U.S. patent application number 13/888447 was filed with the patent office on 2013-09-26 for mixtures comprising benzotriazoles and merocyanines.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is Alexander Mantler, Oliver Reich, Michael Schork, Barbara Winkler. Invention is credited to Alexander Mantler, Oliver Reich, Michael Schork, Barbara Winkler.
Application Number | 20130251650 13/888447 |
Document ID | / |
Family ID | 39494188 |
Filed Date | 2013-09-26 |
United States Patent
Application |
20130251650 |
Kind Code |
A1 |
Winkler; Barbara ; et
al. |
September 26, 2013 |
MIXTURES COMPRISING BENZOTRIAZOLES AND MEROCYANINES
Abstract
The present invention relates to the use of a stabilizing
composition comprising (a) an effective stabilizing amount of at
least one merocyanine derivative having an absorption maximum of
350 to 400 nm, and (b) at least one UV filter selected from
benzotriazole derivatives; and optionally (c) at least one excited
state quencher; for the protection of body care and household
products against the deleterious effects of light, heat and
oxygen.
Inventors: |
Winkler; Barbara; (Lorrach,
DE) ; Reich; Oliver; (Grenzach-Wyhlen, DE) ;
Mantler; Alexander; (Rheinfelden-Karsau, DE) ;
Schork; Michael; (Riehen, CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Winkler; Barbara
Reich; Oliver
Mantler; Alexander
Schork; Michael |
Lorrach
Grenzach-Wyhlen
Rheinfelden-Karsau
Riehen |
|
DE
DE
DE
CH |
|
|
Assignee: |
BASF SE
LUDWIGSHAFEN
DE
|
Family ID: |
39494188 |
Appl. No.: |
13/888447 |
Filed: |
May 7, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12674172 |
Feb 19, 2010 |
8454940 |
|
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PCT/EP2008/060797 |
Aug 18, 2008 |
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13888447 |
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Current U.S.
Class: |
424/59 ; 106/270;
252/589; 424/61; 424/63; 424/64; 424/70.1; 424/70.7; 510/109;
510/119; 510/500; 510/513; 512/2 |
Current CPC
Class: |
C09K 15/30 20130101;
A61Q 17/04 20130101; C11D 3/30 20130101; C11D 3/32 20130101; A61K
8/46 20130101; C11D 3/2086 20130101; A61K 8/40 20130101; A61K 8/41
20130101; C11D 3/42 20130101; C11D 3/349 20130101; C11D 3/2072
20130101; A61K 8/496 20130101 |
Class at
Publication: |
424/59 ;
424/70.1; 424/64; 424/63; 424/70.7; 424/61; 512/2; 510/109;
510/500; 510/119; 510/513; 252/589; 106/270 |
International
Class: |
C09K 15/30 20060101
C09K015/30 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 24, 2007 |
EP |
07114913.2 |
Claims
1. A stabilizing composition for the protection of body care and
household products against the deleterious effects of light, heat
and oxygen comprising (a) an effective stabilizing amount of at
least one merocyanine derivative having an absorption maximum of
350 to 400 nm, and (b) at least one UV filter selected from
benzotriazole derivatives; and optionally (c) at least one excited
state quencher; and optionally (d) at least one salicylate.
2. A composition according to claim 1, wherein (a) corresponds to
compounds of formula (1) ##STR00114## wherein R.sub.1 and R.sub.2
independently of each other are hydrogen; C.sub.1-C.sub.22alkyl;
C.sub.2-C.sub.22 alkenyl, C.sub.2-C.sub.22alkinyl,
C.sub.3-C.sub.12cycloalkyl, C.sub.3-C.sub.12cycloalkenyl,
C.sub.7-C.sub.20aralkyl, C.sub.1-C.sub.20heteroalkyl,
C.sub.3-C.sub.12cycloheteroalkyl, C.sub.5-C.sub.11heteroaralkyl,
C.sub.6-C.sub.20aryl, C.sub.4-C.sub.9heteroaryl, COR.sub.13 or
CONR.sub.13R.sub.14; R.sub.3 is CN; --COOR.sub.5; --CONHR.sub.5;
--COR.sub.5; --SO.sub.2R.sub.5; --CONR.sub.5R.sub.6;
C.sub.6-C.sub.20aryl; or C.sub.4-C.sub.9heteroaryl; R.sub.4 is CN;
--COOR.sub.7; --CONHR.sub.7; --COR.sub.7; --SO.sub.2R.sub.7;
--CONR.sub.7R.sub.8; C.sub.1-C.sub.22 alkyl;
C.sub.2-C.sub.22alkenyl; C.sub.2-C.sub.22 alkinyl;
C.sub.3-C.sub.12cycloalkyl; C.sub.3-C.sub.12cycloalkenyl;
C.sub.7-C.sub.20aralkyl; C.sub.1-C.sub.20heteroalkyl;
C.sub.3-C.sub.12cycloheteroalkyl; C.sub.5-C.sub.11 heteroaralkyl;
C.sub.6-C.sub.20 aryl; or C.sub.4-C.sub.9 heteroaryl; R.sub.5,
R.sub.6, R.sub.7 and R.sub.8 independently of each other are
hydrogen; C.sub.1-C.sub.22alkyl; C.sub.2-C.sub.22alkenyl;
C.sub.2-C.sub.22 alkinyl; C.sub.3-C.sub.12cycloalkyl;
C.sub.3-C.sub.12cycloalkenyl; C.sub.7-C.sub.20aralkyl;
C.sub.1-C.sub.20heteroalkyl; C.sub.3-C.sub.12cycloheteroalkyl;
C.sub.5-C.sub.11heteroaralkyl; C.sub.6-C.sub.20aryl;
C.sub.4-C.sub.9heteroaryl; SiR.sub.15R.sub.16R.sub.17;
Si(OR.sub.15)(OR.sub.16)(OR.sub.17);
SiR.sub.15(OR.sub.16)(OR.sub.17); SiR.sub.15R.sub.16(OR.sub.17); or
a radical --XS; L.sub.1, L.sub.2 and L.sub.3 independently of each
other are hydrogen; C.sub.1-C.sub.22alkyl; C.sub.2-C.sub.22alkenyl;
C.sub.2-C.sub.22alkinyl; C.sub.3-C.sub.12cycloalkyl;
C.sub.3-C.sub.12cycloalkenyl; C.sub.7-C.sub.20aralkyl;
C.sub.1-C.sub.20heteroalkyl; C.sub.3-C.sub.12cycloheteroalkyl;
C.sub.5-C.sub.11heteroaralkyl; C.sub.6-C.sub.20 aryl;
C.sub.4-C.sub.9heteroaryl; CN; OH; OR.sub.9; or COOR.sub.9; R.sub.9
is hydrogen; C.sub.1-C.sub.22alkyl; C.sub.2-C.sub.22alkenyl;
C.sub.2-C.sub.22alkinyl; C.sub.3-C.sub.12cycloalkyl;
C.sub.3-C.sub.12cycloalkenyl; C.sub.7-C.sub.20aralkyl;
C.sub.1-C.sub.20heteroalkyl; C.sub.3-C.sub.12cycloheteroalkyl;
C.sub.5-C.sub.11heteroaralkyl; C.sub.6-C.sub.20 aryl; or
C.sub.4-C.sub.9heteroaryl; or L.sub.1 and L.sub.2, L.sub.1 and
L.sub.3, L.sub.2 and L.sub.3, L.sub.1 and R.sub.4, L.sub.2 and
R.sub.4, L.sub.1 and R.sub.1, L.sub.2 and R.sub.1, L.sub.3 and
R.sub.1, L.sub.3 and R.sub.5, R.sub.3 and R.sub.4, R.sub.1 and
R.sub.2, R.sub.7 and R.sub.8, R.sub.5 and R.sub.6 may be linked
together to form 1, 2, 3 or 4 carbocyclic or N, O and/or
S-heterocyclic rings, which may be further fused with other
aromatic rings; R.sub.10 represents R.sub.13; COR.sub.13;
COOR.sub.13; CONH.sub.2, CONHR.sub.13; or CONR.sub.13R.sub.14;
R.sub.11 represents halogen; OH; NH.sub.2; NHR.sub.15;
NR.sub.15R.sub.16; NR.sub.15OR.sub.16; O--R.sub.15;
O--CO--R.sub.15; S--R.sub.15; CO--R.sub.15; oxo; thiono; CN; COOH;
CONH.sub.2; COOR.sub.15; CONHR.sub.15; CONR.sub.15R.sub.16;
SO.sub.2NH.sub.2; SO.sub.2NHR.sub.15; SO.sub.2NR.sub.15R.sub.16;
SO.sub.2R.sub.15; SO.sub.3R.sub.15; SiR.sub.15R.sub.16R.sub.17;
SiOR.sub.15(OR.sub.16)(OR.sub.17);
SiR.sub.15(OR.sub.16)(OR.sub.17); SiR.sub.15R.sub.16(OR.sub.17);
O--Si--R.sub.15R.sub.16R.sub.17;
O--Si--OR.sub.15(OR.sub.16)(OR.sub.17);
O--Si--R.sub.15R.sub.16(OR.sub.17);
O--SiR.sub.15(OR.sub.16)(OR.sub.17); PO(OR.sub.15)(OR.sub.16); or a
radical *--XS; R.sub.12 represents halogen, CN, SH, OH, CHO,
R.sub.18; OR.sub.18; SR.sub.18; C(R.sub.18).dbd.CR.sub.19R.sub.20;
O--CO--R.sub.19; NHR.sub.19; NR.sub.18R.sub.19; CONH.sub.2;
CONHR.sub.18, CONR.sub.18R.sub.19; SO.sub.2NH.sub.2;
SO.sub.2NHR.sub.18; SO.sub.2NR.sub.18R.sub.19; SO.sub.2R.sub.18;
COOH; COOR.sub.18; OCOOR.sub.18; NHCOR.sub.18; NR.sub.18COR.sub.19;
NHCOOR.sub.19; NR.sub.19COOR.sub.20; SiR.sub.15R.sub.16R.sub.17;
SiOR.sub.15(OR.sub.16)(OR.sub.17);
SiR.sub.15(OR.sub.16)(OR.sub.17); SiR.sub.15R.sub.16(OR.sub.17);
OSiR.sub.15R.sub.16R.sub.17; OSiOR.sub.15(OR.sub.16)(OR.sub.17);
OSiR.sub.15R.sub.16(OR.sub.17); OSiR.sub.15(OR.sub.16)(OR.sub.17);
P(.dbd.O)OR.sub.19OR.sub.20; P(.dbd.O)R.sub.19OR.sub.20;
P(.dbd.O)R.sub.19R.sub.20; or a radical *--XS; or is selected from
the group consisting of C.sub.1-C.sub.22alkyl;
C.sub.3-C.sub.12cycloalkyl; C.sub.1-C.sub.12alkenyl;
C.sub.3-C.sub.12cycloalkenyl; C.sub.1-C.sub.12alkylthio;
C.sub.3-C.sub.12cycloalkylthio; C.sub.1-C.sub.12alkenylthio;
C.sub.3-C.sub.12cycloalkenylthio; C.sub.1-C.sub.12alkoxy;
C.sub.3-C.sub.12cycloalkoxy; C.sub.1-C.sub.12alkenyloxy; and
C.sub.3-C.sub.12cycloalkenyloxy, which may be unsubstituted or
substituted by one or more, identical or different R.sub.11;
R.sub.13, R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18,
R.sub.19 and R.sub.20 independently of each other are
C.sub.1-C.sub.22alkyl; C.sub.3-C.sub.12cycloalkyl;
C.sub.2-C.sub.12alkenyl; C.sub.3-C.sub.12cycloalkenyl;
C.sub.6-C.sub.14aryl; C.sub.4-C.sub.12heteroaryl;
C.sub.7-C.sub.18aralkyl or C.sub.5-C.sub.16heteroaralkyl; or
R.sub.13 and R.sub.14, R.sub.15 and R.sub.16, R.sub.16 and R.sub.17
and/or R.sub.18 and R.sub.19 may be linked together to form
unsubstituted or C.sub.1-C.sub.4alkyl substituted pyrrolidine,
piperidine, piperazine or morpholine; X represents a linker; S
signifies a silane-, oligosiloxane- or polysiloxane-moiety; the
term "oligosiloxane" denotes a group of formula
Si(R.sub.15).sub.m[OSi(R.sub.16)].sub.o wherein m has a value of 0,
1 or 2, o has a value of 3, 2 or 1; and m+o have a value of 3 or
refers to groups of formula (1a) or (b) ##STR00115## wherein A
represents a bond to the linker X; and p has a value of 1 to 9; the
term "polysiloxane" refers in this context to groups of formula
(1c) or (1d) ##STR00116## wherein A represents a bond to the linker
X; s has a value of 4 to 250; t has a value of 5 to 250; q has a
value of 1 to 30; n is 1 or integer; n is from 1 to 6; when n=2,
R.sub.1, R.sub.5 or R.sub.4 is a bivalent alkyl group; or R.sub.1
and R.sub.2 together with the 2 nitrogen atoms linking them form a
unsubstituted or alkyl-substituted ##STR00117## ring; v is from 1
to 4, w is from 1 to 4; when n=3, R.sub.1, R.sub.5 or R.sub.4 is a
trivalent alkyl group; when n=4, R.sub.1, R.sub.5 or R.sub.4 is a
tetravalent alkyl group; and R.sub.1 and R.sub.2 in formula (1) are
not simultaneously hydrogen.
3. A composition according to claim 2, wherein in formula (1)
R.sub.1 and R.sub.2 independently of each other are hydrogen;
COR.sub.13; or C.sub.1-C.sub.22alkyl; R.sub.3 is CN; --COOR.sub.5;
or --SO.sub.2R.sub.5; R.sub.5 is hydrogen; C.sub.1-C.sub.22alkyl;
C.sub.6-C.sub.20aryl; or the radical *--X--S; L.sub.1, L.sub.2 and
L.sub.3 independently of each other are hydrogen; or
C.sub.1-C.sub.22alkyl; or L.sub.1 and L.sub.2, L.sub.1 and L.sub.3,
L.sub.2 and L.sub.3, may be linked together to form a carbocyclic
ring comprising 6 to 10 carbon atoms, which may be further fused
with other aromatic rings; and which may be further substituted by
one or more than one C.sub.1-C.sub.4alkyl; X represents a linker; S
refers to groups of formula (2a) ##STR00118## wherein R.sub.15,
R.sub.16 and R.sub.17 independently from each other are
C.sub.1-C.sub.22alkyl; or the radical
*--OSi(R.sub.18)((R.sub.19)(R.sub.20); R.sub.18, R.sub.19 and
R.sub.20 independently of each other are C.sub.1-C.sub.22alkyl; A
represents a bond to the linker X; and p has a value of 1 to 9.
4. A composition according to claim 1, wherein component (a)
corresponds to at least one compound of formula (2) ##STR00119##
wherein R.sub.1 and R.sub.2, independently from each other are
hydrogen; or C.sub.1-C.sub.12alkyl; R.sub.3 is COOR.sub.5; or --CN;
R.sub.4 is --CN; and R.sub.6 and R.sub.7 independently from each
other are hydrogen; or C.sub.1-C.sub.3alkyl.
5. A composition according to claim 1, wherein component (a)
corresponds to at least one compound of formula (3) ##STR00120##
wherein R.sub.1 and R.sub.2, independently from each other are
hydrogen; or C.sub.1-C.sub.12alkyl; R.sub.3 is --CN; or COOR.sub.5;
R.sub.4 and R.sub.5, independently from each other are
C.sub.1-C.sub.22alkyl; or a radical *--X--S; X represents a linker;
S refers to groups of formula (1a) ##STR00121## wherein R.sub.15,
R.sub.16 and R.sub.17 independently of each other are
C.sub.1-C.sub.22alkyl; A represents a bond to the linker X; and p
has a value of 1 to 9.
