WO2011048011A2

WO2011048011A2 - Benzotropolone derivatives as antimicrobial agents

Info

Publication number: WO2011048011A2
Application number: PCT/EP2010/065464
Authority: WO
Inventors: Barbara Wagner; Dietmar Ochs; Karin Bieler
Original assignee: Basf Se
Priority date: 2009-10-23
Filing date: 2010-10-14
Publication date: 2011-04-28
Also published as: WO2011048011A3; WO2011048011A4

Abstract

Disclosed is the use of benzotropolone derivatives of Formula (1) as antimicrobial and/or preserving agents.

Description

Benzotropolone derivatives as antimicrobial agents

The present invention relates to the use of specific benzotropolone derivatives for the antimicrobial treatment of surfaces, as antimicrobial active substances against gram-positive and gram-negative bacteria, yeasts and fungi and also for the preservation of cosmetics, household products, textiles and plastics and for use as disinfectants.

Th refore, the present invention relates to the use of benzotropolone derivatives of formula

, wherein

R₂, R3, R₄, R5 and R₆ independently of one another are hydrogen; OH; d-C₃oalkyl, C₂-C₃₀al- kenyl, CrC₃oalkoxy, C₃-Ci₂cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆-C₂oaryl, which may be substituted by one or more G; C₄-C₂oheteroaryl, which may be substituted by one or more G, C₂- Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C₂₅aralkyl, or -CO-Ri₇; Ci-C₃₀mono- or dialkylamino; COR₉; COORg; CONR₉R₁₀; CN; S0₂R₉; OCOOR₉; OCOR₉; NHCOOR₉; NR₉CORi₀; NH₂; sulphate; sulphonate; phosphate; phosphonate;

Ri, R₇ and R₈ independently of one another are hydrogen; Ci-Ci₂alkyl or C₃-Ci₂-cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆- C₂₀aryl, which may be substituted by one or more G; C₄-C₂₀heteroaryl, which may be substituted by one or more G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C₂₅aralkyl, or COOR₉;

COR₉; CONR₉R₁₀; S0₃R₉; S0₂R₉; P0₃(R₉)₂; P0₂(R₉)₂; or

R₇ and R₈ together form a five or six membered ring; or

R₆ and R₇ together form a five or six membered ring; or

R₉ and R10 independently from each other are hydrogen; Ci-Ci₈alkyl or C₃-Ci₂-cycloalkyl which may be substituted by one or more E and/or interrupted by one or more D; C₆-

C₂₀aryl, which may be substituted by one or more G; C₄-C₂₀heteroaryl, which may be substituted by one or more G; organosilanyl; or

R₉ and R₁₀ together form a five or six membered ring;

D is -CO-; -COO-; -S-; -SO-; -S0₂-; -0-; -NR₁₄-; -SiR_i9R₂o-; -PORn-;

or

-C≡C-; and E is -OR_i8; -SRi₈; -N R₁₄Ri₅; -N R₁₄CORi₅; -CORi₇; -COORi₆; -CON R₁₄R₁₅; -CN ; halogen; or OS0₃Ri₈; S0₃Ri₈; S0₂Ri₈; P0₃(Ri₈)₂; OP0₃(Ri₈)₂;

G is E; CrCi₈alkyl, which is optionally interrupted by D; Ci-Ci₈perfluoroalkyl; CrCi₈alkoxy, which is optionally substituted by E and/or interrupted by D; wherein

R12, Ri3, Ri₄ and Ri₅ independently of each other are hydrogen; C₆-Ci₈aryl which is optionally substituted by OH , CrCi₈alkyl or CrCi₈alkoxy; CrCi₈alkyl, which is optionally interrupted by -0-; or

Ri₄ and R₁₅ together form a five or six membered ring,

R16 is hydrogen; C₆-Ci₈aryl which is optionally substituted by OH , CrCi₈alkyl or d- Ci₈alkoxy; CrCi₈alkyl which is optionally interrupted by -O-;

