U.S. patent application number 10/855350 was filed with the patent office on 2004-10-28 for photoprotecting/cosmetic compositions comprising benzotriazole and bis-resorcinyltriazine sunscreens.
This patent application is currently assigned to L'OREAL. Invention is credited to Candau, Didier.
Application Number | 20040213746 10/855350 |
Document ID | / |
Family ID | 9541966 |
Filed Date | 2004-10-28 |
United States Patent
Application |
20040213746 |
Kind Code |
A1 |
Candau, Didier |
October 28, 2004 |
Photoprotecting/cosmetic compositions comprising benzotriazole and
bis-resorcinyltriazine sunscreens
Abstract
Topically applicable sunscreen/cosmetic compositions suited for
the improved photoprotection of human skin and/or hair against the
damaging effects of UV-irradiation, particularly solar radiation,
comprise an effective SPF-maintaining and water remanence-enhancing
amount of intimate admixture of (a) at least one benzotriazole
first sunscreen compound and (b) at least one
bis-resorcinyltriazine second sunscreen compound, formulated into
(c) a topically applicable, cosmetically acceptable vehicle,
diluent or carrier therefor.
Inventors: |
Candau, Didier; (Bievres,
FR) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Assignee: |
L'OREAL
14, rue Royale
Paris
FR
75008
|
Family ID: |
9541966 |
Appl. No.: |
10/855350 |
Filed: |
May 28, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10855350 |
May 28, 2004 |
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09927488 |
Aug 13, 2001 |
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09927488 |
Aug 13, 2001 |
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PCT/FR00/00257 |
Feb 3, 2000 |
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Current U.S.
Class: |
424/59 |
Current CPC
Class: |
A61K 8/4966 20130101;
A61Q 17/04 20130101; A61K 8/496 20130101 |
Class at
Publication: |
424/059 |
International
Class: |
A61K 007/42 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 12, 1999 |
FR |
99/01729 |
Claims
What is claimed is:
1. A topically applicable sunscreen/cosmetic composition suited for
the photoprotection of human skin and/or hair, comprising an
effective SPF-maintaining and water remanence-enhancing amount of
combinatory immixture of (a) at least one benzotriazole first
sunscreen compound and (b) at least one bis-resorcinyltriazine
second sunscreen compound, formulated into (c) a topically
applicable, cosmetically acceptable vehicle, diluent or carrier
therefor.
2. A topically applicable sunscreen/cosmetic composition suited for
the photoprotection of human skin and/or hair, comprising an
effective SPF-maintaining and water remanence-enhancing amount of
combinatory immixture of (a) at least one benzotriazole first
sunscreen compound having the structural formula (I): 17in which A
is a hydrogen atom or a divalent radical -L-W--; n is 1, 2, or 3;
the radicals Y, which may be identical or different, are each a
C.sub.1-C.sub.10 alkyl radical, a halogen atom, a C.sub.1-C.sub.10
alkoxy radical or a sulfonic group, with the proviso that, in the
latter instance, two adjacent groups Y on the same aromatic nucleus
can together form an alkylidenedioxy group in which the alkylidene
moiety has 1 or 2 carbon atoms and with the further proviso that
the radicals Y are other than a sulfonic group when A is other than
a hydrogen atom; L is a divalent radical having the formula (II)
below: 18in which X is O or NH; Z is a hydrogen atom or a
C.sub.1-C.sub.4 alkyl radical; n is an integer ranging from 0 to 3,
inclusive; m is 0 or 1; p is an integer ranging from 1 to 10,
inclusive; W is a radical of formula (1), (2) or (3) below: 19in
which the radicals R, which may be identical or different, are each
a C.sub.1-C.sub.10 alkyl, phenyl or 3,3,3-trifluoropropyl radical,
at least 80%, by number of the radicals R being methyl radicals;
the radicals B, which may be identical or different, are each a
radical R or the radical V having the following formula: 20in which
Y, n and L are as defined above; r is an integer ranging from 0 to
50, inclusive, and s is an integer ranging from 1 to 20, inclusive,
and, if s=0, then at least one of the two radicals B is a radical
V; u is an integer ranging from 1 to 6, inclusive, and t is an
integer ranging from 0 to 10, inclusive, with the proviso that t+u
is greater than or equal to 3, and (b) at least one bis-resorcinyl
second sunscreen compound, formulated into (c) a topically
applicable, cosmetically acceptable vehicle, diluent or carrier
therefor.
3. A topically applicable sunscreen/cosmetic composition suited for
the photoprotection of human skin and/or hair, comprising an
effective SPF-maintaining and water remanence-enhancing amount of
combinatory immixture of (a) at least one benzotriazole first
sunscreen compound and (b) at least one bis-resorcinyltriazine
second sunscreen compound having the structural formula (III): 21in
which (i) the radicals R.sub.1 and R.sub.2, which may be identical
or different, are each a C.sub.3-C.sub.18 alkyl radical, a
C.sub.2-C.sub.18 alkenyl radical, or a residue of formula
--CH.sub.2--CH(OH)--CH.sub.2--OT.sub.1 wherein T.sub.1 is a
hydrogen atom or a C.sub.1-C.sub.8 alkyl radical; (ii) the radicals
R.sub.1 and R.sub.2, which may be identical or different, can also
be a residue of formula (4) below: 22in which R.sub.6 is a covalent
bond, a linear or branched C.sub.1-C.sub.4 alkyl radical, or a
residue of formula --C.sub.m1H.sub.2m1-- or
--C.sub.m1H.sub.2m1--O-- wherein m.sub.1 is a number ranging from
0.1 to 4; p.sub.1 is a number ranging from 0 to 5; the radicals
R.sub.7, R.sub.8 and R.sub.9, which may be identical or different,
are each a C.sub.1-C.sub.18 alkyl radical, a C.sub.1-C.sub.18
alkoxy radical, or a residue of formula: 23in which R.sub.10 is a
C.sub.1-C.sub.5 alkyl radical; A.sub.1 is a residue having one of
the following formulae: 24in which R.sub.3 denotes a hydrogen atom,
a C.sub.1-C.sub.10 alkyl radical, a radical of formula
--(CH.sub.2CHR.sub.5--O).sub.n1R.sub.11 wherein n.sub.1 is a number
ranging from 1 to 16, R.sub.11 is a hydrogen atom or methyl radical
or a residue of structure --CH.sub.2--CH(OH)--CH.sub.2OT.sub.1
wherein T.sub.1 is as defined above; R.sub.4 is a hydrogen atom, a
metal cation M, a C.sub.1-C.sub.5 alkyl radical, or a residue of
formula --(CH.sub.2)m.sub.2--OT.sub.1 wherein m.sub.2 is a number
ranging from 1 to 4 and T.sub.1 is as defined above, and Q.sub.1 is
a C.sub.1-C.sub.18 alkyl radical, formulated into (c) a topically
applicable, cosmetically acceptable vehicle, diluent or carrier
therefor.