6. A composition according to claim 1, wherein component (a)
corresponds to a compound of formula (MC-03) ##STR00122##
7. A composition according to claim 1, wherein component (a)
corresponds to a compound of formula (MC-08) ##STR00123##
8. A composition according to claim 1, wherein component (b) is at
least one benzotriazole of formula (4) ##STR00124## wherein R.sub.1
is C.sub.1-C.sub.30alkyl; C.sub.1-C.sub.5alkoxy;
C.sub.1-C.sub.5alkoxycarbonyl; C.sub.5-C.sub.7cycloalkyl;
C.sub.6-C.sub.10aryl; aralkyl; --SO.sub.3M; or a radical of formula
(4a); ##STR00125## R.sub.3 is hydrogen; C.sub.1-C.sub.5alkyl;
C.sub.1-C.sub.5alkoxy; halogen; or hydroxy; R.sub.4 and R.sub.5
each independently of the other are hydrogen; or
C.sub.1-C.sub.5alkyl; m is 1 or 2; n is 0 or 1; if m=1, R.sub.2 is
hydrogen; unsubstituted or phenyl-substituted
C.sub.1-C.sub.12alkyl; or C.sub.6-C.sub.10aryl; if m=2, R.sub.2 is
the direct bond; or --(CH.sub.2).sub.p--; and p is 1 to 3.
9. A composition according to claim 1, wherein component (b) is at
least one benzotriazole of formula (5) ##STR00126## wherein R.sub.1
is a random statistical mixture of at least three isomeric branched
secondary alkyl groups each having 8 to 30 carbon atoms of the
radical ##STR00127## E.sub.1 is a straight-chain
C.sub.1-C.sub.14alkyl; E.sub.2 is a straight-chain
C.sub.4-C.sub.15alkyl; wherein the total number of carbon atoms in
E.sub.1 plus E.sub.2 is from 7 to 29; and R.sub.2 is
C.sub.1-C.sub.5alkyl.
10. A composition according to claim 1, wherein component (b) is
2-(2H-benzotriazol-2-yl)-6-dodecycl-4-methyl-phenol, (BT-01)
##STR00128##
11. A composition according to claim 1, wherein component (a)
corresponds a compound of formula (MC-03) ##STR00129## and
component (b) corresponds to a compound of formula (BT-01)
##STR00130##
12. A composition according to claim 1, comprising component (c)
which is at least one quencher selected from (c.sub.1) hindered
nitroxyl compounds of formula (6a); ##STR00131## (c.sub.2) hindered
hydroxylamine compounds of formula (6b) ##STR00132## and (c.sub.3)
hindered hydroxylamine salt compounds of formula (6c) ##STR00133##
wherein G.sub.1 and G.sub.2 independently from each other are
C.sub.1-C.sub.4alkyl alkyl; or are together pentamethylene, Z.sub.1
and Z.sub.2 are each methyl; or Z.sub.1 and Z.sub.2 together form a
linking moiety which may additionally be substituted by an ester,
ether, hydroxy, oxo, cyanohydrine, amide, amino, carboxy or
urethane group; X is an inorganic or organic anion selected from
phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride,
bromide, bisulfite, sulfite, bisulfate, sulfate, borate, formate,
acetate, benzoate, citrate, oxalate, tartrate, acrylate,
polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate,
malate, mandelate, tiglate, ascorbate, polymethacrylate, a
carboxylate of nitrilotriacetic acid,
hydroxyethylethylenediaminetriacetic acid,
ethylene-diaminetetraacetic acid or of
diethylenetriaminepentaacetic acid, a
diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or
an arylsulfonate; and where the total charge of cations h is equal
to the total charge of anions j.
13. A composition according to claim 12, wherein component (c)
corresponds to a compound of formula (ESS-01) ##STR00134##
14. A composition according to claim 1, comprising component (d),
which is at least one salicylate selected from salicylic acid,
homosalate, 2-ethylhexyl salicylate, benzyl salicylate, ethyl
salicylate, methyl salicylate, isoamyl salicylate, acetylsalicylic
acid and isobutyl salicylate.
15. A composition according to claim 1, wherein the component (a)
corresponds to a compound of formula (MC-03); ##STR00135##
component (b) corresponds to a compound of formula (BT-01)
##STR00136## and component (c) corresponds to a compound of formula
(ESS-01) ##STR00137##
16. A composition according to claim 1, wherein component (a)
corresponds a compound of formula (MC-03); ##STR00138## component
(b) corresponds to a compound of formula (BT-01) ##STR00139## and
component (d) corresponds to a compound of formula ##STR00140##
17. A body-care or a household product comprising a stabilizing
composition according to claim 1, wherein the stabilizing
composition is present in the body-care or household product in a
concentration of about 5 to about 50000 ppm.
18. A stabilizing composition according to claim 1, wherein the
weight ratio of component (a) to component (b) is from 20:1 to
1:20.
19. A stabilizing composition according to claim 1, wherein the
weight ratio of component (a) to component (c) is from 1:1 to
1000:1.
20. A product according to claim 17, wherein the body-care product
is selected from skin-care products, bath or shower additives,
preparations containing fragrances or odoriferous substances,
hair-care products, dentifrices, deodorizing or antiperspirant
preparations, decorative preparations, light protection
formulations and preparations containing active ingredients and
wherein the household product is selected from washing, rinsing or
dishwashing agents, shoe polishes, polishing waxes, floor
detergents or polishes, all purpose cleaners, bath or toilet
cleaners, kitchen cleaners, car shampoos or waxes, neutral, acidic
or alkaline cleaners, metal, glass or ceramic cleaners, textile
care agents, agents for removing rust, color or stains (stain
remover salt), bleaches, furniture or multipurpose polishes,
surface protecting formulations, film forming formulations, air
care formulations and candles.
Description
[0001] This application is a divisional of U.S. application Ser.
No. 12/674,172, filed Feb. 19, 2010, granted which is a national
stage of PCT/EP2008/060796, filed Aug. 18, 2008, the contents of
both herein incorporated entirely by reference.
[0002] The present invention relates to the use of merocyanine
compounds having an absorption maximum of 350 to 400 nm and
2-hydroxyphenyl benzotriazole UV filters for the protection of body
care and household products against the deleterious effects of
light, heat and oxygen.
[0003] The present invention also relates to a mixture of at least
one merocyanine having an absorption maximum of 350 to 400 nm and
of at least one 2-hydroxyphenyl benzotriazole UV filter and
optionally at least one excited state quencher.
[0004] Since consumers can choose from a large variety of Home
& Personal Care products, producers need to communicate clearly
how their brands are unique. Sophisticated products containing new
fragrances and actives in many colourful formulations, displayed in
transparent and translucent packaging are very common.
[0005] It is mandatory for commercial success that the pleasant
appearance, product efficacy and the fresh smell of a consumer
product will last during its whole product life cycle even when
exposed heavily to UV-light. This exposure can result in
decomposition processes and strong color fading destroying the
product appearance, active ingredients and fragrances.
[0006] Various stabilization techniques of clear packaged products
by absorption of UV light are commonly used and well known. For
example broad-band UV light stabilizers of the benzotriazole class
enhance product's stability and shelf live due to their very good
UV-A and UV-B absorption properties.
[0007] The most effective stabilizers known as of today to prevent
or delay light induced fading of transparent packaged products are
e.g. benzotriazoles like known under the trade names Ciba TINOGARD
HS or Ciba TINOGARD TL. These proved to be very effective, due to
their broadband absorption properties and strong extinction in the
UV-A range.
[0008] WO 2004/006878, WO 2005/058269, WO 2006/016806 A1, WO
2006/009451, WO 2006/125676 A1 and WO 2006/032741 A1 disclose
merocyanine UV-A absorbers and their use for protecting human and
animal hair and skin from UV radiation as well as their application
in cosmetic and dermatological formulations.
[0009] WO 2007/014848 discloses various merocyanine structures
which have superior properties in stabilizing cosmetic and
dermatological formulations and household products.
[0010] These references also describe that the merocyanine UV
absorbers can be mixed with any other UV filter substance.
[0011] It was now surprisingly found that the combination of
specific merocyanine derivatives which have an absorption maximum
in the range of 350 to 400 nm with benzotriazole UV-B filters and
optionally with at least one excited state quencher have
outstanding stabilizing properties.
[0012] Therefore, the present invention relates to the use of
stabilizing composition comprising [0013] (a) an effective
stabilizing amount of at least one merocyanine derivative having an
absorption maximum of 350 to 400 nm, and [0014] (b) at least one UV
filter selected from benzotriazole derivatives; and optionally
[0015] (c) at least one excited state quencher; and optionally
[0016] (d) a salicylate; for the protection of body care and
household products against the deleterious effects of light, heat
and oxygen.
[0017] Examples of merocyanine compounds which correspond to
component (a) are disclosed in WO 2004/006878, WO 2005/058269, WO
2006/016806, WO 2006/009451, WO 2006/125676, WO 2006/032741 and WO
2007/081209.
[0018] The merocyanine compounds of component (a) preferably
correspond to the compounds of formula
(a) corresponds to the compounds of formula
##STR00001##
wherein [0019] R.sub.1 and R.sub.2 independently of each other are
hydrogen; C.sub.1-C.sub.22alkyl; C.sub.2-C.sub.22 alkenyl,
C.sub.2-C.sub.22alkinyl, C.sub.3-C.sub.12cycloalkyl,
C.sub.3-C.sub.12cycloalkenyl, C.sub.7-C.sub.20aralkyl,
C.sub.1-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl,
C.sub.5-C.sub.11heteroaralkyl, C.sub.6-C.sub.20aryl,
C.sub.4-C.sub.9heteroaryl, COR.sub.13 or CONR.sub.13R.sub.14;
[0020] R.sub.3 is CN; --COOR.sub.5; --CONHR.sub.5; --COR.sub.5;
--SO.sub.2R.sub.5; --CONR.sub.5R.sub.6, C.sub.6-C.sub.20aryl; or
C.sub.4-C.sub.9 heteroaryl; [0021] R.sub.4 is CN; --COOR.sub.7;
--CONHR.sub.7; --COR.sub.7; --SO.sub.2R.sub.7; --CONR.sub.7R.sub.8;
C.sub.1-C.sub.22 alkyl; C.sub.2-C.sub.22alkenyl; C.sub.2-C.sub.22
alkinyl; C.sub.3-C.sub.12cycloalkyl; C.sub.3-C.sub.12cycloalkenyl;
C.sub.7-C.sub.20aralkyl; C.sub.1-C.sub.20heteroalkyl;
C.sub.3-C.sub.12cycloheteroalkyl; C.sub.5-C.sub.11 heteroaralkyl;
C.sub.6-C.sub.20 aryl; or C.sub.4-C.sub.9 heteroaryl; [0022]
R.sub.5, R.sub.6, R.sub.7 and R.sub.8 independently of each other
are hydrogen; C.sub.1-C.sub.22alkyl; C.sub.2-C.sub.22alkenyl;
C.sub.2-C.sub.22 alkinyl; C.sub.3-C.sub.12cycloalkyl;
C.sub.3-C.sub.12cycloalkenyl; C.sub.7-C.sub.20aralkyl;
C.sub.1-C.sub.20heteroalkyl, C.sub.3-C.sub.12cycloheteroalkyl;
C.sub.5-C.sub.11heteroaralkyl; C.sub.6-C.sub.20aryl;
C.sub.4-C.sub.9heteroaryl; SiR.sub.15R.sub.16R.sub.17;
Si(OR.sub.15)(OR.sub.16)(OR.sub.17);
SiR.sub.15(OR.sub.16)(OR.sub.17); SiR.sub.15R.sub.16(OR.sub.17); or
a radical --XS; [0023] L.sub.1, L.sub.2 or L.sub.3 independently of
each other are hydrogen, C.sub.1-C.sub.22alkyl;
C.sub.2-C.sub.22alkenyl, C.sub.2-C.sub.22alkinyl;
C.sub.3-C.sub.12cycloalkyl; C.sub.3-C.sub.12cycloalkenyl;
C.sub.7-C.sub.20aralkyl; C.sub.1-C.sub.20heteroalkyl;
C.sub.3-C.sub.12cycloheteroalkyl; C.sub.5-C.sub.11heteroaralkyl;
C.sub.6-C.sub.20 aryl; C.sub.4-C.sub.9heteroaryl; CN; OH; OR.sub.9;
or COOR.sub.5; [0024] R.sub.9 is hydrogen; C.sub.1-C.sub.22alkyl;
C.sub.2-C.sub.22alkenyl; C.sub.2-C.sub.22alkinyl;
C.sub.3-C.sub.12cycloalkyl; C.sub.3-C.sub.12cycloalkenyl;
C.sub.7-C.sub.20aralkyl; C.sub.1-C.sub.20heteroalkyl;
C.sub.3-C.sub.12cycloheteroalkyl; C.sub.5-C.sub.11heteroaralkyl;
C.sub.6-C.sub.20 aryl; or C.sub.4-C.sub.9heteroaryl; [0025] L.sub.1
and L.sub.2, L.sub.1 and L.sub.3, L.sub.2 and L.sub.3, L.sub.1 and
R.sub.4, L.sub.2 and R.sub.4, L.sub.1 and R.sub.1, L.sub.2 and
R.sub.1, L.sub.3 and R.sub.1, L.sub.3 and R.sub.5, R.sub.3 and
R.sub.4, R.sub.1 and R.sub.2, R.sub.7 and R.sub.8, R.sub.5 and
R.sub.6 may be linked together to form 1, 2, 3 or 4 carbocyclic or
N, O and/or S-heterocyclic rings, which may be further fused with
other aromatic rings; [0026] R.sub.10 represents R.sub.13;
COR.sub.13; COOR.sub.13; CONH.sub.2; CONHR.sub.13; or
CONR.sub.13R.sub.14; [0027] R.sub.11 represents halogen; OH;
NH.sub.2; NHR.sub.15; NR.sub.15R.sub.16; NR.sub.15OR.sub.16;
O--R.sub.15; O--CO--R.sub.15; S--R.sub.15; CO--R.sub.15; oxo;
thiono; CN; COOH; CONH.sub.2; COOR.sub.15; CONHR.sub.15;
CONR.sub.15R.sub.16; SO.sub.2NH.sub.2; SO.sub.2NHR.sub.15;
SO.sub.2NR.sub.15R.sub.16; SO.sub.2R.sub.15; SO.sub.3R.sub.15;
SiR.sub.15R.sub.16R.sub.17; SiOR.sub.15(OR.sub.16)(OR.sub.17);
SiR.sub.15(OR.sub.16)(OR.sub.17); SiR.sub.15R.sub.16(OR.sub.17);
O--Si--R.sub.15R.sub.16R.sub.17;
O--Si--OR.sub.15(OR.sub.16)(OR.sub.17);
O--Si--R.sub.15R.sub.16(OR.sub.17);
O--SiR.sub.15(OR.sub.16)(OR.sub.17); PO(OR.sub.15)(OR.sub.16); or a
radical *--XS; [0028] R.sub.12 represents halogen, CN, SH, OH, CHO,
R.sub.18; OR.sub.18; SR.sub.18; C(R.sub.18).dbd.CR.sub.19R.sub.20;
O--CO--R.sub.19; NHR.sub.19; NR.sub.18R.sub.19; CONH.sub.2;
CONHR.sub.18; CONR.sub.18R.sub.19; SO.sub.2NH.sub.2;
SO.sub.2NHR.sub.18; SO.sub.2NR.sub.18R.sub.19; SO.sub.2R.sub.18;
COOH; COOR.sub.18; OCOOR.sub.18; NHCOR.sub.18; NR.sub.18COR.sub.19;
NHCOOR.sub.19; NR.sub.19COOR.sub.20; SiR.sub.15R.sub.16R.sub.17;
SiOR.sub.15(OR.sub.16)(OR.sub.17);
SiR.sub.15(OR.sub.16)(OR.sub.17); SiR.sub.15R.sub.16(OR.sub.17);
OSiR.sub.15R.sub.16R.sub.17; OSiOR.sub.15(OR.sub.16)(OR.sub.17);
OSiR.sub.15R.sub.16(OR.sub.17); OSiR.sub.15(OR.sub.16)(OR.sub.17);
P(.dbd.O)OR.sub.19OR.sub.20; P(.dbd.O)R.sub.19OR.sub.20;
P(.dbd.O)R.sub.19R.sub.20; or a radical --XS; or is selected from
the group consisting of C.sub.1-C.sub.22alkyl;
C.sub.3-C.sub.12cycloalkyl; C.sub.1-C.sub.12alkenyl;
C.sub.3-C.sub.12cycloalkenyl; C.sub.1-C.sub.12alkylthio;
C.sub.3-C.sub.12cycloalkylthio; C.sub.1-C.sub.12alkenylthio;
C.sub.3-C.sub.12cycloalkenylthio; C.sub.1-C.sub.12alkoxy;
C.sub.3-C.sub.12cycloalkoxy; C.sub.1-C.sub.12alkenyloxy; or
C.sub.3-C.sub.12cycloalkenyloxy, which may be unsubstituted or
substituted by one or more, identical or different R.sub.11; [0029]
R.sub.13, R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18,
R.sub.19 and R.sub.20 independently of each other are
C.sub.1-C.sub.22alkyl; C.sub.3-C.sub.12cycloalkyl;
C.sub.2-C.sub.12alkenyl; C.sub.3-C.sub.12cycloalkenyl;
C.sub.6-C.sub.14aryl; C.sub.4-C.sub.12heteroaryl;
C.sub.7-C.sub.18aralkyl or C.sub.5-C.sub.16heteroaralkyl; or [0030]
R.sub.13 and R.sub.14, R.sub.15 and R.sub.16, R.sub.16 and R.sub.17
and/or R.sub.18 and R.sub.19 may be linked together to form
unsubstituted or with C.sub.1-C.sub.4alkyl substituted pyrrolidine,
piperidine, piperazine or morpholine; [0031] X represents a linker;
[0032] S signifies a silane-, oligosiloxane- or
polysiloxane-moiety; the term "oligosiloxane" denotes a group of
the general formula Si(R.sub.15).sub.m[OSi(R.sub.16)].sub.3 wherein
[0033] m has a value of 0, 1 or 2, [0034] o has a value of 3, 2 or
1; and m+o have a value of 3 or refers to groups of the general
formula
[0034] ##STR00002## [0035] wherein [0036] A represents a bond to
the linker X; and [0037] p has a value of 1 to 9; the term
"polysiloxane" refers in this context to groups of the general
formula
##STR00003##
[0037] wherein [0038] A represents a bond to the linker X; [0039] s
has a value of 4 to 250; [0040] t has a value of 5 to 250; [0041] q
has a value of 1 to 30; [0042] n is 1 or integer; [0043] n is from
1 to 6; [0044] when n=2, R.sub.1, R.sub.5 or R.sub.4 is a bivalent
alkyl group; or R.sub.1 and R.sub.2 together with the 2 nitrogen
atoms linking them form a unsubstituted or alkyl-substituted
##STR00004##
[0044] -ring; [0045] v is from 1 to 4, [0046] w is from 1 to 4;
[0047] when n=3, R.sub.1, R.sub.5 or R.sub.4 is a trivalent alkyl
group; [0048] when n=4, R.sub.1, R.sub.5 or R.sub.4 is a
tetravalent alkyl group; and [0049] R.sub.1 and R.sub.2 in formula
(1) are not simultaneously hydrogen.
