made, preferably the emulsion is an
oil-in-water emulsion, wherein the oil phase is primarily formed
from a mixture of the UV filter compound(s) and one or more organic
solvents.
[0019] A typical photoactive composition includes one or more
photoactive compounds, wherein the photoactive compound(s) act to
absorb UV radiation and thereby protect the substrate (e.g., human
skin, resins, films, and the like) from the harmful effects of UV
radiation. The absorption process causes a photoactive compound to
reach an excited state, wherein the excited state is characterized
by the presence of excited electronic energy (e.g., singlet state
energy or triplet state energy), as compared to the ground state of
the photoactive compound. Once a photoactive compound reaches an
excited state there exists a number of pathways by which the
excited photoactive compound can dissipate its excess energy (e.g.,
singlet and/or triplet energy), however, many of those pathways
adversely affect the ability of the photoactive compound to further
absorb UV radiation. The alkoxy crylene molecules described herein
accept electronic singlet excited state energy from UV-absorbers,
particularly Avobenzone, octyl methoxycinnamate (Octinoxate), and
octyl salicylate (Octisalate). The alkoxy crylenes also are very
effective UVA absorbers in addition to providing electronic singlet
state energy quenching of other UV-absorbing compounds in sunscreen
compositions. The alkoxy crylene molecules described herein are
especially effective when combined with one or more additional
electronic singlet excited state quenching compounds such as
oxybenzone. Particularly surprising photostabilization is achieved
in sunscreen compositions containing the alkoxy crylene molecules
described herein together with octyl methoxycinnamate and
Avobenzone.
[0020] A photoactive compound is one that responds to light
photoelectrically. In the compositions and methods of
photostabilization disclosed herein, a photoactive compound is one
that responds to UV radiation photoelectrically. For example, all
photoactive compound-containing compositions that respond to UV
radiation photoelectrically by photoactive compound
photodegradation benefit highly by the inclusion of the alkoxy
crylene molecules described herein. The alkoxy crylenes described
herein are useful photostabilizers and/or photoactive compounds
when combined with any single or combination photoactive compounds
identified in Shaath, Nadim, Encyclopedia of UV filters, .COPYRGT.
2007, hereby incorporated by reference. Photostability is a problem
with all UV filters because they all reach an electronic singlet
excited state upon exposure to UV radiation.
[0021] It is theorized that the following UV filters are
photostabilized by the alkoxy crylene molecules described herein,
including all of the following, including combinations of any two
or more, and include compounds selected from the following
categories (with specific examples) including: p-aminobenzoic acid,
its salts and its derivatives (ethyl, isobutyl, glyceryl esters;
p-dimethylaminobenzoic acid); anthranilates (o-aminobenzoates;
methyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl,
and cyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl,
menthyl(homosalate), glyceryl, and dipropyleneglycol esters);
cinnamic acid derivatives (menthyl and benzyl esters, alpha-phenyl
cinnamonitrile; butyl cinnamoyl pyruvate); dihydroxycinnamic acid
derivatives (umbelliferone, methylumbelliferone,
methylaceto-umbelliferone); camphor derivatives (3 benzylidene, 4
methylbenzylidene, polyacrylamidomethyl benzylidene, benzalkonium
methosulfate, benzylidene camphor sulfonic acid, and
terephthalylidene dicamphor sulfonic acid); trihydroxycinnamic acid
derivatives (esculetin, methylesculetin, daphnetin, and the
glucosides, esculin and daphnin); hydrocarbons (diphenylbutadiene,
stilbene); dibenzalacetone; benzalacetophenone; naphtholsulfonates
(sodium salts of 2-naphthol-3,6-disulfonic and of
2-naphthol-6,8-disulfonic acids); dihydroxy-naphthoic acid and its
salts; o- and p-hydroxydiphenyldisulfonates; coumarin derivatives
(7-hydroxy, 7-methyl, 3-phenyl); diazoles
(2-acetyl-3-bromoindazole, phenyl benzoxazole, methyl
naphthoxazole, various aryl benzothiazoles); quinine salts
(bisulfate, sulfate, chloride, oleate, and tannate); quinoline
derivatives (8-hydroxyquinoline salts, 2-phenylquinoline); hydroxy-
or methoxy-substituted benzophenones; uric acid derivatives;
vilouric acid derivatives; tannic acid and its derivatives;
hydroquinone; and benzophenones (oxybenzone, sulisobenzone,
dioxybenzone, benzoresorcinol, octabenzone,
4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane,
etocrylene, and 4-isopropyl-dibenzoylmethane).
[0022] The following UV filters should be particularly
photostabilized by the alkoxy crylene molecules described herein:
2-ethylhexyl p-methoxycinnamate, 4,4'-t-butyl
methoxydibenzoylmethane, octyldimethyl p-aminobenzoate,
digalloyltrioleate, ethyl 4-[bis(hydroxypropyl)]aminobenzoate,
2-ethylhexylsalicylate, glycerol p-aminobenzoate,
3,3,5-trimethylcyclohexylsalicylate, and combinations thereof.
[0023] Photoactive compositions disclosed herein can include a
variety of photoactive compounds, preferably including one or more
UV-A photoactive compounds and one or more UV-B photoactive
compounds. Preferably, a sunscreen composition includes a
photoactive compound selected from the group consisting of
p-aminobenzoic acid and salts and derivatives thereof; anthranilate
and derivatives thereof; dibenzoylmethane and derivatives thereof;
salicylate and derivatives thereof; cinnamic acid and derivatives
thereof; dihydroxycinnamic acid and derivatives thereof; camphor
and salts and derivatives thereof; trihydroxycinnamic acid and
derivatives thereof; dibenzalacetone naphtholsulfonate and salts
and derivatives thereof; benzalacetophenone naphtholsulfonate and
salts and derivatives thereof; dihydroxy-naphthoic acid and salts
thereof; o-hydroxydiphenyldisulfonate and salts and derivatives
thereof; p-hydroxydiphenyldisulfonate and salts and derivatives
thereof; coumarin and derivatives thereof; diazole derivatives;
quinine derivatives and salts thereof; quinoline derivatives; uric
acid derivatives; vilouric acid derivatives; tannic acid and
derivatives thereof; hydroquinone; diethylamino hydroxybenzoyl
hexyl benzoate and salts and derivatives thereof; and combinations
of the foregoing.
[0024] UV A radiation (about 320 nm to about 400 nm), is recognized
as contributing to causing damage to skin, particularly to very
lightly colored or sensitive skin. A sunscreen composition
disclosed herein preferably includes a UV-A photoactive compound.
Preferably, a sunscreen composition disclosed herein includes a
dibenzoylmethane derivative UV-A photoactive compound. Preferred
dibenzoylmethane derivatives include, 2-methyldibenzoylmethane;
4-methyldibenzoylmethane; 4-isopropyldibenzoylmethane;
4-tert-butyldibenzoylmethane; 2,4-dimethyldibenzoylmethane;
2,5-dimethyldibenzoylmethane; 4,4'-diisopropyldibenzoylmethane;
4,4'-dimethoxydibenzoylmethane;
4-tert-butyl-4'-methoxydibenzoylmethane;
2-methyl-5-isopropyl-4'-methoxydibenzoylmethane;
2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane;
2,4-dimethyl-4'-methoxydibenzoylmethane;
2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane, and
combinations thereof.
[0025] For a product marketed in the United States, preferred
cosmetically acceptable photoactive compounds and concentrations
(reported as a percentage by weight of the total cosmetic sunscreen
composition) include: aminobenzoic acid (also called para
aminobenzoic acid and PABA; 15% or less), Avobenzone (also called
butyl methoxy dibenzoylmethane; 3% or less), cinoxate (also called
2 ethoxyethyl p methoxycinnamate; 3% or less), dioxybenzone (also
called benzophenone 8; 3% or less), homosalate ((also called
3,3,5-trimethylcyclohexyl salicylate, 15% or less), menthyl
anthranilate (also called menthyl 2 aminobenzoate; 5% or less),
octocrylene (also called 2 ethylhexyl 2 cyano 3,3 diphenylacrylate;
10% or less), octyl methoxycinnamate (7.5% or less), octyl
salicylate (also called 2 ethylhexyl salicylate; 5% or less),
oxybenzone (also called benzophenone 3; 6% or less), padimate O
(also called octyl dimethyl PABA; 8% or less), phenylbenzimidazole
sulfonic acid (water soluble; 4% or less), sulisobenzone (also
called benzophenone 4; 10% or less), titanium dioxide (25% or
less), trolamine salicylate (also called triethanolamine
salicylate; 12% or less), and zinc oxide (25% or less).
[0026] Other preferred cosmetically acceptable photoactive
compounds and preferred concentrations (percent by weight of the
total cosmetic sunscreen composition) include diethanolamine
methoxycinnamate (10% or less),
ethyl-[bis(hydroxypropyl)]aminobenzoate (5% or less), glyceryl
aminobenzoate (3% or less), 4 isopropyl dibenzoylmethane (5% or
less), 4 methylbenzylidene camphor (6% or less), terephthalylidene
dicamphor sulfonic acid (10% or less), and sulisobenzone (also
called benzophenone 4, 10% or less).
[0027] For a product marketed in the European Union, preferred
cosmetically acceptable photoactive compounds and preferred
concentrations (reported as a percentage by weight of the total
cosmetic sunscreen composition) include: PABA (5% or less), camphor
benzalkonium methosulfate (6% or less), homosalate (10% or less),
benzophenone 3 (10% or less), phenylbenzimidazole sulfonic acid (8%
or less, expressed as acid), terephthalidene dicamphor sulfonic
acid (10% or less, expressed as acid), butyl
methoxydibenzoylmethane (5% or less), benzylidene camphor sulfonic
acid (6% or less, expressed as acid), octocrylene (10% or less,
expressed as acid), polyacrylamidomethyl benzylidene camphor (6% or
less), ethylhexyl methoxycinnamate (10% or less), PEG 25 PABA (10%
or less), isoamyl p methoxycinnamate (10% or less), ethylhexyl
triazone (5% or less), drometrizole trielloxane (15% or less),
diethylhexyl butamido triazone (10% or less), 4 methylbenzylidene
camphor (4% or less), 3 benzylidene camphor (2% or less),
ethylhexyl salicylate (5% or less), ethylhexyl dimethyl PABA (8% or
less), benzophenone 4 (5%, expressed as acid), methylene bis
benztriazolyl tetramethylbutylphenol (10% or less), disodium phenyl
dibenzimidazole tetrasulfonate (10% or less, expressed as acid),
bis ethylhexyloxyphenol methoxyphenol triazine (10% or less),
methylene bisbenzotriazolyl tetramethylbutylphenol (10% or less,
also called TINOSORB M or Bisoctrizole), and bisethylhexyloxyphenol
methoxyphenyl triazine. (10% or less, also called TINOSORB S or
Bemotrizinol).
