# Patent

## Title
Stabilization of body-care and household products against degradation by uv radiation using merocyanine derivatives

## Abstract

Described is the use of specific merocyanine derivatives for protecting body-care and household products from photolytic and oxidative degradation. These compounds perform outstanding UV absorber properties.

## Background
The present invention relates to the use of selected light stabilizers for protecting body-care and household products from photolytic and oxidative degradation.
The product trend of recent years towards increasing use of natural substances based on oil and fat in cosmetic formulations and household products also increases the problem of the oxidative degradation of fats and oils, resulting in rancidity. Natural oils or unsaturated fatty acids are hardly ever absent from emulsions. Oxidative changes may sometimes produce reactive metabolites, for example ketones, aldehydes, acids, epoxides and lipoperoxides.
As a result there is on the one hand an undesirable change in the smell of the products and on the other hand substances may be obtained which may alter the skin tolerance. The uncontrolled formation of free radicals on the skin contributes primarily to the initiation and progression of a multitude of pathophysical modulations, for example inflammation, cancerogenesis and the like.
However, oxidative degradation processes are not only found in the case of natural substances based on oil and fat. They are also found in a number of other cosmetic ingredients, such as fragrances and odoriferous substances, vitamins, colourants and the like.
To prevent oxidative degradation processes (photooxidation, autooxidation), so-called anti-oxidants (AO) are therefore used in cosmetic and food products. These antioxidants may be classified into compounds which prevent oxidation (complex formers, reducing agents and the like) and into compounds which interrupt the free radical chain reactions, for example butylated hydroxytoluene (BHT), butylated hydroxyanisol (BHA), gallates, such as propylgallate (PG), or t-butylhydroquinone (TBHQ). However, the latter compounds often do not meet the requirements with respect to pH stability as well as to light and temperature stability.
As a consequence the actives in such containers unadvantageously change their properties due to autoxidative processes. This results for example in a reduction of viscosity and changes in color or smell.
Furthermore, the growing product trend in the recent years has also resulted in an increased use of transparent (glass, PET etc.) containers for cosmetic formulations and household products. Although both glass and ordinary plastics have a certain inherent absorption in the UV-B-range the absorption in the UV-A range is very low.
Various stabilization techniques for clear package products by UV absorption are commonly used and well known. For example broad-band UV light stabilizers of the benzotriazole class enhance product stability and shelf live due to their very good UV-A and UV-B absorption properties compared to other absorbers such as benzophenones which mainly absorb UV-B. The most effective today known stabilizers for preventing or delaying light induced fading of transparent packaged products are e.g. benzotriazole derivativess known under the trade names Ciba TINOGARD HS or Ciba TINOGARD TL.
Surprisingly, it has been found that specific light stabilizers based on merocyanine derivatives perform outstanding UV absorber properties and are therefore suitable for product protection.
Therefore, the present invention relates to the use of merocyanine derivatives of formula




wherein

    L1, L2 or L3 independently of each other hydrogen; hydroxy; C1-C22alkyl; C1-C22alkoxy; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl C5-C11heteroaralkyl; C6-C20aryl; C6-C20aryl-C1-C5alkenylene; C4-C9heteroaryl; CN; —(CH2)t—OR9; or COOR9;
    R4 is CN; —COR7; —COOR7; —SO2R7; —CONR7R8; C1-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; C1-C1alkylcarbonylamino-C6-C20aryl; C4-C9heteroaryl;
    R5, R6, R7 and R8 are independently of each other hydrogen; C1-C22alkyl, C2-C22alkenyl, C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; COR9; —(CO)—COO—R9; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; C1-C5alkoxy-C6-C20aryl; —(CH2)t—SO3H; —(CH2)t—(CO)—OR9; —(CH2)t—O—C6-C10aryl; —(CH2)vCOO—R9; C4-C9heteroaryl; —(CH2)u—SiR15R16R17; or a radical —X-Sil;
    R9 is hydrogen; C1-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; or C4-C9heteroaryl; or
    L1 and L2, L1 and L3, L2 and L3, L1 and R4, L2 and R4, L1 and R1, L2 and R1, L3 and R1, L3 and R5, R3 and R4, R1 and R2, R7 and R8, R5 and R6 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 and each N in a N-heterocyclic ring may be unsubstituted or substituted by R10;
    
        and each alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkylene group may be unsubstituted or substituted by one or more R11;
        and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R12;
    
    
    R10 is R13; COR13; COOR13; or CONR13R14;
    R11 is halogen, OH; NR15R16; O—R15; S—R15; O—CO—R15; CO—R15; oxo; thiono; CN; COOR15; CONR15R16; SO2NR15R16; SO2R15; SO3R15; SiR15R16R17; OSiR15R16R17; POR15R16; or a radical —X-Sil;
    R12 is C1-C12alkylthio; C3-C12cycloalkylthio; C1-C12alkenylthio; C3-C12cycloalkenylthio; C1-C12alkoxy; C3-C12cycloalkoxy; C1-C12alkenyloxy; or C3-C12cycloalkenyloxy which may be unsubstituted or substituted by one or more R11; halogen; CN; SH; OH; CHO; R18; OR18; SR18; C(R18)═CR19R20; O—CO—R19; NR18R19; CONR18R19; SO2NR18R19; SO2R18; COOR18, OCOOR18; NR18COR19; NR19COOR20; SiR15R16R17; OSiR15R16R17; P(═O)R19R20; or a radical —X-Sil;
    R13, R14, R15, R16, R17, R18, R19 and R20 independently of each other are hydrogen; C1-C22alkyl; C3-C12cycloalkyl; C2-C12alkenyl; C3-C12cycloalkenyl; C6-C14aryl; C4-C12heteroaryl; C7-C18aralkyl; or C5-C16heteroaralkyl; or
    R13 and R14, R15 and R16, R16 and R17 and/or R18 and R19 may be linked together to form unsubstituted or C1-C4alkyl-substituted pyrrolidine, piperidine, piperazine or morpholine;
    X is a linker; and
    Sil is a silane-, oligosiloxane or polysiloxane moiety;
    t is a number from 0 to 12;
    u is a number from 1 to 12;
    v is a number from 0 to 12;

if n=1

    R1 and R2 independently of each other hydrogen; C1-C22 alkyl; hydroxy-C1-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C6-C20aryl; C5-C1 heteroaralkyl; C4-C9heteroaryl; or a radical of formula






    R2, R22, R23 independently form each other are C1-C22alkyl; or C1-C22alkoxy;
    a is the bond to the linker X;
    R3 is CN; NR5R6; —COR5; —COOR5; —SO2R5; —CONR5R6; C6-C20aryl; or C4-C9heteroaryl;
    p is a number from 0 to 100
    q is a number from 1 to 20;
    s is a number from 0 to 4;

if n=2

    R1 and R2 are each a bivalent radical selected from C1-C5alkylene which may be interrupted by one or more oxygen atoms; or
    R1 and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and simultaneously R3 is defined as for n=1; or
    R3 is a bivalent radical of formula —CO—V1—C1-C12alkylene-W1—*, wherein
    the asterix indicates the bond to the second R3 
    V1 is —O—; or —NR7—; or the direct bond;
    W1 is the linkage to the second R3, wherein W1 is the direct bond; or selected from C1-C12alkylene; or phenylene; and
    R1 and R2 simultaneously are defined as for n=1;

if n=3

    one of R1, R2 or R3 is a trivalent radical;

if n=4

    R1 or R2 is a radical of formula






wherein the asterices indicate the bond to the second, third and fourth R1/R2;

    W2 is






    R3 is defined as for n=1; or
    R3 is a radical of formula






wherein the asterices indicate the bond to the second (2), third (3) and fourth (4) R3; and

    W3 is






or

    R1 or R2 is a radical of formula






the asterices indicate the bond to the second, third and fourth R1/R2;

    R24 is C1-C22alkyl; or C1-C22alkoxy;

for protecting body-care and household products from photolytic and oxidative degradation.



The term “oligosiloxane” denotes a group of the general formula

Si(R21)m[OSi(R22)]o; wherein

m is 0; 1; or 2,

o is 3, 2 or 1; and

m and o are 3; or

“oligosiloxane” is a group of formula





wherein

A is a bond to the linker X;

p is a number from 0 to 10,

q is a number from 1 to 10; and

v is a number from 0 to 1.

The term “polysiloxane” in this context refers to groups of the general formula




wherein

R21, R22 and R23, independently from each other are C1-C22alkyl or C1-C22alkoxy;

A is a bond to the linker X;

s is a number from 4 to 250;

t is a number from 5 to 250; and

q is a number from 1 to 30;

Halogen is chloro, bromo, fluoro or iodo, preferably a fluoro, more preferably fluoro alkyl like trifluormethyl, α,α,α-trifluorethyl or perfluorinated alkyl groups like heptafluorpropyl.
Alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl residues can be straight-chain or branched, or also monocyclic or polycyclic.
Alkenyl is for example straight-chain C2-C12alkenyl or preferably branched C3-C12alkenyl.
C1-C22alkyl 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-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl, oder dodecyl.
C3-C12cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl or 2-adamantyl.
C2-C12alkenyl or C3-C12cycloalkenyl refers to unsaturated hydrocarbon residues containing one or multiple double bonds such vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-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)-thujene-10-yl, 2-norbornene-1-yl, 2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaradiene-3-yl or different isomers selected from hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
C7-C18Aralkyl is for example benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, 9-fluorenyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω-phenyl-octyl, ω-phenyl-dodecyl or 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl.
The C7-C18aralkyl moiety may be unsubstituted or substituted on the alkyl- as well at the aryl-moiety of the aralkyl-group, but preferably is substituted on the aryl-moiety.
(C1-C6)-Alkylidene is for example methylene, ethyl-1-ene or propyl-2-ene.
C6-C14aryl is for example phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or terphenylyl.
C4-C12heteroaryl is for example an unsaturated or aromatic radical with 4n+2 conjugated π-electrons, such as 2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ringsystem consisting of thiophene-, furan-, pyridine, thiazol, oxazol, imidazol, isothiazol, triazol, pyridine- and phenyl rings, which are unsubstituted or substituted by 1 to 6 ethyl, methyl, ethylene and/or methylene groups, such as benzotriazolyl.
C5-C16heteroaralkyl is for example a C1-C8 alkyl moiety which is substituted by a C4-C8heteroaryl group.
Preferably compounds of formula (1) are used, wherein

    L1, L2 or L3, independently from each other are hydrogen; hydroxy; C1-C5alkyl, which may be interrupted by one or more oxygen; COOR9; phenyl, which may be substituted by one or more halogen, C1-C5alkyl, C1-C5alkoxy, trifluoroalkyl, C2-C5alkenyl; C4-C9heteroaryl; and
    R9 is defined as in claim 1; and
    n is 1; and more preferably compounds of formula (1), wherein
    L1, L2 and L3, independently from each other are hydrogen, methyl, phenyl; or —COOR9; wherein
    R9 is C1-C5alkyl; and
    n is 1.


