Stabilization of body-care and household products against degradation by uv radiation using merocyanine derivatives
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.
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
L 1 , L 2 or L 3 independently of each other hydrogen; hydroxy; C 1 -C 22 alkyl; C 1 -C 22 alkoxy; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cyclo-heteroalkyl, C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; C 6 -C 20 aryl-C 1 -C 5 alkenylene; C 4 -C 9 heteroaryl; CN; —(CH 2 ) t —OR 9 ; or COOR 9 ;
R 4 is CN; —COR 7 ; —COOR 7 ; —SO 2 R 7 ; —CONR 7 R 8 ; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; C 1 -C 1 alkylcarbonylamino-C 6 -C 20 aryl; C 4 -C 9 heteroaryl;
R 5 , R 6 , R 7 and R 8 are independently of each other hydrogen; C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; COR 9 ; —(CO)—COO—R 9 ; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; C 1 -C 5 alkoxy-C 6 -C 20 aryl; —(CH 2 ) t —SO 3 H; —(CH 2 ) t —(CO)—OR 9 ; —(CH 2 ) t —O—C 6 -C 10 aryl; —(CH 2 ) v COO—R 9 ; C 4 -C 9 heteroaryl; —(CH 2 ) u —SiR 15 R 16 R 17 ; or a radical —X-Sil;
R 9 is hydrogen; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; or C 4 -C 9 heteroaryl; or
L 1 and L 2 , L 1 and L 3 , L 2 and L 3 , L 1 and R 4 , L 2 and R 4 , L 1 and R 1 , L 2 and R 1 , L 3 and R 1 , L 3 and R 5 , R 3 and R 4 , R 1 and R 2 , R 7 and R 8 , R 5 and R 6 may be linked together to form 1, 2, 3 or 4 carbocyclic or N, O and/or S-heterocyclic rings, which may be further fused with other aromatic rings and each N in a N-heterocyclic ring may be unsubstituted or substituted by R 10 ;
and each alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylene group may be unsubstituted or substituted by one or more R 11 ;
and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R 12 ;
R 10 is R 13 ; COR 13 , COOR 13 ; or CONR 13 R 14 ;
R 11 is halogen, OH; NR 15 R 16 ; O—R 15 ; S—R 15 ; O—CO—R 15 ; CO—R 15 ; oxo; thiono; CN; COOR 15 ; CONR 15 R 16 ; SO 2 NR 15 R 16 ; SO 2 R 15 ; SO 3 R 15 ; SiR 15 R 16 R 17 ; OSiR 15 R 16 R 17 ; POR 15 R 16 ; or a radical —X-Sil;
R 12 is C 1 -C 12 alkylthio; C 3 -C 12 cycloalkylthio; C 1 -C 12 alkenylthio; C 3 -C 12 cycloalkenylthio; C 1 -C 12 alkoxy; C 3 -C 12 cycloalkoxy; C 1 -C 12 alkenyloxy; or C 3 -C 12 cycloalkenyloxy which may be unsubstituted or substituted by one or more R 11 ; halogen; CN; SH; OH; CHO; R 18 ; OR 18 ; SR 18 ; C(R 18 )═CR 19 R 20 ; O—CO—R 19 ; NR 18 R 19 ; CONR 18 R 19 , SO 2 NR 18 R 19 , SO 2 R 18 , COOR 18 , OCOOR 18 ; NR 18 COR 19 , NR 19 COOR 20 ; SiR 15 R 16 R 17 ; OSiR 15 R 16 R 17 ; P(═O)R 19 R 20 ; or a radical —X-Sil;
R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 independently of each other are hydrogen; C 1 -C 22 alkyl; C 3 -C 12 cycloalkyl; C 2 -C 12 alkenyl; C 3 -C 12 cycloalkenyl; C 6 -C 14 aryl; C 4 -C 12 heteroaryl; C 7 -C 18 aralkyl; or C 5 -C 16 heteroaralkyl; or
R 13 and R 14 , R 15 and R 16 , R 16 and R 17 and/or R 18 and R 19 may be linked together to form unsubstituted or C 1 -C 4 alkyl-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
R 1 and R 2 independently of each other hydrogen; C 1 -C 22 alkyl; hydroxy-C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 6 -C 20 aryl; C 5 -C 11 heteroaralkyl; C 4 -C 9 heteroaryl; or a radical of formula
R 21 , R 22 , R 23 independently from each other are C 1 -C 22 alkyl; or C 1 -C 22 alkoxy;
a is the bond to the linker X;
R 3 is CN; NR 5 R 6 ; —COR 5 ; —COOR 5 ; —SO 2 R 5 ; —CONR 5 R 6 ; C 6 -C 20 aryl; or C 4 -C 9 heteroaryl;
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
R 1 and R 2 are each a bivalent radical selected from C 1 -C 5 alkylene which may be interrupted by one or more oxygen atoms; or
R 1 and R 2 together with the nitrogen atoms form a six-membered heterocyclic ring; and simultaneously R 3 is defined as for n=1; or
R 3 is a bivalent radical of formula —CO—V 1 —C 1 -C 12 alkylene-W 1 —*, wherein