[0050] Halogen is chloro, bromo, fluoro or iodo, preferably fluoro,
more preferably fluoroalkyl (for example trifluoromethyl,
.alpha.,.alpha.,.alpha.-trifluoroethyl or perfluorinated alkyl
groups like heptafluoropropyl).
[0051] Alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl
residues can be straight-chain or branched, or also monocyclic or
polycyclic.
[0052] Alkyl can be for example methyl, straight-chain
C.sub.2-C.sub.22alkyl or preferably branched
C.sub.3-C.sub.22alkyl.
[0053] Alkenyl can be e.g. straight-chain C.sub.2-C.sub.22alkenyl
or preferably branched C.sub.3-C.sub.22alkenyl.
[0054] C.sub.1-C.sub.22alkyl is for example methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl,
n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl,
1,1,3,3-tetra-methylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl,
eicosyl, cetyl-, myristyl- or dodecyl.
[0055] C.sub.3-C.sub.12cycloalkyl is for example cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl,
thujyl, bornyl, 1-adamantyl or 2-adamantyl.
[0056] C.sub.2-C.sub.22alkenyl or C.sub.3-C.sub.12cycloalkenyl
refers to unsaturated hydrocarbon residues containing one or
multiple double bonds such vinyl, allyl, 2-propene-2-yl,
2-butene-1-yl, 3-butene-1-yl, 1,3-butadiene-2-yl,
2-cyclobutene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl,
2-methyl-1-butene-3-yl, 2-methyl-3-butene-2-yl,
3-methyl-2-butene-1-yl, 1,4-pentadiene-3-yl, 2-cyclopentene-1-yl,
2-cyclohexene-1-yl, 3-cyclohexene-1-yl, 2,4-cyclohexadiene-1-yl,
1-p-menthene-8-yl, 4(10)-thujen-10-yl, 2-norbornene-1-yl,
2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaradiene-3-yl or
signifies different isomers of hexenyl, octenyl, nonenyl, decenyl
or dodecenyl.
[0057] C.sub.7-C.sub.20aralkyl is for example benzyl,
2-benzyl-2-propyl, .beta.-phenyl-ethyl, 9-fluorenyl,
.alpha.,.alpha.-dimethylbenzyl, .omega.-phenyl-butyl,
.omega.-phenyl-octyl, .omega.-phenyl-dodecyl or
3-methyl-5-(1',1',3',3'-tetramethyl-butyl)-benzyl.
[0058] A C.sub.7-C.sub.20aralkyl moiety can be unsubstituted or
substituted at the alkyl- as well at the aryl-moiety of the
aralkyl-group, but preferably substituted at the aryl-moiety.
[0059] (C.sub.1-C.sub.6)-alkylidene signifies for example
methylene, ethyl-1-ene, propyl-2-ene.
[0060] C.sub.6-C.sub.20aryl is for example phenyl, naphthyl,
biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or
terphenylyl.
[0061] C.sub.4-C.sub.12heteroaryl signifies a unsaturated or
aromatic radical with 4n+2 conjugated .pi.-electrons, such as
2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl,
2-imidazolyl, iso-thiazolyl, triazolyl or any other ring system
consisting of thiophene-, furan-, pyridine, thiazole, oxazole,
imidazole, isothiazole, triazole, pyridine- and phenyl rings, which
are unsubstituted or substituted with 1 to 6 ethyl, methyl,
ethylene and/or methylene groups, such as benzotriazolyl.
[0062] C.sub.5-C.sub.16heteroaralkyl signifies for example a
C.sub.1-C.sub.8 alkyl moiety which is substituted with a
C.sub.4-C.sub.8heteroaryl group.
[0063] Preferably merocyanines of formula (1) are used, wherein
[0064] R.sub.1 and R.sub.2 independently of each other are
hydrogen; COR.sub.13; or C.sub.1-C.sub.22alkyl; [0065] R.sub.3 is
CN; --COOR.sub.5; or --SO.sub.2R.sub.5; [0066] R.sub.5 is hydrogen;
C.sub.1-C.sub.22alkyl; C.sub.6-C.sub.20aryl; or the radical
*--X--S; [0067] L.sub.1, L.sub.2 or L.sub.3 independently of each
other are hydrogen; or C.sub.1-C.sub.22alkyl; or [0068] L.sub.1 and
L.sub.2, L.sub.1 and L.sub.3, L.sub.2 and L.sub.3, may be linked
together to form a carbocyclic ring comprising 6 to 10 carbon
atoms, which may be further fused with other aromatic rings; and
which may be further substituted by one or more than one
C.sub.1-C.sub.4alkyl; [0069] X represents a linker; [0070] S refers
to groups of the general formula
##STR00005##
[0070] wherein [0071] R.sub.15, R.sub.16 and R.sub.17 independently
from each other are C.sub.1-C.sub.22alkyl; or the radical
*--OSi(R.sub.18)((R.sub.19)(R.sub.20); [0072] R.sub.18, R.sub.19
and R.sub.20 independently of each other are C.sub.1-C.sub.22alkyl;
[0073] A represents a bond to the linker X; and [0074] p has a
value of 1 to 9.
[0075] More preferably merocyanines of formula
##STR00006##
wherein [0076] R.sub.1 and R.sub.2, independently from each other
are hydrogen; or C.sub.1-C.sub.12alkyl; [0077] R.sub.3 is
COOR.sub.5; or --CN; [0078] R.sub.4 is --CN; and [0079] R.sub.6 and
R.sub.7 independently from each other are hydrogen; or
C.sub.1-C.sub.3alkyl.
[0080] Furthermore, more preferably merocyanines of formula
##STR00007##
wherein [0081] R.sub.1 and R.sub.2, independently from each other
are hydrogen; or C.sub.1-C.sub.12alkyl; [0082] R.sub.3 is --CN; or
COOR.sub.5; [0083] R.sub.4 and R.sub.5, independently from each
other are C.sub.1-C.sub.22alkyl; or a radical *--X--S; [0084] X
represents a linker; [0085] S refers to groups of the general
formula
##STR00008##
[0085] wherein [0086] R.sub.15, R.sub.16 and R.sub.17 independently
of each other are C.sub.1-C.sub.22alkyl; [0087] A represents a bond
to the linker X; and [0088] p has a value of 1 to 9.
[0089] Most preferably component (a) the component (a) corresponds
to the formula
##STR00009##
[0090] Particularly preferred merocyanine compounds as used in the
present invention as component (a) are listed in the Table 1
below:
TABLE-US-00001 TABLE 1 Examples of preferred Merocyanine compounds
(MC-01) ##STR00010## (MC-02) ##STR00011## (MC-03) ##STR00012##
(MC-04) ##STR00013## (MC-05) ##STR00014## (MC-06) ##STR00015##
(MC-07) ##STR00016## (MC-08) ##STR00017## (MC-09) ##STR00018##
(MC-10) ##STR00019## (MC-11) ##STR00020## (MC-12) ##STR00021##
[0091] Examples of benzotriazole UV filters (component (b)) are
disclosed in WO 00/25730, WO 03070819, EP 1342748, WO 9406404 A1
and EP 796613 A1.
[0092] Preferably benzotriazole derivatives of formula
##STR00022##
wherein [0093] R.sub.1 is C.sub.1-C.sub.30alkyl;
C.sub.1-C.sub.5alkoxy; C.sub.1-C.sub.5alkoxycarbonyl;
C.sub.5-C.sub.7cycloalkyl; C.sub.6-C.sub.10aryl; aralkyl; [0094]
--SO.sub.3M; or a radical of formula
[0094] ##STR00023## [0095] R.sub.3 is hydrogen;
C.sub.1-C.sub.5alkyl; C.sub.1-C.sub.5alkoxy; halogen, preferably
Cl; or hydroxy; [0096] R.sub.4 and R.sub.5 each independently of
the other are hydrogen; or C.sub.1-C.sub.5alkyl; [0097] m is 1 or
2; [0098] n is 0 or 1; [0099] if m=1, [0100] R.sub.2 is hydrogen;
unsubstituted or phenyl-substituted C.sub.1-C.sub.12alkyl; or
C.sub.6-C.sub.10aryl; [0101] if m=2, [0102] R.sub.2 is the direct
bond; or --(CH.sub.2).sub.p--; and [0103] p is 1 to 3.
[0104] More preferably the benzotriazoles as used in the present
invention correspond to the formula
##STR00024##
wherein [0105] R.sub.1 is a random statistical mixture of at least
three isomeric branched secondary alkyl groups each having 8 to 30
carbon atoms of the radical
[0105] ##STR00025## [0106] E.sub.1 is a straight-chain
C.sub.1-C.sub.14alkyl; [0107] E.sub.2 is a straight-chain
C.sub.4-C.sub.15alkyl; wherein the total number of carbon atoms in
E.sub.1 plus E.sub.2 is from 7 to 29; and [0108] R.sub.2 is
C.sub.1-C.sub.5alkyl.
[0109] Most preferred is the benzotriazole derivative
2-(2H-benzotriazol-2-yl)-6-dodecycl-4-methyl-phenol which
corresponds to the formula
##STR00026##
[0110] Particularly preferred benzotriazole compounds (component
(b)) are listed in Table 2 below:
TABLE-US-00002 TABLE 2 Examples of preferred benzotriazole
compounds BT-01 ##STR00027## .sctn.BT-02 ##STR00028## BT-03
##STR00029## BT-04 ##STR00030## BT-05 ##STR00031## BT-06
##STR00032##
[0111] Mostly preferred is the use of a composition comprising as
component (a) the compound of formula
##STR00033##
and as component (b) the compound of formula
##STR00034##
[0112] The stabilized composition of the present invention may
additionally comprise an Excited State Quencher (ESQ.TM.)
(=component (c)). It interacts with high-energy states of
molecules, e.g. caused by UV-radiation or visible light, and
significantly reduces the probability of degradation reactions and
scavengers radical intermediates. This mechanism works
complimentarily to that of UV light stabilizers.
[0113] Examples of excited state quenchers selected from the group
of hindered amine stabilizers are disclosed in the patent
applications WO 01/07550, WO 2005/042828 A2 and U.S. Pat. No.
6,254,724.
[0114] Particularly preferred hindered amine stabilizers are [0115]
(c.sub.1) hindered nitroxyl compounds of formula
[0115] ##STR00035## [0116] (c.sub.2) hindered hydroxylamine
compounds of formula
##STR00036##
[0116] and [0117] (c.sub.3) hindered hydroxylamine salt compounds
of formula
[0117] ##STR00037## [0118] wherein [0119] G.sub.1 and G.sub.2
independently from each other are C.sub.1-C.sub.4alkyl alkyl; or
are together pentamethylene, [0120] Z.sub.1 and Z.sub.2 are each
methyl; or Z.sub.1 and Z.sub.2 together form a linking moiety which
may additionally be substituted by an ester, ether, hydroxy, oxo,
cyanohydrine, amide, amino, carboxy or urethane group, [0121] X is
an inorganic or organic anion selected from phosphate, phosphonate,
carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite,
sulfite, bisulfate, sulfate, borate, formate, acetate, benzoate,
citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate,
maleate, itaconate, glycolate, gluconate, malate, mandelate,
tiglate, ascorbate, polymethacrylate, a carboxylate of
nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid,
ethylene-diaminetetraacetic acid or of
diethylenetriaminepentaacetic acid, a
diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or
an arylsulfonate; and [0122] where the total charge of cations h is
equal to the total charge of anions j.
[0123] Examples of particularly preferred excited state stabilizers
are listed in Table 3 below:
TABLE-US-00003 TABLE 3 Preferred excited state stabilizers ESS-01
##STR00038## ESS-02 ##STR00039## ESS-03 ##STR00040## ESS-04
##STR00041## ESS-05 ##STR00042## ESS-06 ##STR00043## ESS-07
##STR00044## ESS-08 ##STR00045## ESS-09 Polycrylene CAS 866102-82-1
ESS-10 ##STR00046##
[0124] Combinations of excited state stabilizers like the compound
(ESS-01) with UV absorbers like other Tinogard UV light stabilizers
show a synergistic stabilizing effect.
[0125] This "boosting" effect allows for high demanding shelf life
enhancements as well as cost effective ingredient protection.
[0126] In the literature also excited state quenchers based on the
naphthalene structure are known.
[0127] Particularly preferred are dialkyl naphthalates structures
such as disclosed US 2002/197285, US 2006/228311 and WO
2002/087528.
[0128] Another group of particularly preferred excited state
quenchers are those based on the .beta.,.beta.-diphenylacrylate
structure which are for example described in US 2004/047818, US
2006/257338, US 2006/228311, US 2004/062726 and US 2004/057916.
[0129] The stabilizing composition comprising [0130] (a) an
effective stabilizing amount of at least one merocyanine derivative
having an absorption maximum of 350 to 400 nm, [0131] (b) at least
one UV filter selected from benzotriazole derivatives; and
optionally [0132] (c) at least one excited state quencher; and
optionally [0133] (d) at least one salicylate; is novel and
represents a further subject matter of the present invention.