Furthermore, compounds of formula (1) are used, wherein
L1 and L2 or L1 and L3 or L2 and L3 together form a bivalent radical selected from




Furthermore, compounds of formula (1) are preferably used, wherein

    R1 and R2 independently from each other are C1-C12alkyl; hydroxy-C1-C12alkyl; phenyl or phenyl-C1-C5alkyl, which may be substituted by one or more C1-C5alkyl, or SO3M; or a radical of formula






wherein

n is 1; and more preferably compounds of formula (1), wherein

R1 and R2, independently form each other are C1-C4alkyl;

M is hydrogen; or metal ion; and

n is 1.

Furthermore, compounds of formula (1) are preferably used, wherein
R1 and R2 together form a bivalent radical selected from




Furthermore, compounds of formula (1) are preferably used, wherein

    R3 and R4, independently from each other are CN; COR7; COOR7; CONR7R8; SO2R7; wherein
    R7 and R8, independently from each other are C1-C22alkyl; phenyl; or a radical —X-Sil;
    n is 1; and
    X and Sil are defined as in claim 1; and more preferably compounds of formula (1), wherein
    R3 and R4 together form a carboyclic or heterocyclic biradical selected from






Preferred is also the use of compounds of formula (1), wherein
R2 and L3 form a bivalent radical selected from




Most preferred is the use of compounds of formula (1), wherein

    L1, L2 or L3, independently from each other are hydrogen; hydroxy; C1-C5alkyl, which may be interrupted by one or more oxygen; COOR9; phenyl, which may be substituted by one or more halogen, C1-C5alkyl, C1-C5alkoxy, trifluoroalkyl, C2-C5alkenyl; C4-C9heteroaryl; or
    L1 and L2 or L1 and L3 or L2 and L3 together form a bivalent radical selected from






    R1 and R2 independently from each other are C1-C12alkyl; hydroxy-C1-C12alkyl; phenyl or phenyl-C1-C5alkyl, which may be substituted by one or more C1-C5alkyl, or SO3M; or a radical of formula






    R1 and R2 together form a bivalent radical selected from






    R3 and R4, independently from each other are CN; COR7; COOR7; CONR7R8; SO2R7;
    R7 and R8, independently from each other are C1-C22alkyl; phenyl; or a radical —X-Sil; or
    R3 and R4 together form a carboyclic or heterocyclic biradical selected from






    R2 and L3 form a bivalent radical selected from






and

    R9, R21, R22, R23, X and Sil are Defined as in claim 1.


Furthermore, compounds of formula (1) are preferred, wherein the stabilizers correspond to formula




wherein

R1, R2, R3, R4, L1, L2, L3, W1 and W2 are defined as in formula (1).

Preferably compounds of formula (2a) are used, wherein
R3 is a radical of formula —CO—V1—C1-C12alkylene-**, wherein
V1 is —O; or —NH—;
W1 is the direct bond; C1-C4alkylene; or phenylene;
R1 and R2, independently from each other are C1-C12alkyl;
L1, L2 and L3 independently form each other are hydrogen; or C1-C5alkyl; or
L3 and R2 together form a heterocyclic ring;
R4 is CN; COR7; COOR7; CONR7R8; SO2R7; and
R7 is C1-C22alkyl; or phenyl.
Preferred compounds of formula (2b) are those, wherein
R1 is C1-C3alkylene;
L1, L2 and L3 independently form each other are hydrogen; or C1-C5alkyl; or
L1 and L3 together form a carbocyclic ring;
R2 is hydrogen; or C1-C5alkyl;
W1 is C1-C3alkylene; or the direct bond;
R3 and R4 independently from each other are CN; COR7; COOR7; CONR7R8; SO2R7; and
R7 and R8, independently from each other are C1-C22alkyl; or phenyl.
Furthermore, the use of compounds of formula




wherein

R1, R2, R3, R4, L1, L2, L3, W2 and W3 are defined as in claim 1.

More preferred compounds of formula (3a) are those, wherein

    L1, L2 and L3 independently from each other are hydrogen; hydroxy; C1-C5alkyl; or L1 and L3 together form a carbocyclic ring;
    R1 and R2 independently from each other are hydrogen; or C1-C12alkyl;
    R3 is *—CO—V1—C1-C12alkylene-**;
    V1 is —O; or —NH—;
    W2 is a tetravalent radical of formula






    R4 is CN; COR7; COOR7; CONR7R8; SO2R7; and
    R7 and R8, independently from each other are C1-C22alkyl; or phenyl.


Further preference is given to the use of polymeric or oligomeric compounds comprising structural elements of formula




wherein

at least one of the asterix-marked radicals may be bound to the oligomeric or polymeric radical; and

L1, L2, L3, R2 and R4 are defined as in formula (1).

Compounds of formula (4) are known and examples are disclosed in DE 3531383 on the pages 8-11.
Examples of merocyanine derivatives which are useful for the present invention are listed in the table below:







TABLE MC1a













 















R1
R2
L1
L2
L3
R3
R4


















MC01
CH3
CH3
H
H
H
—COOCH3
—COOCH3


MC02
C2H5
C2H5
H
H
H
—COO C2H5
—COOSi(CH3)3


MC03
C2H5
C2H5
H
H
H
COOC8H17-(n)
SO2C6H5


MC04
C2H5
C2H5
H
H
H
CN
COOC8H17-(i)


MC05
C4H9
C4H9
H
H
H
COOC6H13-(n)
SO2C6H5


MC06
C4H9
C4H9
H
H
H
—COO C4H9-(n)
SO2C6H5


 


MC07
C4H9
C4H9
H
H
H
—COO C4H9-(t)






 


MC08
n-C6H13
n-C6H13
H
H
H
CN
CN


MC09
i-C8H17
i-C8H17
H
H
H
CN
CN


MC10
C2H5
C2H5
CH3
H
H
—COOC2H5
—COOSi(CH3)3


MC11
C2H5
C2H5
CH3
H
H
—CONHC2H5
—CONHC2H5


MC12
C2H5
C2H5
CH3
H
CH3
—CON(C2H5)2
—CON(C2H5)2


MC13
C2H5
C2H5
CH3
H
H
CN
COOC8H17-(i)


MC14
C2H5
C2H5
CH3
H
CH3
CN
COOCH3


MC15
C2H5
C2H5
CH3
H
H
SO2C6H5
COOC8H17-(n)


 


MC16
C2H5
C2H5
CH3
H
H




COOC2H5


 


MC17
C2H5
C2H5
CH3
H
CH3
—CONHC2H5
—CONHC2H5


MC18
C2H5
C2H5
CH3
H
CH3
—CON(C2H5)2
—CON(C2H5)2


MC19
CH3
CH3
CH3
H
CH3
CN
COOC8H17-(i)


MC20
CH3
CH3
CH3
H
CH3
CN
—CON(C2H5)2


 


MC21
CH3
CH3
CH3
H
CH3




—CONHC2H5


 













MC22 MC23 MC24




H CH3 CH3
H H H
H H CH3



   CN   



COOC2H5 COOC8H17-(i) COOC2H5


 


MC25 MC26 MC27 MC28




CH3 CH3 CH3 CH3
H H CH3 CH3
H H CH3 CH3
SO2C6H5   


   CN CN
—COO C2H5 —COOSi(CH3)3 COOC8H17-(i) SO2C6H5


 














MC29


CH3
H
H
CN
COOC8H17-(i)


 













MC30
i-propyl
i-propyl
CH3
H
H






 


MC31
CH3
CH3
CH3
H
H






 














MC32
CH3




H
H
—
SO2—C6H5
COO-n-C6H13


 


MC33
CH3




H
H
—
CN
COO-n-C12H25


 


MC34
n-C12H25




H
H
—
CN
CN


 


MC35
n-C10H21




H
H
—




COOC2H5


 


MC36
CH3




H
H
—




COO-n-C10H21


 


MC37
C2H5




H
H
—
CONH-n-C12H25
CN


 


MC38
n-C10H21




H
H
—




COOC2H5


 


MC39
n-C10H21




H
H
—




COOC6H13-(n)


 


MC40
n-C10H21




H
H
—
*—SO2-n-C6H13
COOH


 


MC41
n-C6H13
n-C6H13
H
H
H
—COOC2H5






 













MC42
n-C4H9
n-C4H9
H
H
H






 














MC43
CH3
CH3
H
H
H










 


MC44
n-C6H13
n-C6H13
H
H
H
COCH3
COCH3


MC45
n-C6H13
n-C6H13
H
H
H
CN
CN


 













MC46
n-C6H13
n-C6H13
H
H
H






 













MC47




H
H
H




COCH3


 














MC48
n-C6H13
n-C6H13
H
H
H










 


MC49
n-C4H9
n-C4H9
H
H
H
CO2CH3






 













MC50




H
H
H
COCH3






 













MC51
n-C6H13
n-C6H13
H
H
H






 














MC52




n-C16H33
H
H
H
CO2C4 H9-(n)






 


MC53
C2H5
C2H5
H
H
H
COOC12H25-(n)






 


MC54
n-C4H9
n-C4H9
H
H
H
COOC14H29-(n)






 


MC55
H
sec-butyl




H
—




CN


 


MC56
H
n-hexyl




H
—
COOC2H5
CN


 













MC57
CH3
CH3
CH3
H
H






 












MC58




CH3
H
H






 













MC59
CH3




CH3
H
—






 














MC60
H
CH3
CH3
H
CH3
—COOCH3
—COOCH3


 












MC61




H
CH3
H






 














MC62
CH3
n-butyl
CH3
H
CH3
—COOC2H5
—COOC2H5


 













MC63
CH3
CH3
H
H
CH3






 













MC64
CH3
CH3
H




CN
COCH3


 














MC65
CH3
CH3
CH3
H
H










 













MC66




CH3
H
CH3




COCOOC2H5


 














MC67
CH3




t-butyl
H
—
CON(C2H5)2
COCH3


 













MC68
i-propyl
i-propyl




H
CN
CN


 


MC69
CH3
CH3




H
CN
CN


 














MC70








CH3
H
H










 













MC71




H
CH3
H










 














MC72
n-propyl
n-propyl
CH3
H
H
CO-t-butyl






 


MC73
CH3
CH3
C2H5
H
H




CN


 


MC74
C2H5
C2H5
CH3
CH3
CH3
COOC2H5
COOC2H5


 


MC75
CH3
CH3




H
CH3
COOC2H5
COOC2H5


 


MC76
CH3
CH3
H




CH3
COOC2H5
CN


 


MC77
CH3
CH3




H




COOC2H5
COOC2H5


 


MC78
CH3
CH3




H
CH3
CN
COOC2H5


 


MC79
CH3
CH3




H
CH3
CN
COOC2H5


 













MC80
CH3
CH3




H
COOC2H5
CN


 