the asterix indicates the bond to the second R 3
V 1 is —O—; or —NR 7 —; or the direct bond;
W 1 is the linkage to the second R 3 , wherein W 1 is the direct bond; or selected from C 1 -C 12 alkylene; or phenylene; and
R 1 and R 2 simultaneously are defined as for n=1;
if n=3
one of R 1 , R 2 or R 3 is a trivalent radical;
if n=4
R 1 or R 2 is a radical of formula
wherein
the asterices indicate the bond to the second, third and fourth R 1 /R 2 ;
W 2 is
R 3 is defined as for n=1; or
R 3 is a radical of formula
wherein the asterices indicate the bond to the second (2), third (3) and fourth (4) R 3 ; and
W 3 is
or
R 1 or R 2 is a radical of formula
the asterices indicate the bond to the second, third and fourth R 1 /R 2 ;
R 24 is C 1 -C 22 alkyl; or C 1 -C 22 alkoxy
and
pigments, lakes or soluble dyes.
2. A method according to claim 1 , wherein
L 1 , L 2 or L 3 , independently from each other are hydrogen; hydroxy; C 1 -C 5 alkyl, which may be interrupted by one or more oxygen; COOR 9 ; phenyl, which may be substituted by one or more halogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, trifluoroalkyl, C 2 -C 5 alkenyl; C 4 -C 9 heteroaryl; and
R 9 is defined as in claim 1 ; and
n is 1.
3. A method according to claim 1 , wherein
L 1 , L 2 and L 3 , independently from each other are hydrogen, methyl, phenyl; or —COOR 9 ; wherein
R 9 is C 1 -C 5 alkyl; and
n is 1.
4. A method according to claim 1 , wherein L 1 and L 3 together form a bivalent radical selected from the group consisting of
R 4 is CN;
R 3 is —COOR 5 ;
R 5 is C 1 -C 22 alkyl;
R 1 is hydrogen and R 2 is C 1 -C 22 alkyl.
5. A method according to claim 1 , wherein
R 1 and R 2 independently from each other are C 1 -C 12 alkyl; hydroxy-C 1 -C 12 alkyl; phenyl or phenyl-C 1 -C 5 alkyl, which may be substituted by one or more C 1 -C 5 alkyl, or SO 3 M; or a radical of formula
wherein
n is 1; and
R 21 , R 22 , R 23 and s are defined as in claim 1 .
6. A method according to claim 5 , wherein
R 1 and R 2 , independently from each other are C 1 -C 4 alkyl; and
n is 1.
7. A method according to claim 1 , wherein
R 1 and R 2 together form a bivalent radical selected from the group consisting of;
8. A method according to claim 1 , wherein
R 3 is CN; —COR 5 ; —COOR 5 ; —SO 2 R 5 ; or —CONR 5 R 6 ;
R 4 , is CN; —COR 7 ; —COOR 7 ; —CONR 7 R 8 ; or —SO 2 R 7 ; wherein
R 5 , R 6 , R 7 and R 8 , independently from each other are C 1 -C 22 alkyl; 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
R 3 and R 4 together form a carbyclic or heterocyclic biradical selected from the group consisting of
10. A method according to claim 1 , wherein
R 2 and L 3 form a bivalent radical selected from the group consisting of
11. A method according to claim 1 , wherein
L 1 , L 2 or L 3 , independently from each other are hydrogen; hydroxy; C 1 -C 5 alkyl, which may be interrupted by one or more oxygen; COOR 9 ; phenyl, which may be substituted by one or more halogen, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, trifluoroalkyl, C 2 -C 5 alkenyl; C 4 -C 9 heteroaryl; or
L 1 and L 2 or L 1 and L 3 or L 2 and L 3 together form a bivalent radical selected from the group consisting of
R 1 and R 2 independently from each other are C 1 -C 12 alkyl; hydroxy-C 1 -C 12 alkyl; phenyl or phenyl-C 1 -C 5 alkyl, which may be substituted by one or more C 1 -C 5 alkyl, or SO 3 M; or a radical of formula
or
R 1 and R 2 together form a bivalent radical selected from the group consisting of
R 3 is CN; COR 5 ; COOR 5 ; CONR 5 R 8 ; or SO 2 R 5 ;
R 4 is CN; COR 7 ; COOR 7 ; CONR 7 R 8 ; or SO 2 R 7 ;
R 7 , R 5 and R 8 , independently from each other are C 1 -C 22 alkyl; phenyl; or a radical —X-Sil; or
R 3 and R 4 together form a carbocyclic or heterocyclic biradical selected from the group consisting of
or
R 2 and L 3 form a bivalent radical selected from the group consisting o
and
R 9 , R 21 , R 22 , R 23 , X and Sil are defined as in claim 1 .