[0134] Particularly preferred mixtures are listed in Table 4
below:
TABLE-US-00004 TABLE 4 Preferred Combinations Component (a)
Component (b) Component (c) (M1) ##STR00047## ##STR00048## (M1A)
##STR00049## ##STR00050## ##STR00051## (M2) ##STR00052##
##STR00053## (M2A) ##STR00054## ##STR00055## ##STR00056## (M3)
##STR00057## ##STR00058## (M3A) ##STR00059## ##STR00060##
##STR00061## (M4) ##STR00062## ##STR00063## ##STR00064## (M4A)
##STR00065## ##STR00066## ##STR00067## (M5) ##STR00068##
##STR00069## ##STR00070## (M6) ##STR00071## ##STR00072##
##STR00073## (M7) ##STR00074## ##STR00075## ##STR00076## (M8)
##STR00077## ##STR00078## (M9) ##STR00079## ##STR00080##
##STR00081## (M10) ##STR00082## ##STR00083## (M10A) ##STR00084##
##STR00085## ##STR00086## (M11) ##STR00087## ##STR00088##
##STR00089## (M12) ##STR00090## ##STR00091## (M13) ##STR00092##
##STR00093## (M14) ##STR00094## ##STR00095## (M15) ##STR00096##
##STR00097## (M16) ##STR00098## ##STR00099## (M17) ##STR00100##
##STR00101## (M18) ##STR00102## ##STR00103## (M19) ##STR00104##
##STR00105## (M20) ##STR00106## ##STR00107## (M21) ##STR00108##
##STR00109## (M22) ##STR00110## ##STR00111## (M23) ##STR00112##
##STR00113##
[0135] Advantageously the stabilizing composition is also mixed
with a salicylate. Preferred salicylates are salicylic acid
(CAS-No. 69-72-7), homosalate (CAS-No.
118-56-9,3,3,5-trimethylcyclohexyl salicylate), 2-ethylhexyl
salicylate (CAS-No. 118-60-5), benzyl salicylate (CAS-No.
118-58-1), ethyl salicylate (CAS-No. 118-61-6), methyl salicylate
(CAS-No. 119-36-8), isoamyl salicylate (CAS-No. 87-20-7),
acetylsalicylic acid (CAS-No. 50-78-2) and isobutyl salicylate
(CAS-No. 87-19-4). Even more preferred is to mix the stabilizing
composition of the present invention with homosalate and/or
2-ethylhexyl salicylate.
[0136] Particularly preferred mixtures with salicylates are listed
in Table 5 below:
TABLE-US-00005 TABLE 5 Preferred Combinations with salicylates
Component Component Component (a) (b) (c) salicylate M24 MC-03
BT-01 2-ethylhexylsalicylate M25 MC-03 BT-01 homosalate M26 MC-01
BT-01 2-ethylhexylsalicylate M27 MC-03 BT-01 ESS-01
2-ethylhexylsalicylate M28 MC-03 BT-01 ESS-06
2-ethylhexylsalicylate
[0137] The stabilizing composition of the present invention is
particularly suitable for protecting body-care and household
products against photolytic degradation.
Personal Care Uses
[0138] The stabilizing composition of the present invention may be
used as single component or in mixture with other stabilizers in
particular for skin-care products, bath and shower additives,
preparations containing fragrances and odoriferous substances,
hair-care products, dentifrices, deodorizing and antiperspirant
preparations, decorative preparations, light protection
formulations and preparations containing active ingredients.
[0139] Skin-care products are, in particular, body oils, body
lotions, body gels, treatment creams, skin protection ointments,
shaving preparations, such as shaving foams or gels, skin powders,
such as baby powder, moisturizing gels, moisturizing sprays,
revitalizing body sprays, cellulite gels and peeling
preparations.
[0140] Suitable bath and shower additives are shower gels,
bath-salts, bubble baths and soaps.
[0141] Preparations containing fragrances and odoriferous
substances are in particular scents, per-fumes, toilet waters and
shaving lotions (aftershave preparations).
[0142] Suitable hair-care products are, for example, shampoos for
humans and animals, in particular dogs, hair conditioners, products
for styling and treating hair, perming agents, hair sprays and
lacquers, hair gels, hair fixatives and hair dyeing or bleaching
agents.
[0143] Suitable dentifrices are in particular tooth creams,
toothpastes, mouth-washes, mouth rinses, anti-plaque preparations
and cleaning agents for dentures.
[0144] Suitable decorative preparations are in particular
lipsticks, nail varnishes, eye shadows, mascaras, dry and moist
make-up, rouge, powders, depilatory agents and suntan lotions.
[0145] Suitable cosmetic formulations containing active ingredients
are in particular hormone preparations, vitamin preparations,
vegetable extract preparations and antibacterial preparations.
[0146] The mentioned body-care products may be in the form of
creams, ointments, pastes, foams, gels, lotions, powders, make-ups,
sprays, sticks or aerosols.
[0147] They preferably contain the stabilizing mixture according to
the present invention and, optionally, further UV absorbers,
sterically hindered amines, complexing agents and phenolic or
non-phenolic antioxidants.
[0148] The present invention therefore also relates to a body-care
product comprising a stabilizing mixture according to the present
invention.
[0149] In the stabilizing composition the weight ratio of component
(a) to component (b) is from 20:1 to 1:20 and the weight ratio of
component (a) to component (c) is from 1:1 to 1000:1, more
preferably from 10:1 to 100:1. When the synergistic combination is
combined with a salicylate the weight ratio of component (a) to the
salicylate is from 20:1 to 1:20, more preferably from 10:1 to
1:10.
[0150] The stabilizing mixture according to the present invention
is present in the body care and household products in a
concentration of about 5 to about 50000 ppm, based on the total
formulation, preferably from about 10 to about 10000 ppm, and most
preferably from about 100 to about 1000 ppm.
[0151] The body-care products according to the present invention
may also contain one or one more additional compounds as described
below.
Fatty Alcohols
[0152] Guerbet alcohols based on fatty alcohols having from 6 to
18, preferably from 8 to 10 carbon atoms including cetyl alcohol,
stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol,
benzoate of C.sub.12-C.sub.15 alcohols, acetylated lanolin alcohol,
etc.
Esters of Fatty Acids
[0153] Esters of linear C.sub.6-C.sub.24 fatty acids with linear
C.sub.3-C.sub.24 alcohols, esters of branched
C.sub.6-C.sub.13-carboxylic acids with linear C.sub.6-C.sub.24
fatty alcohols, esters of linear C.sub.6-C.sub.24 fatty acids with
branched alcohols, especially 2-ethylhexanol, esters of
hydroxycarboxylic acids with linear or branched C.sub.6-C.sub.22
fatty alcohols, especially dioctyl malates, esters of linear and/or
branched fatty acids with polyhydric alcohols (for example
propylene glycol, dimer diol or trimer triol) and/or Guerbet
alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic
acid, capric acid, lauric acid, isotridecanoic acid, myristic acid,
palmitic acid, palmitoleic acid, stearic acid, isostearic acid,
oleic acid, elaidic acid, petroselinic acid, linoleic acid,
linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid,
behenic acid and erucic acid and technical-grade mixtures thereof
(obtained, for example, in the pressure removal of natural fats and
oils, in the reduction of aldehydes from Roelen's ox synthesis or
in the dimerisation of unsaturated fatty acids) with alcohols, for
example, isopropyl alcohol, caproic alcohol, capryl alcohol,
2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl
alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol,
stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl
alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol,
elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl
alcohol, erucyl alcohol and brassidyl alcohol and technical-grade
mixtures thereof (obtained, for example, in the high-pressure
hydrogenation of technical-grade methyl esters based on fats and
oils or aldehydes from Roelen's oxo synthesis and as monomer
fractions in the dimerisation of unsaturated fatty alcohols).
[0154] Examples of such ester oils are isopropylmyristate,
isopropylpalmitate, isopropylstearate, isopropyl isostearate,
isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate,
isooctylstearate, isononylstearate, isononyl isononanoate,
2-ethylhexylpalmitate, 2-hexyl-laurate, 2-hexyldecylstearate,
2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate,
erucylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate,
cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate,
myristyl behenate, myristyl oleate, myristyl stearate, myristyl
palmitate, myristyl lactate, propylene glycol dicaprylate/caprate,
stearyl heptanoate, diisostearyl malate, octyl hydroxystearate,
etc.
Natural or Synthetic Triglycerides Including Glyceryl Esters and
Derivatives
[0155] Di- or tri-glycerides, based on C.sub.6-C.sub.18 fatty
acids, modified by reaction with other alcohols (caprylic/capric
triglyceride, wheat germ glycerides, etc.). Fatty acid esters of
polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate,
polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated
vegetable oil, sweet almond oil, wheat germ oil, sesame oil,
hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil,
hydrogenated castor oil, shea butter, cocoa butter, soybean oil,
mink oil, sunflower oil, safflower oil, macadamia nut oil, olive
oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago
oil, etc.
Waxes
[0156] including esters of long-chain acids and alcohols as well as
compounds having wax-like properties, e.g., carnauba wax, beeswax
(white or yellow), lanolin wax, candellila wax, ozokerite, japan
wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters
wax, synthetic beeswax etc. Also, hydrophilic waxes as Cetearyl
Alcohol or partial glycerides.
Pearlescent Waxes
[0157] Alkylene glycol esters, especially ethylene glycol
distearate; fatty acid alkanolamides, especially coco fatty acid
diethanolamide; partial glycerides, especially stearic acid
monoglyceride; esters of polyvalent, unsubstituted or
hydroxy-substituted carboxylic acids with fatty alcohols having
from 6 to 22 carbon atoms, especially long-chained esters of
tartaric acid; fatty substances, for example fatty alcohols, fatty
ketones, fatty aldehydes, fatty ethers and fatty carbonates, which
in total have at least 24 carbon atoms, especially laurone and
distearyl ether; fatty acids, such as stearic acid, hydroxystearic
acid or behenic acid, ring-opening products of olefin epoxides
having from 12 to 22 carbon atoms with fatty alcohols having from
12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon
atoms and from 2 to 10 hydroxy groups, and mixtures thereof.
Hydrocarbon Oils
[0158] Mineral oil (light or heavy), petrolatum (yellow or white),
microcrystalline wax, paraffinic and isoparaffinic compounds,
hydrogenated isoparaffinic molecules as polydecenes and
poly-butene, hydrogenated polyisobutene, squalane, isohexadecane,
isododecane and others from plant and animal kingdom.
Silicones or Siloxanes (Organosubstituted Polysiloxanes)
[0159] Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic
silicones, and also amino-, fatty acid-, alcohol-, polyether-,
epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone
compounds, which at room temperature may be in either liquid or
resinous form, linear polysiloxanes, dimethicone (Dow Corning 200
fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids,
cyclopentasiloxanes volatiles (Dow Corning 345 fluid),
phenyltrimethicone (Dow Corning 556 fluid). Also suitable are
simethicones, which are mixtures of dimethicones having an average
chain length of from 200 to 300 dimethylsiloxane units with
hydrogenated silicates.
[0160] A detailed survey by Todd et al. of suitable volatile
silicones may in addition be found in Cosm. Toil. 91, 27
(1976).
Fluorinated or Perfluorinated Oils
[0161] Perfluorohexane, dimethylcyclohexane, ethylcyclopentane,
polyperfluoromethylisopropyl ether.
Emulsifiers
[0162] Any conventionally usable emulsifier can be used for the
compositions. Emulsifier systems may comprise for example:
carbocyclic acids and their salts: alkaline soap of sodium,
potassium and ammonium, metallic soap of calcium or magnesium,
organic basis soap such as Lauric, palmitic, stearic and oleic acid
etc., alkyl phosphates or phosphoric acid esters, acid phosphate,
diethanolamine phosphate, potassium cetyl phosphate, ethoxylated
carboxylic acids or polyethyleneglycol esters, PEG-n acrylates,
linear fatty alcohols having from 8 to 22 carbon atoms, branched
from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene
oxide with fatty acids having from 12 to 22 carbon atoms and with
alkyl-phenols having from 8 to 15 carbon atoms in the alkyl group,
fatty alcohol polyglycolether such as laureth-n, ceteareth-n,
steareth-n, oleth-n, fatty acid polyglycolether such as PEG-n
stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol
esters. C.sub.12-C.sub.22 fatty acid mono- and di-esters of
addition products of from 1 to 30 mol of ethylene oxide with
polyols. Fatty acid and polyglycerol ester such as monostearate
glycerol, diisostearoyl polyglyceryl-3-diisostearates,
polyglyceryl-3-diisostearates, triglyceryl diisostearates,
polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates
(mixtures of compounds from a plurality of those substance classes
are also suitable); fatty acid polyglycolesters such as
monostearate diethylene glycol, fatty acid and polyethylene glycol
esters, fatty acid and saccharose esters such as sucro esters,
glycerol and saccharose esters such as sucro glycerides, sorbitol
and sorbitan, sorbitan mono- and di-esters of saturated and
unsaturated fatty acids having from 6 to 22 carbon atoms and
ethylene oxide addition products, polysorbate-n series, sorbitan
esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate
sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan,
glucose derivatives, C.sub.8-C.sub.22 alkyl-mono and
oligo-glycosides and ethoxylated analogues with glucose being
preferred as the sugar component, 0/W emulsifiers such as methyl
gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate,
methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside,
W/O emulsifiers such as methyl glucose dioleate/methyl glucose
isostearate, sulfates and sulfonated derivatives,
dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate,
linear sulfonated paraffins, sulfonated tetrapropylene sulfonate,
sodium lauryl sulfates, ammonium and ethanolamine lauryl sulfates,
lauryl ether sulfates, sodium laureth sulfates, sulfosuccinates,
acetyl isothionates, alkanolamide sulfates, taurines, methyl
taurines, imidazole sulfates, amine derivatives, amine salts,
ethoxylated amines, oxide amine with chains containing an
heterocycle such as alkyl imidazolines, pyridine derivatives,
isoquinoteines, cetyl pyridinium chloride, cetyl pyridinium
bromide, quaternary ammonium such as cetyltrimethylbroide ammonium
bromide (CTBA), stearylalkonium, amide derivatives, alkanolamides
such as acylamide DEA, ethoxylated amides such as PEG-n acylamide,
oxydeamide, polysiloxane/polyalkyl/polyether copolymers and
derivatives, dimethicone, copolyols, silicone polyethylene oxide
copolymer, silicone glycol copolymer, propoxylated or POE-n ethers
(Meroxapols), polaxamers or
poly-(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene),
zwitterionic surfactants that carry at least one quaternary
ammonium group and at least one carboxylate and/or sulfonate group
in the molecule, zwitterionic surfactants that are especially
suitable are betaines, such as N-alkyl-N,N-dimethylammonium
glycinates, cocoalkyldimethylammonium glycinate,
N-acylaminopropyl-N,N-dimethylammonium glycinates,
cocoacylaminopropyldimethylammonium glycinate and
2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from
8 to 18 carbon atoms in the alkyl or acyl group and also
cocoacylaminoethylhydroxy-ethylcarboxymethylglycinate,
N-alkylbetaine, N-alkylaminobetaines, alkylimidazolines,
alkylopeptides, lipoaminoacids, self emulsifying bases and the
compounds as described in K. F. DePolo, A short textbook of
cosmetology, Chapter 8, Table 8-7, p 250-251.
[0163] Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6
stearate (and) polyglyceryl-2-isostearate [Apifac], glyceryl
stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl
stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3
ricinoleate. [Arlacel 1689], sorbitan stearate and sucrose cocoate
[arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945],
cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol
and colysorbate 60 and PEG-150 and stearate-20[Polawax GP 200,
Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade
PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI,
Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F
Special], cetearyl alcohol and PEG-40 castor oil and sodium
cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and
steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and
steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75
stearate [Gelot 64], propylene glycol ceteth-3 acetate. [Hetester
PCS], propylene glycol isoceth-3acetate [Hetester PHA], cetearyl
alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG-6
stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and
ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and
ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561],
glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
[0164] Anionic emulsifiers such as PEG-2 stearate SE, glyceryl
stearate SE [Monelgine, Cutina KD], propylene glycol stearate
[Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N,
Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate
[Lanette W], trilaneth-4phopshate and glycol stearate and PEG-2
stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate
[Teginacid Special]. Cationic acid bases such as cetearyl alcohol
and cetrimonium bromide.
[0165] The emulsifiers may be used in an amount of, for example,
from 1 to 30% by weight, especially from 4 to 20% by weight and
preferably from 5 to 10% by weight, based on the total weight of
the composition.
[0166] When formulated in O/W emulsions, the preferably amount of
such emulsifier system could represent 5% to 20% of the oil
phase.