4. A topically applicable sunscreen/cosmetic composition suited for
the photoprotection of human skin and/or hair, comprising an
effective SPF-maintaining and water remanence-enhancing amount of
combinatory immxture of (a) at least one benzotriazole first
sunscreen compound having the structural formula (I): 25in which A
is a hydrogen atom or a divalent radical -L-W--; n is 1, 2, or 3;
the radicals Y, which may be identical or different, are each a
C.sub.1-C.sub.10 alkyl radical, a halogen atom, a C.sub.1-C.sub.10
alkoxy radical or a sulfonic group, with the proviso that, in the
latter instance, two adjacent groups Y on the same aromatic nucleus
can together form an alkylidenedioxy group in which the alkylidene
moiety has 1 or 2 carbon atoms and with the further proviso that
the radicals Y are other than a sulfonic group when A is other than
a hydrogen atom; L is a divalent radical having the formula (II)
below: 26in which X is O or NH; Z is a hydrogen atom or a
C.sub.1-C.sub.4 alkyl radical; n is an integer ranging from 0 to 3,
inclusive; m is 0 or 1; p is an integer ranging from 1 to 10,
inclusive; W is a radical of formula (1), (2) or (3) below: 27or
--Si(R).sub.3 (3) in which the radicals R, which may be identical
or different, are each a C.sub.1-C.sub.10 alkyl, phenyl or
3,3,3-trifluoropropyl radical, at least 80%, by number of the
radicals R being methyl radicals; the radicals B, which may be
identical or different, are each a radical R or the radical V
having the following formula: 28in which Y, n and L are as defined
above; r is an integer ranging from 0 to 50, inclusive, and s is an
integer ranging from 1 to 20, inclusive, and, if s=0, then at least
one of the two radicals B is a radical V; U is an integer ranging
from 1 to 6, inclusive, and t is an integer ranging from 0 to 10,
inclusive, with the proviso that t+u is greater than or equal to 3,
and (b) at least one bis-resorcinyltriazine second sunscreen
compound, having the structural formula (III): 29in which (i) the
radicals R.sub.1 and R.sub.2, which may be identical or different,
are each a C.sub.3-C.sub.18 alkyl radical, a C.sub.2-C.sub.18
alkenyl radical, or a residue of formula
--CH.sub.2--CH(OH)--CH.sub.2--OT.sub.1 wherein T.sub.1 is a
hydrogen atom or a C.sub.1-C.sub.8 alkyl radical; (ii) the radicals
R.sub.1 and R.sub.2, which may be identical or different, can also
be a residue of formula (4) below: 30in which R.sub.6 is a covalent
bond, a linear or branched C.sub.1-C.sub.4 alkyl radical, or a
residue of formula --C.sub.m1H.sub.2m1-- or
--C.sub.m1H.sub.2m1--O-- wherein m.sub.1 is a number ranging from 1
to 4; p.sub.1 is a number ranging from 0 to 5; the radicals
R.sub.7, R.sub.8, and R.sub.9, which may be identical or different,
are each a C.sub.1-C.sub.18 alkyl radical, a C.sub.1-C.sub.18
alkoxy radical, or a residue of formula: 31in which R.sub.10 is a
C.sub.1-C.sub.5 alkyl radical; A.sub.1 is a residue having one of
the following formulae: 32in which R.sub.3 denotes a hydrogen atom,
a C.sub.1-C.sub.10 alkyl radical, a radical of formula
--(CH.sub.2CHR.sub.5--O).sub.n1R.sub.11 wherein n.sub.1 is a number
ranging from 1 to 16, R.sub.11 is a hydrogen atom or methyl radical
or a residue of structure --CH.sub.2--CH(OH)--CH.sub.2OT.sub.1
wherein T.sub.1 is as defined above; R.sub.4 is a hydrogen atom, a
metal cation M, a C.sub.1-C.sub.5 alkyl radical, or a residue of
formula --(CH.sub.2)m.sub.2--OT.sub.1 wherein m.sub.2 is a number
ranging from 1 to 4 and T.sub.1 is as defined above, and Q.sub.1 is
a C.sub.1-C.sub.18 alkyl radical, formulated into (c) a topically
applicable, cosmetically acceptable vehicle, diluent or carrier
therefor.
5. The topically applicable sunscreen/cosmetic composition as
defined by claim 2, said at least one benzotriazole first sunscreen
compound (a) comprising
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-3'-butyl-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, or
2-(2'-hydroxy-3'-sec-but- yl-5'-benzenesulfonato)benzotriazole.
6. The topically applicable sunscreen/cosmetic composition as
defined by claim 2, wherein formula (1), A is a divalent radical
-L-W-- and W has the formula (1), at least one of the following
conditions being satisfied: R is an alkyl radical, r ranges from 0
to 15, inclusive; s ranges from 1 to 5, inclusive, n is other than
zero and Y is a methyl, tert-butyl or C.sub.1-C.sub.4 alkoxy
radical, Z is a hydrogen atom or methyl, m=0 or [m=1 and X=O], p is
equal to 1.