MC81
CH3
CH3




H
CH3
CN
COOC2H5


 


MC82




CH3
H
H




CN
COOC2H5


 


MC83
n-butyl
n-butyl
CH3
H
H
COOCH3






 


MC84
CH3
CH3
H
H




COCH3






 


MC85
CH3
CH3
H
H




CN
COOCH3


 


MC86
CH3
CH3




H
H
COOCH3
COOCH3


 


MC87
CH3
CH3
H
H




CN
COO-t-butyl


 


MC88
n-butyl
n-butyl
H
H




CN
COO-t-butyl


 


MC89
C2H5
C2H5
H
H




CN






 


MC90
CH3
CH3




H
CH3
CN
COO-i-propyl


 













MC91




H
H




CN
COO-t-butyl


 














MC92
C2H5
C2H5
H
H




CN
COO—C2H5


 


MC93
CH3
CH3
H
H
CN
CN
COO—CH3


 


MC94
C2H5OH
C2H5OH
H
H




CN
COO—C2H5


 


MC95
H
C2H5
H
H




CN
COO—C2H5


 













MC96
C2H5
n-propyl




H
CN
CN


 














MC97
C2H5
C2H5
C2H5
H
H










 


MC98
C2H5OH
C2H5OH
CH3
CH3
H




CN


 


MC99
H




CH3
H
H




COCH3


 













MC100




C2H5
H
H




CN


 


MC101




C2H5
H
H
COOSi(CH3)3






 













MC102
i-propyl
i-propyl
OH
H
H






 


MC103
CH3
CH3
OH
H
H






 


MC104
CH3
CH3
OH
H
H






 


MC105
CH3
CH3
OH
H
H






 


MC106
CH3




OH
H
—






 


MC107
CH3
CH3
OH
H
H






 












MC108




OH
H
H






 













MC109
CH3
n-butyl
OH
H
H






 













MC110
CH3
CH3
OH




CN
COCH3


 














MC111
CH3
CH3
CH3
H
H










 













MC112




OH
H
H










 














MC113
CH3




OH
H
—
CON(C2H5)2
COCH3


 












MC114




OH
H
H






 













MC115
CH3
CH3
OH
H
H






 


MC116
CH3
n-butyl
OH
H
H






 


MC117
i-propyl
i-propyl
OH
H
H






 


MC118
CH3
CH3
OH
H
H






 


MC119
CH3
CH3
OH
H
H






 














MC120
CH3
CH3




H
H
COOCH3
CN


 


MC121
CH3
CH3
OCH3
H
H
COOCH3
CN


 













MC122




OC2H5
H




COOCH3
—


 














MC123
C2H5




OC2H5
H
—
COOC2H5
COOC2H5


 


MC124
CH3
CH3




—
H
COOC2H5
CN


 


MC125
CH3
CH3




H
H
—
COOC2H5


 


MC126
CH3
CH3




H
—
COOCH3
CN


 


MC127
C2H5
C2H5
H
H
H
n-COOC6H13


























MC128






 


MC129






 


MC130






 


MC131






 


MC132






 


MC133






 


MC134






 


MC135






 


MC136






 


MC137






 


MC138






 


MC139






 


MC140






 


MC141






 


MC142






 


MC143






 


MC144






 


MC145






 


MC146






 


MC147






 


MC148






 


MC149






 


MC150






 


MC151






 


MC152






 


MC153






 


MC154






 


MC155






 


MC156






 


MC157






 


MC158






 


MC159






 


MC160






 


MC 161






 


MC 162






 


MC 163






 


MC 164






 


MC 165






 


MC 166






 


MC 167






 


MC 168






 


MC 169






 


MC 170






 


MC 171













The compounds of formula (1) are known, for example from WO04/006878
Compounds however, which correspond to the formula




wherein

    R3 is CN; NR5R6; —COR5; —COOR5; —SO2R5; —CONR5R6; C6-C20aryl; or C4-C9heteroaryl;
    R4 is CN; —COR7; —COOR7; —CONR7R8; C1-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; C1-C1alkylcarbonylamino-C6-C20aryl; C4-C9heteroaryl;
    R5, R6, R7 and R8 are independently of each other hydrogen; C1-C22alkyl, C2-C22alkenyl, C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; COR9; —(CO)—COO—R9; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; C1-C5alkoxy-C6-C20aryl; —(CH2)t—SO3H; —(CH2)t—(CO)—OR9; —(CH2)t—O—C6-C20aryl; —(CH2)vCOO—R9; C4-C9heteroaryl; —(CH2)u—SiR15R16R17; or a radical —X-Sil;
    R9 is hydrogen; C1-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; or C4-C9heteroaryl; or
    L1 and L3, are H or 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 and each N in a N-heterocyclic ring may be unsubstituted or substituted by R10;
    
        and each alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkylene group may be unsubstituted or substituted by one or more R11;
        and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R12;
    
    
    R10 is R13; COR13; COOR13; or CONR13R14;
    R11 is halogen, OH; NR15R16; O—R15; S—R15; CO—R15; oxo; thiono; CN; COOR15; CONR15R16; SO2NR15R16; SO2R15; SO3R15; SiR15R16R17; OSiR15R16R17; POR15R16; or a radical —X-Sil;
    R12 is C1-C12alkylthio; C3-C12cycloalkylthio; C1-C12alkenylthio; C3-C12cycloalkenylthio; C1-C12alkoxy; C3-C12cycloalkoxy; C1-C12alkenyloxy; or C3-C12cycloalkenyloxy which may be unsubstituted or substituted by one or more R11; halogen; CN; SH; OH; CHO; R18; OR18; SR18; C(R18)═CR19R20; O—CO—R19; NR18R19; CONR18R19; SO2NR18R19; SO2R18; COOR18, OCOOR18; NR18COR19; NR19COOR20; SiR15R16R17; OSiR15R16R17; P(═O)R19R20; or a radical —X-Sil;
    R13, R14, R15, R16, R17, R18, R19 and R20 independently of each other are hydrogen; C1-C22alkyl; C3-C12cycloalkyl; C2-C12alkenyl; C3-C12cycloalkenyl; C6-C14aryl; C4-C12heteroaryl; C7-C18aralkyl; or C5-C16heteroaralkyl; or
    R13 and R14, R15 and R16, R16 and R17 and/or R18 and R19 may be linked together to form unsubstituted or C1-C4alkyl-substituted pyrrolidine, piperidine, piperazine or morpholine;
    X is a linker; and
    Sil is a silane-, oligosiloxane or polysiloxane moiety;
    t is a number from 0 to 12;
    u is a number from 1 to 12;
    v is a number from 0 to 12;

if n=1

    R1 and R2 independently of each other hydrogen; C1-C22 alkyl; hydroxy-C1-C22alkyl; C2-C22alkenyl; C2-C22alkinyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C6-C20aryl; C5-C1 heteroaralkyl; C4-C9heteroaryl; or a radical of formula






    R21, R22, R23 independently form each other are C1-C22alkyl; or C1-C22alkoxy;
    p is a number from 0 to 100
    q is a number from 1 to 20;
    s is a number from 0 to 4;
    R3 is CN; NR5R6; —COR5; —COOR5; —SO2R5; —CONR5R6; C6-C20aryl; or C4-C9heteroaryl;

if n=2

    R1 and R2 are each a bivalent radical selected from C1-C5alkylene which may be interrupted by one or more oxygen atoms; or
    R1 and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and simultaneously R3 is defined as for n=1; or
    R3 is a bivalent radical of formula —CO—V1—C1-C12alkylene-W1—*, wherein
    the asterix indicates the bond to the second R3 
    V1 is —O—; or —NR7—; or the direct bond;
    W1 is the linkage to the second R3, wherein W1 is the direct bond; or selected from C1-C12alkylene; or phenylene; and
    R1 and R2 simultaneously are defined as for n=1;

if n=3

    one of R1, R2 or R3 is a trivalent radical;

if n=4

    R1 or R2 is a radical of formula






wherein

    the asterices indicate the bond to the second, third and fourth R1/R2;
    W2 is






    R3 is defined as for n=1; or
    R3 is a radical of formula






wherein the asterices indicate the bond to the second (2), third (3) and fourth (4) R3; and

    W3 is






    or
    R1 or R2 is a radical of formula






the asterices indicate the bond to the second, third and fourth R1/R2;

    R24 is C1-C22alkyl; or C1-C22alkoxy;

wherein at least one of the radicals R1, R2, R3 or R4 is a silicon organic compound, are novel and represent a further object of the present invention.



The light stabilizers of formula (1) as well as mixtures of these compounds with other UV absorbers as listed in Tables 1-3, phenolic or non-phenolic antioxidants or with complex formers are particularly suitable for protecting body-care and household products against photolytic degradation.
Examples of organic UV filters that can be used in admixture with the compounds of formula (1) are listed in the following Table:







TABLE 1





Suitable UV filter substances which can be additionally used with the compounds


of formula (1)















p-aminobenzoic acid derivatives, for example 4-dimethylaminobenzoic acid 2-ethylhexyl


ester;


salicylic acid derivatives, for example salicylic acid 2-ethylhexyl ester;


benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its


5-sulfonic acid derivative;


diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3-(benzo-


furanyl) 2-cyanoacrylate;


3-imidazol-4-ylacrylic acid and esters;


benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran derivatives, described in


EP-A-582 189, U.S. Pat. No. 5,338,539, U.S. Pat. No. 5,518,713 and EP-A-613 893;


polymeric UV absorbers, for example the benzylidene malonate derivatives described in


EP-A-709 080;


camphor derivatives, for example 3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidene-


bornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4′-


trimethylammonium)-benzylidene-bornan-2-one methyl sulfate, 3,3′-(1,4-phenylenedi-


methine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic acid) and salts,


3-(4′-sulfo)benzylidene-bornan-2-one and salts; camphorbenzalkonium methosulfate;


hydroxyphenyltriazine compounds, for example 2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-


n-octyloxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-


phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-


phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine; 2,4-bis{[4-(tris-


(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;


2,4-bis{[4-(2′′-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;


2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2′′-methyl-propyloxy)-2-hydroxy]-phenyl}-6-


(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-


hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;


benzotriazole compounds, for example 2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-


(1,1,3,3-tetramethylbutyl)-phenol;


trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-


triazine and the UV absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104, EP-A-507 691,


WO 93/17002 and EP-A-570 838;


2-phenylbenzimidazole-5-sulfonic acid and salts thereof;


menthyl o-aminobenzoates;


physical sunscreens coated or not as titanium dioxide, zinc oxide, iron oxides, mica, MnO,


Fe2O3, Ce2O3, Al2O3, ZrO2. (surface coatings: polymethylmethacrylate, methicone


(methylhydrogenpolysiloxane as described in CAS 9004-73-3), dimethicone, isopropyl


titanium triisostearate (as described in CAS 61417-49-0), metal soaps as magnesium


stearate (as described in CAS 4086-70-8), perfluoroalcohol phosphate as C9-15


fluoroalcohol phosphate (as described in CAS 74499-44-8; JP 5-86984, JP 4-330007)).