12. A method according to claim 1 , wherein the stabilizers correspond to formula
wherein
R 1 , R 2 , R 3 , R 4 , L 1 , L 2 , L 3 W 1 and W 2 are defined as in claim 1 .
13. A method according to claim 12 , wherein
in formula (2a)
R 3 is a radical of formula —CO—V 1 —C 1 -C 12 alkylene-**, wherein
V 1 is —O; or —NH—;
W 1 is the direct bond; C 1 -C 4 alkylene; or phenylene;
R 1 and R 2 , independently from each other are C 1 -C 12 alkyl;
L 1 , L 2 and L 3 independently form each other are hydrogen; or C 1 -C 5 alkyl; or
L 3 and R 2 together form a heterocyclic ring;
R 4 is CN; COR 7 ; COOR 7 ; CONR 7 R 8 ; or SO 2 R 7 ; and
R 7 is C 1 -C 22 alkyl; or phenyl.
14. A method according to claim 12 , wherein
in formula (2b)
R 1 is C 1 -C 3 alkylene;
L 1 , L 2 and L 3 independently from each other are hydrogen; or C 1 -C 5 alkyl; or
L 1 and L 3 together form a carbocyclic ring;
R 2 is hydrogen; or C 1 -C 5 alkyl;
W 1 is C 1 -C 3 alkylene; or the direct bond;
R 3 and R 4 independently from each other are CN; COR 7 ; COOR 7 ; CONR 7 R 8 ; or SO 2 R 7 ; and
R 7 and R 8 , independently from each other are C 1 -C 22 alkyl; or phenyl.
15. A method according to claim 1 , wherein the stabilizers correspond to the formula
wherein
R 1 , R 2 , R 3 , R 4 , L 1 , L 2 , L 3 , W 2 and W 3 are defined as in claim 1 .
16. A method according to claim 15 , wherein
in formula (3a)
L 1 , L 2 and L 3 independently from each other are hydrogen; hydroxy; C 1 -C 5 alkyl; or L 1 and L 3 together form a carbocyclic ring;
R 1 and R 2 independently from each other are hydrogen; or C 1 -C 12 alkyl;
R 3 is *—CO—V 1 —C 1 -C 12 alkylene-**;
V 1 is —O; or —NH—;
W is a tetravalent radical of formula
R 4 is CN; COR 7 ; COOR 7 ; CONR 7 R 8 ; or SO 2 R 7 ; and
R 7 and R 8 , independently from each other are C 1 -C 22 alkyl; 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
R 3 is CN; NR 5 R 6 ; —COR 5 ; —COOR 5 ; —SO 2 R 5 ; —CONR 5 R 6 ; C 6 -C 20 aryl; or C 4 -C 9 heteroaryl;
R 4 is CN; —COR 7 ; —COOR 7 ; —CONR 7 R 8 ; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; C 1 -C 1 alkylcarbonylamino-C 6 -C 20 aryl; or C 4 -C 9 heteroaryl;
R 5 , R 6 , R 7 and R 8 are independently of each other hydrogen; C 1 -C 22 alkyl, C 2 -C 22 alkenyl, C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; COR 9 , —(CO)—COO—R 9 , C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; C 1 -C 5 alkoxy-C 6 -C 20 aryl; —(CH 2 ) t —SO 3 H; —(CH 2 ) t —(CO)—OR 9 ; —(CH 2 ) t —O—C 6 -C 10 aryl; —(CH 2 ) v COO—R 9 ; C 4 -C 9 heteroaryl; —(CH 2 ) u —SiR 15 R 16 R 17 ; or a radical —X-Sil;
R 9 is hydrogen; C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 5 -C 11 heteroaralkyl; C 6 -C 20 aryl; or C 4 -C 9 heteroaryl; or
L 1 and L 3 , 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 R 10 ;
and each alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylene group may be unsubstituted or substituted by one or more R 11 ;
and each aryl, heteroaryl, aralkyl, arylene, heteroarylene or aralkylene may be unsubstituted or substituted by one or more R 12 ;
R 10 is R 13 ; COR 13 , COOR 13 ; or CONR 13 R 14 ;