[0028] All of the above described UV filters are commercially
available. For example, suitable commercially available organic UV
filters are identified by trade name and supplier in Table I
below:
TABLE-US-00001 TABLE I CTFA Name Trade Name Supplier benzophenone-3
UVINUL M-40 BASF Chemical Co. benzophenone-4 UVINUL MS-40 BASF
Chemical Co. benzophenone-8 SPECTRA-SORB UV-24 American Cyanamid
DEA-methoxycinnamate BERNEL HYDRO Bernel Chemical diethylamino
hydroxybenzoyl hexyl UVINUL A-PLUS BASF Chemical Co. benzoate
diethylhexyl butamido triazone UVISORB HEB 3V-Sigma disodium phenyl
dibenzylimidazole NEO HELIOPAN AP Symrise ethyl
dihydroxypropyl-PABA AMERSCREEN P Amerchol Corp. glyceryl PABA NIPA
G.M.P.A. Nipa Labs. homosalate KEMESTER HMS Humko Chemical menthyl
anthranilate SUNAROME UVA Felton Worldwide octocrylene UVINUL N-539
BASF Chemical Co. octyl dimethyl PABA AMERSCOL Amerchol Corp. octyl
methoxycinnamate PARSOL MCX Bernel Chemical PABA PABA National
Starch 2-phenylbenzimidazole-5- EUSOLEX 6300 EM Industries
sulphonic acid TEA salicylate SUNAROME W Felton Worldwide
2-(4-methylbenzildene)-camphor EUSOLEX 6300 EM Industries
benzophenone-1 UVINUL 400 BASF Chemical Co. benzophenone-2 UVINUL
D-50 BASF Chemical Co. benzophenone-6 UVINUL D-49 BASF Chemical Co.
benzophenone-12 UVINUL 408 BASF Chemical Co. 4-isopropyl dibenzoyl
methane EUSOLEX 8020 EM Industries butyl methoxy dibenzoyl methane
PARSOL 1789 Givaudan Corp. etocrylene UVINUL N-35 BASF Chemical Co.
methylene bisbenzotriazolyl TINOSORB M Ciba Specialty
tetramethylbutylphenol Chemicals bisethylhexyloxyphenol TINOSORB S
Ciba Specialty methoxyphenyl triazine. Chemicals
[0029] Commonly-assigned U.S. Pat. Nos. 6,485,713 and 6,537,529,
the disclosures of which are hereby incorporated herein by
reference, describe compositions and methods for increasing the
photostability of photoactive compounds in a sunscreen composition,
e.g., by the addition of polar solvents to the oil phase of a
composition. By increasing the polarity of the oil phase of a
sunscreen composition including the alkoxy crylenes described
herein, e.g., methoxy crylene, the stability of the sunscreen
composition is surprisingly increased in comparison to octocrylene.
In the sunscreen compositions described herein, preferably, one or
more of a highly polar solvent is present in the oil-phase of the
composition. Preferably, a sufficient amount of a polar solvent is
present in the sunscreen composition to raise the dielectric
constant of the oil-phase of the composition to a dielectric
constant of at least about 7, preferably at least about 8. With or
without the highly polar solvent in the oil phase, the methoxy
crylene molecules described herein yield unexpected photostability
in comparison to octocrylene.
[0030] A photoactive compound can be considered stable when, for
example, after 30 MED irradiation the photoactive compound has
retained at least about 90% of its original absorbance at a
wavelength, or over a range of wavelengths of interest (e.g., the
wavelength at which a photoactive compound has a peak absorbance,
such as 350-370 nm for Avobenzone). Likewise, a sunscreen
composition can include a plurality of photoactive compounds and a
sunscreen composition, as a whole, can be considered stable when,
for example, after 30 MED irradiation the sunscreen composition has
retained at least about 90% of its original absorbance at one or
more wavelengths of interest (e.g., at or near the peak absorbance
wavelength of the primary photoactive compound).
[0031] In accordance with one important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with a water soluble UV filter compound
and/or a broad-band filter compound and optionally, but preferably,
together with a dibenzoylmethane derivative and/or a dialkyl
naphthalate.
[0032] Advantageous water-soluble UV filter substances for the
purposes of the present invention are sulfonated UV filters, in
particular:
phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic acid,
which has the following structure:
##STR00006##
and its salts, especially the corresponding sodium, potassium or
triethanolammonium salts, in particular
phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulfonic acid
bissodium salt
##STR00007##
with the INCI name disodium phenyl dibenzimidazole tetrasulfonate
(CAS No.: 180898-37-7), which is obtainable for example under the
proprietary name Neo Heliopan A P from Haarmann & Reimer.
[0033] Further advantageous sulfonated UV filters for the purposes
of the present invention are the salts of
2-phenylbenzimidazole-5-sulfonic acid, such as its sodium,
potassium or its triethanolammonium salts, and the sulfonic acid
itself
##STR00008##
[0034] with the INCI name phenylbenzimidazole sulfonic acid (CAS
No. 27503-81-7), which is obtainable for example under the
proprietary name Eusolex 232 from Merck or under Neo Heliopan Hydro
from Haarmann & Reimer.
[0035] Further advantageous water-soluble UV-B and/or broad-band
filter substances for the purposes of the present invention are,
for example, sulfonic acid derivatives of 3-benzylidenecamphor,
such as, for example, 4-(2-oxo-3-bornylidenemethyl)benzene-sulfonic
acid, 2-methyl-5-(2-oxo-3-bornylidenemethyl)sulfonic acid and the
salts thereof.
[0036] The total amount of one or more water-soluble UV filter
substances in the finished cosmetic or dermatological preparations
is advantageously chosen from the range 0.01% by weight to 20% by
weight, preferably from 0.1 to 10% by weight, in each case based on
the total weight of the preparations.
[0037] In accordance with another important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with a hydroxybenzophenone compound
and/or a broad-band filter compound and optionally, but preferably,
together with a dibenzoylmethane derivative and/or a dialkyl
naphthalate.
[0038] With an alkoxycrylene, it is possible to completely dispense
with the use of other UV stabilizers, in particular the use of
ethylhexyl-2-cyano-3,3-diphenylacrylate(octocrylene) or
4-methylbenzylidenecamphor.
[0039] Hydroxybenzophenones are characterized by the following
structural formula:
##STR00009##
where R.sup.1 and R.sup.2 independent of one another are hydrogen,
C.sub.1 C.sub.20-alkyl, C.sub.3-C.sub.10-cycloalkyl or
C.sub.3-C.sub.10-cyloalkenyl, wherein the substituents R.sup.1 and
R.sup.2 together with the nitrogen atom to which they are bound can
form a 5- or 6-ring and R.sup.3 is a C.sub.1-C.sub.20 alkyl
radical.
[0040] A particularly advantageous hydroxybenzophenone is the
2-(4'-diethylamino-2'-hydroxybenzoyl)benzoic acid hexyl ester
(also: aminobenzophenone) which is characterized by the following
structure:
##STR00010##
and is available from BASF under the Uvinul A Plus.
[0041] According to the invention, cosmetic or dermatological
preparations contain 0.1 to 20% by weight, advantageously 0.1 to
15% by weight, very particularly preferred 0.1 to 10% by weight, of
one or more hydroxybenzophenones.
[0042] Within the scope of the present invention, dialkyl
naphthalates for which R.sup.1 and/or R.sup.2 represent branched
alkyl groups with 6 to 10 carbon atoms are advantageous. Within the
scope of the present invention diethylhexyl naphthalate is very
particularly preferred which is available, e.g., under the trade
name Hallbrite TQ.TM. from CP Hall or Corapan TQ.TM. from
H&R.
[0043] According to one embodiment of the invention cosmetic or
dermatological preparations advantageously contain 0.001 to 30% by
weight, preferably 0.01 to 20% by weight, very particularly
preferred 0.5 to 15% by weight, of one or more dialkyl
naphthalates.
[0044] The cosmetic or dermatological light-protection formulations
according to the invention can be composed as usual and be used for
cosmetic or dermatological light-protection, furthermore for the
treatment, care and cleansing of the skin and/or hair and as a
cosmetic product in decorative cosmetics.
[0045] In accordance with another important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with a benzotriazole derivatives
compound and/or a broad-band filter compound and optionally, but
preferably, together with a dibenzoylmethane derivative and/or a
dialkyl naphthalate.
[0046] An advantageous benzotriazole derivative is
2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)ph-
enol), which has the chemical structural formula
##STR00011##
[0047] (INCI: bisoctyltriazole). It is obtainable under the
proprietary name Tinosorb.RTM. from CIBA-Chemikalien GmbH and is
distinguished by good UV absorption properties. The disadvantage of
this substance is the characteristic of forming imperceptibly thin
films on the skin which have unpleasant tactile properties.
[0048] Another disadvantage is that such benzotriazole derivatives
show only inadequate solubility, if any, in conventional oil
components. Well-known solvents can dissolve only up to a maximum
of 15% by weight of these compounds, which usually corresponds to a
concentration of about 1 to 1.5% by weight of dissolved (=active)
filter substance in the complete cosmetic or dermatological
preparation.
[0049] One disadvantage of the prior art is accordingly that
generally only comparatively low sun protection factors have been
achievable with these filter substances because their solubility or
dispersibility in the formulations is too low, i.e. they can be
satisfactorily incorporated into such formulations only with
difficulty or not at all.
[0050] Even if it is also possible in principle to achieve a
certain UV protection when the solubility is limited, another
problem frequently occurs, that is recrystallization.
[0051] Substances of low solubility in particular recrystallize
comparatively rapidly, which may be induced by fluctuations in
temperature or other influences. Uncontrolled recrystallization of
an essential ingredient of a preparation such as a UV filter has,
however, extremely disadvantageous effects on the properties of the
given preparation and, not least, on the desired light
protection.
[0052] In accordance with another embodiment, the
alkoxycrylene-containing compositions described herein can contain
an increased content of unsymmetrically substituted triazine
derivatives when combined together with an alkoxycrylene of formula
(I) to obtain an increased sun protection factor.
[0053] It was, however, surprising and not predictable for the
skilled worker that the disadvantages of the prior art are remedied
by active ingredient combinations effective for light protection
and composed of
(a) one or more UV filter substances selected from the group of
benzotriazole derivatives; (b) an alkoxycrylene of formula (I); and
optionally (c) one or more dialkyl naphthalates having the
structural formula:
##STR00012##
in which R.sup.1 and R.sup.2 are, independently of one another,
selected from the group of branched and unbranched alkyl groups
having 6 to 24 carbon atoms.