The primary particle size is an average of 15 nm-35 nm and the particle size in dispersion is


in the range of 100 nm-300 nm.


aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP 1133980 and EP


1046391


phenyl-benzimidazole derivatives as disclosed in EP 1167358


the UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker,


Inc., New York and Basle or in Cosmetics & Toiletries (107), 50ff (1992) also can be used


as additional UV protective substances.
















TABLE 2





Suitable UV filter substances which can be additionally used with the UV


absorbers according to the present invention
















DE 10013318
T 1 pp 8-9, all Examples pp 10-13, T 2 pp 13-14, all Examples p



14, Ex A, B, C, D, E, F pp 19-20


DE102004038485 A1
Formula 1 on p 2; Ex 1-4 on p 13;


DE102004039281 A1
Formulas I-II on p 1; Ex Ia-Iae on pp 7-12; Ex IIa-IIm on pp 14-15;



Ex 1-25 on pp 42-56;


DE 10206562 A1
Ex 1-3 p 10, Ex 4-7 p 11, Ex 8-15 pp 12-14


DE 10238144 A1
Ex on p 3-5;


DE 10331804
T 1 p 4, T 2 + 3 p 5


DE 19704990 A1
Ex 1-2 on pp 6-7;


EP 613 893
Ex 1-5 + 15, T 1, pp 6-8


EP 0 998 900 A1
Ex on pp 4-11


EP 1 000 950
Comp. In Table 1, pp 18-21


EP 1 005 855
T 3, p 13


EP 1 008 586
Ex 1-3, pp 13-15


EP 1 008 593
Ex 1-8, pp 4-5


EP 1 027 883
Compound VII, p 3


EP 1 027 883
Comp I-VI, p 3


EP 1 028 120
Ex 1-5, pp 5-13


EP 1 059 082
Ex 1; T 1, pp 9-11


EP 1 060 734
T 1-3, pp 11-14


EP 1 064 922
Compounds 1-34, pp 6-14


EP 1 077 246 A2
Ex 1-16 on pp 5-11;


EP 1 081 140
Ex 1-9, pp 11-16


EP 1 103 549
Compounds 1-76, pp 39-51


EP 1 108 712
4,5-Dimorpholino-3-hydroxypyridazine


EP 1 123 934
T 3, p 10


EP 1 129 695
Ex 1-7, pp 13-14


EP 1 167 359
Ex 1, p 11 and Ex 2, p 12


EP 1 232 148 B1
Ex 4-17 on pp 3-5;


EP 1 258 481
Ex 1, pp 7, 8


EP 1 310 492 A1
Ex 1-16 on pp 22-30


EP 1 371 654 A1
Ex on pp 5-7


EP 1 380 583 A2
Ex 1, p 6;


EP 1 423 351 A2
Ex 1-16 on pp 31-37;


EP 1 423 371 A1
T 1 on pp 4-8, Ex on p 9, Ex 1-9 on pp 36-42;


EP 1 454 896 A1
Ex 1-5 on pp 10-13, Examples on pp 4-5;


EP 1 471 059 A1
Ex 1-5 on pp 4-5;


EP 1 484051 A2
Formula III-VII on pp18-19, Ex 7-14 on pp 7-9, Ex 18-23 on pp 11-12,



Ex 24-40 on pp 14-17;


EP 1648849 A2
Formula 1 on p 4; Ex 1-2 on pp 13-17; Ex C10 and O10 on pp15-16;


EP 420 707 B1
Ex 3, p 13 (CAS Reg. No 80142-49-0)


EP 503 338
T 1, pp 9-10


EP 517 103
Ex 3, 4, 9, 10 pp 6-7


EP 517 104
Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8


EP 626 950
all compounds


EP 669 323
Ex 1-3, p 5


EP 743 309 A1
Ex 1-12 on pp 18-24;


EP 780 382
Ex 1-11, pp 5-7


EP 823 418
Ex 1-4, pp 7-8


EP 826 361
T 1, pp 5-6


EP 832 641
Ex 5 + 6 p 7; T 2, p 8


EP 832 642
Ex 22, T 3, pp 10-15; T 4, p 16


EP 848944 A2
Formulas I and II on p 1; Ex on p 8; Examples on p 10;


EP 852 137
T 2, pp 41-46


EP 858 318
T 1, p 6


EP 863 145
Ex 1-11, pp 12-18


EP 878 469 A1
T 1, pp 5-7;


EP 895 776
Comp. In rows 48-58, p 3; R 25 + 33, p 5


EP 911 020
T 2, pp 11-12


EP 916 335
T 2-4, pp 19-41


EP 924 246
T 2, p 9


EP 933 376
Ex 1-15, pp 10-21


EP 944 624
Ex 1 + 2, pp 13-15


EP 945 125
T 3 a + b, pp 14-15


EP 95 097
Ex 1, p 4


EP 967 200
Ex 2; T 3-5, pp 17-20


EP 969 004
Ex 5, T 1, pp 6-8


FR 2842806 A1
Ex I p 10, Ex II p 12


FR 2861075 A1
Ex 1-3 on pp 12-14;


FR 2862641
Formula 3 on p4; Ex A-J on pp 7-9;


FR 2869907 A1
Formula 1 on p 6; T 1 on p 7-8; Ex 4-39 on pp 12-35;


KR 2004025954
all kojyl benzoate derivatives


JP 06135985 A2
Formula 1 on p 2; Ex 1-8 on pp 7-8;


JP 2000319629
CAS Reg Nos. 80142-49-0, 137215-83-9, 307947-82-6


JP 2003081910 A
Ex on p 1;


JP 2005289916 A
Formula I on p 1; Ex Ia-Id on pp 2-3;


JP 2005290240 A
Formulas I on p 2, Ex II on p 2;


US 2003/0053966 A1
Ex on pp 3-6


US 2004057912 A1
Ex on p 7-9, Ex 1 on p 10;


US 2004057914 A1
Ex on p 8-12, Ex 1 on p 12;


US 2004/0057911 A1
Formula I and II on p 1; formula III and IV on p3; Ex 1-3 on pp 5-6;


US 2004/0071640 A1
Ex 1-12 on pp 4-7;


US 2004/0091433 A1
Ex 1-6 on pp 14-16;


US 2004/0136931 A1
Ex 1-3 on p 7;


US 2004/0258636 A1
Ex 1-11 on pp 9-15;


US 2005/0019278 A1
Ex 1-9 on pp 6-8;


US 2005/0136012 A1
Formula 1 on p 2;


US 2005/0136014 A1
Formula a-c on p 2; Examples on p 3;


US 2005/0201957 A1
Formula 1 on p1; Ex A, B, C, D, E, F, G on pp 2-3;


US 2005/0249681 A1
all compounds on pp 2-3, Ex 1 on p 6;


US 2005186157 A1
Formula 1 on p 1; Ex 1-6 on pp 2-4;


US 2005260144 A1
Formula I on p1; Formula II on p 3; Ex 1-10 on pp 8-11;


US 2006018848 A1
Ex a-p on pp 3-4;


US 2006045859 A1
Formula 1 on p 1; Ex 1-10 on pp 2-4;


U.S. Pat. No. 5,635,343
all compounds on pp 5-10


U.S. Pat. No. 5,332,568
Ex 1, p 5, T 1 + 2, pp 6-8


U.S. Pat. No. 5,338,539
Ex 1-9, pp 3 + 4


U.S. Pat. No. 5,346,691
Ex 40, p 7; T 5, p 8


U.S. Pat. No. 5,801,244
Ex 1-5, pp 6-7


U.S. Pat. No. 6,613,340
Ex I, II pp 9-11, Examples on rows 28-53 p 6


U.S. Pat. No. 6,800,274 B2
Formulas I-VI and IX-XII on pp 14-18;


U.S. Pat. No. 6,890,520 B2
Ex 1-10 on pp 6-9;


U.S. Pat. No. 6,926,887 B2
Ex A on pp5/6; Formulas I-VIII on pp 27-29;


U.S. Pat. No. 6,936,735 B2
Formulas 1-2 on p 2; formula 3-4 on p 6;


U.S. Pat. No. 6,962,692 B2
Formulas VII and VIII on p 6; Formulas I, II, IV-VI, IX, X on pp 14-16;



Formula III on p 19;


WO 0149686
Ex 1-5, pp 16-21


WO 0168047
Tables on pp 85-96


WO 0181297
Ex 1-3, pp 9-11


WO 0191695
Formula I on p 4, T on p 8


WO 0202501 A1
Ex Ia-c, p 5


WO 02069926 A1
Ex on p 9, Ex on pp 17-23


WO 02072583
T on pp 68-70


WO 02080876
Ex 1 on pp 7-9


WO 0238537
All compounds p 3, compounds on rows 1-10 p 4


WO 03004557 A1
Ex A1-A29 on pp 36-57;


WO 03007906
Ex I-XXIII, pp 42-48


WO 03086341 A2
Formula 2-21, pp 4-6;


WO 03092643 A1
T on pp 34-35, compounds listed on p 16


WO 03097577 A1
Ex on pp 6-8; Ex 1-3 on pp 15-18;


WO 03104183 A1
Formula I-IV on p 1; Ex 1-5 on pp 27-28;


WO 04000256 A1
Ex 1-10 on pp 18-24


WO 04020398 A1
Ex 1-3 on pp 14-17


WO 04020398 A1
Formulas I-VI on pp 21-24, Formula IX on p 25;


WO 04075871
Ex 1-3 on pp 17-18; Ex 7-9 on pp 21-22;


WO 05009938 A2
Formula I on p 1; Ex 1-2 on pp 14-15;


WO 05065154 A2
Formula a-c on pp 5-6;


WO 05080341 A1
Formula 1 on p 3; Examples on pp 9-13;


WO 05107692 A1
Formula 1 on p 2; Ex 1-9 on pp 27-29;


WO 05118562 A1
Formula I on p 4; Ex Ia-Ig on p 5;


WO 05121108 A1
Formula I on p 3; Formula Ia on p 5; T 1 on p 7; Ex 3-22 on pp 11-23;


WO 06009451
T 1 on pp 5-8; Formulas III and UV0 on p 9;


WO 06016806
T 1 on pp 6-7; T 2 on p 10; T 3 on p 11; T 4 on p 15;


WO 06032741
Formulas 1-3 on p 1; Ex a-k on pp 5-7; Ex 1-4 on pp 18-20;


WO 9217461
Ex 1-22, pp 10-20


WO 9220690
Polymeric Comp in Examples 3-6


WO 9301164
T 1 + 2, pp 13-22


WO 9714680
Ex 1-3, p 10





(Abbreviations T: Table, R: row, Comp: compound, Ex: compound(s) of Patent Example, p: page; the generic scope of the UV absorbers is described in the left-hand column; specific compounds are indicated in the right-hand column)













TABLE 3







Suitable UV filter substances and adjuvants which can be additionally used with the


compounds of formula (1)









No.
Chemical Name
CAS No.