R 11 is halogen, OH; NR 15 R 16 ; O—R 15 ; S—R 15 ; CO—R 15 ; oxo; thiono; CN; COOR 15 ; CONR 15 R 16 ; SO 2 NR 15 R 16 ; SO 2 R 15 ; SO 3 R 15 ; SiR 15 R 16 R 17 ; OSiR 15 R 16 R 17 ; POR 15 R 16 ; or a radical —X-Sil;
R 12 is C 1 -C 12 alkylthio; C 3 -C 12 cycloalkylthio; C 1 -C 12 alkenylthio; C 3 -C 12 cycloalkenylthio; C 1 -C 12 alkoxy; C 3 -C 12 cycloalkoxy; C 1 -C 12 alkenyloxy; or C 3 -C 12 cycloalkenyloxy which may be unsubstituted or substituted by one or more R 11 ; halogen; CN; SH; OH; CHO; R 18 ; OR 18 ; SR 18 ; C(R 18 )═CR 19 R 20 ; O—CO—R 19 ; NR 18 R 19 ; CONR 18 R 19 , SO 2 NR 18 R 19 , SO 2 R 18 , COOR 18 , OCOOR 18 ; NR 18 COR 19 , NR 19 COOR 20 ; SiR 15 R 16 R 17 ; OSiR 15 R 16 R 17 ; P(═O)R 19 R 20 ; or a radical —X-Sil;
R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 independently of each other are hydrogen; C 1 -C 22 alkyl; C 3 -C 12 cycloalkyl; C 2 -C 12 alkenyl; C 3 -C 12 cycloalkenyl; C 6 -C 14 aryl; C 4 -C 12 heteroaryl; C 7 -C 18 aralkyl; or C 5 -C 16 heteroaralkyl; or
R 13 and R 14 , R 15 and R 16 , R 16 and R 17 and/or R 18 and R 19 may be linked together to form unsubstituted or C 1 -C 4 alkyl-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
R 1 and R 2 independently of each other hydrogen; C 1 -C 22 alkyl; hydroxy-C 1 -C 22 alkyl; C 2 -C 22 alkenyl; C 2 -C 22 alkynyl; C 3 -C 12 cycloalkyl; C 3 -C 12 cycloalkenyl; C 7 -C 20 aralkyl; C 1 -C 20 heteroalkyl; C 3 -C 12 cycloheteroalkyl; C 6 -C 20 aryl; C 5 -C 11 heteroaralkyl; C 4 -C 9 heteroaryl; or a radical of formula
R 21 , R 22 , R 23 independently from each other are C 1 -C 22 alkyl; or C 1 -C 22 alkoxy;
p is a number from 0 to 100
q is a number from 1 to 20;
s is a number from 0 to 4;
R 3 is CN; NR 5 R 6 ; —COR 5 ; —COOR 5 ; —SO 2 R 5 ; —CONR 5 R 6 ; C 6 -C 20 aryl; or C 4 -C 9 heteroaryl;
if n=2
R 1 and R 2 are each a bivalent radical selected from C 1 -C 5 alkylene which may be interrupted by one or more oxygen atoms; or
R 1 and R 2 together with the nitrogen atoms form a six-membered heterocyclic ring; and simultaneously R 3 is defined as for n=1; or
R 3 is a bivalent radical of formula —CO—V 1 —C 1 -C 12 alkylene-W 1 —*, wherein
the asterix indicates the bond to the second R 3
V 1 is —O—; or —NR 7 —; or the direct bond;
W 1 is the linkage to the second R 3 , wherein W 1 is the direct bond; or selected from C 1 -C 12 alkylene; or phenylene; and
R 1 and R 2 simultaneously are defined as for n=1;
if n=3
one of R 1 , R 2 or R 3 is a trivalent radical;
if n=4
R 1 or R 2 is a radical of formula
wherein
the asterices indicate the bond to the second, third and fourth R 1 /R 2 ;
W 2 is
R 3 is defined as for n=1; or
R 3 is a radical of formula
wherein the asterices indicate the bond to the second (2), third (3) and fourth (4) R 3 ; and
W 3 is
or
R 1 or R 2 is a radical of formula
the asterices indicate the bond to the second, third and fourth R 1 /R 2 ;
R 24 is C 1 -C 22 alkyl; or C 1 -C 22 alkoxy;
wherein at least one of the radicals R 1 , R 2 , R 3 or R 4 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.