Ri7 is H ; C₆-Ci₈aryl which is optionally substituted by OH , CrCi₈alkyl or CrCi₈alkoxy; or d-

Ci₈alkyl which is optionally interrupted by -0-;

R18 is hydrogen; C₆-Ci₈aryl, which is optionally substituted by OH , CrCi₈alkyl or d- Ci₈alkoxy; d-d₈alkyl, which is optionally interrupted by -O-; and

Rig and R₂₀ independently of each other are hydrogen; d-d₈alkyl; C₆-Ci₈aryl which is optionally substituted by d-d₈alkyl;

as antimicrobial and/or preserving agents.

Pr ferred are the compounds of formula

, wherein

R21 and R22 independently of one another are hydrogen; OH ; d-doalkyl or d-doalkoxy, which may be substituted by one or more E and/or interrupted by one or more D; Ri , R3, R3, R₄, R5, Re, E and D are defined as in formula (1 ).

More preferred are compounds of formula (1 a), wherein

R21 is hydrogen or d-doalkyl;

R22 is hydrogen; d-doalkyl or d-doalkoxy;

Preferred are also the compounds of formula

R21 and R22 independently of one another are hydrogen; OH; d-C₃oalkyl or CrC₃oalkoxy, which may be substituted by one or more E and/or interrupted by one or more D; and Ri , R3, R3, R₄, R5, R6, E and D are defined as in formula (1 ).

More preferred are compounds of formula (1 b), wherein

R21 is hydrogen or CrC₃oalkyl; and

R22 is hydrogen; CrC₃oalkyl or CrC₃₀alkoxy; CrC₃₀alkyl are straight chain or branched radicals like methyl, ethyl, n-propyl, isopropyl, n- butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooc- tyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, undecyl, eicosyl, tetracosyl, pentacosyl, hepta- cosyl, octacosyl or triacontyl. CrC₃₀alkoxy are straight chain or branched radicals like methoxy, ethoxy, n-propoxy, iso- propoxy, n-butyloxy, sek-butyloxy, tert-butyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, 2-ethylhexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecy- loxy, tetradecyloxy, undecyloxy eicosyloxy tetracosyloxy, pentacosyloxy, heptacosyloxy, oc- tacosyloxy or triacontyloxy.

C₂-C₃₀alkenyl are straight chain or branched radicals like allyl, methallyl, isopropenyl, 2-bu- tenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2- enyl, iso-dodecenyl, n-dodec-2-enyl, n-octadec-4-enyl, eicosenyl, tetracosenyl, pentacoensyl, heptacosenyl, octacosenyl or triacontenyl.

C₃-Ci₂cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl and preferably cyclohexyl.

Each alkyl or cycloalkyl can be saturated or unsaturated. Each alkyl, cycloalkyi or alkoxy can preferably be substituted by one or more E and/or interrupted by one or more D. Each aryl can be preferably substituted by G.

Each heteroaryl can be preferably substituted by G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C₂₅aral-

The compounds of formula (1 ) and (1 a) and (1 b) can be present in their protonated or depro- tonated form.

Preference is given to compounds of formula (1 ), wherein

Ri , R₇ and R₈ are hydrogen; and

R₂, R3, R₄, R5 and R₆ are defined as in formula (1 ).

Further preference is given to compounds of formula (1 ), wherein

R₂, R₃, R₄, R5 and R₆ independently of one another are hydrogen; OH; CrC₃oalkyl, C₂-C₃₀al- kenyl, CrC₃oalkoxy, C₃-Ci₂cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; COR₉; COOR₉; CONR₉R₁₀; S0₂R₉;

OCOOR₉; N HCOORg; N RgCORio;

Ri , R₇ and R₈ independently of one another are hydrogen; Ci-Ci₂alkyl or C₃-Ci₂-cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; COR₉;

CONR₉R₁₀; S0₃R₉; S0₂R₉; P0₃(R₉)₂; P0₂(R₉)₂;