1
(+/−)-1,7,7-trimethyl-3-[(4-methylphenyl)methylene]bicyclo[2.2.1]-
36861-47-9



heptan-2-one; p-methyl benzylidene camphor


2
1,7,7-trimethyl-3-(phenylmethylene)bicyclo[2.2.1]heptan-2-one;
15087-24-8



benzylidene camphor


3
(2-Hydroxy-4-methoxyphenyl)(4-methylphenyl)methanone
1641-17-4


4
2,4-dihydroxybenzophenone
131-56-6


5
2,2′,4,4′-tetrahydroxybenzophenone
131-55-5


6
2-Hydroxy-4-methoxy benzophenone
131-57-7


7
2-Hydroxy-4-methoxy benzophenone-5-sulfonic acid
4065-45-6


8
2,2′-dihydroxy-4,4′-dimethoxybenzophenone
131-54-4


9
2,2′-Dihydroxy-4-methoxybenzophenone
131-53-3


10
Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts;
56039-58-8



Mexoryl SL


11
1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)propane-1,3-
70356-09-1



dione; avobenzone


12
Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2-
52793-97-2



ylidene)methyl]anilinium sulphate; Mexoryl SO


22
3,3,5-Trimethyl cyclohexyl-2-hydroxy benzoate; homosalate
118-56-9


27
Menthyl-o-aminobenzoate
134-09-8


28
Menthyl salicylate
89-46-3


29
2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; Octocrylene
6197-30-4


30
2-ethylhexyl 4-(dimethylamino)benzoate
21245-02-3


32
2-ethylhexyl salicylate
118-60-5


33
Benzoic acid, 4,4′,4′′-(1,3,5-triazine-2,4,6-triyltriimino)tris-,
88122-99-0



tris(2-ethylhexyl)ester; 2,4,6-Trianilino-(p-carbo-2′-ethylhexyl-1′-oxi)-



1,3,5-triazine; octyl triazone


34
4-aminobenzoic acid
150-13-0


35
Benzoic acid, 4-amino-, ethyl ester, polymer with oxirane
113010-52-9


38
2-phenyl-1H-benzimidazole-5-sulphonic acid;
27503-81-7



phenylbenzimidazolsulfonic acid


39
2-Propenamide, N-[[4-[(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-2-
147897-12-9



ylidene)methyl]phenyl]methyl]-, homopolymer


40
Triethanolamine salicylate
2174-16-5


41
3,3′-(1,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-
90457-82-2



bicyclo[2.2.1]heptane-1 methanesulfonic acid]; Cibafast H


42
Titanium dioxide
13463-67-7


44
Zinc oxide
1314-13-2


45
2,2′-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl-
103597-45-1



butyl)-phenol]; Tinosorb M


46
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-
187393-00-6



(1,3,5)-triazine; Tinosorb S


47
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-,
180898-37-7



disodium salt


48
Benzoic acid, 4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]phenyl]-
154702-15-5



amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhexyl)ester; di-



ethylhexyl butamido triazone; Uvasorb HEB


49
Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-
155633-54-8



tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizole



trisiloxane; Mexoryl XL


50
Dimethicodiethylbenzalmalonate; Polysilicone 15; Parsol SLX
207574-74-1


51
Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-
92484-48-5



methylpropyl)-, monosodium salt; Tinogard HS


53
1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]propyl]-
156679-41-3



N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1); Escalol



HP610


54
1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)-
177190-98-6



amino]-, chloride


55
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-
170864-82-1


56
1,3,5-Triazine, 2,4,6-tris(4-methoxyphenyl)-
7753-12-0


57
1,3,5-Triazine, 2,4,6-tris[4-[(2-ethylhexyl)oxy]phenyl]-
208114-14-1


58
1-Propanaminium, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethyl-
340964-15-0



ethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-,



methyl sulfate (salt)


59
2-Propenoic acid, 3-(1H-imidazol-4-yl)-
104-98-3


60
Benzoic acid, 2-hydroxy-, [4-(1-methylethyl)phenyl]methyl ester
94134-93-7


61
1,2,3-Propanetriol, 1-(4-aminobenzoate); glyceryl PABA
136-44-7


62
Benzeneacetic acid, 3,4-dimethoxy-a-oxo-
4732-70-1


63
2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester
5232-99-5


64
Anthralinic acid, p-menth-3-yl ester
134-09-8


65
2,2′-bis(1,4-phenylene)-1H-benzimidazole-4,6-disulphonic acid mono
349580-12-7,



no sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate or



Neoheliopan AP


66
1,3,5-Triazine-2,4,6-triamine, N,N′-bis[4-[5-(1,1-dimethylpropyl)-2-
288254-16-0



benzoxazolyl]phenyl]-N′′-(2-ethylhexyl)- or Uvasorb K2A


68
sterols (cholesterol, lanosterol, phytosterols), as described in



WO0341675


69
mycosporines and/or mycosporine-like amino acids as described in



WO2002039974, e.g. Helioguard 365 from Milbelle AG, isolated



mycosporine like amino acids from the red alga porphyra umbilicalis



(INCI: Porphyra Umbilicalis) that are encapsulated into liposomes,)


70
alpha-lipoic-acid as described in DE 10229995


71
synthetic organic polymers as described in EP 1371358, [0033]-[0041]


72
phyllosilicates as described in EP 1371357 [0034]-[0037]


73
silica compounds as described in EP1371356, [0033]-[0041]


74
inorganic particles as described in DE10138496 [0043]-[0055]


75
latex particles as described in DE10138496 [0027]-[0040]


76
1H-Benzimidazole-4,6-disulfonic acid, 2,2′-(1,4-phenylene)bis-,
180898-37-7



disodium salt; Bisimidazylate; Neo Heliopan APC


77
Pentanenitrile, 2-[2,3-dihydro-5-methoxy-3,3-dimethyl-6-[(2-methyl-
425371-15-9



2-propenyl)oxy]-1H-inden-1-ylidene]-4,4-dimethyl-3-oxo-


78
Pentanenitrile, 2-(2,3-dihydro-6-hydroxy-5-methoxy-3,3-dimethyl-1H-
425371-14-8



inden-1-ylidene)-4,4-dimethyl-3-oxo-


79
Benzenepropanenitrile, α-(2,3-dihydro-3,3,5-trimethyl-1H-inden-1-
425371-11-5



ylidene)-β-oxo-


80
Cyclohexanepropanenitrile, α-[5-(1,1-dimethylethyl)-2,3-dihydro-3,3-
425371-10-4



dimethyl-1H-inden-1-ylidene]-1-methyl-β-oxo-


81
Pentanenitrile, 2-[6-(acetyloxy)-2,3-dihydro-5-methoxy-3,3-dimethyl-
425371-09-1



1H-inden-1-ylidene]-4,4-dimethyl-3-oxo-


82
Pentanenitrile, 2-[2,3-dihydro-5-methoxy-3,3-dimethyl-6-[2-methyl-3-
425371-08-0



[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]-1H-



inden-1-ylidene]-4,4-dimethyl-3-oxo-


83
Pentanenitrile, 2-(2,3-dihydro-5-methoxy-3,3,6-trimethyl-1H-inden-1-
425371-07-9



ylidene)-4,4-dimethyl-3-oxo-


84
Pentanenitrile, 4,4-dimethyl-3-oxo-2-(2,3,7,8-tetrahydro-8,8-
425371-06-8



dimethyl-6H-indeno[5,6-b]-1,4-dioxin-6-ylidene)-


85
Pentanenitrile, 2-(2,3-dihydro-3,3,6-trimethyl-1H-inden-1-ylidene)-
425371-05-7



4,4-dimethyl-3-oxo-


86
Pentanenitrile, 2-(2,3-dihydro-3,3,5,6-tetramethyl-1H-inden-1-
425371-04-6



ylidene)-4,4-dimethyl-3-oxo-


87
Pentanenitrile, 2-(2,3-dihydro-5-methoxy-3,3,4,6-tetramethyl-1H-
425371-03-5



inden-1-ylidene)-4,4-dimethyl-3-oxo-


88
Pentanenitrile, 2-(2,3-dihydro-5,6-dimethoxy-3,3-dimethyl-1H-inden-
261356-13-2



1-ylidene)-4,4-dimethyl-3-oxo-









The compounds of formula (1) may also be used in admixture with phenolic or lactone-type antioxidants as disclosed for example in WO00/25731.
The compounds of formula (1) may also be used in admixture with hindered amine light stabilizers as disclosed in WO 03/103622, e.g, hindered nitroxyl, hydroxylamine and hydroxylamine salt compounds.
Personal Care Uses
The merocyanines of formula (1) 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.
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.
Suitable bath and shower additives are shower gels, bath-salts, bubble baths and soaps.
Preparations containing fragrances and odoriferous substances are in particular scents, perfumes, toilet waters and shaving lotions (aftershave preparations).
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.
Suitable dentifrices are in particular tooth creams, toothpastes, mouth-washes, mouth rinses, anti-plaque preparations and cleaning agents for dentures.
Suitable decorative preparations are in particular lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions.
Suitable cosmetic formulations containing active ingredients are in particular hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
The mentioned body-care products may be in the form of creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols.
They preferably contain the light stabilizers of formulae (1) and, optionally, other UV absorbers, sterically hindered amines, complexing agents and phenolic or non-phenolic antioxidants.