Super-Fatting Agents
[0167] Substances suitable for use as super-fatting agents are, for
example, lanolin and lecithin and also polyethoxylated or acrylated
lanolin and lecithin derivatives, polyol fatty acid esters,
monoglycerides and fatty acid alkanolamides, the latter
simultaneously acting as foam stabilizers.
Surfactants
[0168] Examples of suitable mild surfactants, that is to say
surfactants especially well tolerated by the skin, include fatty
alcohol polyglycol ether sulfates, monoglyceride sulfates, mono-
and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty
acid sarcosinates, fatty acid taurides, fatty acid glutamates,
.alpha.-olefin sulfonates, ether carboxylic acids, alkyl
oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or
protein fatty acid condensation products, the latter preferably
being based on wheat proteins.
Consistency Regulators/Thickeners and Rheology Modifiers silicon
dioxide, magnesium silicates, aluminum silicates, polysaccharides
or derivatives thereof for example hyaluronic acid, xanthan gum,
guar-guar, agar-agar, alginates, carraghenan, gellan, pectines, or
modified cellulose such as hydroxycellulose,
hydroxypropyl-methylcellulose. In addition polyacrylates or
homopolymer of reticulated acrylic acids and polyacrylamides,
carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez
10) or Salcare range such as Salcare SC80(steareth-10 allyl
ether/acrylates copolymer), Salcare SC81(acrylates copolymer),
Salcare SC91 and Salcare AST(sodium acrylates copolymer/PPG-1
trideceth-6), sepigel 305(polyacrylamide/laureth-7), Simulgel NS
and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl
taurate copolymer), Stabilen 30 (acrylates/vinyl isodecanoate
crosspolymer), Pemulen TR-1 (acrylates/C10-30 alkyl acrylate
crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28
(acrylates/beheneth-25 methacrylate copolymer), etc.
Polymers
[0169] Suitable cationic polymers are, for example, cationic
cellulose derivatives, for example a quaternized hydroxymethyl
cellulose obtainable under the name Polymer JR 400 from Amerchol,
cationic starches, copolymers of diallylammonium salts and
acrylamides, quaternized vinylpyrrolidone/vinyl imidazole polymers,
for example Luviquata (BASF), condensation products of polyglycols
and amines, quaternized collagen polypeptides, for example lauryl
diammonium hydroxypropyl hydrolyzed collagen (LamequataL/Grunau),
quaternised wheat polypeptides, polyethyleneimine, cationic
silicone polymers, for example amidomethicones, copolymers of
adipic acid and dimethylaminohydroxypropyldiethylenetriamine
(Cartaretin/Sandoz), copolymers of acrylic acid with
dimethyldiallylammonium chloride (Merquat 550/Chemviron),
polyaminopolyamides, as described, for example, in FR-A-2 252 840,
and the crosslinked water-soluble polymers thereof, cationic chitin
derivatives, for example of quaternized chitosan, optionally
distributed as microcrystals; condensation products of
dihaloalkyls, for example dibromobutane, with bisdialkylamines, for
example bisdimethylamino-1,3-propane, cationic guar gum, for
example Jaguar C-17, Jaguar C-16 from Celanese, quaternized
ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1,
Mirapol AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and
non-ionic polymers there come into consideration, for example,
vinyl acetate/crotonic acid copolymers, vinyl-pyrrolidone/vinyl
acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate
copolymers, methyl vinyl ether/maleic anhydride copolymers and
esters thereof, uncrosslinked polyacrylic acids and polyacrylic
acids crosslinked with polyols, acrylamidopropyl-trimethyl-ammonium
chloride/acrylate copolymers, octyl acrylamide/methyl
methacrylatetert. butyl-aminoethyl methacrylate/2-hydroxypropyl
methacrylate copolymers, polyvinylpyrrolidone,
vinylpyrrolidone/vinyl acetate copolymers,
vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam
terpolymers and also optionally derivatised cellulose ethers and
silicones. Furthermore the polymers as described in EP 1093796
(pages 3-8, paragraphs 17-68) may be used.
Cationic Surfactants
[0170] cetyl trimethyl ammonium bromide (CTAB), dimethicone
copolyols, amidomethicones, acrylamidopropyltrimonium
chloride/Acrylamide copolymer, guar hydroxypropyl trimonium
chloride, hydroxyacetyl hydroxyethyl dimonium chloride quaternium
compounds as listed in International Cosmetic Ingredient Dictionary
and Handbook, 7.sup.th Edition 1997, for example Quaternium-80,
polyquaternium compounds, as listed in International Cosmetic
Ingredient Dictionary and Handbook, 7.sup.th Edition 1997, for
example polyquaternium-5, polyquaternium-6, polyquaternium-7,
polyquaternium-10, polyquaternium-11, polyquaternium-17,
polyquaternium-18, polyquaternium-24 or polyquaternium-27,
polyquaternium-28, polyquaternium-32, polyquaternium-37.
Biogenic Active Ingredients
[0171] Biogenic active ingredients are to be understood as meaning,
for example, tocopherol, tocopherol acetate, tocopherol palmitate,
ascorbic acid, deoxyribonucleic acid, retinol, bisabolol,
allantoin, phytantriol, panthenol, AHA acids, amino acids,
ceramides, pseudoceramides, essential oils, plant extracts and
vitamin complexes.
Deodorizing Active Ingredients
[0172] As deodorizing active ingredients are for example,
antiperspirants, for example aluminium chlorohydrates (see J. Soc.
Cosm. Chem. 24, 281 (1973)). Under the trade mark Locrona of
Hoechst AG, Frankfurt (FRG), there is available commercially, for
example, an aluminium chlorohydrate corresponding to formula
Al2(OH)5Cl.times.2.5 H2O, the use of which is especially preferred
(see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the
chlorohydrates, it is also possible to use aluminium
hydroxyacetates and acidic aluminium/zirconium salts. Esterase
inhibitors may be added as further deodorizing active ingredients.
Such inhibitors are preferably trialkyl citrates, such as trimethyl
citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate
and especially triethyl citrate (Hydagen CAT, Henkel), which
inhibit enzyme activity and hence reduce odor formation. Further
substances that come into consideration as esterase inhibitors are
sterol sulfates or phosphates, for example lanosterol, cholesterol,
campesterol, stigmasterol and sitosterol sulfate or phosphate,
dicarboxylic acids and esters thereof, for example glutaric acid,
glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic
acid, adipic acid monoethyl ester, adipic acid diethyl ester,
malonic acid and malonic acid diethyl ester and hydroxycarboxylic
acids and esters thereof, for example citric acid, malic acid,
tartaric acid or tartaric acid diethyl ester. Antibacterial active
ingredients that influence the germ flora and kill or inhibit the
growth of sweat-decomposing bacteria can likewise be present in the
preparations (especially in stick preparations). Examples include
chitosan, phenoxyethanol and chlorhexidine gluconate.
5-chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan, Irgasan, Ciba
Specialty Chemicals Inc.) has also proved especially effective.
Anti-Dandruff Agents
[0173] As anti-dandruff agents there may be used, for example,
climbazole, octopirox and zinc pyrithione. Customary film formers
include, for example, chitosan, microcrystalline chitosan,
quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl
acetate copolymers, polymers of quaternary cellulose derivatives
containing a high proportion of acrylic acid, collagen, hyaluronic
acid and salts thereof and similar compounds.
Hydrotropic Agents
[0174] For improvement of the flow behavior it is also possible to
employ hydrotropic agents, for example ethoxylated or non
ethoxylated mono-alcohols, diols or polyols with a low number of
carbon atoms or their ethers (e.g. ethanol, isopropanol,
1,2-dipropanediol, propyleneglycol, glycerin, ethylene glycol,
ethylene glycol monoethylether, ethylene glycol monobutylether,
propylene glycol monomethylether, propylene glycol monoethylether,
propylene glycol monobutylether, diethylene glycol monomethylether;
diethylene glycol monoethylether, diethylene glycol monobutylether
and similar products). The polyols for that purpose comprise
preferably 2 to 15 carbon atoms and at least two hydroxy groups.
The polyols may also contain further functional groups, especially
amino groups, and/or may be modified with nitrogen. Typical
examples are as follows: glycerol, alkylene glycols, for example
ethylene glycol, diethylene glycol, propylene glycol, butylene
glycol, hexylene glycol and also polyethylene glycols having an
average molecular weight of from 100 to 1000 Dalton; technical
oligo-glycerol mixtures having an intrinsic degree of condensation
of from 1.5 to 10, for example technical diglycerol mixtures having
a diglycerol content of from 40 to 50% by weight; methylol
compounds, such as, especially, trimethylolethane,
trimethylolpropane, trimethylolbutane, pentaerythritol and
dipentaerythritol; lower alkyl-glucosides, especially those having
from 1 to 8 carbon atoms in the alkyl radical, for example methyl
and butyl glucoside; sugar alcohols having from 5 to 12 carbon
atoms, for example sorbitol or mannitol; sugars having from 5 to 12
carbon atoms, for example glucose or saccharose; amino sugars, for
example glutamine; dialcohol amines, such as diethanolamine or
2-amino-1,3-propanediol.
Preservatives
[0175] Suitable preservatives include, for example methyl-, ethyl-,
propyl-, butyl-parabens, benz-alkonium chloride,
2-bromo-2-nitro-propane-1,3-diol, dihydroacetic acid, diazolidinyl
urea, 2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde
solution, methyldibromoglutanitrile, phenoxyethanol, sodium
hydroxymethylglycinate, imidazolidinyl urea, Triclosan and further
substance classes listed in the following reference: K. F.
Depolo--A Short Textbook Of Cosmetology, Chapter 7, Table 7-2, 7-3,
7-4 And 7-5, P 210-219.
Bacteria-Inhibiting Agents
[0176] Typical examples of bacteria-inhibiting agents are
preservatives that have a specific action against gram-positive
bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether,
chlor-hexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC
(3,4,4'-trichlorocarbanilide). A large number of aromatic
substances and ethereal oils also have antimicrobial properties.
Typical examples are the active ingredients eugenol, menthol and
thymol in clove oil, mint oil and thyme oil. A natural deodorizing
agent of interest is the terpene alcohol farnesol
(3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in
lime blossom oil. Glycerol monolaurate has also proved to be a
bacteriostatic agent. The amount of the additional
bacteria-inhibiting agents present is usually from 0.1 to 2% by
weight, based on the solids content of the preparations.
Perfume Oils
[0177] Mixtures of natural and/or synthetic aromatic substances.
Natural aromatic substances are, for example, extracts from blossom
(lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems
and leaves (geranium, patchouli, petitgrain), from fruit (aniseed,
coriander, carraway, juniper), from fruit peel (bergamot, lemons,
oranges), from roots (mace, angelica, celery, cardamom, costus,
iris, calmus), from wood (pinewood, sandalwood, guaiacum wood,
cedarwood, rosewood), from herbs and grasses (tarragon, lemon
grass, sage, thyme), from needles and twigs (spruce, pine, Scots
pine, mountain pine), from resins and balsams (galbanum, elemi,
benzoin, myrrh, olibanum, opoponax). Animal raw materials also come
into consideration, for example civet and castoreum. Typical
synthetic aromatic substances are, for example, products of the
ester, ether, aldehyde, ketone, alcohol or hydrocarbon type.
Aromatic substance compounds of the ester type are, for example,
benzyl acetate, phenoxy-ethyl isobutyrate, p-tert-butylcyclohexyl
acetate, linalyl acetate, dimethylbenzylcarbinyl acetate,
phenylethyl acetate, linalyl benzoate, benzyl formate,
ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl
propionate and benzyl salicylate. The ethers include, for example,
benzyl ethyl ether; the aldehydes include, for example, the linear
alkanals having from 8 to 18 hydrocarbon atoms, citral,
citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde,
hydroxycitronellal, lilial and bourgeonal; the ketones include, for
example, the ionones, isomethylionone and methyl cedryl ketone; the
alcohols include, for example, anethol, citronellol, eugenol,
isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol;
and the hydrocarbons include mainly the terpenes and balsams. It is
preferable, however, to use mixtures of various aromatic substances
that together produce an attractive scent. Ethereal oils of
relatively low volatility, which are chiefly used as aroma
components, are also suitable as perfume oils, e.g. sage oil,
camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime
blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum
oil, labolanum oil and lavandin oil. Preference is given to the use
of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol,
phenyl ethyl alcohol, hexyl cinnamaldehyde, geraniol, benzyl
acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan,
indole, hedione, sandelice, lemon oil, tangerine oil, orange oil,
allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil,
damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix
coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenyl
acetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat,
irotyl and floramat alone or in admixture with one another.
Other Adjuvants
[0178] It is furthermore possible for the cosmetic preparations to
contain, as adjuvants, anti-foams, such as silicones, structurants,
such as maleic acid, solubilizers, such as ethylene glycol,
propylene glycol, glycerol or diethylene glycol, opacifiers, such
as latex, styrene/PVP or styrene/acrylamide copolymers,
propellants, such as propane/butane mixtures, N2O, dimethyl ether,
CO2, N2 or air, so-called coupler and developer components as
oxidation dye precursors, reducing agents, such as thioglycolic
acid and derivatives thereof, thiolactic acid, cysteamine,
thiomalic acid or mercaptoethanesulfonic acid, or oxidizing agents,
such as hydrogen peroxide, potassium bromate or sodium bromate.
[0179] Suitable insect repellents are, for example,
N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535;
suitable self-tanning agents are, for example, dihydroxyacetone
and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone
precursors as described in WO 01/85124 and/or erythrulose.
[0180] The present stabilized compositions are particularly
suitable for stabilizing body care products, in particular: [0181]
skin-care preparations, e.g. skin-washing and cleansing
preparations in the form of tablet-form or liquid soaps, soapless
detergents or washing pastes, [0182] bath preparations, e.g. liquid
(foam baths, milks, shower preparations) or solid bath
preparations, e.g. bath cubes and bath salts; [0183] skin-care
preparations, e.g. skin emulsions, multi-emulsions or skin oils;
body oils, body lotions, body gels; skin protection ointments;
[0184] cosmetic personal care preparations, e.g. facial make-up in
the form of day creams or powder creams, face powder (loose or
pressed), rouge or cream make-up, eye-care preparations, e.g. eye
shadow preparations, mascara, eyeliner, eye creams or eye-fix
creams; lip-care preparations, e.g. lipsticks, lip gloss, lip
contour pencils, nail-care preparations, such as nail varnish, nail
varnish removers, nail hardeners or cuticle removers; [0185]
foot-care preparations, e.g. foot baths, foot powders, foot creams
or foot balsams, special deodorants and antiperspirants or
callus-removing preparations; [0186] light-protective preparations,
such as sun milks, lotions, creams or oils, sun blocks or
tropicals, pre-tanning preparations or after-sun preparations;
[0187] skin-tanning preparations, e.g. self-tanning creams; [0188]
depigmenting preparations, e.g. preparations for bleaching the skin
or skin-lightening preparations; [0189] insect-repellents, e.g.
insect-repellent oils, lotions, sprays or sticks; [0190]
deodorants, such as deodorant sprays, pump-action sprays, deodorant
gels, sticks or roll-ons; [0191] antiperspirants, e.g.
antiperspirant sticks, creams or roll-ons; [0192] preparations for
cleansing and caring for blemished skin, e.g. synthetic detergents
(solid or liquid), peeling or scrub preparations or peeling masks;
[0193] hair-removal preparations in chemical form (depilation),
e.g. hair-removing powders, liquid hair-removing preparations,
cream- or paste-form hair-removing preparations, hair-removing
preparations in gel form or aerosol foams; [0194] shaving
preparations, e.g. shaving soap, foaming shaving creams,
non-foaming shaving creams, foams and gels, preshave preparations
for dry shaving, aftershaves or aftershave lotions; [0195]
fragrance preparations, e.g. fragrances and odoriferous substances
containing preparations (scents, eau de Cologne, eau de toilette,
eau de perfume, perfume de toilette, perfume), perfume oils or
perfume creams; [0196] cosmetic hair-treatment preparations, e.g.
hair-washing preparations in the form of shampoos and conditioners,
hair-care preparations, e.g. pretreatment preparations, hair
tonics, styling creams, styling gels, pomades, hair rinses,
treatment packs, intensive hair treatments, hair-structuring
preparations, e.g. hair-waving preparations for permanent waves
(hot wave, mild wave, cold wave), hair-straightening preparations,
liquid hair-setting preparations, hair foams, hairsprays, bleaching
preparations, e.g. hydrogen peroxide solutions, lightening
shampoos, bleaching creams, bleaching powders, bleaching pastes or
oils, temporary, semi-permanent or permanent hair colorants,
preparations containing self-oxidizing dyes, or natural hair
colorants, such as henna or camomile; [0197] dentifrices, in
particular tooth creams, toothpastes, mouth-washes, mouth rinses,
anti-plaque preparations and cleaning agents for dentures; [0198]
decorative preparations, in particular lipsticks, nail varnishes,
eye shadows, mascaras, dry and moist make-up, rouge, powders,
depilatory agents and suntan lotions [0199] cosmetic formulations
containing active ingredients, in particular hormone preparations,
vitamin preparations, vegetable extract preparations and
antibacterial preparations.