C₂₀aryl, which may be substituted by one or more G; or

R₉ and R₁₀ together form a five or six membered ring,

D is -CO-; -COO-; -S-; -SO-; -S0₂-; -0-; -NR₁₄-; -SiR_i9R₂o-; -PORn-;

or

-C≡C-; and

E is -OR_{i 8}; -SR_i8; -N R₁₄R₁₅; -N R₁₄CORi₅; -COR_{i 7}; -COORi₆; -CON R₁₄R₁₅; -CN ; halogen; or OS0₃Ri₈; S0₃Ri₈; S0₂Ri₈; P0₃(Ri₈)₂; OP0₃(Ri₈)₂;

G is E; CrCi₈alkyl, which is optionally interrupted by D; CrCi₈alkoxy, which is optionally substituted by E and/or interrupted by D; wherein Ri₂, Ri₃, Ri4 and Ri₅ independently of each other are hydrogen; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl or CrCi₈alkoxy; CrCi₈alkyl, which is optionally interrupted by -0-; or

R-I4 and R₁₅ together form a five or six membered ring,

Ri₆ is hydrogen; C₆-Ci₈aryl which is optionally substituted by Ci-Ci₈alkyl or Ci-Ci₈alkoxy; C Ci₈alkyl which is optionally interrupted by -0-;

Ri₇ is H; C₆-Ci₈aryl which is optionally substituted by Ci-Ci₈alkyl or Ci-Ci₈alkoxy; or d-

Ci₈alkyl which is optionally interrupted by -0-;

Ri₈ is hydrogen; C₆-Ci₈aryl, which is optionally substituted by Ci-Ci₈alkyl or Ci-Ci₈alkoxy;

CrCi₈alkyl, which is optionally interrupted by -0-; and

Rig and R₂₀ independently of each other are hydrogen; Ci-Ci₈alkyl; C₆-Ci₈aryl which is optionally substituted by Ci-Ci₈alkyl.

Further preferred are compounds of formula (1 ), wherein

R₆ is hydrogen; OH; CrC₃oalkyl orCrC₃oalkoxy, which may be substituted by one or more E and/or interrupted by one or more D;

R₅ is hydrogen; substituted or unsubstituted Ci-Ci₈alkyl;

R₂ and R₄ independently from each other are hydrogen; or substituted or unsubstituted C

C_i8alkyl;

R₃ is hydrogen; or carboxylate COOX; wherein

X is Na, K or NH₄; and

D and E are defined as in formula (1 ).

Preference is given to compounds wherein

R₂, R3, R₄, R5 and R₆, independently of one another are hydrogen; d-C^alkyl, CrC₃oalkoxy or CrCi₂alkenyl substituted by E;

E is carboxylate; OCOR₉; sulphate; sulphonate; phosphonate; or phosphate; and

R₉ is defined as in formula (1 ). Further preferred are compounds of formula (1 ), wherein

R₃ is a radical of formula , wherein

is hydrogen; CrCi₂alkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆-C₂oaryl, which may be substituted by one or more G; C₄- C₂oheteroaryl, which may be substituted by one or more G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C25aralkyl, or -CO-Ri₇;

Ri₇ is H; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl or Ci-Ci₈alkoxy; or d- Ci₈alkyl which is optionally interrupted by -O-; and

Ri , R₂, R₄, Rs, R6, R7 and R₈, R₉, R10, D, G and E are defined as in formula (1 ).

Further preferred are ocmpounds of formula (1 ), wherein

R₂, R3, R₄, R5, R6, R9, Rio, Rii , and Ri₂ independently of one another are sulphate; sulpho- nate; phosphate; or phosphonate and/or R-i , R₇ and R₈ together with the adjacent oxy- gen independently of one another form a sulphate, sulphonate, phosphate or phosphonate group.