7. The topically applicable sunscreen/cosmetic composition as
defined by claim 6, each of said conditions being satisfied.
8. The topically applicable sunscreen/cosmetic composition as
defined by claim 2, said at least one benzotriazole first sunscreen
compound (a) having the structural formula (I'): 33in which:
0.ltoreq.r.ltoreq.15, 1.ltoreq.s.ltoreq.5, and D is the divalent
radical: 34
9. The topically applicable sunscreen/cosmetic composition as
defined by claim 8, wherein formula (I') r=0, s=1 and 35
10. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, comprising from 0.1% to 15% by weight of said
at least one benzotriazole first sunscreen compound (a).
11. The topically applicable sunscreen/cosmetic composition as
defined by claim 10, comprising from 0.2% to 10% by weight of said
at least one benzotriazole first sunscreen compound (a).
12. The topically applicable sunscreen/cosmetic composition as
defined by claim 3, said at least one bis-resorcinyl second
sunscreen compound (b) comprising
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphe-
nyl)-1,3,5-triazine;
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hyd-
roxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(2-ethylhexylo-
xy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethylcarboxyl)phenylamino]-1,3,5-tria-
zine;
2,4-bis{[4-(tris(trimethylsiloxy)silylpropyloxy)-2-hydroxy]phenyl}-6-
-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(2"-methylpropenyloxy)-2-hyd-
roxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(1',
1', 1',3',5',
5',5'-heptamethyltrisiloxy-2"-methylpropyloxy)-2-hydroxy]phenyl-
}-6-(4-methoxyphenyl)-1,3,5-triazine;
2,4-bis{[4-(3-(2-propyloxy)-2-hydrox-
ypropyloxy)-2-hydroxy]phenyl}-6-[4-(ethoxycarbonyl)phenylamino]-1,3,5-tria-
zine; or
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol--
2-yl)-1,3,5-triazine.
13. The topically applicable sunscreen/cosmetic composition as
defined by claim 3, said at least one bis-resorcinyl second
sunscreen compound (b) comprising
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphe-
nyl)-1,3,5-triazine;
2,4-bis{[4-(tris(trimethylsiloxy)silylpropyloxy)-2-hy-
droxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; or
2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethyltrisiloxy-2"-methylpropyloxy)-
-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.
14. The topically applicable sunscreen/cosmetic composition as
defined by claim 8, wherein formula (I'), r=0, s=1 and 36
15. The topically applicable sunscreen/cosmetic composition as
defined by claim 10, comprising from 0.1% to 15% by weight of said
at least one bis-resorcinyltriazine second sunscreen compound
(b).
16. The topically applicable sunscreen/cosmetic composition as
defined by claim 11, comprising from 0.2% to 10% by weight of said
at least one bis-resorcinyltriazine second sunscreen compound
(b).
17. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, formulated as an oil-in-water emulsion.
18. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, further comprising at least one additional
hydrophilic or lipophilic organic UV-A and/or UV-B sunscreen.
19. The topically applicable sunscreen/cosmetic composition as
defined by claim 18, further comprising at least one cinnamic
derivative, salicylic derivative, camphor derivative, triazine
derivative, benzophenone derivative, dibenzoylmethane derivative,
benzimidazole derivative, .beta.-.beta.-diphenylacrylate
derivative, p-aminobenzoic acid derivative, sunscreen polymer, or
sunscreen silicone.
20. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, further comprising a photoprotecting effective
amount of particulates of at least one coated or uncoated inorganic
pigment or nanopigment.
21. The topically applicable sunscreen/cosmetic composition as
defined by claim 20, said at least one pigment or nanopigment
comprising titanium dioxide, zinc oxide, iron oxide, zirconium
oxide, cerium oxide, or mixture thereof.
22. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, further comprising at least one active agent
for the artificially tanning and/or browning of human skin.
23. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, further comprising at least one cosmetically
acceptable adjuvant or additive.
24. The topically applicable sunscreen/cosmetic composition as
defined by claim 23, said at least one adjuvant or additive
comprising a fat, organic solvent, thickening agent, softener,
antioxidant, opacifying agent, stabilizing agent, emollient,
hydroxy acid, anti-foaming agent, hydrating agent, vitamin,
fragrance, preservative, surfactant, filler, sequestering agent,
polymer, propellant, basifying or acidifying agent, dye, colorant,
or mixture thereof.
25. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, comprising a nonionic vesicular dispersion,
emulsion, cream, milk, gel, cream gel, ointment, suspension,
dispersion, powder, solid stick or tube, foam or spray.
26. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, comprising a makeup.
27. The topically applicable sunscreen/cosmetic composition as
defined by claim 26, comprising an anhydrous or aqueous solid or
paste, emulsion, suspension or dispersion.
28. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, comprising a shampoo, lotion, gel, nonionic
vesicular dispersion, hair lacquer, or rinse.
29. The topically applicable sunscreen/cosmetic composition as
defined by claim 1, having a sun protection factor of at least
2.
30. A regime/regimen for protecting human skin and/or hair against
the deleterious effects of ultraviolet irradiation, comprising
topically applying thereto an effective amount of the topically
applicable sunscreen/cosmetic composition as defined by claim
1.
31. A regime/regimen for protecting human skin and/or hair against
the deleterious effects of solar radiation, comprising topically
applying thereto a effective amount of the topically applicable
sunscreen/cosmetic composition as defined by claim 1.