[0054] Particularly advantageous light protection filters for the
purpose of this embodiment of the present invention include a
benzotriazole compound having a structural formula:
##STR00013##
where R.sub.1 and R.sub.2 are, independently of one another,
selected from the group of branched or unbranched
C.sub.1-C.sub.18-alkyl radicals, of C.sub.5-C.sub.12-cycloalkyl or
aryl radicals which are optionally substituted by one or more
C.sub.1-C.sub.4 alkyl groups.
[0055] The preferred benzotriazole derivative is
2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)ph-
enol) which is characterized by the chemical structural
formula:
##STR00014##
[0056] An advantageous broadband filter for the purpose of the
present invention is moreover
2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(-
trimethyl-silyl)oxy]disiloxanyl]propyl]phenol (CAS No.:
155633-54-8) with the INCI name drometrizole trisiloxane, which is
characterized by the chemical structural formula
##STR00015##
[0057] The total amount of one or more benzotriazole derivatives,
in particular of
2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)ph-
enol) and/or
2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(-
trimethylsilyl)oxy]disiloxa-nyl]propyl]phenol, in the finished
cosmetic or dermatological preparations is advantageously chosen
from the range from 0.1 to 15.0% by weight, preferably 0.5 to 10.0%
by weight, based on the total weight of the preparations.
[0058] The cosmetic or dermatological light protection formulations
of the invention may have conventional compositions and be used for
cosmetic or dermatological light protection and for the treatment,
care and cleansing of skin and/or the hair and as a make-up product
in decorative cosmetics.
[0059] For use, the cosmetic and dermatological preparations are
applied to the skin and/or the hair in a sufficient quantity in the
manner customary for cosmetics.
[0060] Cosmetic and dermatological preparations according to the
invention can comprise cosmetic auxiliaries such as those
conventionally used in such preparations, e.g. preservatives,
bactericides, perfumes, antifoams, dyes, pigments which have a
coloring effect, thickeners, moisturizers and/or humectants, fats,
oils, waxes or other conventional constituents of a cosmetic or
dermatological formulation, such as alcohols, polyols, polymers,
foam stabilizers, electrolytes, organic solvents or silicone
derivatives.
[0061] An additional content of antioxidants is generally
preferred. According to the invention, favorable antioxidants which
can be used are any antioxidants suitable or conventional for
cosmetic and/or dermatological applications.
[0062] The antioxidants are particularly advantageously chosen from
the group consisting of 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), carotenoids, carotenes (e.g. .alpha.-carotene,
.beta.-carotene, lycopene) and derivatives thereof, chlorogenic
acid and derivatives thereof, lipoic acid and derivatives thereof
(e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and
other thiols (e.g. thioredoxin, glutathione, cysteine, cystine,
cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl,
butyl and lauryl, palmitoyl, oleyl, .gamma.-linoleyl, cholesteryl
and glyceryl esters thereof) and salts thereof, dilauryl
thiodipropionate, distearyl thiodipropionate, thiodipropionic acid
and derivatives thereof (esters, ethers, peptides, lipids,
nucleotides, nucleosides and salts) and sulfoximine compounds (e.g.
buthionine sulfoximines, homocysteine sulfoximine, buthionine
sulfones, penta-, hexa-, heptathionine sulfoximine) in very low
tolerated doses (e.g. pmol to .mu.mol/kg), and also (metal)
chelating agents (e.g. alpha.-hydroxy fatty acids, palmitic acid,
phytic acid, lactoferrin), .alpha.-hydroxy acids (e.g. citric acid,
lactic acid, malic acid), humic acid, bile acid, bile extracts,
bilirubin, biliverdin, EDTA, EGTA and derivatives thereof,
unsaturated fatty acids and derivatives thereof (e.g.
gamma.-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, Mg
ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives
(e.g. vitamin E acetate), vitamin A and derivatives (vitamin A
palmitate) and coniferyl benzoate of gum benzoin, rutinic acid and
derivatives thereof, .alpha.-glycosylrutin, ferulic acid,
furfurylideneglucitol, carnosine, butylhydroxytoluene,
butylhydroxyanisole, nordihydroguaiaretic acid,
trihydroxybutyro-phenone, uric acid and derivatives thereof,
mannose and derivatives thereof, zinc and derivatives thereof (e.g.
ZnO, ZnSO.sub.4), selenium and derivatives thereof (e.g.
selenomethionine), stilbenes and derivatives thereof (e.g. stilbene
oxide, trans-stilbene oxide) and the derivatives (salts, esters,
ethers, sugars, nucleotides, nucleosides, peptides and lipids) of
said active ingredients which are suitable according to the
invention.
[0063] In accordance with another important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with hydrophilic skincare active
ingredients and/or a broad-band filter compound and optionally, but
preferably, together with a dibenzoylmethane derivative.
[0064] Advantageous hydrophilic active ingredients which
(individually or in any combinations with one another) are
stabilized by their use together with an alkoxycrylene according to
the invention include those listed below:
biotin; camitine and derivatives; creatine and derivatives; folic
acid; pyridoxine niacinamide; polyphenols (in particular
flavonoids, very particularly alpha-glucosylrutin) ascorbic acid
and derivatives; Hamamelis; Aloe Vera; panthenol; amino acids.
[0065] Particularly advantageous hydrophilic active ingredients for
the purposes of the present invention are also water-soluble
antioxidants, such as, for example, vitamins.
[0066] The amount of hydrophilic active ingredients (one or more
compounds) in the preparations is preferably 0.0001 to 10% by
weight, particularly preferably 0.001 to 5% by weight, based on the
total weight of the preparation.
[0067] Particularly advantageous preparations are also obtained
when antioxidants are used as additives or active ingredients.
According to the invention, the preparations advantageously
comprise one or more antioxidants. Favorable, but nevertheless
optional antioxidants which may be used are all antioxidants
customary or suitable for cosmetic and/or dermatological
applications.
[0068] The amount of antioxidants (one or more compounds) in the
preparations is preferably 0.001 to 30% by weight, particularly
preferably 0.05 to 20% by weight, in particular 0.1 to 10% by
weight, based on the total weight of the preparation.
[0069] If vitamin E and/or derivatives thereof are the antioxidant
or antioxidants, it is advantageous to choose their respective
concentrations from the range from 0.001 to 10% by weight, based on
the total weight of the formulation.
[0070] If vitamin A or vitamin A derivatives, or carotenes or
derivatives thereof are the antioxidant or antioxidants, it is
advantageous to choose their respective concentrations from the
range from 0.001 to 10% by weight, based on the total weight of the
formulation.
[0071] It is particularly advantageous when the cosmetic
preparations according to the present invention comprise further
cosmetic or dermatological active ingredients, preferred active
ingredients being antioxidants which can protect the skin against
oxidative stress.
[0072] Advantageous further active ingredients are natural active
ingredients and/or derivatives thereof, such as e.g. ubiquinones,
retinoids, carotenoids, creatine, taurine and/or
.beta.-alanine.
[0073] Formulations according to the invention, which comprise e.g.
known antiwrinkle active ingredients, such as flavone glycosides
(in particular .alpha.-glycosylrutin), coenzyme Q10, vitamin E
and/or derivatives and the like, are particularly advantageously
suitable for the prophylaxis and treatment of cosmetic or
dermatological changes in skin, as arise, for example, during skin
aging (such as, for example, dryness, roughness and formation of
dryness wrinkles, itching, reduced refatting (e.g. after washing),
visible vascular dilations (teleangiectases, couperosis),
flaccidity and formation of wrinkles and lines, local
hyperpigmentation, hypopigmentation and abnormal pigmentation (e.g.
age spots), increased susceptibility to mechanical stress (e.g.
cracking) and the like). In addition, they are advantageously
suitable against the appearance of dry or rough skin.
[0074] In accordance with still another important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with particulate UV filter substances
and/or a broad-band filter compound and optionally, but preferably,
together with a dibenzoylmethane derivative and/or a dialkyl
naphthalate.
[0075] Preferred particulate UV filter substances for the purposes
of the present invention are inorganic pigments, especially metal
oxides and/or other metal compounds which are slightly soluble or
insoluble in water, especially oxides of titanium (TiO.sub.2), zinc
(ZnO), iron (e.g. Fe.sub.2O.sub.3), zirconium (ZrO.sub.2), silicon
(SiO.sub.2), manganese (e.g. MnO), aluminum (Al.sub.2O.sub.3),
cerium (e.g. Ce.sub.2O.sub.3), mixed oxides of the corresponding
metals, and mixtures of such oxides, and the sulfate of barium
(BaSO.sub.4).
[0076] Zinc oxides for the purposes of the present invention may
also be used in the form of commercially available oily or aqueous
predispersions. Zinc oxide particles and predispersions of zinc
oxide particles which are suitable according to the invention are
distinguished by a primary particle size of <300 nm and can be
obtained under the following proprietary names from the stated
companies:
TABLE-US-00002 Proprietary name Coating Manufacturer Z-Cote HP1 2%
Dimethicone BASF Z-Cote / BASF ZnO NDM 5% Dimethicone H&R ZnO
Neutral / H&R MZ-300 / Tayca Corporation MZ-500 / Tayca
Corporation MZ-700 / Tayca Corporation MZ-303S 3% Methicone Tayca
Corporation MZ-505S 5% Methicone Tayca Corporation MZ-707S 7%
Methicone Tayca Corporation MZ-303M 3% Dimethicone Tayca
Corporation MZ-505M 5% Dimethicone Tayca Corporation MZ-707M 7%
Dimethicone Tayca Corporation Z-Sperse Ultra ZnO (>=
56%)/Ethylhexyl Collaborative Hydroxystearate Benzoate/
Laboratories Dimethicone/Cyclomethicone Samt-UFZO- ZnO (60%)/
Miyoshi Kasei 450/D5 (60%) Cyclomethicone/Dimethicone
[0077] Particularly preferred zinc oxides for the purposes of the
invention are Z-Cote HPl and Z-Cote from BASF and zinc oxide NDM
from Haarmann & Reimer.
[0078] Titanium dioxide pigments of the invention may be in the
form of both the rutile and anatase crystal modification and may
for the purposes of the present invention advantageously be
surface-treated ("coated"), the intention being for example to form
or retain a hydrophilic, amphiphilic or hydrophobic character. This
surface treatment may consist of providing the pigments by
processes known per se with a thin hydrophilic and/or hydrophobic
inorganic and/or organic layer. The various surface coatings may
for the purposes of the present invention also contain water.