The present invention therefore also relates to a body-care product comprising at least one compound of formula (1).
The compounds of formula (1) are present in the body care and household products in a concentration of about 5 to about 10000 ppm, based on the total formulation, preferably from about 10 to about 5000 ppm, and most preferably from about 100 to about 1000 ppm.
The cosmetic compositions according to the present invention may also contain one or one more additional compounds as described below.
Fatty Alcohols
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, octyidodecanol, benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc.
Esters of Fatty Acids
Esters of linear C6-C24 fatty acids with linear C3-C24 alcohols, esters of branched C6-C13-carboxylic acids with linear C6-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).
Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, iso-octylstearate, iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, 2-octyidodecylpalmitate, 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
Di- or tri-glycerides, based on C6-C18 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
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
Ikylene 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
Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.
Silicones or Siloxanes (Organosubstituted Polysiloxanes)
Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear polysiloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).
Fluorinated or Perfluorinated Oils
Perfluorhexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethyl isopropyl ether.
Emulsifiers
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 acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan, glucose derivatives, C8-C22 alkyl-mono and oligoglycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanol-amine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl 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 chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroide amonium broide (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, lipoaminoacides, self emulsifying bases and the compounds as described in K. F. DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7, p 250-251.
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 szeareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate. [Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 [Lanbritol Wax N 21], PEG-6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N. Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.
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.
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
Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.
Surfactants
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, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Consistency Regulators/Thickeners and Rheology Modifiers
silicon dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carraghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, 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 alkyl 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 acryloyidimethyl 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
Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternised vinylpyrrolidone/vinyl imidazole polymers, for example Luviquata (BASF), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryidimonium hydroxypropyl hydrolyzed collagen (LamequatâL/Grünau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretin/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate/crotonic acid copolymers, 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-trimethylammonium chloride/acrylate copolymers, octyl acrylamide/methyl methacrylatetert. butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in EP 1093796 (pages 3-8, paragraphs 17-68) may be used.
Cationic Surfactants
cetyl trimethyl ammonium bromide (CTAB), dimethicone copolyols, amidomethicones, acrylamidopropyltrimonium chloride/Acrylamide copolymer, guar hydroxypropyl trimonium chloride, hydroxycetyl hydroxyethyl dimonium chloride quaternium compounds as listed in International Cosmetic Ingredient Dictionary and Handbook, 7th Edition 1997, for example Quaternium-80, polyquaternium compounds, as listed in International Cosmetic Ingredient Dictionary and Handbook, 7th 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
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.
Deodorising Active Ingredients
As deodorising 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×2.5H2O, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Henkel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.
Anti-Dandruff Agents
As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyrithione. Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.
Hydrotropic Agents
For improvement of the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin, 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 oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50% by weight; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.
Preservatives
Suitable preservatives include, for example methyl-, ethyl-, propyl-, butyl-parabens, benzalkonium chloride, 2-bromo-2-nitro-propane-1,3-diol, dehydroacetic acid, diazolidinyl urea, 2-dichloro-benzyl alcohol, dmdm hydantoin, formaldehyde solution, methyldibromoglutanitrile, phenoxyethanol, sodium hydroxymethylglycinate, imidazolidinyl urea, triclosan and further substance classes listed in the following reference: K. F. Depolo—A Short Textbook Of Cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 And 7-5, P210-219.
Bacteria-Inhibiting Agents
Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4′-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2% by weight, based on the solids content of the preparations.
Perfume Oils
Mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, 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, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.
Other Adjuvants
It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, 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 oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.
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.
The present stabilizer systems are particularly suitable for stabilizing body care products, in particular:

    
    
        skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, soapless detergents or washing pastes,
        bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;
        skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; body oils, body lotions, body gels; skin protection ointments;
        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. eyeshadow 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;
        foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations;
        light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations;
        skin-tanning preparations, e.g. self-tanning creams;
        depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations;
        insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
        deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;
        antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;
        preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;
        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;
        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;
        fragrance preparations, e.g. fragrances and odoriferous substances containing preparations (scents, eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams;
        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 colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile;
        dentifrices, in particular tooth creams, toothpastes, mouth-washes, mouth rinses, anti-plaque preparations and cleaning agents for dentures;
        decorative preparations, in particular lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions
        cosmetic formulations containing active ingredients, in particular hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
    
    


Suitable cosmetic formulations containing active ingredients are in particular hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.
Presentation Forms
The final formulations listed may exist in a wide variety of presentation forms, for example:

    
    
        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,
        in the form of a gel,
        in the form of an oil, a cream, milk or lotion,
        in the form of a stick,
        in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol,
        in the form of a foam, or
        in the form of a paste.
    
    


Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks 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.
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.
A shampoo has, for example, the following composition:
0.01 to 5% by weight of the compound of formula (1),
12.0% by weight of sodium laureth-2-sulfate,
4.0% by weight of cocamidopropyl betaine,
3.0% by weight of sodium chloride,
and water ad 100%.
For example, especially the following hair-cosmetic formulations may be used:

    a1) spontaneously emulsifying stock formulation, comprising the compound of formula (1) according to the 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;
    a2) spontaneously emulsifying stock formulation comprising the compound of formula (1) according to the 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;
    b) quat-doped solutions comprising the compound of formula (1) according to the invention in butyl triglycol and tributyl citrate; and optionally another stabilizer;
    c) mixtures or solutions comprising the compound of formula (1) according to the invention with alkylpyrrolidone; and optionally another stabilizer.


Examples of body care products of the present invention are listed in the Table below:











Body care



product
Ingredients







moisturising
vegetable oil, emulsifier, thickener, perfume, water,


cream
antioxidant, UV absorbers


shampoo
surfactant, emulsifier, preservatives, perfume, antioxidant,



UV absorbers


Toothpaste
cleaning agent, thickener, sweetener, flavor, colorant,



antioxidant, water, UV absorbers


lip-care stick
vegetable oil, wax, TiO2, antioxidant, UV absorbers









Household Products

The stabilizer systems 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.
Household cleaning agents are aqueous or alcoholic (ethanol or isopropyl alcohol) solutions of one or more of the following components:

    
    
        anionic, nonionic, amphoteric and/or cationic surfactants
        soaps, prepared by saponification of animal and vegetable greases
        organic acids, like hydrochloric acid, phosphoric acid, or sulfuric acid,
        for basic products inorganic (NaOH or KOH) or organic bases;
        abrasives for improved cleaning of surfaces,
        waxes and/or silicones for maintenance and protection of surfaces,
        polyphosphates,
        substances which eliminate hypochlorite or halogens;
        peroxides comprising bleaching activators like TAED, for example sodium perborate or H2O2;
        enzymes;
        in washing detergents discoloration inhibitors, soil-release compounds, grey scale inhibitors, foam inhibitors, fluorescent whitening agents;
        cleaning agents based on wax may comprise solvents selected from benzine, turpentine and/or paraffines and emulsifiers based on wax;
        filling agents like silicates, polyphosphates, Zeolithes for powdery cleaning agents;
        pigments, lakes or soluble dyes;
        perfumes; and
        light stabilizers, antioxidants and chelating agents.
    
    


Colored cleaning agents and decorative cosmetic products can comprise the following dyes:

    
    
        inorganic pigments, for example iron oxide (Iron Oxide Red, Iron Oxide Yellow, Iron Oxide Black, etc.), Ultramarines, Chromium Oxide Green or Carbon Black;
        natural or synthetic orgnic pigments;
        disperse dyes which may be solubilzed 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;
        color varnishes (insoluble salts of soluble dyes, like many Ca-, Ba- or Al-salts of anionic dyes);
        soluble anionic or cationic dyes, like acid dyes (anionic), basic dyes (cationic), direct dyes, reactive dyes or solvent dyes.
    
    


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.
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. Antioxidants are suitable to protect fragrances in above products as well as in dryer sheets. The present invention also relates to home care products such as candles, gel candles, air fresheners and fragrance oils (for the home).
Typical examples of household cleaning and treating agents are listed in the table below:











Household cleaners/



household


treating agents
Ingredients







detergent
surfactant mixture, ethanol, antioxidant, water, UV


concentrate
absorbers, antioxidants


shoe polishwax
wax emulsifier, antioxidant, water, preservative, UV



absorbers, antioxidants


wax-containing
emulsifier, wax, sodium chloride, light stabiliser of


floor cleaning agent
formulae (1) and (2), water, preservative UV



absorbers, antioxidant









The stabilizers of formula (1) according to the present invention are for example incorporated by dissolution in an oil phase or alcoholic or water phase, where required at elevated temperature.
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.
The following Examples illustrate the invention.
In the following Examples the stabilizers listed in the Table below have been used:











Comp. of formula
Structure







(101)






 


(102)






 


(103)






 


(104)






 


(105)






 


AO 01






 


AO 02






 


AO 03






 


AO 04






 


AO 05






 


AO 06






 


AO 07













Efficacy Comparison to State-of-the Art Stabilizers
EXAMPLE 1
The following colored basic shampoo formulation is prepared:
















Sodium Laureth Ether Sulfate
10% 



Cocamidopropylbetaine
3%



Citric Acid
to pH 5



FD & C Blue No. 1
0.002%   



Stabilizer
q.a.










The following stabilized und unstabilized samples of this formulation are prepared for light stability testing:
1. unstabilized basic shampoo formulation
2. basic shampoo formulation plus 0.05% of the compound of formula (AO 07)
3. basic shampoo formulation plus 0.05% of compound of formula (101)
4. basic shampoo formulation plus 0.05% of compound of formula (102)
5. basic shampoo formulation plus 0.05% of compound of formula (103)
6. basic shampoo formulation plus 0.05% of compound of formula (104)
7. basic shampoo formulation plus 0.05% of compound of formula (105)
The formulations were filled into 30 ml glass bottles and irradiated in an ATLAS Suntest XLS+Xenon Lamp (light intensity 500 W/m2, spectrum of light adjusted to indoor conditions, sample chamber temperature: 32° C.).
The results are listed in the table below.












Irradiation Time until


Sample
samples were significantly faded







1
 8 hours (colorless)


2
15 hours (colorless)


3
21 hours (faded, but still colored)


4
70 hours (faded, but still colored)


5
70 hours (faded, but still colored)


6
70 hours (faded, but still colored)


7
40 hours (faded, but still colored)









Sample 3-7 comprising a stabilizer according to the present invention exhibits significantly better light stability compared to the state-of-the-art UV absorber of formula (AO 07).
EXAMPLE 2
The following colored basic shampoo formulation is prepared:
















Sodium Laureth Ether Sulfate
  10%



Cocamidopropylbetaine
   3%



Citric Acid
to pH 5



FD&C Blue No. 1
0.002%



Stabilizer
q.a.










The following stabilized und unstabilized samples of this formulation are prepared for light stability testing:

    1. unstabilized basic shampoo formulation
    2. basic shampoo formulation plus 0.05% of the compound of formula (AO 07)
    3. basic shampoo formulation plus 0.05% of the compound (AO 07) plus 0.003% or compound AO 02
    4. basic shampoo formulation plus 0.05% of compound of formula (104).


The formulations were filled into 30 ml glass bottles and irradiated in an ATLAS Suntest XLS+ Xenon Lamp (light intensity 500 W/m2, spectrum of light adjusted to indoor conditions, sample chamber temperature: 32° C.).
The results are listed in the table below.















Irradiation Time until




samples were



Sample
significantly faded









1
 8 hours



2
25 hours



3
45 hours



4
65 hours










Sample 4 comprises a stabilizer according to the present invention. It exhibits significantly better light stability compared to the state-of-the-art UV absorber of formula (AO 01), and performed even better than the highly effective stabilizer combination of sample 3.
EXAMPLE 3
The following stabilized and unstabilized samples were prepared for antioxidation testing:
1. pure linoleic acid
2. linoleic acid containing 0.05% of compound of formula (104).
The samples were placed in a RACIMAT and heated to 80° C. An airflow of 15 L/min was adjusted. The airstream bubbles through each heated sample and afterwards through a water reservoir. Thus all volatile organic compounds formed by the oxidation process are carried into the water reservoir by the airstream. The conductivity of the water reservoir is monitored online during the measurement. Once oxidation starts volatile organic compounds like formic acid are transported into the water reservoir which results in a rapid (exponential) increase of conductivity. The time until oxidation starts is called “induction time”.
The results are listed in the table below.