Description
CROSS-REFERENCE TO PRIORITY/PCT APPLICATIONS
[0001] This application claims priority under 35 U.S.C. .sctn. 119
of FR-99/01729, filed Feb. 12, 1999, and is a continuation of
PCT/FR00/00257, filed Feb. 3, 2000 and designating the United
States (published in the French language on Aug. 17, 2000 as WO
00/47176; the title and abstract were also published in English),
both hereby expressly incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field of the Invention:
[0003] The present invention relates to novel cosmetic compositions
for topical application, for photoprotecting the skin and/or the
hair against the deleterious effects of ultraviolet radiation (such
compositions hereinbelow more simply referred to as antisun or
sunscreen compositions), and to the use of same for the cosmetic
applications indicated above.
[0004] This invention more especially relates to the aforesaid
sunscreen/cosmetic compositions comprising, formulated into a
cosmetically acceptable support (vehicle, diluent or carrier),
admixture of (a) a benzotriazole compound first screening agent and
(b) a specific bis-resorcinyltriazine compound second screening
agent.
[0005] 2. Description of the Prior Art
[0006] It is known to this art that light radiation with
wavelengths of from 280 nm to 400 nm promotes tanning of the human
epidermis, and that irradiation with wavelengths of from 280 nm to
320 nm, i.e., UV-B radiation, causes skin burns and erythema which
may be harmful to the development of a natural tan; this UV-B
radiation should thus be screened from the skin.
[0007] It is also known to this art that UV-A radiation, with
wavelengths of from 320 nm to 400 nm, which causes tanning of the
skin, can also induce an adverse change therein, especially in the
case of sensitive skin or of skin which is continually exposed to
solar radiation. UV-A rays cause, in particular, a loss of
elasticity of the skin and the appearance of wrinkles, leading to
premature skin aging. Such irradiation promotes triggering of the
erythemal reaction or amplifies this reaction in certain
individuals and may even be the cause of phototoxic or
photoallergic reactions. It is thus desirable to also screen out
UV-A radiation.
[0008] A wide variety of cosmetic compositions for the
photoprotection (UV-A and/or UV-B) of human skin are known to this
art.
[0009] These antisun/sunscreen compositions are quite often in the
form of an emulsion of oil-in-water type (namely, a cosmetically
acceptable vehicle comprising a continuous aqueous dispersing phase
and a discontinuous oily dispersed phase) which contains, in
various concentrations, one or more conventional lipophilic and/or
hydrophilic organic screening agents which are capable of
selectively absorbing harmful UV radiation. These screening agents
(and their amounts) are selected as a function of the desired sun
protection factor (the sun protection factor (SPF) which is
expressed mathematically by the ratio of the irradiation time
necessary to attain the erythemogenic threshold with the UV
screening agent to the time necessary to attain the erythemogenic
threshold without UV screening agent).
[0010] EP-B-0,742,003 describes antisun/cosmetic compositions
having high sun protection factors; these compositions comprise a
combination of two sunscreens, namely, (a)
benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid), optionally
in partially or totally neutralized form, as a first screening
agent, and (b), as a second screening agent, a benzotriazole
silicone such as those described in EP-B-0,660,701. However, these
sunscreen/photoprotecting products are usually considered to
possess insufficient water remanence.
SUMMARY OF THE INVENTION
[0011] It has now surprisingly and unexpectedly been determined
that intimate admixture of (a) at least one benzotriazole compound
as a first screening agent and (b) at least one specific
bis-resorcinyltriazine compound as a second screening agent
provides sunscreen/photoprotecting compositions whose water
remanence is substantially improved, while at the same time having
a level of sun protection which is as high as that of the
above-indicated photoprotective compositions of the prior art.
[0012] Briefly, the present invention features novel cosmetic or
dermatological, in particular antisun/sunscreen, compositions which
are essentially characterized in that they comprise, formulated
into a cosmetically acceptable support, (a) as a first screening
agent, at least one benzotriazole compound of formula (I) below:
1
[0013] in which A is a hydrogen atom or a divalent radical -L-W--;
the radicals Y, which may be identical or different, are each a
C.sub.1-C.sub.10 alkyl radical, a halogen atom, a C.sub.1-C.sub.10
alkoxy radical or a sulfonic group, with the proviso that, in the
latter case, two adjacent Y radicals on the same aromatic nucleus
can together form an alkylidenedioxy group in which the alkylidene
moiety has 1 or 2 carbon atoms; with the further proviso that the
radicals Y are other than a sulfonic group when A is other than a
hydrogen atom; n is 1, 2, or 3; L is a divalent radical of formula
(II) below: 2
[0014] in which X is O or NH; Z is a hydrogen atom or a
C.sub.1-C.sub.4 alkyl radical; n is an integer ranging from 0 to 3,
inclusive, m is 0 or 1; p is an integer ranging from 1 to 10,
inclusive; W is a radical of formula (1), (2) or (3) below: 3
[0015] or
--Si(R).sub.3 (3)
[0016] in which the radicals R, which may be identical or
different, are each a C.sub.1-C.sub.10 alkyl, phenyl or
3,3,3-trifluoropropyl radical, at least 80%, by number, of the
radicals R being methyl radicals; the radicals B, which may be
identical or different, are each a radical R or the radical V
having the following formula: 4
[0017] in which Y, n and L are as defined above; r is an integer
ranging from 0 to 50, inclusive, and s is an integer ranging from 1
to 20, inclusive, and, if s=0, then at least one of the two
radicals B is a radical V; u is an integer ranging from 1 to 6,
inclusive, and t is an integer ranging from 0 to 10, inclusive,
with the proviso that t+u is greater than or equal to 3; and (b),
as a second screening agent, at least one bis-resorcinyltriazine
compound having the formula (III) below: 5
[0018] in which (i) the radicals R.sub.1 and R.sub.2, which may be
identical or different, are each a C.sub.3-C.sub.18 alkyl radical,
a C.sub.2-C.sub.18 alkenyl radical, or a residue of formula
--CH.sub.2--CH(OH)--CH.sub.2--OT.sub.1 wherein T.sub.1 is a
hydrogen atom or a C.sub.1-C.sub.8 alkyl radical; or (ii) the
radicals R.sub.1 and R.sub.2, which again may be identical or
different, can also be a residue of formula (4) below: 6
[0019] in which R.sub.6 is a covalent bond, a linear or branched
C.sub.1-C.sub.4 alkyl radical, or a residue of formula
--C.sub.m1H.sub.2m1-- or --C.sub.m1H.sub.2m1--O-- wherein m.sub.1
is a number ranging from 1 to 4; p.sub.1 is a number ranging from 0
to 5; the radicals R.sub.7, R.sub.8, and R.sub.9, which may be
identical or different, are each a C.sub.1-C.sub.18 alkyl radical,
a C.sub.1-C.sub.18 alkoxy radical, or a residue of formula (5)
below: 7
[0020] in which R.sub.10 is a C.sub.1-C.sub.5 alkyl radical;
A.sub.1 is a residue having one of the following formulae (6), (7)
or (8): 8
[0021] in which R.sub.3 is a hydrogen atom, a C.sub.1-C.sub.10
alkyl radical, a radical of formula
--(CH.sub.2CHR.sub.5--O).sub.n1R.sub.11 wherein n, is a number
ranging from 1 to 16, R.sub.11, is a hydrogen atom, a methyl
radical, or a residue of the formula
--CH.sub.2--CH--(OH)--CH.sub.2OT.sub.1 wherein T.sub.1 is as
defined above; R.sub.4 is a hydrogen atom; a metal cation M, a
C.sub.1-C.sub.5 alkyl radical, or a residue of formula
--(CH.sub.2)m.sub.2--OT.sub.1 wherein m.sub.2 is a number ranging
from 1 to 4 and T.sub.1 is as defined above; and Q.sub.1 is a
C.sub.1-C.sub.18 alkyl radical.