[0079] Inorganic surface coatings for the purposes of the present
invention may consist of aluminum oxide (Al.sub.2O.sub.3), aluminum
hydroxide Al(OH).sub.3 or aluminum oxide hydrate (also: alumina,
CAS No.: 1333-84-2), sodium hexametaphosphate (NaPO.sub.3).sub.6,
sodium metaphosphate (NaPO.sub.3).sub.n, silicon dioxide
(SiO.sub.2) (also: silica, CAS No.: 7631-86-9), or iron oxide
(Fe.sub.2O.sub.3). These inorganic surface coatings may occur
alone, in combination and/or in combination with organic coating
materials.
[0080] Organic surface coatings for the purposes of the present
invention may consist of vegetable or animal aluminum stearate,
vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane
(also: dimethicones), methylpolysiloxane (methicones), simethicones
(a mixture of dimethylpolysiloxane with an average chain length of
from 200 to 350 dimethylsiloxane units and silica gel) or alginic
acid. These organic surface coatings may occur alone, in
combination and/or in combination with inorganic coating
materials.
[0081] Coated and uncoated titanium dioxides of the invention may
be used in the form of commercially available oily or aqueous
predispersions. It may be advantageous to add dispersion aids
and/or solubilization mediators.
[0082] Suitable titanium dioxide particles and predispersions of
titanium dioxide particles for the purposes of the present
invention are obtainable under the following proprietary names from
the stated companies:
TABLE-US-00003 Additional ingredients of the Proprietary name
Coating predispersion Manufacturer MT-150W None -- Tayca
Corporation MT-150A None -- Tayca Corporation MT-500B None -- Tayca
Corporation MT-600B None -- Tayca Corporation MT-100TV Aluminum --
Tayca Corporation hydroxide Stearic acid MT-100Z Aluminum -- Tayca
Corporation hydroxide Stearic acid MT-100T Aluminum -- Tayca
Corporation hydroxide Stearic acid MT-500T Aluminum -- Tayca
Corporation hydroxide Stearic acid MT-100S Aluminum -- Tayca
Corporation hydroxide Lauric acid MT-100F Stearic acid Iron --
Tayca Corporation oxide MT-100SA Alumina Silica -- Tayca
Corporation MT-500SA Alumina Silica -- Tayca Corporation MT-600SA
Alumina Silica -- Tayca Corporation MT-100SAS Alumina Silica --
Tayca Corporation Silicone MT-500SAS Alumina Silica -- Tayca
Corporation Silicone MT-500H Alumina -- Tayca Corporation MT-100AQ
Silica -- Tayca Corporation Aluminum hydroxide Alginic acid Eusolex
T Water -- Merck KgaA Simethicone Eusolex T-2000 Alumina -- Merck
KgaA Simethicone Eusolex T-Olio F Silica C.sub.12-15 Merck KgaA
Dimethylsilate Alkylbenzoate Water Calcium Poly- hydroxystearate
Silica Dimethylsilate Eusolex T-Olio P Water Octyl Palmitate Merck
KgaA Simethicone PEG-7 Hydrogenated Castor Oil Sorbitan Oleate
Hydrogenated Castor Oil Beeswax Stearic acid Eusolex T-Aqua Water
Alumina Phenoxyethanol Merck KgaA Sodium Sodium metaphosphate
Methylparabens Sodium metaphosphate Eusolex T-45D Alumina Isononyl
Merck KgaA Simethicone Isononanuate Polyglyceryl Ricinoleate Kronos
1171 None -- Kronos (Titanium dioxide 171) Titanium dioxide P25
None -- Degussa Titanium dioxide Octyltri- -- Degussa T805
methylsilane (Uvinul TiO.sub.2) UV-Titan X610 Alumina -- Kemira
Dimethicone UV-Titan X170 Alumina -- Kemira Dimethicone UV-Titan
X161 Alumina Silica -- Kemira Stearic acid UV-Titan M210 Alumina --
Kemira UV-Titan M212 Alumina Glycerol Kemira UV-Titan M262 Alumina
-- Kemira Silicone UV-Titan M160 Alumina Silica -- Kemira Stearic
acid Tioveil AQ 10PG Alumina Silica Water Propylene Solaveil
Uniquema glycol Mirasun TiW 60 Alumina Silica Water
Rhone-Poulenc
[0083] The titanium dioxides of the invention are distinguished by
a primary particle size between 10 nm to 150 nm.
[0084] Titanium dioxides particularly preferred for the purposes of
the present invention are MT-100 Z and MT-100 TV from Tayca
Corporation, Eusolex T-2000 from Merck and titanium dioxide T 805
from Degussa.
[0085] Further advantageous pigments are latex particles. Latex
particles which are advantageous according to the invention are
described in the following publications: U.S. Pat. No. 5,663,213
and EP 0 761 201. Particularly advantageous latex particles are
those formed from water and styrene/acrylate copolymers and
available for example under the proprietary name "Alliance
SunSphere" from Rohm & Haas.
[0086] An advantageous organic pigment for the purposes of the
present invention is
2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl-)p-
henol) (INCI: bis-octyltriazol), which is obtainable under the
proprietary name Tinosorb.RTM. M from CIBA-Chemikalien GmbH.
[0087] It is particularly advantageous for the purposes of the
present invention for particulate UV filter substances which are
not already in the form of a predispersion first to be dispersed in
one or more dialkyl naphthalates of the invention and for this
basic dispersion then to be further processed. Whereas auxiliaries
which may enter into unwanted interactions with other substances of
the cosmetic or dermatological formulation are usually added for
stabilization to commercially available predispersions, it is
astonishingly possible to dispense with the addition of such
stabilizers when preparing basic dispersions of the invention.
[0088] The total amount of one or more water-soluble UV filter
substances in the finished cosmetic or dermatological preparations
is advantageously chosen from the range 0.01% by weight to 20% by
weight, preferably from 0.1 to 10% by weight, in each case based on
the total weight of the preparations.
[0089] In accordance with still another important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with asymmetrically substituted triazine
UV filter compounds and/or a broad-band filter compound and
optionally, but preferably, together with a dibenzoylmethane
derivative.
[0090] Asymmetrically substituted triazine derivatives display a
good light protection effect. Their main disadvantage is, however,
that their solubility is low in conventional oil components.
Well-known solvents can dissolve only up to a maximum of 15% by
weight of these compounds, which usually corresponds to a
concentration of about 1 to 1.5% by weight of dissolved (=active)
filter substance in the complete cosmetic or dermatological
preparation.
[0091] One disadvantage of the prior art is accordingly that
generally only comparatively low sun protection factors have been
achievable with these filter substances because their solubility or
dispersibility in the formulations is too low, i.e. they can be
satisfactorily incorporated into such formulations only with
difficulty or not at all.
[0092] Even if it is also possible in principle to achieve a
certain UV protection when the solublity is limited, another
problem frequently occurs, that is recrystallization. Substances of
low solubility in particular recrystallize comparatively rapidly,
which may be induced by fluctuations in temperature or other
influences. Uncontrolled recrystallization of an essential
ingredient of a preparation such as a UV filter has, however,
extremely disadvantageous effects on the properties of the given
preparation and, not least, on the desired light protection.
[0093] It was an object of the present invention to obtain in a
simple manner preparations which are distinguished by an increased
content of asymmetrically substituted triazine derivatives and a
correspondingly high sun protection factor.
[0094] Disadvantages of the prior art are remedied by active
ingredient combinations effective for light protection and composed
of:
(a) one or more UV filter substances selected from the group of
asymmetrically substituted triazine derivatives, and (b) one or
more alkoxycrylenes having the structural formula (I); and (c)
optionally a dibenzoylmethane derivative and/or a dialkyl
naphthalate.
[0095] Advantageous asymmetrically substituted s-triazine
derivatives within the meaning of this embodiment of the present
invention are, for example, those described in EP-A-570 838, whose
chemical structure is represented by the generic formula
##STR00016##
where R is a branched or unbranched C.sub.1-C.sub.18-alkyl radical,
a C.sub.5-C.sub.12-cycloalkyl radical, optionally substituted by
one or more C.sub.1-C.sub.4-alkyl groups, and X is an oxygen atom
or an NH group, R.sub.1 is a branched or unbranched
C.sub.1-C.sub.18-alkyl radical, a C.sub.5-C.sub.12-cycloalkyl
radical, optionally substituted by one or more
C.sub.1-C.sub.4-alkyl groups, or a hydrogen atom, an alkali metal
atom, an ammonium group or a group of the formula
##STR00017##
in which A is a branched or unbranched C.sub.1-C.sub.18-alkyl
radical, a C.sub.5-C.sub.12-cycloalkyl or aryl radical, optionally
substituted by one or more C.sub.1-C.sub.4-alkyl groups, R.sub.3 is
a hydrogen atom or a methyl group, n is a number from 1 to 10,
R.sub.2 is a branched or unbranched C.sub.1-C.sub.18-alkyl radical,
a C.sub.5-C.sub.12-cycloalkyl radical, optionally substituted by
one or more C.sub.1-C.sub.4-alkyl groups, and if X is the NH group,
a branched or unbranched C.sub.1-C.sub.18-alkyl radical, a
C.sub.5-C.sub.12-cycloalkyl radical, optionally substituted by one
or more C.sub.1-C.sub.4-alkyl groups, or a hydrogen atom, an alkali
metal atom, an ammonium group or a group of the formula
##STR00018##
in which A is a branched or unbranched C.sub.1-C.sub.18-alkyl
radical, a C.sub.5-C.sub.12-cycloalkyl or aryl radical, optionally
substituted by one or more C.sub.1-C.sub.4-alkyl groups, R.sub.3 is
a hydrogen atom or a methyl group, n is a number from 1 to 10, if X
is an oxygen atom.
[0096] In a preferred form of this triazine embodiment, the
compositions are sunscreen, cosmetic or dermatological formulations
that include a content of least one asymmetrically substituted
s-triazine selected from the group of substances having the
following structural formula:
##STR00019##
[0097] All the bisresorcinyltriazines, are advantageous for this
embodiment of the purpose of the present invention. R.sub.4 and
R.sub.5 are very particularly advantageously selected from the
group of branched or unbranched alkyl groups of 1 to 18 carbon
atoms. The alkyl groups may also again advantageously be
substituted by silyloxy groups.
[0098] A.sub.1 is advantageously a substituted-homocyclic or
heterocyclic aromatic five-membered ring or six-membered ring.