Sample
Induction Time









1
1.15 hours



2
1.98 hours










Sample 2 comprising a stabilizer according to the present invention exhibits better oxidation stability compared to the unstabilized sample.
EXAMPLE 4-15
Preparation of Body-Care and Household Formulations










Example 4: Preparation of a sprayable hair styling gel









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



light stabilizer of formula (101)
0.10









Preparation:

The components (A) are dispersed at room temperature.
(B) is mixed under heating until the paraben is completely dissolved and then (B) is added with gentle stirring to (A).
(C) is blended until it is completely dissolved and is slowly added under stirring to the mixture of (A) and (B).
The transparency of the gel can be increased by adding small amounts of triethanolamine (pH=5.6-5.75).










Example 5: 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



light stabilizer of formula (102)
0.02



Compound of formula (AO 01)
0.02



colorant (D&C Yellow No. 5)
0.02



sodium chloride
0.30










Preparation:
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.










Example 6: Preparation of a perfumed toilet water










Ingredients
(w/w) %














ethanol, 96%
60



d-limonene
5



cedrene
1.5



citronellol
0.5



savin
0.5



light stabilizer of formula (103)
0.05



light stabilizer of formala (AO 01)
0.05



light stabilizer of formula (AO 02)
0.03



Antioxidant of formula (AO 06)
0.02



S,S-EDDS
0.01



colorant (D&C Yellow No. 5)
0.1



water
ad. 100










Preparation:
The components are thoroughly mixed in the indicated sequence at 50° C. A clear homogeneous solution is obtained.










Example 7: 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



CI Pigment Red 4
9.0



CI Pigment Blue 15
1.0



Light stabilizer of formula (101)
0.1



Castor Oil
ad 100




















Example 8: 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



Antioxidant of formula (AO 04)
0.10



light stabilizer of formula (101)
0.10




















Example 9: Preparation of a Rouge (powder)










Ingredients
(w/w) %














Talcum
56



Zinc Stearate
15



Rice starch
15



Iron Oxide Red
12



Perfume
q.s.



light stabilizer of formula (101)
0.1




















Example 10: 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



CI Pigment Brown 6
0.37



Carboxymethyl cellulose
0.10



light stabilizer of formula (101)
0.10



Water
ad 100




















Example 11: Preparation of an Eyeliner










Ingredients
(w/w) %







Polysaccharide resin (Kama KM 13, Kama)
8.00



Iron Oxide Black
6.50



Carnauba wax
1.00



Triethanolamin, 99%
1.00



Hydrogenated polyisobutane
1.00



Hydrogenated polydecene
1.00



Sorbitan sesquioleate
1.00



Xanthum gum
0.50



Polysaccharide resin (Kama KM 13, Kama)
8.00



Carboxymethyl cellulose
0.40



Magnesium aluminium silicate
0.40



Methyl paraben
0.35



Stearic acid
2.50



Lecithin
0.20



Imidazolidinyl urea
0.10



light stabilizer of formula (102)
0.10



Antioxidant of formula (AO 05)
0.05



Water
to 100




















Example 12: 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



Light stabilizer of formula (103)
0.05



Water
ad 100




















Example 13: 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



Light stabilizer of formula (101)
0.20



Light stabilizer of formula (AO 03)
0.10










Preparation of Formulations of Household Products











Example 14: 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



light stabilizer of formula (AO 02)
0.05



light stabilizer of formula (102)
0.05



water, demin.
ad. 100










Preparation:
The components are dissolved in the indicated sequence until a clear homogeneous mixture is obtained.










Example 15: Preparation of a floor wax










Ingredients
(w/w) %














wax mixture
12



white spirit
ad 100



d-limonene
4.00



light stabiliser of formula (103)
0.10










Preparation:
The components are stirred in the indicated sequence until a homogeneous mixture is obtained.

## Claims

1. A method for protecting body-care and household products from photolytic and oxidative degradation wherein said body-care and household products are stored in a container, said container has a low absorption in the UV-A range said method comprises adding to said body-care and household products about 5 to about 10000 ppm of at least one stabilizer of formula




wherein
L1, L2 or L3 independently of each other hydrogen; hydroxy; C1-C22alkyl; C1-C22alkoxy; C2-C22alkenyl; C2-C22alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cyclo-heteroalkyl, C5-C11heteroaralkyl; C6-C20aryl; C6-C20aryl-C1-C5alkenylene; C4-C9heteroaryl; CN; —(CH2)t—OR9; or COOR9;
R4 is CN; —COR7; —COOR7; —SO2R7; —CONR7R8; C1-C22alkyl; C2-C22alkenyl; C2-C22 alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20 aryl; C1-C1alkylcarbonylamino-C6-C20aryl; C4-C9heteroaryl;
R5, R6, R7 and R8 are independently of each other hydrogen; C1-C22alkyl, C2-C22alkenyl, C2-C22alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20 aralkyl; COR9; —(CO)—COO—R9; C1-C20 heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20 aryl; C1-C5alkoxy-C6-C20aryl; —(CH2)t—SO3H; —(CH2)t—(CO)—OR9; —(CH2)t—O—C6-C10aryl; —(CH2)vCOO—R9; C4-C9heteroaryl; —(CH2)u—SiR15R16R17; or a radical —X-Sil;
R9 is hydrogen; C1-C22alkyl; C2-C22alkenyl; C2-C22alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20 aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; or C4-C9heteroaryl; or
L1 and L2, L1 and L3, L2 and L3, L1 and R4, L2 and R4, L1 and R1, L2 and R1, L3 and R1, L3 and R5, R3 and R4, R1 and R2, R7 and R8, R5 and R6 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 and each N in a N-heterocyclic ring may be unsubstituted or substituted by R10;
and each alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylene group may be unsubstituted or substituted by one or more R11;
and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R12;

R10 is R13; COR13, COOR13; or CONR13R14;
R11 is halogen, OH; NR15R16; O—R15; S—R15; O—CO—R15; CO—R15; oxo; thiono; CN; COOR15; CONR15R16; SO2NR15R16; SO2R15; SO3R15; SiR15R16R17; OSiR15R16R17; POR15R16; or a radical —X-Sil;
R12 is C1-C12alkylthio; C3-C12cycloalkylthio; C1-C12alkenylthio; C3-C12cycloalkenylthio; C1-C12alkoxy; C3-C12cycloalkoxy; C1-C12alkenyloxy; or C3-C12cycloalkenyloxy which may be unsubstituted or substituted by one or more R11; halogen; CN; SH; OH; CHO; R18; OR18; SR18; C(R18)═CR19R20; O—CO—R19; NR18R19; CONR18R19, SO2NR18R19, SO2R18, COOR18, OCOOR18; NR18COR19, NR19COOR20; SiR15R16R17; OSiR15R16R17; P(═O)R19R20; or a radical —X-Sil;
R13, R14, R15, R16, R17, R18, R19 and R20 independently of each other are hydrogen; C1-C22alkyl; C3-C12cycloalkyl; C2-C12alkenyl; C3-C12cycloalkenyl; C6-C14aryl; C4-C12heteroaryl; C7-C18aralkyl; or C5-C16heteroaralkyl; or
R13 and R14, R15 and R16, R16 and R17 and/or R18 and R19 may be linked together to form unsubstituted or C1-C4alkyl-substituted pyrrolidine, piperidine, piperazine or morpholine;
X is a linker; and
Sil is a silane-, oligosiloxane or polysiloxane moiety;
t is a number from 0 to 12;
u is a number from 1 to 12;
v is a number from 0 to 12;
if n=1
R1 and R2 independently of each other hydrogen; C1-C22 alkyl; hydroxy-C1-C22alkyl; C2-C22alkenyl; C2-C22 alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C6-C20aryl; C5-C11heteroaralkyl; C4-C9heteroaryl; or a radical of formula




R21, R22, R23 independently from each other are C1-C22alkyl; or C1-C22alkoxy;
a is the bond to the linker X;
R3 is CN; NR5R6; —COR5; —COOR5; —SO2R5; —CONR5R6; C6-C20aryl; or C4-C9heteroaryl;
p is a number from 0 to 100
q is a number from 1 to 20;
s is a number from 0 to 4;
if n=2
R1 and R2 are each a bivalent radical selected from C1-C5alkylene which may be interrupted by one or more oxygen atoms; or
R1 and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and simultaneously R3 is defined as for n=1; or
R3 is a bivalent radical of formula —CO—V1—C1-C12alkylene-W1—*, wherein
the asterix indicates the bond to the second R3 
V1 is —O—; or —NR7—; or the direct bond;
W1 is the linkage to the second R3, wherein W1 is the direct bond; or selected from C1-C12alkylene; or phenylene; and
R1 and R2 simultaneously are defined as for n=1;
if n=3
one of R1, R2 or R3 is a trivalent radical;
if n=4
R1 or R2 is a radical of formula





wherein
the asterices indicate the bond to the second, third and fourth R1/R2;
W2 is




R3 is defined as for n=1; or
R3 is a radical of formula





wherein the asterices indicate the bond to the second (2), third (3) and fourth (4) R3; and
W3 is





or
R1 or R2 is a radical of formula





the asterices indicate the bond to the second, third and fourth R1/R2;
R24 is C1-C22alkyl; or C1-C22alkoxy
and
pigments, lakes or soluble dyes.

2. A method according to claim 1, wherein
L1, L2 or L3, independently from each other are hydrogen; hydroxy; C1-C5alkyl, which may be interrupted by one or more oxygen; COOR9; phenyl, which may be substituted by one or more halogen, C1-C5alkyl, C1-C5alkoxy, trifluoroalkyl, C2-C5alkenyl; C4-C9heteroaryl; and
R9 is defined as in claim 1; and
n is 1.

3. A method according to claim 1, wherein
L1, L2 and L3, independently from each other are hydrogen, methyl, phenyl; or —COOR9; wherein
R9 is C1-C5alkyl; and
n is 1.

4. A method according to claim 1, wherein L1 and L3 together form a bivalent radical selected from the group consisting of



R4 is CN;
R3 is —COOR5;
R5 is C1-C22alkyl;
R1 is hydrogen and R2 is C1-C22 alkyl.

5. A method according to claim 1, wherein
R1 and R2 independently from each other are C1-C12alkyl; hydroxy-C1-C12alkyl; phenyl or phenyl-C1-C5alkyl, which may be substituted by one or more C1-C5alkyl, or SO3M; or a radical of formula





wherein
n is 1; and
R21, R22, R23 and s are defined as in claim 1.