[0022] The present invention also features the manufacture of
cosmetic compositions for protecting the skin and/or the hair
against ultraviolet radiation, in particular solar radiation.
[0023] Too, the present invention features a cosmetic
regime/regimen for protecting the skin and/or the hair against
ultraviolet radiation, in particular solar radiation, and which
comprises topically applying an effective amount of a subject
composition onto the skin and/or the hair.
DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED
EMBODIMENTS OF THE INVENTION
[0024] More particularly according to the present invention, the
subject benzotriazole compounds of formula (I) are UV-screening
agents that are per se known to this art. These are described and
prepared according to the syntheses indicated in U.S. Pat. Nos.
4,316,033 and 4,328,346; EP-B-0,354,145, EP-B-0,392,883 and
EP-B-0,660,701 hereby expressly incorporated by reference.
[0025] Among the non-silicone compounds of formula (I) in which A
is a hydrogen atom according to the invention, particularly
exemplary are:
[0026] 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (n=1 and
Y=CH.sub.3), such as the product marketed under the trademark
Uvazol P by Enichem Synth and the product marketed under the
trademark Tinuvin P by Ciba Geigy;
[0027] 2-(2'-hydroxy-3'-butyl-5'-methylphenyl)benzotriazole (n=2
and Y=CH.sub.3 and --C(CH.sub.3).sub.3), such as the product
marketed under the trademark Uvazol 236 by Enichem Synth;
[0028] 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole (n=1 and
Y=--C(CH.sub.3).sub.2--CH.sub.2--C(CH.sub.3).sub.3), such as the
product marketed under the trademark Uvazol 311 by Enichem
Synth;
[0029] 2-(2'-hydroxy-3'-sec-butyl-5'-benzenesulfonato)benzotriazole
(n=2 and Y=SO.sub.3H; Y=CH(CH.sub.3)--CH.sub.2--CH.sub.3), such as
the product marketed under the trademark Cibafast by Ciba
Geigy.
[0030] For the silicone compounds of formula (1) in which A is a
divalent radical -L-W--, in the definition of formulae (1), (2) and
(3) as defined above, the alkyl radicals may be linear or branched
and are selected, in particular, from among methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl,
isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and
tert-octyl radicals. The alkyl radicals R that are preferred
according to the invention are methyl, ethyl, propyl, n-butyl,
n-octyl and 2-ethylhexyl radicals. Even more preferably, the
radicals R are all methyl radicals.
[0031] For the silicone compounds of formula (I) in which A is a
divalent radical -L-W--, it is preferred to employ those in which W
corresponds to formula (1), i.e., diorganosiloxanes containing a
linear chain.
[0032] Among the linear diorganosiloxanes according to the present
invention, those more particularly preferred are the random
derivatives or the derivatives well-defined in blocks having at
least one, and more preferably all, of the following
characteristics:
[0033] R is an alkyl radical and even more preferably is a methyl
radical;
[0034] B is an alkyl radical and even more preferably is a methyl
radical;
[0035] r ranges from 0 to 15, inclusive; s ranges from 1 to 5,
inclusive;
[0036] n is other than zero and preferably is equal to 1, and Y is
then selected from among methyl, tert-butyl and C.sub.1-C.sub.4
alkoxy;
[0037] Z is a hydrogen atom or a methyl radical;
[0038] m=0 or [m=1 and X=O];
[0039] p is equal to 1.
[0040] As will be seen from formula (I) above, the bonding of the
divalent radical --(X).sub.m--(CH2).sub.p--CH(Z)-CH.sub.2-- to the
benzotriazole structural unit, which thus links said benzotriazole
unit to the silicon atom of the silicone backbone, can, according
to the present invention, be at any of the available positions
presented by the two aromatic nuclei of the benzotriazole: 9
[0041] Preferably, this attachment is at position 3-, 4-, 5-
(aromatic nucleus bearing the hydroxyi function) or 4'- (benzene
nucleus adjacent to the triazole ring), and even more preferably at
position 3-, 4- or 5-. In one preferred embodiment of the
invention, the attachment is at position 3-.