[0099] The following compounds are very particularly
advantageous:
##STR00020##
where R.sub.6 is a hydrogen atom or a branched or unbranched alkyl
group with 1 to 10 carbon atoms, in particular
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5--
triazine (INCI: aniso triazine), which is obtainable under the
proprietary name Tinosorb.RTM. S from CIBA-Chemikalien GmbH and is
characterized by the following structure:
##STR00021##
[0100] Also advantageous is
2,4-bis{[4-(3-sulfonato-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-methox-
y phenyl)-1,3,5-triazine sodium salt, which is characterized by the
following structure:
##STR00022##
[0101] Also advantageous is
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-(4-me-
thoxyphenyl)-1,3,5-triazine, which is characterized by the
following structure:
##STR00023##
[0102] Also advantageous is
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethoxycarbo-
nyl)phenylamino]-1,3,5-triazine, which is characterized by the
following structure:
##STR00024##
[0103] Also advantageous is
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-[4-(e-
thoxycarbonyl)phenylamino]-1,3,5-triazine which is characterized by
the following structure:
##STR00025##
[0104] Also advantageous is
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2-yl)1,3-
,5-triazine, which is characterized by the following structure:
##STR00026##
[0105] Also advantageous is
2,4-bis{[4-tris(trimethylsiloxysilylpropyloxy)-2-hydroxy]phenyl}-6-(4-met-
hoxyphenyl)-1,3,5-triazine, which is characterized by the following
structure:
##STR00027##
[0106] Also advantageous is
2,4-bis{[4-(2-methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,-
3,5-triazine, which is characterized by the following
structure:
##STR00028##
[0107] Also advantageous is
2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethylsiloxy-2-methylpropyloxy)-2-h-
ydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine, which is
characterized by the following structure:
##STR00029##
[0108] In a particularly preferred embodiment, the present
invention relates to cosmetic or dermatological formulations with a
content of an asymmetrically substituted s-triazine whose chemical
structure is represented by the formula
##STR00030##
which is also referred to hereinafter as dioctylbutylamidotriazone
(INCI) and is obtainable under the proprietary name UVASORB HEB
from Sigma 3 V.
[0109] The asymmetrically substituted s-triazine derivative(s) of
the invention are advantageously incorporated into the oil phase of
the cosmetic or dermatological formulations.
[0110] The total amount of one or more asymmetrically substituted
s-triazine derivatives, in particular of dioctylbutylamidotriazone,
in the finished cosmetic or dermatological preparations is
advantageously chosen from the range from 0.1 to 15.0% by weight,
preferably 0.5 to 10.0% by weight, based on the total weight of the
preparations.
[0111] The cosmetic or dermatological light protection formulations
of the invention may have conventional compositions when used for
cosmetic or dermatological light protection and for the treatment,
care and cleansing of skin and/or the hair and as a make-up product
in decorative cosmetics.
[0112] In accordance with one important embodiment, an
alkoxycrylene of formula (I) is combined in a sunscreen or
dermatological formulation with a lipophilic oxidation or
UV-sensitive active ingredients, such as retinoic acid and its
derivatives, e.g., tretinoin or isotretinoin and/or a broad-band
filter compound and optionally, but preferably, together with a
dibenzoylmethane derivative.
[0113] Advantageous lipophilic active ingredients which are
stabilized in an excellent manner by the use according to the
invention are those whose log P value is greater than 3.5. P is the
partition coefficient, which is defined as the ratio of the
equilibrium concentration of a dissolved substance in a two-phase
system which consists of two solvents which are essentially
immiscible with one another. These two solvents are, in the present
case, n-octanol and water, i.e.
P ow = C n - octanol C water . ##EQU00001##
[0114] It is advantageous for the purposes of the present invention
to choose the lipophilic active ingredients from the group of
ubiquinones and plastoquinones. For the purposes of the present
invention, coenzyme Q10, which has a log P value of about 15, is
very particularly advantageous.
[0115] It was particularly surprising that very advantageous
preparations according to the present invention can be obtained
when the active ingredient(s) is/are chosen only from the group of
ubiquinones.
[0116] Further lipophilic active ingredients which are advantageous
according to the invention are retinoids (vitamin A acid and/or
derivatives thereof) or vitamin A and/or derivatives thereof. The
group of retinoids advantageous according to the invention is
defined as including all cosmetically and/or pharmaceutically
acceptable retinoids, including retinol and its esters, retinal and
also retinoic acid (vitamin A acid) and esters thereof. For the
purposes of the present invention, retinol (with a log P value of
about 7) and retinyl palmitate (with a log P value of about 13) are
particularly advantageous.
[0117] It was also particularly surprising that very advantageous
preparations can be obtained according to the present invention
when the active ingredient(s) is/are chosen only from the group of
retinoids.
[0118] Further lipophilic acid ingredients advantageous according
to the invention are carotenoids. For the purposes of the present
invention, .beta.-carotene, which has a log P value of 15, for
example, is particularly advantageous.
[0119] Further lipophilic active ingredients advantageous according
to the invention are: lipoic acid and derivatives, vitamin E and
derivatives, vitamin F, dioic acid [8-hexadecene-1,16-dicarboxylic
acid (CAS number 20701-68-2)]
[0120] The amount of lipophilic active ingredients (one or more
compounds) in the preparations is preferably 0.0001 to 10% by
weight, particularly preferably 0.001 to 5% by weight, based on the
total weight of the preparation.
Synthesis of methyl or ethyl
2-cyano-3-(4'-methoxyphenyl)-3-phenylpropenoate (Methyl or Ethyl
Methoxycrylene or Methyl or Ethyl MeOcrylene)
##STR00031##
[0122] 4-Methoxy benzophenone (MW=182.22 g/mole; 500 g; 2.74 mole;
1 mole equivalence) and methyl cyanoacetate (MW=99.09 g/mole;
367.06 g; 3.70 mole; 1.35 mole equivalence) were placed in 1-L
3-neck flask assembled with mechanical stirrer and nitrogen inlet,
which provided continuous flow of nitrogen through the reaction
mixture (nitrogen is bubbled through the reaction mixture). Next,
toluene (1200 ml) and acetic acid (240 ml; ratio of toluene/acetic
acid=5/1) are added to the flask followed by ammonium acetate
(MW=77.09 g/mole; 21.12 g; 0.274 mole, 0.1 mole equivalence; the
catalyst is added 4 times this amount during reaction time). The
flask is then assembled with Dean-Stark receiver through which
reaction water is being continuously removed.
Comments:
[0123] 1. Aliquots of the reaction mixture are taken to check the
rate of completion of the reaction. [0124] 2. The amount of water
expected from this reaction is 49.5 ml. However, I collected about
120 ml of water phase. This is due to the fact that the water is
distilled in form of a mixture, water/acetic acid/toluene. [0125]
3. To prevent from loosing the methyl acetate from the reaction
mixture, it helps to put a short packed column between Dean-Stark
receiver and the flask.
[0126] Work-Up:
[0127] The reaction mixture is cooled to room temperature and ethyl
acetate is added to dissolve all solids before the crude mixture is
washed several time with water, to remove acetic acid and salts.
The solvents are then removed from the reaction mixture by
distillation. The crude solid product is re-crystallized from hot
methanol (or toluene/methanol mixture, if such is preferred).
[0128] Comments:
[0129] The finished product begins to crystallize out from the
cooling reaction mixture and thus can be filtered off, but it still
is very acidic, so the crystals ought to be washed with
water/methanol mixture to wash out any acetic acid and salts
residues. Thus obtained the product then can be re-crystallized and
the mother liquor can be washed with water, dried, and second crop
of the product can be obtained.
Synthesis of Alkyl
2-cyano-3-(4'-methoxyphenyl)-3-phenylpropenoate
##STR00032##
[0131] Reaction Procedure:
[0132] Methyl (or ethyl)
2-cyano-3-(4'-methoxyphenyl)-3-phenylpropenoate (900 g, 3.06 mole;
MW=293.32), alkyl alcohol (3.84 mole; 1.25 mole equivalence), and
Tegokat 250 (0.03% of total batch weight) were placed in 2 L 3-neck
round-bottom flask and heated to temperature set at 185.degree. C.
(365.degree. F.), with nitrogen purging it well to remove forming
methanol (or ethanol) via the simple distillation setup with packed
column.
[0133] After 3 h, GC showed full conversion of methyl
2-cyano-3-(4'-methoxyphenyl)-3-phenylpropenoate to the desired
product.
[0134] Work-Up:
[0135] The unreacted alkyl alcohol was completely removed by vacuum
distillation. Temperature of the reaction was lowered to
110.degree. C. (230.degree. F.) and calculated amount (2% of total
batch weight) of the SSP (tin removing agent) was added. The
product was stirred at this temperature for 2 hours and then
filtered hot. Small amount of celite was added right before
filtration to enhance the filtration--with celite the filtration
was more efficient and faster.
[0136] Results:
TABLE-US-00004 Yield of the product 94% of stoichiometric amount
Purity of finished product 99.81% (area count, GC).
EXAMPLES
[0137] The following compositions (Table I) were prepared according
to the procedure indicated in order to show the surprisingly
superior photostabilizing effect on avobenzone of the
alkoxycrylenes (4.5 wt. %) described herein in comparison to an
equimolar amount (2.75 wt. %) of octocrylene. The compound
described as "methoxycrylene" had the following formula (IV):
##STR00033##
TABLE-US-00005 TABLE 1 **Reported as Coefficients of Variation on
report generated by Labsphere instrument COMPOSITIONS OF
FORMULATIONS TESTED FOR PHOTOSTABILITY Example 1 Example 2 Example
3 # Ingredients (4.5% C20 Methoxycrylene) (POS: 2.75% OC Only)
(NEG: No Photostabilizer) Oil Phase Ingredients 1 Avobenzone 3.00%
3.00% 3.00% 2 Octisalate 5.00% 5.00% 5.00% 3 Homosalate 7.50% 7.50%
7.50% 4 Benzophenone-3 0.49% 0.49% 0.49% 5 Octocrylene*** (OC)
0.00% 2.75% 0.00% 6 C20 Methoxycrylene*** (C20MC) 4.50% 0.00% 0.00%
7 Phenylethyl benzoate 0.00% 0.00% 2.75% 8 Dimethicone (350 cSt)
1.25% 1.25% 1.25% 9 Methyl trimethicone 0.00% 1.75% 1.75% 10
VP/Eicosene copolymer 1.00% 1.00% 1.00% 11 Cetearyl alcohol 0.36%
0.36% 0.36% Total Oil Ingredients 23.10% 23.10% 23.10% Emulsifiers
12 Steareth-21 0.80% 0.80% 0.80% 13 Steareth-2 0.60% 0.60% 0.60% 14
Potassium cetyl phosphate & Hydrogenated palm glycerides 3.00%
3.00% 3.00% Total Emulsifiers 4.40% 4.40% 4.40% x Water Phase
Ingredients 15 Disodium EDTA 0.10% 0.10% 0.10% 16 Glycerin 4.00%
4.00% 4.00% 17 Benzyl alcohol 1.00% 1.00% 1.00% 18 Methylparaben
0.10% 0.10% 0.10% 19 Propylparaben 0.05% 0.05% 0.05% 20 Water
62.25% 62.25% 62.25% Total Water Ingredients 67.50% 67.50% 67.50%
Other Ingredients 21 Acrylamide/Sodium acryloyldimethyl taurate
copolymer 2.50% 2.50% 2.50% 22 Aluminum starch octenyl succinate
2.50% 2.50% 2.50% Total Other Ingredients 5.00% 5.00% 5.00% Total
100.00% 100.00% 100.00% ***On a molar basis, 4.5% C20
methoxycrylene is equal to 2.75% Octocrylene PROCEDURE 1. Charge
secondary vessel with 1-7. With stirring, heat to 90.degree. C. Add
in order 10-14. Continue stirring until homogeneous. 2. Charged
primary vessel with water (20). With stirring, ad 15-16. Heat to
90.degree. C. 3. Add oil phase (1-7, 10-14) to water phase (20, 15,
16). Stir vigorously for 10 minutes. Switch to homomixer and
homogenize until temperature is below 55 4. When temperature of
emulsion is below 55.degree. C., switch to sweep stirring. Preblend
17-19. Add to emulsion when temperature is below 45.degree. C. 5.