6. A method according to claim 5, wherein
R1 and R2, independently from each other are C1-C4alkyl; and
n is 1.

7. A method according to claim 1, wherein
R1 and R2 together form a bivalent radical selected from the group consisting of;

8. A method according to claim 1, wherein
R3 is CN; —COR5; —COOR5; —SO2R5; or —CONR5R6;
R4, is CN; —COR7; —COOR7; —CONR7R8; or —SO2R7; wherein
R5, R6, R7 and R8, independently from each other are C1-C22alkyl; phenyl; or a radical —X-Sil;
n is 1; and
X and Sil are defined as in claim 1.

9. A method according to claim 1, wherein
R3 and R4 together form a carbyclic or heterocyclic biradical selected from the group consisting of

10. A method according to claim 1, wherein
R2 and L3 form a bivalent radical selected from the group consisting of

11. A method according to claim 1, wherein
L1, L2 or L3, independently from each other are hydrogen; hydroxy; C1-C5alkyl, which may be interrupted by one or more oxygen; COOR9; phenyl, which may be substituted by one or more halogen, C1-C5alkyl, C1-C5alkoxy, trifluoroalkyl, C2-C5alkenyl; C4-C9heteroaryl; or
L1 and L2 or L1 and L3 or L2 and L3 together form a bivalent radical selected from the group consisting of




R1 and R2 independently from each other are C1-C12alkyl; hydroxy-C1-C12alkyl; phenyl or phenyl-C1-C5alkyl, which may be substituted by one or more C1-C5alkyl, or SO3M; or a radical of formula





or
R1 and R2 together form a bivalent radical selected from the group consisting of




R3 is CN; COR5; COOR5; CONR5R8; or SO2R5;
R4 is CN; COR7; COOR7; CONR7R8; or SO2R7;
R7, R5 and R8, independently from each other are C1-C22alkyl; phenyl; or a radical —X-Sil; or
R3 and R4 together form a carbocyclic or heterocyclic biradical selected from the group consisting of





or
R2 and L3 form a bivalent radical selected from the group consisting o





and
R9, R21, R22, R23, X and Sil are defined as in claim 1.

12. A method according to claim 1, wherein the stabilizers correspond to formula




wherein
R1, R2, R3, R4, L1, L2, L3 W1 and W2 are defined as in claim 1.

13. A method according to claim 12, wherein
in formula (2a)
R3 is a radical of formula —CO—V1—C1-C12alkylene-**, wherein
V1 is —O; or —NH—;
W1 is the direct bond; C1-C4alkylene; or phenylene;
R1 and R2, independently from each other are C1-C12alkyl;
L1, L2 and L3 independently form each other are hydrogen; or C1-C5alkyl; or
L3 and R2 together form a heterocyclic ring;
R4 is CN; COR7; COOR7; CONR7R8; or SO2R7; and
R7 is C1-C22alkyl; or phenyl.

14. A method according to claim 12, wherein
in formula (2b)
R1 is C1-C3alkylene;
L1, L2 and L3 independently from each other are hydrogen; or C1-C5alkyl; or
L1 and L3 together form a carbocyclic ring;
R2 is hydrogen; or C1-C5alkyl;
W1 is C1-C3alkylene; or the direct bond;
R3 and R4 independently from each other are CN; COR7; COOR7; CONR7R8; or SO2R7; and
R7 and R8, independently from each other are C1-C22alkyl; or phenyl.

15. A method according to claim 1, wherein the stabilizers correspond to the formula




wherein
R1, R2, R3, R4, L1, L2, L3, W2 and W3 are defined as in claim 1.

16. A method according to claim 15, wherein
in formula (3a)
L1, L2 and L3 independently from each other are hydrogen; hydroxy; C1-C5alkyl; or L1 and L3 together form a carbocyclic ring;
R1 and R2 independently from each other are hydrogen; or C1-C12alkyl;
R3 is *—CO—V1—C1-C12alkylene-**;
V1 is —O; or —NH—;
W is a tetravalent radical of formula




R4 is CN; COR7; COOR7; CONR7R8; or SO2R7; and
R7 and R8, independently from each other are C1-C22alkyl; or phenyl.

17. A method according to claim 1 wherein the body-care products are for the skin and its adnexa.

18. A method according to claim 17, wherein the body-care products are selected from the group consisting of 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.

19. A method according to claim 17, wherein the body-care products are selected from the group consisting of body oils, body lotions, body gels, treatment creams, skin protection ointments, shaving preparations and skin powders.

20. A method according to claim 18, wherein the preparations contain fragrances and odoriferous substances which are selected from the group consisting of scents, perfumes, toilet waters and shaving lotions.

21. A method according to claim 18, wherein the hair-care products are selected from the group consisting of shampoos, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents.

22. A method according to claim 18, wherein the decorative preparations are selected from the group consisting of lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions.

23. A method according to claim 18, wherein the body-care products contain active ingredients and are selected from the group consisting of hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations.

24. A method according to claim 1 wherein the household products are selected from the group consisting of household cleaning and treating agents.

25. A method according to claim 24 wherein the household cleaning and treating agents are selected from the group consisting of washing, rinsing and dishwashing agents, shoe polishes, polishing waxes, floor detergents and polishes, all purpose cleaners, bath and toilet cleaners, kitchen cleaners, car shampoos and waxes, neutral, acidic and alkaline cleaners, metal, glass and ceramic cleaners, textile care agents, agents for removing rust, color and stains, bleaches, furniture and multipurpose polishes, surface protecting formulations, film forming formulations, air care formulations and candles.

26. A body-care or household product wherein said body-care and household products are stored in a container and said container has a low absorption in the UV-A range comprising about 5 to about 10000 ppm of compounds of formula




wherein
R3 is CN; NR5R6; —COR5; —COOR5; —SO2R5; —CONR5R6; C6-C20aryl; or C4-C9heteroaryl;
R4 is CN; —COR7; —COOR7; —CONR7R8; C1-C22alkyl; C2-C22alkenyl; C2-C22 alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20 aryl; C1-C1alkylcarbonylamino-C6-C20aryl; or C4-C9heteroaryl;
R5, R6, R7 and R8 are independently of each other hydrogen; C1-C22alkyl, C2-C22alkenyl, C2-C22alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20 aralkyl; COR9, —(CO)—COO—R9, C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20 aryl; C1-C5alkoxy-C6-C20aryl; —(CH2)t—SO3H; —(CH2)t—(CO)—OR9; —(CH2)t—O—C6-C10aryl; —(CH2)vCOO—R9; C4-C9heteroaryl; —(CH2)u—SiR15R16R17; or a radical —X-Sil;
R9 is hydrogen; C1-C22alkyl; C2-C22alkenyl; C2-C22alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20 aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C5-C11heteroaralkyl; C6-C20aryl; or C4-C9heteroaryl; or
L1 and L3, are H or 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 and each N in a N-heterocyclic ring may be unsubstituted or substituted by R10;
and each alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylene group may be unsubstituted or substituted by one or more R11;
and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R12;

R10 is R13; COR13, COOR13; or CONR13R14;
R11 is halogen, OH; NR15R16; O—R15; S—R15; CO—R15; oxo; thiono; CN; COOR15; CONR15R16; SO2NR15R16; SO2R15; SO3R15; SiR15R16R17; OSiR15R16R17; POR15R16; or a radical —X-Sil;
R12 is C1-C12alkylthio; C3-C12cycloalkylthio; C1-C12alkenylthio; C3-C12cycloalkenylthio; C1-C12alkoxy; C3-C12cycloalkoxy; C1-C12alkenyloxy; or C3-C12cycloalkenyloxy which may be unsubstituted or substituted by one or more R11; halogen; CN; SH; OH; CHO; R18; OR18; SR18; C(R18)═CR19R20; O—CO—R19; NR18R19; CONR18R19, SO2NR18R19, SO2R18, COOR18, OCOOR18; NR18COR19, NR19COOR20; SiR15R16R17; OSiR15R16R17; P(═O)R19R20; or a radical —X-Sil;
R13, R14, R15, R16, R17, R18, R19 and R20 independently of each other are hydrogen; C1-C22alkyl; C3-C12cycloalkyl; C2-C12alkenyl; C3-C12cycloalkenyl; C6-C14aryl; C4-C12heteroaryl; C7-C18aralkyl; or C5-C16heteroaralkyl; or
R13 and R14, R15 and R16, R16 and R17 and/or R18 and R19 may be linked together to form unsubstituted or C1-C4alkyl-substituted pyrrolidine, piperidine, piperazine or morpholine;
X is a linker; and
Sil is a silane-, oligosiloxane or polysiloxane moiety;
t is a number from 0 to 12;
u is a number from 1 to 12;
v is a number from 0 to 12;
if n=1
R1 and R2 independently of each other hydrogen; C1-C22 alkyl; hydroxy-C1-C22alkyl; C2-C22alkenyl; C2-C22 alkynyl; C3-C12cycloalkyl; C3-C12cycloalkenyl; C7-C20aralkyl; C1-C20heteroalkyl; C3-C12cycloheteroalkyl; C6-C20aryl; C5-C11heteroaralkyl; C4-C9heteroaryl; or a radical of formula




R21, R22, R23 independently from each other are C1-C22alkyl; or C1-C22alkoxy;
p is a number from 0 to 100
q is a number from 1 to 20;
s is a number from 0 to 4;
R3 is CN; NR5R6; —COR5; —COOR5; —SO2R5; —CONR5R6; C6-C20aryl; or C4-C9heteroaryl;
if n=2
R1 and R2 are each a bivalent radical selected from C1-C5alkylene which may be interrupted by one or more oxygen atoms; or
R1 and R2 together with the nitrogen atoms form a six-membered heterocyclic ring; and simultaneously R3 is defined as for n=1; or
R3 is a bivalent radical of formula —CO—V1—C1-C12alkylene-W1—*, wherein
the asterix indicates the bond to the second R3 

V1 is —O—; or —NR7—; or the direct bond;
W1 is the linkage to the second R3, wherein W1 is the direct bond; or selected from C1-C12alkylene; or phenylene; and
R1 and R2 simultaneously are defined as for n=1;
if n=3
one of R1, R2 or R3 is a trivalent radical;
if n=4
R1 or R2 is a radical of formula





wherein

the asterices indicate the bond to the second, third and fourth R1/R2;

W2 is




R3 is defined as for n=1; or
R3 is a radical of formula





wherein the asterices indicate the bond to the second (2), third (3) and fourth (4) R3; and
W3 is




or
R1 or R2 is a radical of formula





the asterices indicate the bond to the second, third and fourth R1/R2;
R24 is C1-C22alkyl; or C1-C22alkoxy;
wherein at least one of the radicals R1, R2, R3 or R4 is a silicon organic compound.

27. The method according to claim 1, wherein the body-care products are selected from the group consisting of 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 and the household products are a household cleaning product and the household cleaning product are selected from the group consisting of washing, rinsing and dishwashing agents, floor detergents and polishes, all purpose cleaners, bath and toilet cleaners, kitchen cleaners, car shampoos, neutral, acidic and alkaline cleaners, metal, glass and ceramic cleaners and agents for removing rust, color and stains, bleaches.