[0042] Similarly, the attachment of the substituent Y can be at any
of the other positions available on the benzotriazole. However,
this attachment preferably is at position 3-, 4-, 4'-, 5- and/or
6-. In one preferred embodiment of the invention, the attachment is
at position 5-.
[0043] One family of compounds which is particularly suitable for
the invention is that having the following general formula (I'):
10
[0044] in which 0.ltoreq.r.ltoreq.15, preferably
0.ltoreq.r.ltoreq.10,
[0045] 1.ltoreq.s.ltoreq.5, preferably 1.ltoreq.s.ltoreq.3, and in
which D represents the divalent radical: 11
[0046] In one particularly preferred embodiment of the invention,
the benzotriazole silicone has the structural formula (I') in
which:
[0047] r=0
[0048] s=1 12
[0049] In another particularly preferred embodiment of the
invention, the benzotriazole silicone has the structural formula
(I') in which:
r=0
s=1 13
[0050] The benzotriazole compounds of formula (I) are
advantageously present in amounts of from 0.1% to 15% and
preferably from 0.2% to 10% by weight, relative to the total weight
of the composition.
[0051] In formulae (III) and (4) to (8) described above:
[0052] the alkyl radicals are linear or branched and are selected,
for example, from among methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, heptyl,
octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl and octadecyl radicals;
[0053] the alkenyl radicals are selected, for example, from among
allyl, methylallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl,
n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl,
n-dodec-2-enyl, isododecenyl and n-octadec-4-enyl radicals;
[0054] the alkoxy radicals are linear or branched and are selected,
for example, from among methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy and
tert-amyloxy radicals;
[0055] the C.sub.1-C.sub.5 mono- or dialkylamino radicals are
selected, for example, from among methylamino, ethylamino,
propylamino, n-butylamino, sec-butylamino, tert-butylamino,
pentylamino, dimethylamino, diethylamino, dibutylamino and
methylethylamino radicals;
[0056] the metal cations are preferably alkali metal or alkaline
earth metal cations or metallic cations selected, for example, from
among lithium, potassium, sodium, calcium, magnesium, copper and
zinc cations.
[0057] The bis-resorcinyltriazine compounds of formula (III) of the
invention are UV-screening agents that are also per se known to
this art. These are described and prepared according to the
syntheses indicated in EP-A-0,775,698 hereby expressly incorporated
by reference.
[0058] Exemplary compounds of formula (III) include:
[0059] 2,4-bis
{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-
-1,3,5-triazine;
[0060]
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-
-(4-methoxyphenyl)-1,3,5-triazine;
[0061]
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-[4-(2-methoxyethyl-
carboxyl)phenylamino]-1,3,5-triazine;
[0062]
2,4-bis{[4-(tris(trimethylsiloxy)silylpropyloxy)-2-hydroxy]phenyl}--
6-(4-methoxyphenyl)-1,3,5-triazine;
[0063]
2,4-bis{[4-(2"-methylpropenyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphe-
nyl)-1,3,5-triazine;
[0064]
2,4-bis{[4-(1',1',1',3',5',5',5'-heptamethyltrisiloxy-2"-methylprop-
yloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;
[0065]
2,4-bis{[4-(3-(2-propyloxy)-2-hydroxypropyloxy)-2-hydroxy]phenyl}-6-
-[4-(ethoxycarbonyl)phenylamino]-1,3,5-triazine;
[0066]
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(1-methylpyrrol-2--
yl)-1,3,5-triazine.
[0067] The compounds derived from bis-resorcinyltriazine that are
more particularly preferred according to the invention are selected
from the group consisting of:
[0068]
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)--
1,3,5-triazine;
[0069] 2,4-bis
{[4-(tris(trimethylsiloxy)silylpropyloxy)-2-hydroxy]phenyl}-
-6-(4-methoxyphenyl)-1,3,5-triazine;
[0070] 2,4-bis{[4-(1',1',1',3',5',
5',5'-heptamethyltrisiloxy-2"-methylpro-
pyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine.
[0071] The sunscreen(s) of the bis-resorcinyltriazine compound type
of formula (III) are advantageously present in the compositions
according to the invention at a concentration of from 0.1% to 15%
and preferably from 0.2% to 10% by weight relative to the total
weight of the composition.
[0072] As indicated above, according to an essential characteristic
of the present invention, the two types of sunscreen should both be
present in the final composition in a respective proportion such
that a synergistic effect on the water remanence imparted by the
resulting combination is obtained in an appreciable, substantial
and significant manner.
[0073] In addition and in general, it should be appreciated that
the concentrations and ratios of benzotriazole compounds of formula
(I) and of bis-resorcinyltriazine compounds of formula (III) as
described above are selected such that the sun protection factor of
the final composition is preferably at least 2.
[0074] In another preferred embodiment of the present invention,
the cosmetically acceptable support in which the various types of
screening agent are formulated is an emulsion of oil-in-water
type.
[0075] It will of course be appreciated that the antisun/sunscreen
cosmetic compositions according to the invention can contain one or
more additional hydrophilic or lipophilic UVA-active and/or
UVB-active sunscreen(s) (absorbers) other than the subject two
screening agents. These additional screening agents are
advantageously selected, in particular, from among cinnamic
derivatives; salicylic derivatives; camphor derivatives; triazine
derivatives other than those described above, such as those
described in EP-863,145, EP-517,104, EP-570,838 and EP-796,851;
benzophenone derivatives; dibenzoylmethane derivatives;
.beta.,.beta.'-diphenylacrylate derivatives, benzimidazole
derivatives; p-aminobenzoic acid derivatives; screening polymers
and screening silicones, such as those described in
WO-93/04665.