Add 21 and continue sweep stirring as emulsion thickens. When
smooth, add 22. Pre-blend 8 and 9 and add to batch. 6. Q.S. water
and package when temperature of batch is less than 35.degree.
C.
[0138] The surprising photostability of the sunscreen composition
of Example 1, Table 1, including methoxycrylene, in comparison to
the octocrylene of the prior art, is shown in FIG. 1, which is a
graph of the data of Examples 1 through 3, above, and in the
following SPF reports for Examples 4-6.
TABLE-US-00006 TABLE 2 Example 4 Example 5 (7% Ethylhexyl (0%
Ethylhexyl Example 6 Results of Irradiation with 35 MED
methoxycrylene) methoxycrylene) 8.8% Octocrylene) Loss of UVA
protection** -18.26% -80.47% -55.96% Loss of UVB protection**
-6.46% -52.01% -4.51% Loss of SPF** -7.43% -70.42% -16.00%
COMPOSITIONS OF FORMULATIONS TESTED FOR PHOTOSTABILITY CAB6-057
CAB6-058 CAB6-060 (7% Ethylhexyl (0% Ethylhexyl (0% Ethylhexyl #
Ingredients methoxycrylene) methoxycrylene) methoxycrylene) Oil
Phase Ingredients 1 Avobenzone 2.00% 2.00% 2.00% 2 Octyl
methoxycinnamate (OMC) 5.00% 5.00% 5.00% 3 Phenylethyl benzoate
7.50% 7.50% 7.50% 4 Benzophenone-3 0.49% 0.49% 0.49% 5 Octocrylene
1.80% 1.80% 8.80% 6 Ethylhexyl methoxycrylene*** 7.00% 0.00% 0.00%
7 Polyisobutene 0.00% 7.00% 0.00% Total Oil Ingredients 23.79%
23.79% 23.79% Emulsifier 8 Acrylates/C10-30 alkyl acrylate
crosspolymer 0.25% 0.25% 0.25% 9 Sorbitan laurate 0.20% 0.20% 0.20%
Total Emulsifiers 0.45% 0.45% 0.45% x Water Phase Ingredients 10
Disodium EDTA 0.10% 0.10% 0.10% 11 Cetyl hydroxyethylcellulose
0.30% 0.30% 0.30% 12 Glycerin 4.00% 4.00% 4.00% 13 Benzyl alcohol
1.00% 1.00% 1.00% 14 Methylparaben 0.10% 0.10% 0.10% 15
Propylparaben 0.05% 0.05% 0.05% 16 Triethanolamine 0.40% 0.40%
0.40% 17 Water 69.81% 69.81% 69.81% Total Water Ingredients 75.76%
75.76% 75.76% Total 100.00% 100.00% 100.00% **Reported as
Coefficients of Variation on report generated by Labsphere
instrument software. PROCEDURE 1. Charge primary vessel with water
(16). Dissolve 10. Heatto 85 degrees C. Disperse 11. Remove from
heat. Continue stirring until 11 is fully dissolved. 2. In
secondary vessel, add 2-7 and 9 with stirring. Add 1 and heat to 45
degrees C. Continue stirring until solution is clear. 3. Add 8 to
oil and stir until completely incorporated. 4. When oil phase and
water phase are 45 degrees C., add oil (1-7, 8, 9) to water (17,
10, 11). Maintain temperature and stir for 30 minutes. 5. Remove
batch from heat. Preblend 12 and 16. Add to batch with stirring.
Increase agitation as batch thickens. 6. Preblend 13-15, making
sure that 14 and 15 are completely dissolved. Add to batch. Q.S.
water and package when temperature of batch is less than 35.degree.
C.
[0139] Additional alkoxycrylene molecules were tested in accordance
with the procedure indicated in Table 2, wherein radical R.sub.3 of
the alkoxycrylene of formula (I) has an R.sub.3=ethyl hexyl
(formula IV):
##STR00034##
The data for the sunscreen composition of Example 4 is shown in the
graph of FIG. 2 and the data for the composition of Example 5 is
shown in the graph of FIG. 3. For Examples 4-6, the data of Example
6 (shown in graph form as FIG. 4) compares 7% ethylhexyl
methoxycrylene (formula V) and 1.8% octocrylene (Example 4) to 8.8%
octocrylene with no alkoxycrylene. As shown in the graph of FIG. 4
and the following SPF reports for Examples 4-6, the alkoxy crylenes
described herein are unexpectedly better photostabilizers than
octocrylene.
TABLE-US-00007 SPF REPORT Sample: Example 4 UV Photostability
Comment: 0, 35 MED Wavelength Range: 290-400 nm Units: SPF T(UVA)
T(UVB) # of Scans: 2 2 2 Mean: 24.67 4.52% 5.43% STD: 1.83 0.83%
0.35% COV: 7.43% 18.26% 6.46% UVA/UVB Ratio: 1.1 Boots Star Rating:
N/A less than 5 Scans Scan # SPF Critical Wavelength 1 25.97 385 2
23.37 384 Sample: Example 5 UV Photostability Comment: 0, 35 MED
Wavelength Range: 290-400 nm Units: SPF T(UVA) T(UVB) # of Scans: 2
2 2 Mean: 16.76 23.10% 8.07% STD: 11.8 18.59% 4.20% COV: 70.42%
80.47% 52.01% UVA/UVB Ratio: 0.72 Boots Star Rating: N/A less than
5 Scans Scan # SPF Critical Wavelength 1 25.11 380 2 8.41 372
Sample: Example 6 UV Photostability Comment: 0, 35 MED Wavelength
Range: 290-400 nm Units: SPF T(UVA) T(UVB) # of Scans: 2 2 2 Mean:
23.83 11.80% 5.27% STD: 3.81 6.61% 0.24% COV: 16.00% 55.96% 4.51%
UVA/UVB Ratio: 0.88 Boots Star Rating: N/A less than 5 Scans Scan #
SPF Critical Wavelength 1 26.52 382 2 21.13 375
[0140] As shown in the above-referenced formulations and data of
Examples 4-6, the combination of avobenzone (UVA) with
octylmethoxycinnamate (UVB) has particularly surprising results
when combined with a stabilizing amount of an alkoxycrylene of
formula I. It is well know that octocrylene stabilizes octyl
methoxycinnamate (OMC), a UVB filter, but does not photostabilizer
avobenzone, a UVA filter. In accordance with the compositions and
methods described herein, it has been found that the alkoxycrylene
of formula I photostabilize octyl methyoxycinnemate (OMC) much
better than OMC, and also photostabilizes avobenzone. The
alkoxycrylenes, therefore, can photostabilize sunscreen
compositions. Accordingly, by adding an alkoxycrylene, both
avobenzone and OMC can be photostabilized by the alkoxycrylene.
[0141] Example 4 (7% alkoxycrylene and 1.8% octocrylene) loses only
18.26% UVA; 6.46% UVB; and 7.43% of its SPM when subjected to 35
MED irradiation. The same formulation containing no alkoxycrylene
(Example 5) loses 80.47% UVA; 52.01% UVB; and 70.42% of its SPF.
Example 6, containing 8.8% octocrylene and no alkoxycrylene loses
55.96% UVA; 4.51% UVB (octocrylene photostabilizes OMC but not
avobenzone); and 16% of its SPF, Examples 4, 5 and 6 are shown
graphically in FIGS. 2, 3 and 4.
[0142] Additional sunscreen compositions were prepared containing 0
wt. %, 3 wt. % and 5 wt. % 2-ethylhexyl methoxycrylene, as shown in
Examples 7-10 in Table 3:
TABLE-US-00008 TABLE 3 Example 7 Example 8 Example 9 Example 10 (5%
2-EH (3% 2-EH (0% 2-EH (3% 2-EH # Ingredients Methoxycrylene)
methoxycrylene) methoxycrylene methoxycrylene) Oil Phase
Ingredients 1 Avobenzone 3.00% 3.00% 3.00% 3.00% 2 Octisalate 5.00%
5.00% 5.00% 5.00% 3 Octinoxate (Octyl methoxycinnamate or OMC or
7.50% 7.50% 7.50% 7.50% MCX) 4 Benzophenone-3 0.49% 0.49% 0.49%
0.49% 5 Octocrylene*** (OC) 5.00% 7.00% 10.00% 10.00% 6 Ethylhexyl
methoxycrylene*** (2-EH 5.00% 3.00% 0.00% 3.00% methoxycrylene or
MOC) 7 Cetearyl alcohol 0.35% 0.35% 0.35% 0.35% 8 C30-38
Olefin/Isopropyl maleate/MA copolymer 0.80% 0.80% 0.80% 0.80% Total
Oil Ingredients 27.14% 27.14% 27.14% 30.14% Emulsifiers 9
Steareth-21 0.45% 0.45% 0.00% 0.00% 10 Steareth-2 0.65% 0.65% 0.00%
0.00% 11 Glyceryl stearate/PEG-100 stearate 0.00% 0.00% 1.00% 1.00%
12 Potassium cetyl phosphate & Hydrogenated palm 3.00% 3.00%
3.00% 3.00% glycerides Total Emulsifiers 4.10% 4.10% 4.00% 4.00% x
Water Phase Ingredients 13 Disodium EDTA 0.10% 0.10% 0.10% 0.10% 14
Tromethamine 0.04% 0.04% 0.04% 0.04% 15 Glycerin 4.00% 4.00% 4.00%
4.00% 16 Benzyl alcohol 1.00% 1.00% 1.00% 1.00% 17 Methylparaben
0.10% 0.10% 0.10% 0.10% 18 Propylparaben 0.05% 0.05% 0.05% 0.05% 19
Water 58.47% 58.47% 58.57% 55.57% Total Water Ingredients 63.76%
63.76% 63.86% 60.86% Other Ingredients 20 Acrylamide/Sodium
acryloyldimethyltaurate copolymer (and) Isohexadecane (and)
Polysorbate 80 2.00% 2.00% 2.00% 2.00% 21 Aluminum starch octenyl
succinate 3.00% 3.00% 3.00% 3.00% Total Other Ingredients 5.00%
5.00% 5.00% 5.00% Total 100.00% 100.00% 100.00% 100.00% PROCEDURE
1. Charge secondary vessel with 1-9. With stirring, heat to
90.degree. C. Add in order 9-12. Continue stirring until
homogeneous. 2. Charged primary vessel with water (19). With
stirring, add 14-15. Heat to 90.degree. C. 3. Add oil phase (1-8,
9-12) to water phase (19, 14, 15). Stir vigorously for 10 minutes.