[0200] Suitable cosmetic formulations containing active ingredients
are in particular hormone preparations, vitamin preparations,
vegetable extract preparations and antibacterial preparations.
Presentation Forms
[0201] The final formulations listed may exist in a wide variety of
presentation forms, for example: [0202] in the form of liquid
preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all
kinds of microemulsions, [0203] in the form of a gel, [0204] in the
form of an oil, a cream, milk or lotion, [0205] in the form of a
stick, [0206] in the form of a spray (spray with propellant gas or
pump-action spray) or an aerosol, [0207] in the form of a foam, or
[0208] in the form of a paste.
[0209] Of special importance as cosmetic preparations for the skin
are light-protective preparations, such as sun milks, lotions,
creams, oils, sun blocks or tropicals, pretanning preparations or
after-sun preparations, also skin-tanning preparations, for example
self-tanning creams. Of particular interest are sun protection
creams, sun protection lotions, sun protection milk and sun
protection preparations in the form of a spray.
[0210] Of special importance as cosmetic preparations for the hair
are the above-mentioned preparations for hair treatment, especially
hair-washing preparations in the form of shampoos, hair
conditioners, hair-care preparations, e.g. pretreatment
preparations, hair tonics, styling creams, styling gels, pomades,
hair rinses, treatment packs, intensive hair treatments,
hair-straightening preparations, liquid hair-setting preparations,
hair foams and hairsprays. Of special interest are hair-washing
preparations in the form of shampoos.
[0211] A shampoo has, for example, the following composition:
0.01 to 5% by weight of the stabilized composition of the present
invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by
weight of cocamidopropyl betaine, 3.0% by weight of sodium
chloride, and water ad 100%.
[0212] For example, especially the following hair-cosmetic
formulations may be used: [0213] a1) spontaneously emulsifying
stock formulation, comprising stabilized composition of the present
invention, optionally another stabilizer, PEG-6-C10oxoalcohol and
sorbitan sesquioleate, to which water and any desired quaternary
ammonium compound, for example 4% minkamidopropyl
dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;
[0214] a2) spontaneously emulsifying stock formulation comprising
the stabilized composition of the present invention, optionally
another stabilizer, tributyl citrate and PEG-20-sorbitan
monooleate, to which water and any desired quaternary ammonium
compound, for example 4% minkamidopropyl
dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;
[0215] b) quat-doped solutions comprising the stabilized
composition of the present invention in butyl triglycol and
tributyl citrate; and optionally another stabilizer; [0216] c)
mixtures or solutions comprising the compound stabilized
composition of the present invention with alkylpyrrolidone; and
optionally another stabilizer.
[0217] Examples of body care products of the present invention are
listed in the Table below:
TABLE-US-00006 Body care product Ingredients Sun screen Oils,
emulsifiers, water, UV absorbers, thickeners, antioxidants,
stabilizer according to invention moisturizing cream vegetable oil,
emulsifier, thickener, perfume, water, antioxidant, stabilizer
according to invention Hair or body surfactant, emulsifier,
colorant, preservatives, shampoo perfume, antioxidant, stabilizer
according to invention Hair conditioner surfactant, cationic
polymers, emulsifier, colorant, preservatives, perfume,
antioxidant, stabilizer according to invention Toothpaste cleaning
agent, abrasives, water, thickener, sweetener, flavor, colorant,
antioxidant, stabilizer according to invention lip-care stick
vegetable oil, wax, TiO.sub.2, pigments, antioxidant, stabilizer
according to invention
Household Products
[0218] The stabilized compositions of the present invention are
also used in household cleaning and treatment agents, for example
in laundry products and fabric softeners, liquid cleansing and
scouring agents, glass detergents, neutral cleaners (all-purpose
cleaners), acid household cleaners (bath), bathroom cleaners, WC
cleaners, for instance in washing, rinsing and dishwashing agents,
kitchen and oven cleaners, clear rinsing agents, dishwasher
detergents, shoe polishes, polishing waxes, floor detergents and
polishes, metal, glass and ceramic cleaners, textile-care products,
rug cleaners and carpet shampoos, agents for removing rust, color
and stains (stain remover salt), furniture and multipurpose
polishes and leather and vinyl dressing agents (leather and vinyl
sprays) and air fresheners.
[0219] Household cleaning agents are aqueous or alcoholic (ethanol
or isopropyl alcohol) solutions of one or more of the following
components: [0220] anionic, nonionic, amphoteric and/or cationic
surfactants soaps, prepared by saponification of animal and
vegetable greases [0221] organic acids, like hydrochloric acid,
phosphoric acid, or sulfuric acid, [0222] for basic products
inorganic (NaOH or KOH) or organic bases; [0223] abrasives for
improved cleaning of surfaces, [0224] waxes and/or silicones for
maintenance and protection of surfaces, [0225] polyphosphates,
[0226] substances which eliminate hypochlorite or halogens; [0227]
peroxides comprising bleaching activators like TAED, for example
sodium perborate or H.sub.2O.sub.2; [0228] enzymes; [0229] in
washing detergents discoloration inhibitors, soil-release
compounds, grey scale inhibitors, foam inhibitors, fluorescent
whitening agents; [0230] cleaning agents based on wax may comprise
solvents selected from benzene, turpentine and/or paraffins and
emulsifiers based on wax; [0231] filling agents like silicates,
polyphosphates, Zeolithes for powdery cleaning agents; [0232]
pigments, lakes or soluble dyes; [0233] perfumes; and [0234] light
stabilizers, antioxidants and chelating agents.
[0235] Colored cleaning agents and decorative cosmetic products can
comprise the following dyes: [0236] inorganic pigments, for example
iron oxide (Iron Oxide Red, Iron Oxide Yellow, Iron Oxide Black,
etc.), Ultramarines, Chromium Oxide Green or Carbon Black; [0237]
natural or synthetic organic pigments; [0238] disperse dyes which
may be solubilized in solvents like direct hair dyes of the HC
type, for example HC Red No. 3, HC Blue No. 2 and all other hair
dyes listed in International Cosmetic Ingredient Dictionary and
Handbook, 7th edition 19997) or the dispersion dyes listed in Color
Index International or Society of Dyers and Colourists; [0239]
color varnishes (insoluble salts of soluble dyes, like many Ca-,
Ba- or Al-salts of anionic dyes); [0240] soluble anionic or
cationic dyes, like acid dyes (anionic), basic dyes (cationic),
direct dyes, reactive dyes or solvent dyes.
[0241] Generally, for the coloration of household- and body care
products all substances are suitable which have an absorption in
the visible light of electromagnetic radiation (wave length of ca.
4000 to 700 nm). The absorption is often caused by the following
chromophores:
Azo- (mono-, di, tris-, or poly-)stilbene-, carotenoide-,
diarylmethan-, triarylmethan-, xanthen-, acridin-, quinoline,
methin- (also polymethin-), thiazol-, indamin-, indophenol-, azin-,
oxazin, thiazin-, anthraquinone-, indigoid-, phtalocyanine- and
further synthetic, natural and/or inorganic chromophores.
[0242] The present invention also relates to home care and fabric
care products such as drain cleaners, disinfectant solutions,
upholstery cleaners, automotive care products (e.g., to clean
and/or polish and protect paint, tires, chrome, vinyl, leather,
fabric, rubber, plastic and fabric), degreasers, polishes (glass,
wood, leather, plastic, marble, granite, and tile, etc.), and metal
polishes and cleaners. The present invention also relates to home
care products such as candles, gel candles, air fresheners and
fragrance oils (for the home).
[0243] Typical examples of household cleaning and treating agents
are listed in the table below:
TABLE-US-00007 Household cleaners/ household treating agents
Ingredients detergent surfactant mixture, builders, water, ethanol,
concentrate pH adjuster, antioxidant, antioxidants, stabilizer
according to invention Cleaner Surfactant mixture, water, pH
adjuster, colorant, stabilizer according to invention Bleaches
Hypochlorite or peroxide bleach, water, pH adjuster, EDTA,
stabilizer according to invention shoe polish wax wax emulsifier,
antioxidant, water, preservative, antioxidants, stabilizer
according to invention wax-containing emulsifier, wax, sodium
chloride, water, floor cleaning agent preservative, antioxidant,
stabilizer according to invention
[0244] Colored cleaning agents, personal care and decorative
cosmetic products can comprise the following dyes and pigments:
[0245] inorganic pigments, for example iron oxide (Iron Oxide Red,
Iron Oxide Yellow, Iron Oxide Black, etc.), Ultramarines, Chromium
Oxide Green or Carbon Black; [0246] natural or synthetic organic
pigments; [0247] dispersed dyes which may be solubilized in
solvents like direct hair dyes of the HC type, for example HC Red
No. 3, HC Blue No. 2 [0248] all other hair dyes listed in
International Cosmetic Ingredient Dictionary and Handbook, 7th
edition 19997) or listed in Color Index International or Society of
Dyers and Colourists; [0249] color lakes (insoluble salts of
soluble dyes, like many Ca-, Ba- or Al-salts of anionic dyes);
[0250] soluble anionic or cationic dyes, like acid dyes (anionic),
basic dyes (cationic), direct dyes, reactive dyes or solvent
dyes.
[0251] Generally, for the coloration of household- and body care
products all substances are suitable which have an absorption in
the visible light of electromagnetic radiation (wave length of ca.
4000 to 700 nm). The absorption is often caused by the following
chromophores:
Azo- (mono-, di, tris-, or poly-)stilbene-, carotenoide-,
diarylmethane-, triarylmethan-, xanthen-, acridin-, quinoline,
methin- (also polymethin-), thiazol-, indamin-, indophenol-, azin-,
oxazin, thiazin-, anthraquinone-, indigoid-, phtalocyanine- and
further synthetic, natural and/or inorganic chromophores.
[0252] The stabilized composition of the present invention are for
example incorporated by dissolution in an oil phase or alcoholic or
water phase, where required at elevated temperature.
[0253] The present body care products and household products have
high stability towards color changes and chemical degradation of
the ingredients present in these products. For example, present
compositions that comprise a dye are found to have excellent color
stability.
[0254] The following Examples illustrate the invention.
A. PREPARATION EXAMPLES
Example A1
Preparation of Merocyanine of formula (MC-01)
[0255] 40.13 g dimethylsulfate is added dropwise to 75.43 g
3-[(2-ethylhexyl)amino]-5,5-dimethyl-2-cyclohexen-1-one (CAS:
110186-59-9).
[0256] The mixture is heated under stirring for 40 min at
90-100.degree. C.
[0257] After cooling down the reaction mixture to 60.degree. C.
first 31.33 g methyl cyanoacetate and then subsequently 33.21 g
triethylamine are added.
[0258] The resulting mixture is then stirred at 100-110.degree. C.
for about 70 min.
[0259] After cooling to room temperature the mixture is diluted
with 240 ml toluene.
[0260] The toluene solution is washed with 240 ml water and then
extracted with 120 ml of an aqueous HCl solution (5%) and 3-times
with 120 ml of water.
[0261] The organic phase is then washed with 120 ml aqueous NaOH
solution (5%) and three times with 120 ml water.
[0262] The organic phase is then filtered over a silica gel pad and
eluted with 5 L toluene in total.
[0263] After distilling off the solvent 76 g of the product is
obtained as an orange oil.
[0264] The product can be dissolved in methanol and precipitated by
the addition of water yielding yellowish crystals (melting point:
78-81.degree. C.; .lamda..sub.max (ethanol)=388 nm,
.epsilon.=58075).
B. APPLICATION EXAMPLES
Example B1
[0265] The following colored basic shampoo formulation was
prepared:
TABLE-US-00008 Sodium Laureth Ether Sulfate 10 (w/w) %
Cocamidopropylbetaine 3 (w/w) % Citric Acid to pH 5 FD&C Blue
No. 1 0.001 (w/w) % Aqua ad. 100 (w/w) % Stabilizer q.a.
[0266] The following stabilized and unstabilized samples of this
formulation are prepared for light stability testing: [0267] (1)
unstabilized basic shampoo formulation [0268] (2) basic shampoo
formulation plus 0.03% of the compound (BT-01) [0269] (3) basic
shampoo formulation plus 0.003% of compound (MC-03) [0270] (4)
basic shampoo formulation plus 0.003% of compound (MC-03) and
0.027% of the compound (BT-01) [0271] (5) basic shampoo formulation
plus 0.0075% of compound (MC-03) and 0.0225% of the compound
(BT-01) (corresponds to 0.03% of a 1:3 (w %)-mixture of compound
(MC-03) and of the compound (BT-01)).
[0272] The formulations are filled into 30 ml glass bottles and
irradiated in an ATLAS Sun test XLS+ Xenon Lamp (light intensity
500 W/m2, spectrum of light adjusted to indoor conditions, sample
chamber temperature: 32.degree. C.).
[0273] Results:
TABLE-US-00009 Sample Irradiation Time until samples were
significantly faded (1) 2 hours (colorless) (2) 8 hours (colorless)
(3) 6 hours (faded, but still colored), 8 hours (colorless) (4) 18
hours (colorless) (5) 24 hours (colorless)
[0274] Samples (4) and (5), stabilized by the synergistic
combination of the compound (BT-01) with (MC-03), exhibit
significantly better light stability compared to the samples when
the compound (BT-01) (Sample (2)) or the merocyanine UV filter
(MC-03) (Sample (3)) are used alone.
[0275] Sample (2), stabilized with 0.03% of the compound (BT-01),
is totally faded after 8 hours.
[0276] In Sample (5), where 25% of the compound (BT-01) are
replaced by the merocyanine (MC-03), the fading time is tripled to
24 hours.
Example B2-A
[0277] The following colored basic shampoo formulation is
prepared:
TABLE-US-00010 Texapon NSO 30 (w/w) % Dehyton K 10 (w/w) % Aqua 60
(w/w) % Citric Acid to pH 5 PURICOLOR Blue ABL9 0.001 (w/w) % Aqua
ad. 100 (w/w) % Stabilizer q.a.
[0278] The following stabilized and unstabilized samples of this
formulation were prepared for light stability testing: [0279] (6)
unstabilized basic shampoo formulation [0280] (7) basic shampoo
formulation plus 0.03% of the compound (BT-01); [0281] (8) basic
shampoo formulation plus 0.02% of the compound (BT-01) and 0.01% of
the compound (ESS-01); [0282] (9) basic shampoo formulation plus
0.03% of a 1:3 (w %)-mixture of compound (MC-03) and of the
compound (BT-01); [0283] (10) basic shampoo formulation plus 0.03%
of a 1:4 (w %)-mixture of compound (MC-03) and of the compound
(BT-01); [0284] (11) basic shampoo formulation plus 0.02% of a 1:3
(w %)-mixture of compound (MC-03) and of the compound (BT-01) plus
additional 0.01% of the compound (ESS-01); [0285] (12) basic
shampoo formulation plus 0.02% of a 1:4 (w %)-mixture of compound
(MC-03) and of the compound (BT-01) plus additional 0.01% of the
compound (ESS-01).
[0286] The formulations are filled into 30 ml glass bottles and
irradiated in an ATLAS Sun test XLS+Xenon Lamp (light intensity 500
W/m2, spectrum of light adjusted to indoor conditions, sample
chamber temperature: 32.degree. C.).