[0076] Exemplary such additional UV-A-active and/or UV-B-active
sunscreens include:
[0077] p-aminobenzoic acid;
[0078] oxyethylenated (25 mol) p-aminobenzoate;
[0079] 2-ethylhexyl p-dimethylaminobenzoate;
[0080] N-oxypropylenated ethyl p-aminobenzoate;
[0081] glyceryl p-aminobenzoate;
[0082] homomenthyl salicylate;
[0083] 2-ethylhexyl salicylate;
[0084] triethanolamine salicylate;
[0085] 4-isopropylbenzyl salicylate;
[0086] 4-tert-butyl-4'-methoxydibenzoylmethane;
[0087] 4-isopropyldibenzoylmethane;
[0088] 2-ethylhexyl 4-methoxycinnamate;
[0089] methyl diisopropylcinnamate;
[0090] isoamyl 4-methoxycinnamate;
[0091] diethanolamine 4-methoxycinnamate;
[0092] menthyl anthranilate;
[0093] 2-ethylhexyl 2-cyano-3,3'-diphenylacrylate;
[0094] ethyl 2-cyano-3,3'-diphenylacrylate;
[0095] 2-phenylbenzimidazole-5-sulfonic acid and salts thereof;
[0096] 3-(4'-trimethylammonio)benzylidenebornan-2-one methyl
sulfate;
[0097] benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid) and
salts thereof;
[0098] urocanic acid;
[0099] 2-hydroxy-4-methoxybenzophenone;
[0100] 2-hydroxy-4-methoxybenzophenone-5-sulfonate;
[0101] 2,4-dihydroxybenzophenone;
[0102] 2,2',4,4'-tetrahydroxybenzophenone;
[0103] 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
[0104] 2-hydroxy-4-n-octoxybenzophenone;
[0105] 2-hydroxy-4-methoxy-4'-methylbenzophenone;
[0106] .alpha.-(2-oxoborn-3-ylidene)tolyl-4-sulfonic acid and salts
thereof;
[0107] 3-(4'-sulfo)benzylidenebornan-2-one and salts thereof;
[0108] 3-(4'-methylbenzylidene)-d,1-camphor;
[0109] 3-benzylidene-d,1-camphor;
[0110]
2,4,6-tris[p-(2'-ethylhexyl-1'-oxycarbonyl)anilino]-1,3,5-triazine;
[0111]
2-[p-(tert-butylamido)anilino]-4,6-bis[(p-(2'-ethylhexyl-11'-oxycar-
bonyl)anilino]-1,3,5-triazine;
[0112] 1,4-bis(benzimidazolyl)phenylene-3,3',5,5'-tetrasulfonic
acid and salts thereof;
[0113] the polymer of N-[(2 and
4)-[(2-oxoborn-3-ylidene)methyl]benzyl]acr- ylamide;
[0114] polyorganosiloxanes containing a malonate functional
group.
[0115] The compositions according to the invention may also contain
agents for the artificial tanning and/or browning of the skin
(self-tanning agents) such as, for example, dihydroxyacetone
(DHA).
[0116] The cosmetic compositions according to the invention may
also contain pigments or nanopigments (average size of the primary
particles: generally ranging from 5 nm to 100 nm, preferably from
10 nm to 50 nm) of coated or uncoated metal oxides, for example
nanopigments of titanium dioxide (amorphous or crystallized in
rutile and/or anatase form), of iron oxide, of zinc oxide, of
zirconium oxide or of cerium oxide which are all UV-photoprotective
agents that are well known to this art. Conventional coating agents
include, moreover, alumina and/or aluminum stearate. Such coated or
uncoated metal oxide nanopigments are described, in particular, in
EP-A-0,518,772 and EP-A-0,518,773.
[0117] The compositions of the invention may also comprise
conventional cosmetic additives and adjuvants selected, in
particular, from among fatty substances, organic solvents,
thickeners, softeners, antioxidants, opacifying agents,
stabilizers, emollients, hydroxy acids, anti-foaming agents,
moisturizers, vitamins, fragrances, preservatives, surfactants,
fillers, sequestering agents, polymers, propellants, basifying or
acidifying agents, dyes, colorants, or any other ingredient usually
formulated into cosmetics, in particular for the manufacture of
antisun/sunscreen compositions in the form of emulsions.
[0118] The fatty substances may be an oil or a wax or mixtures
thereof, and may also be fatty acids, fatty alcohols and fatty acid
esters. The oils may be animal, plant, mineral or synthetic oils
and, in particular, liquid petrolatum, liquid paraffin, volatile or
non-volatile silicone oils, isoparaffins, poly-.alpha.-olefins,
fluoro oils and perfluoro oils. Similarly, the waxes may be animal,
fossil, plant, mineral or synthetic waxes that are per se known to
this art.
[0119] Among the organic solvents, exemplary are the lower alcohols
and polyols.
[0120] The thickeners may be selected, in particular, from among
crosslinked acrylic acid homopolymers and modified or unmodified
guar gums and celluloses such as hydroxypropyl guar gum,
methylhydroxyethylcellulose, hydroxypropylmethylcellulose or
hydroxyethylcellulose.
[0121] One skilled in this art will of course take care to select
the optional additional compound or compounds and/or the amounts
thereof such that the advantageous properties, in particular the
water remanence and the level of photoprotection, intrinsically
associated with the binary combination in accordance with the
invention, are not, or are substantially not, adversely affected by
the addition or additions envisaged.
[0122] The compositions of the invention may be prepared according
to techniques which are well known to this art, in particular those
for formulating emulsions of oil-in-water or water-in-oil type.
[0123] Such compositions may be, in particular, in simple or
complex emulsion form (O/W, W/O, O/W/O or W/O/W), such as a cream,
a milk, a lotion, an ointment, a gel or a cream-gel, a powder or a
solid stick and may optionally be packaged as an aerosol and may be
in the form of a foam or a spray.
[0124] When the composition is an emulsion, the aqueous phase
thereof may comprise a nonionic vesicular dispersion prepared
according to known processes (Bangham, Standish and Watkins, J.
Mol. Biol., 13, 238 (1965), FR-2,315,991 and FR-2,416,008).