Switch to homomixer and homogenize until temperature is below
60.degree. C. 4. When temperature of emulsion is below 60.degree.
C., switch to sweep stirring. Preblend 15-18. Add to emulsion when
temperature is below 45.degree. C. 5. Add 20 and continue sweep
stirring as emulsion thickens. When smooth, add 21. 6. Q.S. water
and package when temperature of batch is less than 35.degree. C.
Q.S. = quantity sufficient
[0143] The results were as follows and clearly show that adding
more alkoxycrylene to sunscreen formulation provides more
Photostabilization of both UVA and UVB filters. Example 7, having
the most MOC (5%) and the least OC (5%) provided the best
results.
TABLE-US-00009 Example 7 Example 8 Example 9 Example 10 Results of
Irradiation with 20 MED 5% OC/5% MOC 7% OC/3% MOC 10% OC/0% MOC 10%
OC/3% MOC UVA1/UV ratio before UV irradiation 0.84 0.83 0.79 0.83
UVA1/UV ratio after 20 MED 0.76 0.71 0.54 0.70 Difference after
irradiation 0.09 0.12 0.25 0.13 % change 10.00% 15.00% 32.00%
16.00% OC = Octocrylene; MOC = Ethylhexyl Methoxycrylene; UVA1 =
total area under curve from 340 to 400 nm; UV = total area under
curve from 290 to 400 nm
[0144] More sunscreen compositions were prepared containing 0, 2, 4
and 6 wt. % 2-ethylhexyl methoxycrylene to test the
photostabilizing capacity of the methoxycrylenes to photostabilize
avobenzone and other photodegradable UV-absorbers, as shown in
Examples 11-14 in Table 4:
TABLE-US-00010 TABLE 4 Example 11 Example 12 Example 13 Example 14
# Ingredients 0% MOC 2% MOC 4% MOC 6% MOC Oil Phase Ingredients 1
Avobenzone 3.00% 3.00% 3.00% 3.00% 2 Octisalate 5.00% 5.00% 5.00%
5.00% 3 Homosalate 7.50% 7.50% 7.50% 7.50% 4 Butyloctyl benzoate
9.00% 7.00% 5.00% 3.00% 5 Ethylhexyl methoxycrylene*** (2-EH
methoxycrylene or MOC) 0.00% 2.00% 4.00% 6.00% 6 Cetearyl alcohol
0.35% 0.35% 0.35% 0.35% 7 VP/Eicosene copolymer 1.00% 1.00% 1.00%
1.00% Total Oil Ingredients 25.85% 25.85% 25.85% 25.85% Emulsifiers
8 Steareth-21 0.00% 0.00% 0.00% 0.00% 9 Steareth-2 0.00% 0.00%
0.00% 0.00% 10 Glyceryl stearate/PEG-100 stearate 1.00% 1.00% 1.00%
1.00% 11 Potassium cetyl phosphate & Hydrogenated palm
glycerides 3.00% 3.00% 3.00% 3.00% Total Emulsifiers 4.00% 4.00%
4.00% 4.00% x Water Phase Ingredients 12 Disodium EDTA 0.10% 0.10%
0.10% 0.10% 13 Glycerin 4.00% 4.00% 4.00% 4.00% 14 Benzyl alcohol
1.00% 1.00% 1.00% 1.00% 15 Methylparaben 0.10% 0.10% 0.10% 0.10% 16
Propylparaben 0.05% 0.05% 0.05% 0.05% 17 Water 59.90% 59.90% 59.90%
59.90% Total Water Ingredients 65.15% 65.15% 65.15% 65.15% Other
Ingredients 18 Acrylamide/Sodium acryloyldimethyltaurate copolymer
(and) Isohexadecane (and) Polysorbate 80 2.00% 2.00% 2.00% 2.00% 19
Aluminum starch octenyl succinate 3.00% 3.00% 3.00% 3.00% Total
Other Ingredients 5.00% 5.00% 5.00% 5.00% Total 100.00% 100.00%
100.00% 100.00% PROCEDURE 1. Charge secondary vessel with 1-7. With
stirring, heat to 90.degree. C. Add in order 10-11. Continue
stirring until homogeneous. 2. Charged primary vessel with water
(17). With stirring, add 12. Heat to 90.degree. C. 3. Add oil phase
(1-7, 10-11) to water phase (17, 12). Stir vigorously for 10
minutes. Switch to homomixer and homogenize until temperature is
below 60.degree. C. 4. When temperature of emulsion is below
60.degree. C., switch to sweep stirring. Preblend 13-16. Add to
emulsion when temperature is below 45.degree. C. 5. Add 18 and
continue sweep stirring as emulsion thickens. When smooth, add 19.
6. Q.S. water and package when temperature of batch is less than
35.degree. C. Q.S. = quantity sufficient
[0145] The results were as follows:
TABLE-US-00011 Example 11 Example 12 Example 13 Example 14 Results
of Irradiation with 20 MED 0% MOC 2% MOC 4% MOC 6% MOC UVA1/UV
ratio before UV irradiation 0.88 0.91 0.90 0.91 UVA1/UV ratio after
20 MED 0.32 0.85 0.88 0.90 Difference after irradiation 0.56 0.06
0.02 0.01 % change 63.67% 6.43% 2.00% 1.04% MOC = Ethylhexyl
Methoxycrylene; UVA1 = total area under curve from 340 to 400 nm;
UV = total area under curve from 290 to 400 nm
[0146] It should be noted that the sunscreen formulations of
Examples 11-14 contain no octyl methoxycinnemate or other
photostabilizers. It is clear from the data of Examples 11-14 that
the alkoxycrylene of formula I photostabilize avobenzone and other
dibenzoylmethane derivatives with surprising efficacy.
[0147] Additional sunscreen compositions were prepared containing 5
wt. % 2-ethylhexyl methoxycrylene with and without 1.5 wt. %
Tinosorb S or Tinosorb M, as shown in Examples 15 and 16 in Table
5:
TABLE-US-00012 TABLE 5 Example 15 Example 16 1.5% Bemotrizinol/5%
5% Bisoctrizole/5% # Ingredients MOC MOC Oil Phase Ingredients 1
Avobenzone 3.00% 3.00% 2 Octisalate 5.00% 5.00% 3 Octinoxate (Octyl
methoxycinnamate or OMC or MCX) 7.50% 7.50% 4 Bemotrizinol
(Tinosorb S) 1.50% 0.00% 6 Ethylhexyl methoxycrylene*** (2-EH
methoxycrylene or MOC) 5.00% 5.00% 7 Trideceth-12 1.00% 1.00% 8
VP/Eicosene copolymer 1.00% 1.00% 9 Behenyl alcohol + Glyceryl
stearate + Glyceryl stearate citrate + Sodium
dicocoylethylenediamine PEG-15 sulfate 1.00% 1.00% Total Oil
Ingredients 25.00% 23.50% Emulsifiers (See 7, 9, 12) 0.00% 0.00%
Total Emulsifiers 0.00% 0.00% x Water Phase Ingredients 10 Disodium
EDTA 0.10% 0.10% 11 Xanthan gum 0.10% 0.10% 12 Sodium
dicocoylethylenediamine PEG-15 sulfate + Sodium lauroyl 1.00% 1.00%
lactylate 13 Glycerin 4.00% 4.00% 14 Benzyl alcohol 1.00% 1.00% 15
Methylparaben 0.10% 0.10% 16 Propylparaben 0.05% 0.05% 17 Water
63.65% 60.15% Total Water Ingredients 70.00% 66.50% Other
Ingredients 18 Bisoctrizole (Tinosorb M) 0.00% 5.00% 19
Acrylamide/Sodium acryloyldimethyltaurate copolymer (and)
Isohexadecane (and) Polysorbate 80 2.00% 2.00% 20 Aluminum starch
octenyl succinate 3.00% 3.00% Total Other Ingredients 5.00% 10.00%
Total 100.00% 100.00% PROCEDURE 1. Charge secondary vessel with
1-9. With stirring, heat to 70.degree. C. Continue stirring until
homogeneous. Maintain temperature. 2. Charged a third vessel with
water (19). Dissolve 10 with stirring. Add 11 and stir until
Xanthan gum is completely dissolved. 3. Place 1/3 of (2) in primary
vessel. Heat to 65.degree. C. Add 12 and stir until homogeneous. 4.
Add oil phase (1-9) to water (10-12) in primary vessel. Homogenize
for two minutes, or until emulsion is fully formed. 5. Remove batch
from heat. Slowly add balance of water (see Step 2) to emulsion
with stirring. Stir while cooling. 6. Preblend 13-16. Add to batch
with stirring. Add 18 to batch with stirring. 7. Add 19 and stir
until smooth and homogeneous. Add 20 and stir until fully
incorporated. Q.S. water. Package when batch is < 35.degree. C.
Q.S. = quantity sufficient
[0148] The results were as follows:
TABLE-US-00013 Example 15 Example 16 Results of Irradiation with 20
MED 1.5% Bemotrizinol/5% MOC 5% Bisoctrizole/5% MOC UVA1/UV ratio
before UV irradiation 0.87 0.87 UVA1/UV ratio after 20 MED 0.81
0.84 Difference after irradiation 0.06 0.03 % change 6.66% 3.55%
MOC = Ethylhexyl Methoxycrylene; UVA1 = total area under curve from
340 to 400 nm; UV = total area under curve from 290 to 400 nm
[0149] Tinsorb S of Examples 15 and 16 is a known UVA and UVB
photostabilizer (more effective in the UVA range) for
photostabilizing both avobenzone and octyl methoxycinnamate.