TABLE-US-00011 Results Irradiation Time until samples Sample were
significantly faded (6) 9 hours (nearly colorless) (7) 9 hours
(faded), 24 hours (colorless) (8) 39 hours (strongly faded, but
still colored) (9) 31 hours (faded, but still colored) (10) 31
hours (faded, but still colored) (11) 63 hours (still no fading
observed) (12) 63 hours (still no fading observed)
[0287] Samples 9 and 10, stabilized by the synergistic combination
of the compound (BT-01) with (MC-03), exhibited significantly
better light stability compared to the samples when the compound
(BT-01) (Sample (7)) is used alone.
[0288] Best performance is shown by a combination of the compound
(BT-01) and (MC-03) with the compound (ESS-01). Even after 63 hours
of irradiation no fading is observed in the samples (11) and
(12).
Example B2-B
A Colored Basic Shampoo Formulation is Prepared as Described for
Example B2-A
[0289] The following stabilized and unstabilized samples of this
formulation are prepared for light stability testing: [0290] (13)
unstabilized basic shampoo formulation; [0291] (14) basic shampoo
formulation plus 0.03% of the compound (BT-01); [0292] (15) basic
shampoo formulation plus 0.03% of a 1:3 (w %)-mixture of compound
(MC-03) and of the compound (BT-01); [0293] (16) basic shampoo
formulation plus 0.03% of a 2,5:7,5:1 (w %)-mixture of compound
(MC-03) and of the compound (BT-01) and of homosalate (CAS-No.
118-56-9); [0294] (17) basic shampoo formulation plus 0.03% of a
2,5:7,5:1 (w %)-mixture of compound (MC-03) and of the compound
(BT-01) and of 2-ethylhexyl salicylate;
[0295] The formulations are filled into 30 ml glass bottles and
irradiated in an ATLAS Sun test XLS+ Xenon Lamp (light intensity
500 W/m2, spectrum of light adjusted to indoor conditions, sample
chamber temperature: 32.degree. C.).
TABLE-US-00012 Results Irradiation Time until samples Sample were
significantly faded (13) 6 hours (nearly colorless) (14) 10 hours
(slightly faded), 25 hours (colorless) (15) 25 hours (slightly
faded), 34 hours (strongly faded, but still colored) (16) 25 hours
(slightly faded), 34 hours (strongly faded, but still a bit more
colored than sample 15) (17) 25 hours (slightly faded), 34 hours
(strongly faded, but still a bit more colored than sample 15)
[0296] When compounds (BT-01) is used alone the shampoo formulation
(sample 14) is completely faded after 25 hours. Where else at this
time the sample 15 containing the synergistic combination of the
compound (BT-01) with (MC-03) starts fading and is still colored
after 34 hours. The samples (16) and (17) containing the
synergistic composition of the compound (BT-01) with (MC-03) in
combination with a salicylate exhibit marginal better light
stability compared to the sample (15) when the synergistic
combination is used alone.
Example B3-B17
Preparation of Body-Care and Household Formulations
Example B3
Preparation of a Sprayable Hair Styling Gel
TABLE-US-00013 [0297] Phase Ingredients (w/w) % A carbomer (1%
dispersion) 0.30 water, demin. 30.00 B glycerol 2.00 methylparaben
0.20 C water, demin. ad 100 PVP/VA copolymer 8.00 triethanolamine
(88%) 0.12 EDTA, disodium salt 0.01 (BT-01) (INCI Benzotriazolyl
Dodecyl p-Cresol) 0.08 Merocyanine (MC-01) 0.02
Preparation:
[0298] The components (A) are dispersed at room temperature.
[0299] (B) is mixed under heating until the paraben is completely
dissolved and then (B) is added with gentle stirring to (A).
[0300] (C) is blended until it is completely dissolved and is
slowly added under stirring to the mixture of (A) and (B).
[0301] The transparency of the gel can be increased by adding small
amounts of triethanolamine (pH=5.6-5.75).
TABLE-US-00014 Example B4: Preparation of a baby shampoo
Ingredients (w/w) % cocoamidopropylbetaine 35.00 water, demin. ad.
100 citric acid q.s. (pH) polyquaternium-15 0.15 perfume oil 0.30
chlorophyll 0.20 Merocyanine (MC-03) 0.02 Compound (BT-01) (INCI
Benzotriazolyl Dodecyl p-Cresol) 0.02 colorant (D&C Yellow
No.5) 0.02 sodium chloride 0.30
Preparation:
[0302] Surfactant and water are blended until a homogeneous
solution is obtained. The pH is adjusted to 6.0-6.5 with citric
acid and the other components are added in the indicated sequence.
The mixture is stirred until it is completely dissolved.
TABLE-US-00015 Example B5: Preparation of a perfumed toilet water
Ingredients (w/w) % ethanol, 96% 60 d-limonene 5 cedrene 1.5
citronellol 0.5 savin 0.5 Merocyanine (MC-03) 0.05 Compound (BT-01)
(INCI Benzotriazolyl Dodecyl p-Cresol) 0.05 Compound (ESS-01)
(INCI: Tris (tetramethyl- 0.03 hydroxypiperidinol) citrate)
Tinogard TS (CAS number: 2082-79-3) 0.02 S,S-EDDS 0.01 colorant
(D&C Yellow No.5) 0.1 water ad. 100
Preparation:
[0303] The components are thoroughly mixed in the indicated
sequence at 50.degree. C. A clear homogeneous solution is
obtained.
Preparation of Formulations of Household Products
TABLE-US-00016 [0304] Example B6: Preparation of a green-colored
glass detergent Ingredients (w/w) % anionic/amphoteric surfactants
(Lumorol RK) 0.7 butyl glycol 5.0 isopropanol 20.0 d-limonene 4.00
colorant (D&C Green No.2) 0.05 Compound (ESS-01) (INCI: Tris
(tetramethyl- 0.05 hydroxypiperidinol) citrate) Merocyanine (MC-01)
0.01 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.03
water, demin. ad. 100
Preparation:
[0305] The components are dissolved in the indicated sequence until
a clear homogeneous mixture is obtained.
TABLE-US-00017 Example B7: Preparation of a floor wax Ingredients
(w/w) % wax mixture 12 white spirit ad 100 d-limonene 4.00
Merocyanine (MC-03) 0.025 Compound (BT-01) (INCI Benzotriazolyl
Dodecyl p-Cresol) 0.075
Preparation:
[0306] The components are stirred in the indicated sequence until a
homogeneous mixture is obtained.
TABLE-US-00018 Example B8: Preparation of a lipstick, non-greasy
Ingredients (w/w) % Carnauba wax 2.5 Beeswax, white 20.0 Ozekerite
10.0 Lanoline, anhydrous 5.0 Cetyl alcohol 2.0 Liquid paraffin 3.0
Isopropyl Myristate 3.0 Propylene glycol recinoleate 4.0 Cl Pigment
Red 4 9.0 Cl Pigment Blue 15 1.0 Merocyanine (MC-03) 0.025 Compound
(BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.075 Castor Oil ad
100
TABLE-US-00019 Example B9: Preparation of a lipstick, transfer
resistant Ingredients (w/w) % Cyclomethicone 41.50 Isodecane 10.00
D&C Red No. 7 8.00 Synthetic wax 6.00
Isostearyltrimethylpropane siloxysilicate 5.00
Cetylstearate/acetylated lanolin, 90:10 5.00 Ceresin 4.00 Paraffin
3.00 Titanium dioxide 2.00 Methylparaben 0.30 Propylparaben 0.10
Tinogard AS (INCI Bumetrizole) 0.10 Merocyanine (MC-03) 0.02
Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.08
TABLE-US-00020 Example B10: Preparation of a Rouge (powder)
Ingredients (w/w) % Talcum 56 Zinc Stearate 15 Rice starch 15 Iron
Oxide Red 12 Perfume q.s. Merocyanine (MC-03) 0.02 Compound (BT-01)
(INCI Benzotriazolyl Dodecyl p-Cresol) 0.08
TABLE-US-00021 Example B11: Preparation of a Foundation cream
Ingredients (w/w) % Titanium dioxide 12.79 Oleyl alcohol 4.57
Glyceryl stearate 3.65 Propylene glycol 3.65 Stearic acid 1.83
Magnesium aluminium silicate 0.91 Triethanolamine 99% 0.91 Iron
Oxide Yellow 0.64 Iron Oxide Red 0.32 Cl Pigment Brown 6 0.37
Carboxymethyl cellulose 0.10 Merocyanine (MC-03) 0.025 Compound
(BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.075 Water ad
100
TABLE-US-00022 Example B12: Preparation of an Eyeliner Ingredients
(w/w) % Polysaccharide resin (Kama KM 13, Kama) 8 Iron Oxide Black
6.50 Carnauba wax 1.00 Triethanolamine, 99% 1.00 Hydrogenated
polyisobutane 1.00 Hydrogenated polydecene 1.00 Sorbitan
sesquioleate 1.00 Xanthan gum 0.50 Carboxymethyl cellulose 0.40
Magnesium aluminium silicate 0.40 Methyl paraben 0.35 Stearic acid
2.50 Lecithin 0.20 Imidazolidinyl urea 0.10 Merocyanine (MC-03)
0.02 Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.08
Tinogard TT (INCI Pentaerythritol Tetra-di-t-butyl 0.05
hydroxycinnamate) Water to 100
TABLE-US-00023 Example B13: Preparation of an Eyelash Makeup
Ingredients (w/w) % Paraffin Wax 10.00 Starch 5.00 Polyethylene
5.00 Iron Oxide Black 7.00 Carbomer (Carbopol, BFGoodrich) 0.50
Hydroxyethylcellulose 0.50 Panthenol 2.00 Merocyanine (MC-03) 0.01
Compound (BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.04 Water
ad 100
TABLE-US-00024 Example B14: Preparation of a Nail Varnish
Ingredients (w/w) % Poly(1-trimethylsilylpropylene) 0.30
Nitrocellulose 12.00 Alkyd resin 10.00 Dibutyl phthalate 4.00
Camphor 2.00 Butyl acetate 49.50 Toluene 20.00 Pigment Red 57.1
1.00 Quaternary bentonite 1.00 Merocyanine (MC-03) 0.06 compound
(BT-01) (INCI Benzotriazolyl Dodecyl p-Cresol) 0.14 Tinogard NOA
(INCI Tetrabutyl Ethylidinebisphenol) 0.10
TABLE-US-00025 Example B15: High Protection Sunscreen High
protection sunscreen (1) A B C D INCI-Name % w/w % w/w % w/w % w/w
Synthetic Beeswax 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate 9.8
9.8 9.8 9.8 Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 Ethylhexyl
Salicylate 5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane 4.0 4.0
4.0 4.0 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.0 3.0 2.0 1.0
Octadecene/MA Copolymer (and) Methyl Acetyl 3.0 Ricinoleate (and)
Di-methylhepthyl Adipate C30-38 olefin/isopropyl maleate/MA
copolymer 2.0 Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0
Copolymer Dimethicone 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and)
C20-22 Alcohols 3.0 Candelilla/Jojoba/Rice Bran Polyglyceryl-3
esters 4.0 (and) glyceryl stearate (and) Cetearyl alcohol (and)
Sodium stearoyl lactylate Glyceryl oleate citrate (and)
Caprylic/Capric 6.0 Triglycerides Cetearyl Alcohol (and) Dicetyl
Phosphate (and) 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0
3.0 3.0 Pentaerythrityl Distearate 1.5 Glyceryl Dibehenate (and)
Tribehenin (and) Glyceryl 2.0 Behenate Hydroxypropyl Dimethicone
Behenate 2.2 1.0 2.2 Decyl Cocoate 1.0 1.0 1.0 1.0 Aqua Qs to Qs to
Qs to Qs to 100 100 100 100 Propylene Glycol 3.0 3.0 3.0 3.0
Methylene Bis-Benzotriazolyl Tetramethylbutyl- 5.0 4.0 6.0 8.0
phenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol
(and) Xanthan Gum Decyl Glucoside 0.5 0.5 0.5 0.5 Acrylates/Vinyl
Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate/VP
Copolymer 0.3 0.3 0.3 0.3 Phenylbenzimidazole Sulfonic Acid 2.0 2.0
2.0 2.0 Disteareth-75 IPDI 0.3 3.0 Disteareth-100 IPDI 0.3
Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.2 Disodium EDTA 0.2
0.2 0.2 0.2 Tromethamine 0.8 0.8 0.8 0.8 Cyclohexasiloxane (and)
Cyclopentasiloxane 0.8 0.8 0.8 0.8 Phenoxyethanol (and)
Methylparaben (and) 0.8 0.8 0.8 0.8 Ethylparaben (and) Butylparaben
(and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4
0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone (Octyl 2.0
1.5 2.0 triazone; Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene
3.0 4.0 5.0 CAS-Regno. 180898-37-7, Disodium 3.0 4.0 5.0 3.0
phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan
APC CAS-Regno. 302776-68-7, Uvinul A Plus 4.0 5.0 CAS-Regno.
444811-29-4, Propanedioic acid, [(4- 3.0 1.0
hydroxy-3,5-dimethoxyphenyl)methylene]-, bis(2- ethylhexyl) ester
(Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 1.0
2-phenylethylbenzoate 1.0 1.0 CAS-Regno. 68890-66-4, Octopirox 2.0
3.0 Tinogard TT (INCI Tetradibutyl Pentaerythrityl 1.0 1.0 1.0
Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.0
3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl
Dodecyl 2.0 0.9 1.0 1.0 p-Cresol) Merocyanine (MC-03) 1.0 0.9 0.3
0.3 Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.0 Butylphenol
Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI
Bumetrizole) 2.0 1.0 Tris(tetramethylhydroxypiperidinol) citrate of
the 1.0 1.0 Compound (ESS-01) 220410-74-2 4-Piperidinol,
1-hydroxy-2,2,6,6- 1.0 tetramethyl-,
2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt) CAS-Regno.
1750-49-8, N-(2-Hydroxypropyl)urea 5.0 CAS-Regno. 2078-71-9,
N-(2-Hydroxyethyl)urea 10.0 mixture of n-butylphthalimide and 0.5
5.0 isopropylphthalimide High protection sunscreen (1) E F G H I
INCI-Name % w/w % w/w % w/w % w/w % w/w Synthetic Beeswax 0.5 0.5
0.5 0.5 0.5 Ethylhexyl Methoxycinnamate 9.8 9.8 9.8 9.8 9.8 Isoamyl
p-Methoxycinnamate 2.0 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate 5.0
5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane 4.0 4.0 3.0 4.0 3.0
4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0 4.0
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 1.0 1.0 1.0 1.0 1.0
Cyclopentasiloxane (and) Acrylates/Polytrimethyl- 7.0
siloxymethacrylate Copolymer Isododecane (and)
Acrylates/Polytrimethylsiloxy- 8.0 methacrylate Copolymer
Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone
Copolymer Dimethicone 4.5 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate
(and) C20-22 Alcohols 3.0 Candelilla/Jojoba/Rice Bran
Polyglyceryl-3 esters 4.0 (and) glyceryl stearate (and) Cetearyl
alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate
(and) Caprylic/Capric 6.0 Triglycerides Cetearyl Alcohol (and)
Dicetyl Phosphate (and) 4.5 4.5 Ceteth-10 Phosphate Cetyl
Ricinoleate 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 3.0 5.0
Glyceryl Dibehenate (and) Tribehenin (and) 4.0 Glyceryl Behenate
Hydroxypropyl Dimethicone Behenate 2.2 0.5 2.2 Decyl Cocoate 1.0
1.0 1.0 1.0 1.0 Aqua Qs to Qs to Qs to Qs to Qs to 100 100 100 100
100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 Methylene
Bis-Benzotriazolyl Tetramethylbutyl- 5.0 10.0 10.0 5.0 10.0 phenol
(and) Aqua (and) Decyl Glucoside (and) Propylene Glycol (and)
Xanthan Gum Decyl Glucoside 0.5 0.5 0.5 0.5 0.5 Acrylates/Vinyl
Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate/VP
Copolymer 0.3 0.3 0.3 0.3 0.3
PVP/dimethylconylacrylate/polycarbamyl/polyglycol 10.0 ester
Polyester-5 3.0 Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0
2.0 Disteareth-75 IPDI Disteareth-100 IPDI 3.0 Acrylates/Vinyl
Neodecanoate Crosspolymer 1.5 5.0 8.0 Acrylates/C10-30 Alkyl
Acrylate Crosspolymer 0.2 Disodium EDTA 0.2 0.2 0.2 0.2 0.2
Tromethamine 0.8 0.8 0.8 0.8 0.8 Cyclohexasiloxane (and)
Cyclopentasiloxane 0.8 0.8 0.8 0.8 0.8 Phenoxyethanol (and)
Methylparaben (and) Ethyl- 0.8 0.8 0.8 0.8 0.8 paraben (and)
Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl
Acetate 0.4 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl
triazone 1.0 3.0 (Octyl triazone; Uvinul T 150) CAS-Regno.