[0125] The cosmetic compositions of the invention may be for
protecting the human skin or the hair against ultraviolet rays, as
an antisun/sunscreen composition or as a makeup product.
[0126] When the cosmetic compositions according to the invention
are for protecting the human epidermis against UV rays or as an
antisun/sunscreen composition, same may be in the form of a
suspension or dispersion in solvents or in fatty substances, in the
form of a nonionic vesicular dispersion or, alternatively, in the
form of an emulsion, preferably of oil-in-water type, such as a
cream or a milk, or in the form of an ointment, a gel, a cream-gel,
a powder, a solid tube, a stick, an aerosol foam or a spray.
[0127] When the cosmetic compositions according to the invention
are to protect the hair, it may be in the form of a shampoo, a
lotion, a gel, an emulsion or a nonionic vesicular dispersion and
may constitute, for example, a rinse-out composition to be applied
before or after shampooing, before or after dyeing or bleaching,
before, during or after permanent-waving or straightening of the
hair, a styling or treating lotion or gel, a blow-drying or
hair-setting lotion or gel or a composition for permanent-waving,
straightening, dyeing or bleaching the hair.
[0128] When the composition is used as a makeup product for the
eyelashes, the eyebrows or the skin, such as a treatment cream for
the epidermis, a foundation, a lipstick, an eyeshadow, a blusher, a
mascara or an eyeliner, it may be in anhydrous or aqueous, solid or
pasty form, for example oil-in-water or water-in-oil emulsions,
nonionic vesicular dispersions or suspensions.
[0129] For example, for the antisun/sunscreen formulations in
accordance with the invention which have a support of oil-in-water
emulsion type, the aqueous phase (in particular comprising the
hydrophilic screening agents) generally constitutes from 50% to 95%
by weight, preferably from 70% to 90% by weight, relative to the
total weight of the formulation, the oily phase (in particular
comprising the lipophilic screening agents) from 5% to 50% by
weight, preferably from 10% to 30% by weight, relative to the total
weight of the formulation, and the (co)emulsifying agent(s) from
0.5% to 20% by weight, preferably from 2% to 10% by weight, also
relative to the total weight of the formulation.
[0130] As indicated above, the present invention also features a
cosmetic regime or regimen for the skin or the hair to protect the
skin/hair against the damaging effects of UV irradiation, which
comprises topically applying an effective amount of a cosmetic
composition as described above onto the skin or the hair.
[0131] In order to further illustrate the present invention and the
advantages thereof, the following specific examples are given, it
being understood that same are intended only as illustrative and in
nowise limitative.
EXAMPLE 1
[0132]
1 COMPOSITION 80/20 Mixture of cetylstearyl alcohol and of
oxyethylenated 7 g (33 EO) cetylstearyl alcohol (Sinnowax
AO-Henkel) Mixture of glyceryl mono- and distearate (Cerasynt SD-V-
2 g ISP) Cetyl alcohol 1.5 g Polydimethylsiloxane (Dow Corning 200
Fluid-Dow 1 g Corning) C.sub.12/C.sub.15 Alkyl benzoate (Witconol
TN-Witco) 15 g 2,4-Bis{[4-(2-ethylhexyloxy)-2-hydroxyl]phenyl}-6--
(4- 2 g methoxyphenyl)-1,3,5-triazine Benzotriazole silicone of
formula (I') in which: r = 0; s = 1 3 g and D = 14 Glycerol 15 g
Preservatives qs Demineralized water qs 100 g
EXAMPLE 2
[0133]
2 COMPOSITION Glyceryl mono-/distearate/polyethylene glycol
stearate 2 g (100 EO) mixture (Arlacel 165 FL-ICI) Stearyl alcohol
(Lanette 18-Henkel) 1 g Stearic acid from palm oil (Stearine
TP-Stearinerie Dubois) 2.5 g Polydimethylsiloxane (Dow Corning 200
Fluid-Dow 0.5 g Corning) C.sub.12/C.sub.15 Alkyl benzoate (Witconol
TN-Witco) 20 g Triethanolamine 0.5 g
2,4-Bis{[4-(tris(trimethylsilo- xy)silylpropyloxy)-2- 2.5 g
hydroxy]phenyl}-6-(4-methoxyphenyl)-1,- 3,5-triazine Benzotriazole
silicone of formula (I') in which: r = 0; s = 1 2.5 g and D = 15
Glycerol 5 g Hexadecyl phosphate, potassium salt (Amphisol
K-Hoffman 1 g Laroche) Polyacrylic acid (Synthalen K-3V) 0.3 g
Hydroxypropylmethylcellulose (Methocel F4M-Dow 0.1 g Chemical)
Triethanolamine 0.3 g Preservatives qs Demineralized water qs 100
g
EXAMPLE 3
[0134]
3 COMPOSITION 80/20 Mixture of cetylstearyl alcohol and of
oxyethylenated 7 g (33 EO) cetylstearyl alcohol (Sinnowax
AO-Henkel) Mixture of glyceryl mono- and distearate (Cerasynt SD-V-
2 g ISP) Cetyl alcohol 1.5 g Polydimethylsiloxane (Dow Corning 200
Fluid-Dow 1 g Corning) C.sub.12/C.sub.15 Alkyl benzoate (Witconol
TN-Witco) 15 g
2,4-Bis{[4-(1',1',1',3',5',5',5'-heptamethyltrisiloxy-2"- 2 g
methylpropyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-
1,3,5-triazine Benzotriazole silicone of formula (I') in which: r =
0; s = 1 3 g and D = 16 Glycerol 15 g Preservatives qs
Demineralized water qs 100 g
[0135] While the invention has been described in terms of various
specific and preferred embodiments, the skilled artisan will
appreciate that various modifications, substitutions, omissions,
and changes may be made without departing from the spirit thereof.
Accordingly, it is intended that the scope of the present invention
be limited solely by the scope of the following claims, including
equivalents thereof.
* * * * *