Surprisingly, as shown in the data of Examples 15 and 16 (both
Examples include 5% MOC) omitting the Tinsorb S from Example 16
makes very little difference in photostabilizing the combination of
avobenzone and OMC.
[0150] Additional sunscreen formulations were tested containing 5
wt. % butyloctyl methoxycrylene and a triazine derivative (Uvinul
T-150); a benzophenone derivative (Uvinul A Plus); and three water
soluble UV filters (Mexonylsx; Neo Heliopan AP; and Neo Heliopan
Hydro), as shown in examples 17-21 of table 6:
TABLE-US-00014 TABLE 6 Example Example Example Example Example 17
18 19 20 21 2% 2% 2% 2% Neo 2% Neo Uvinul Uvinul Mexoryl Heliopan
Heliopan Ingredients T-150 A Plus SX AP Hydro Oil Phase Ingredients
1 Avobenzone 3.00% 3.00% 3.00% 3.00% 3.00% 2 Octisalate 5.00% 5.00%
5.00% 5.00% 5.00% 3 Octinoxate (Octyl methoxycinnamate or OMC or
MCX) 7.50% 7.50% 7.50% 7.50% 7.50% 4 Octyl triazone (Uvinul T-150,
BASF) 2.00% 0.00% 0.00% 0.00% 0.00% 5 Diethylamino Hydroxybenzoyl
Hexyl Benzoate (Uvinul A Plus, BASF) 0.00% 2.00% 0.00% 0.00% 0.00%
6 Butyloctyl methoxycrylene 5.00% 5.00% 5.00% 5.00% 5.00% 7
VP/Eicosene copolymer 1.00% 1.00% 1.00% 1.00% 1.00% Total Oil
Ingredients 23.50% 23.50% 21.50% 21.50% 21.50% Emulsifiers 8
Stearyl alcohol 1.00% 1.00% 1.00% 1.00% 1.00% 9 Glyceryl stearate
1.00% 1.00% 1.00% 1.00% 1.00% 10 Polyglyceryl-3 methyl glucose
distearate 3.00% 3.00% 3.00% 3.00% 3.00% Total Emulsifiers 5.00%
5.00% 5.00% 5.00% 5.00% Water Phase Ingredients 11 Disodium EDTA
0.10% 0.10% 0.10% 0.10% 0.10% 12 Ecamsule neutralized with
triethanolamine (Mexoryl SX, Chemex) 0.00% 0.00% 2.00% 0.00% 0.00%
13 Bisdisulizole disodium (Neo Heliopan AP, Symrise) 0.00% 0.00%
0.00% 2.00% 0.00% 14 Ensutizole neutralized with triethanolamine
(Neo Heliopan Hydro, Symrise) 0.00% 0.00% 0.00% 0.00% 2.00% 15
Glycerin 4.00% 4.00% 4.00% 4.00% 4.00% 16 Benzyl alcohol 1.00%
1.00% 1.00% 1.00% 1.00% 17 Methylparaben 0.10% 0.10% 0.10% 0.10%
0.10% 18 Propylparaben 0.05% 0.05% 0.05% 0.05% 0.05% 19 Water
61.25% 61.25% 61.25% 61.25% 61.25% Total Water Ingredients 66.50%
66.50% 68.50% 68.50% 68.50% Other Ingredients 20 Acrylamide/Sodium
acryloyldimethyltaurate copolymer (and) 2.00% 2.00% 2.00% 2.00%
2.00% Isohexadecane (and) Polysorbate 80 21 Aluminum starch octenyl
succinate 3.00% 3.00% 3.00% 3.00% 3.00% Total Other Ingredients
5.00% 5.00% 5.00% 5.00% 5.00% Total 100.00% 100.00% 100.00% 100.00%
100.00% PROCEDURE 1. Charge secondary vessel with 1-7.. With
stirring, heat to 80.degree. C. Add 8-10. Continue stirring until
homogeneous. 2. In another secondary vessel, dissolve 12 or 13 or
14 in water and set aside. 3. Charged primary vessel with water
(19), except amount necessary (or Step 2.. Dissolve 11. Heat to
80.degree. C. 4. Add oil(1-10) to water (11, 19) with stirring.
Remove from heat. Homogenize for 10 minutes. Stir while cooling. 5.
When temperature is below 45.degree. C., add pre-mixed 15-18. 6.
Add pre-dissolved 12, 13, or 14. 7. Add 20 and continue sweep
stirring as emulsion thickens. When smooth, add 21. 8. Q.S. water
and package when temperature of batch is less than 35.degree. C.
Q.S. = quantity sufficient
[0151] Two more sunscreen formulations (Examples 22 and 23) were
prepared each containing butyloctyl methoxycrylene, and Example 23
also containing Tinosorb.RTM. S and Tinosorb.RTM. M. As shown in
the results, the combination of an alkoxycrylene, together with a
dibenzoylmethane derivative, a cinnamate ester, Tinasorb.RTM. S and
Tinasorb.RTM. M, avobenzone and octyl methoxycinnamate is
particularly photostable:
TABLE-US-00015 Example 22 Example 23 0% TinS/0% TinM/7% BMOC 2%
TinS/5% TinM/5% BMOC Results of Irradiation with 20 MED Sheet1
UVA1/UV ratio before UV irradiation 0.84 0.85 UVA1/UV ratio after
20 MED 0.78 0.83 Difference after irradiation 0.06 0.02 % change
7.14% 2.35% Example 22 Example 23 Ingredients 0% TinS/0% TinM/7%
BMOC 2% TinS/5% TinM/5% BMOC Oil Phase Ingredients 1 Avobenzone
3.00% 3.00% 2 Octisalate 5.00% 5.00% 3 Octinoxate (Octyl
methoxycinnamate or OMC or MCX) 7.50% 7.50% 4 Bemotrizinc (Tinsorb
S) 0.00% 2.00% 6 Butyloctyl methoxycrylene*** (C12 methoxycrylene
or BMOC) 7.00% 5.00% 7 Trideceth-12 1.00% 1.00% 8 VP/Eicosene
copolymer 1.00% 1.00% 9 Behenyl alcohol + Glyceryl stearate +
Glyceryl stearate citrate + Sodium dicocoylethylenediamine PEG-15
sulfate 1.00% 1.00% Total Oil Ingredients 25.50% 25.50% Emulsifiers
(See 7, 9, 12) 0.00% 0.00% Total Emulsifiers 0.00% 0.00% Water
Phase Ingredients 10 Disodium EDTA 0.10% 0.10% 11 Xanthan gum 0.10%
0.10% 12 Sodium dicocoylethylenediamine PEG-15 sulfate + Sodium
lauroyl lactylate 1.00% 1.00% 13 Glycerin 4.00% 4.00% 14 Benzyl
alcohol 1.00% 1.00% 15 Methylparaben 0.10% 0.10% 16 Propylparaben
0.05% 0.05% 17 Water 63.15% 58.15% Total Water Ingredients 69.50%
64.50% Other Ingredients 18 Bisoctrizole (Tinsorb M) 0.00% 5.00% 19
Acrylamide/Sodium acryloyldimethyltaurate copolymer (and)
Isohexadecane (and) Polysorbate 50 2.00% 2.00% 20 Aluminum starch
octenyl succinate 3.00% 3.00% Total Other Ingredients 5.00% 10.00%
Total 100.00% 100.00% BMOC = Butylocryl methoxycrylene; TinS =
Tinosorb S (Bermotrizinol); TinM = Tinosorb M (Bisoctrizole) UVA1 =
total area under curve from 340 to 400 nm; UV = total area under
curve from 290 to 400 nm PROCEDURE 1. Charge secondary vessel with
1-9. With stirring, heat to 70.degree. C. Continue stirring until
homogeneous. Maintain temperature. 2. Charged a third vessel with
water (19). Dissolve 10 with stirring. Add 11 and stir until
Xanthan gum is completely dissolved. 3. Place 1/3 of (2) in primary
vessel. Heat to 65.degree. C. Add 12 and stir until homogeneous. 4.
Add oil phase (1-9) to water (10-12) in primary vessel. Homogenize
for two minutes, of until emulsion is fully formed. 5. Remove batch
from heat. Slowly add balance of water (see Step 2) to emulsion
with stirring. Stir while cooling. 6 Preblend 13-16. Add to batch
with stirring. Add 18 to batch with stirring. 7. Add 19 and stir
until smooth and homogeneous. Add 20 and stir until fully
incorporated. Q.S. water Package when batch is <35.degree. C.: Q
S = quantity sufficient
[0152] In addition to the simple ester alkoxy crylene compounds of
formula (I)-(V), the alkoxy crylene moieties can be attached as one
or more terminal moieties on a polyester molecule, such as the
alkoxy derivatives of the Di (NPG Crylene) Fumerate polyesters
disclosed in this assignee's U.S. Pat. No. 7,235,587 ('587), hereby
incorporated by references, as shown in formula (VI):
##STR00035##
wherein A and B are the same or different and are selected from the
group consisting of oxygen, amino and sulfur; R.sup.1 and R.sup.3
are the same or different and are selected from the group
consisting of C.sub.1-C.sub.30 alkyl, C.sub.2-C.sub.30 alkylene,
C.sub.2-C.sub.30 alkyne, C.sub.3-C.sub.8 cycloalkyl,
C.sub.1-C.sub.30 substituted alkylene, C.sub.2-C.sub.30 substituted
alkyne, aryl, substituted aryl, heteroaryl, heterocycloalkyl,
substituted heteroaryl and substituted heterocycloalkyl; R.sup.2 is
selected from the group consisting of C.sub.1-C.sub.30 alkyl,
C.sub.2-C.sub.30 alkylene, C.sub.2C.sub.30 alkyne, C.sub.3-C.sub.8
cycloalkyl, C.sub.1-C.sub.30 substituted alkyl, C.sub.3-C.sub.8
substituted cycloalkyl, C.sub.1-C.sub.30 substituted alkylene,
C.sub.2-C.sub.30 substituted alkyne; R.sup.4, R.sup.5, R.sup.6 and
R.sup.7 are the same or different and are selected from the group
consisting of C.sub.1-C.sub.30 alkoxy straight chain on branched,
and a, b, c and d are each either 0 or 1, and a, b, c and d add up
to 1, 2, 3, or 4.
* * * * *