6197-30-4, Octocrylene 1.0 5.0 CAS-Regno. 180898-37-7, Disodium
phenyldibenz- 2.0 imidazoletetrasulfonate Neo Heliopan AP or Neo-
Heliopan APC CAS-Regno. 68890-66-4, Octopirox 1.0 Tinogard TT (INCI
Tetradibutyl Pentaerythrityl 3.0 1.0 Hydroxy-hydrocinnamate)
Tinogard HS (INCI Sodium Benzotriazolyl 3.0 Butylphenol Sulfonate)
compound (BT-01) (INCI Benzotriazolyl Dodecyl 0.9 1.0 3.0 0.5 1.0
p-Cresol) Merocyanine (MC-03) 0.3 1.0 1.0 0.5 0.3 Cibafast H Liquid
(INCI Sodium Benzotriazolyl Butylphenol Sulfonate, Buteth-3,
Tributyl Citrate) Tinogard AS (INCI Bumetrizole) 1.0 1.0
Tris(tetramethylhydroxypiperidinol) citrate of the 1.0 1.0 Compound
(ESS-01) 220410-74-2 4-Piperidinol, 1-hydroxy-2,2,6,6- 1.0
tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt)
CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea 10.0 CAS-Regno.
2078-71-9, N-(2-Hydroxyethyl)urea 10.0 mixture of
n-butylphthalimide and isopropylphthalimide 3.0
TABLE-US-00026 Example B16: High Protection Sunscreen High
protection sunscreen (2) A B C D INCI-Name % w/w % w/w % w/w % w/w
Synthetic Beeswax 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate
(stabilized by 9.8 9.8 9.8 9.8 incorporating into a polymer )
Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate
5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane (stabilized by 4.0
4.0 5.0 4.0 incorporating into a polymer ) 4-Methylbenzylidene
Camphor 4.0 4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl
Triazine 2.0 3.0 2.0 1.0 Octadecene/MA Copolymer (and) Methyl
Acetyl 3.0 Ricinoleate (and) Di-methylhepthyl Adipate C30-38
olefin/isopropyl maleate/MA copolymer 2.0 Hydrogenated Dimer
Dilinoleyl/Dimethylcarbonate 3.0 Copolymer Dimethicone 4.5 4.5 4.5
4.5 C20-22 Alkyl Phosphate (and) C20-22 Alcohols 3.0
Candelilla/Jojoba/Rice Bran Polyglyceryl-3 esters 4.0 (and)
glyceryl stearate (and) Cetearyl alcohol (and) Sodium stearoyl
lactylate Glyceryl oleate citrate (and) Caprylic/Capric 6.0
Triglycerides Cetearyl Alcohol (and) Dicetyl Phosphate (and) 4.5
Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0 3.0 3.0
Pentaerythrityl Distearate 1.5 Glyceryl Dibehenate (and) Tribehenin
(and) Glyceryl 2.0 Behenate Hydroxypropyl Dimethicone Behenate 2.2
1.0 2.2 Decyl Cocoate 1.0 1.0 1.0 1.0 Aqua Qs to Qs to Qs to Qs to
100 100 100 100 Propylene Glycol 3.0 3.0 3.0 3.0 Decyl Glucoside
0.5 0.5 0.5 0.5 Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium
Acryloyldimethyltaurate/VP Copolymer 0.3 0.3 0.3 0.3
PVP/dimethylconylacrylate/polycarbamyl/polyglycol ester Polyester-5
Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0 Disteareth-75
IPDI 0.3 3.0 Disteareth-100 IPDI 0.3 Acrylates/C10-30 Alkyl
Acrylate Crosspolymer 0.2 Disodium EDTA 0.2 0.2 0.2 0.2 Methylene
Bis-Benzotriazolyl 5.0 5.0 5.0 5.0 Tetramethylbutylphenol
Tromethamine 0.8 0.8 0.8 0.8 Cyclohexasiloxane (and)
Cyclopentasiloxane 0.8 0.8 0.8 0.8 Phenoxyethanol (and)
Methylparaben (and) 0.8 0.8 0.8 0.8 Ethylparaben (and) Butylparaben
(and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4
0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone (Octyl 2.0
1.5 2.0 triazone; Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene
3.0 4.0 5.0 CAS-Regno. 180898-37-7, Disodium phenyldibenz- 3.0 4.0
5.0 3.0 imidazoletetrasulfonate Neo Heliopan AP or Neo- Heliopan
APC CAS-Regno. 302776-68-7, Uvinul A Plus 4.0 5.0 CAS-Regno.
444811-29-4, Propanedioic acid, [(4- 3.0 1.0
hydroxy-3,5-dimethoxyphenyl)methylene]-, bis(2- ethylhexyl) ester
(Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 1.0
2-phenylethylbenzoate 1.0 1.0 CAS-Regno. 68890-66-4, Octopirox 2.0
3.0 Tinogard TT (INCI Tetradibutyl Pentaerythrityl 1.0 1.0 1.0
Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.0
3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl
Dodecyl 2.0 1.0 1.0 1.0 p-Cresol) Merocyanine (MC-03) 2.0 2.0 1.0
1.0 Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.0 Butylphenol
Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI
Bumetrizole) 2.0 1.0 Tris(tetramethylhydroxypiperidinol) citrate
1.0 1.0 Compound (ESS-01) 220410-74-2 4-Piperidinol,
1-hydroxy-2,2,6,6- 1.0 tetramethyl-,
2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt) CAS-Regno.
1750-49-8, N-(2-Hydroxypropyl)urea 5.0 CAS-Regno. 2078-71-9,
N-(2-Hydroxyethyl)urea 10.0 mixture of n-butylphthalimide and 0.5
5.0 isopropylphthalimide High protection sunscreen (2) E F G H I
INCI-Name % w/w % w/w % w/w % w/w % w/w Synthetic Beeswax 0.5 0.5
0.5 0.5 0.5 Ethylhexyl Methoxycinnamate (stabilized by 9.8 9.8 9.8
9.8 9.8 incorporating into a polymer ) Isoamyl p-Methoxycinnamate
2.0 2.0 2.0 2.0 2.0 Ethylhexyl Salicylate 5.0 5.0 5.0 5.0 5.0 Butyl
Methoxydibenzoylmethane (stabilized 4.0 4.0 3.0 5.0 3.0 by
incorporating into a polymer ) 4-Methylbenzylidene Camphor 4.0 4.0
4.0 4.0 4.0 Bis-Ethylhexyloxyphenol Methoxyphenyl 1.0 1.0 1.0 1.0
1.0 Triazine Cyclopentasiloxane (and) Acrylates/ 7.0
Polytrimethylsiloxymethacrylate Copolymer Isododecane (and)
Acrylates/ 8.0 Polytrimethylsiloxymethacrylate Copolymer
Poly(Glycol Adipate)/Bis-Hydroxyethyoxypropyl 5.0 Dimethicone
Copolymer Dimethicone 4.5 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate
(and) C20-22 3.0 Alcohols Candelilla/Jojoba/Rice Bran
Polyglyceryl-3 4.0 esters (and) glyceryl stearate (and) Cetearyl
alcohol (and) Sodium stearoyl lactylate Glyceryl oleate citrate
(and) Caprylic/Capric 6.0 Triglycerides Cetearyl Alcohol (and)
Dicetyl Phosphate 4.5 4.5 (and) Ceteth-10 Phosphate Cetyl
Ricinoleate 3.0 3.0 3.0 3.0 3.0 Pentaerythrityl Distearate 3.0 5.0
Glyceryl Dibehenate (and) Tribehenin (and) 4.0 Glyceryl Behenate
Hydroxypropyl Dimethicone Behenate 2.2 0.5 2.2 Decyl Cocoate 1.0
1.0 1.0 1.0 1.0 Aqua Qs to Qs to Qs to Qs to Qs to 100 100 100 100
100 Propylene Glycol 3.0 3.0 3.0 3.0 3.0 Decyl Glucoside 0.5 0.5
0.5 0.5 0.5 Acrylates/Vinyl Neodecanoate Crosspolymer Ammonium
Acryloyldimethyltaurate/VP 0.3 0.3 0.3 0.3 0.3 Copolymer
PVP/dimethylconylacrylate/polycarbamyl/ 10.0 polyglycol ester
Polyester-5 3.0 Phenylbenzimidazole Sulfonic Acid 2.0 2.0 2.0 2.0
2.0 Disteareth-75 IPDI Disteareth-100 IPDI 3.0 Acrylates/Vinyl
Neodecanoate 1.5 5.0 8.0 Crosspolymer Acrylates/C10-30 Alkyl
Acrylate 0.2 Crosspolymer Disodium EDTA 0.2 0.2 0.2 0.2 0.2
Methylene Bis-Benzotriazolyl Tetramethyl- 5.0 5.0 5.0 5.0 5.0
butylphenol Tromethamine 0.8 0.8 0.8 0.8 0.8 Cyclohexasiloxane
(and) Cyclopentasiloxane 0.8 0.8 0.8 0.8 0.8 Phenoxyethanol (and)
Methylparaben (and) 0.8 0.8 0.8 0.8 0.8 Ethylparaben (and)
Butylparaben (and) Propylparaben (and) Isobutylparaben Tocopheryl
Acetate 0.4 0.4 0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl 1.0
3.0 triazone (Octyl triazone; Uvinul T 150) CAS-Regno. 6197-30-4,
Octocrylene 1.0 5.0 CAS-Regno. 180898-37-7, Disodium 2.0
phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan
APC CAS-Regno. 68890-66-4, Octopirox 1.0 Tinogard TT (INCI
Tetradibutyl 3.0 1.0 Pentaerythrityl Hydroxy-hydrocinnamate)
Tinogard HS (INCI Sodium Benzotriazolyl 3.0 Butylphenol Sulfonate)
compound (BT-01) (INCI Benzotriazolyl 0.5 1.0 3.0 0.9 1.0 Dodecyl
p-Cresol) Merocyanine (MC-03) 0.5 0.8 1.0 0.3 0.33 Tinogard AS
(INCI Bumetrizole) 1.0 1.0 Tris(tetramethylhydroxypiperidinol)
citrate 0.5 0.5 Compound (ESS-01) 220410-74-2 4-Piperidinol,
1-hydroxy-2,2,6,6- 1.0 tetramethyl-, 2-hydroxy-1,2,3-
propanetricarboxylate (3:1) (salt) CAS-Regno. 1750-49-8,
N-(2-Hydroxypropyl)urea 10.0 CAS-Regno. 2078-71-9,
N-(2-Hydroxyethyl)urea 10.0 mixture of n-butylphthalimide and 3.0
isopropylphthalimide
TABLE-US-00027 Example B17: High Protection Sunscreen High
protection sunscreen (3) A B C D INCI-Name % w/w % w/w % w/w % w/w
Synthetic Beeswax 0.5 0.5 0.5 0.5 Ethylhexyl Methoxycinnamate 9.8
9.8 9.8 9.8 Isoamyl p-Methoxycinnamate 2.0 2.0 2.0 2.0 Ethylhexyl
Salicylate 5.0 5.0 5.0 5.0 Butyl Methoxydibenzoylmethane 4.0 4.0
4.0 4.0 4-Methylbenzylidene Camphor 4.0 4.0 4.0 4.0
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.0 3.0 2.0 1.0
Octadecene/MA Copolymer (and) Methyl Acetyl 3.0 Ricinoleate (and)
Di-methylhepthyl Adipate C30-38 olefin/isopropyl maleate/MA
copolymer 2.0 Hydrogenated Dimer Dilinoleyl/Dimethylcarbonate 3.0
Copolymer Dimethicone 4.5 4.5 4.5 4.5 C20-22 Alkyl Phosphate (and)
C20-22 Alcohols 3.0 Candelilla/Jojoba/Rice Bran Polyglyceryl-3
esters 4.0 (and) glyceryl stearate (and) Cetearyl alcohol (and)
Sodium stearoyl lactylate Glyceryl oleate citrate (and)
Caprylic/Capric 6.0 Triglycerides Cetearyl Alcohol (and) Dicetyl
Phosphate (and) 4.5 Ceteth-10 Phosphate Cetyl Ricinoleate 3.0 3.0
3.0 3.0 Pentaerythrityl Distearate 1.5 Glyceryl Dibehenate (and)
Tribehenin (and) 2.0 Glyceryl Behenate Hydroxypropyl Dimethicone
Behenate 2.2 1.0 2.2 Decyl Cocoate 1.0 1.0 1.0 1.0 Aqua Qs to Qs to
Qs to Qs to 100 100 100 100 Propylene Glycol 3.0 3.0 3.0 3.0
Methylene Bis-Benzotriazolyl Tetramethylbutyl- 5.0 4.0 6.0 8.0
phenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol
(and) Xanthan Gum Decyl Glucoside 0.5 0.5 0.5 0.5 Acrylates/Vinyl
Neodecanoate Crosspolymer Ammonium Acryloyldimethyltaurate/VP
Copolymer 0.3 0.3 0.3 0.3 Phenylbenzimidazole Sulfonic Acid 2.0 2.0
2.0 2.0 Disteareth-75 IPDI 0.3 3.0 Disteareth-100 IPDI 0.3
Acrylates/C10-30 Alkyl Acrylate Crosspolymer 0.2 Disodium EDTA 0.2
0.2 0.2 0.2 Tromethamine 0.8 0.8 0.8 0.8 Cyclohexasiloxane (and)
Cyclopentasiloxane 0.8 0.8 0.8 0.8 Phenoxyethanol (and)
Methylparaben (and) 0.8 0.8 0.8 0.8 Ethylparaben (and) Butylparaben
(and) Propylparaben (and) Isobutylparaben Tocopheryl Acetate 0.4
0.4 0.4 0.4 CAS-Regno. 88122-99-0, Ethylhexyl triazone 2.0 1.5 2.0
(Octyl triazone; Uvinul T 150) CAS-Regno. 6197-30-4, Octocrylene
3.0 4.0 5.0 CAS-Regno. 180898-37-7, Disodium 3.0 4.0 5.0 3.0
phenyldibenzimidazoletetrasulfonate Neo Heliopan AP or Neo-Heliopan
APC CAS-Regno. 302776-68-7, Uvinul A Plus 4.0 5.0 CAS-Regno.
444811-29-4, Propanedioic acid, [(4- 3.0 1.0
hydroxy-3,5-dimethoxyphenyl)methylene]-, bis(2- ethylhexyl) ester
(Oxynex ST) CAS-Regno. 477844-93-2, Octofluorene 3.0 1.0
2-phenylethylbenzoate 1.0 1.0 CAS-Regno. 68890-66-4, Octopirox 2.0
3.0 Tinogard TT (INCI Tetradibutyl Pentaerythrityl 1.0 1.0 1.0
Hydroxy-hydrocinnamate) Tinogard HS (INCI Sodium Benzotriazolyl 2.0
3.0 Butylphenol Sulfonate) compound (BT-01) (INCI Benzotriazolyl
Dodecyl 2.0 0.9 1.0 1.0 p-Cresol) Merocyanine (MC-03) 1.0 0.9 0.3
0.3 Cibafast H Liquid (INCI Sodium Benzotriazolyl 1.0 Butylphenol
Sulfonate, Buteth-3, Tributyl Citrate) Tinogard AS (INCI
Bumetrizole) 2.0 1.0 CAS-Regn. 30538-92-2 (Compound ESS-06) 0.05
0.01 220410-74-2 4-Piperidinol, 1-hydroxy-2,2,6,6- 1.0
tetramethyl-, 2-hydroxy-1,2,3-propanetricarboxylate (3:1) (salt)
CAS-Regno. 1750-49-8, N-(2-Hydroxypropyl)urea 5.0 CAS-Regno.
2078-71-9, N-(2-Hydroxyethyl)urea 10.0 mixture of
n-butylphthalimide and 0.5 5.0 isopropylphthalimide
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