Further preferred are compounds of formula (1 ), wherein

R₂ is CrC₃oalkyl, C₂-C₃oalkenyl, CrC₃oalkoxy, C₃-Ci₂-cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆-

C₂₀aryl, which may be substituted by one or more G; COR₉; COOR₉; CONR₉R₁₀;

Ri , R₃, R₄, R₅, R6, R7, Re, R9, R10, E, D and G are defined as in formula (1 ).

Further preference is given to compounds of formula (1 ), wherein

R₂ and R₅ is CrC₃₀alkyl, C₂-C₃₀alkenyl, CrC₃₀alkoxy, C₃-Ci₂-cycloalkyl or d-

C₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆-C₂oaryl, which may be substituted by one or more G; COR₉; COOR₉;

CONR₉R₁₀;

Ri , R₃, R₄, R₆, R7, R₈, R₉, Rio, E, D and G are defined as in formula (1 ).

Examples of benzotropolone compounds according to the present invention are listed in Table 1 below:

The benzotropolone derivatives of formula (1 ) exhibit pronounced antimicrobial action, for example, against pathogenic gram-positive and gram-negative bacteria and against bacteria of the skin and oral flora, and also against yeasts and molds. They are accordingly suitable for disinfection, deodorisation, and for general and antimicrobial treatment of the skin and mucosa and of integumentary appendages (hair), for example, for the disinfection of hands and wounds.

They are accordingly suitable as antimicrobial active substances and preservatives in per- sonal care preparations, for example shampoos, bath additives, hair care preparations, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleaning cloths, wet wipes, oils or powders. For example, the antimicrobial compounds of the invention are effective as anti-dandruff agents in shampoos or other products used in hair treatment such as oils, sprays, hair gels.

Moreover they can be used as agent against dermatophytes in products against seborrheic dermatitis, psoriasis and athlethes foot in formulation types such as creams, lotions, gels, powders, oils, tonics, sprays, wet wipes etc. And as anti-acne agents in facial care producs such as creams, lotions, gels, tonics, powders etc.

The benzotropolone derivatives of formula (1 ) may be active ingredients in a personal care preparation comprising cosmetically tolerable carriers or adjuvants. The personal care preparation contains from 0.01 to 15 % by weight, for example, from 0.1 to 10 % by weight, based on the total weight of the composition, of the benzotropolone derivatives of formula (1 ), and cosmetically tolerable adjuvants.

The personal care preparation may be in the form of a water-in-oil or oil-in-water emulsion, an alcoholic or alcohol-containing formulation, a vesicular dispersion of an ionic or non-ionic ampiphilic lipid, a gel, a solid stick or an aerosol formulation. As a water-in-oil or oil-in-water emulsion, the cosmetically tolerable adjuvant contains preferably from 5 to 50 % of an oil phase, from 5 to 20 % of an emulsifier and from 30 to 90 % water. The oil phase may comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol. Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.

Cosmetic formulations according to the invention are used in various fields. There come into consideration, for example, the following preparations:

skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tab- let-form or liquid soaps, synthetic 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;

cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eye shadow preparations, mascaras, eyeliners, 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; intimate hygiene preparations, e.g. intimate washing lotions or intimate sprays;

- 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, sun-blocks 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 (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams;

dental care, denture-care and mouth-care preparations, e.g. toothpastes, gel toothpastes, tooth powders, mouthwash concentrates, anti-plaque mouthwashes, denture cleaners or denture fixatives;

cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair- setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing self-oxidising dyes, or natural hair colorants, such as henna or camomile.

The following examples represent various formulations containing the antimicrobials of the invention. Obviously, these are simple, basic formulations only and a wide variety of similar formulations are known in the art into which the present antimicrobials at various concentrations are readily incorporated. An antimicrobial soap has, for example, the following composition: 0.01 to 5 % by weight of at least one of the benzotropolone derivative of formula (1 ), 0.3 to 1 % by weight of titanium dioxide,

1 to 10 % by weight of stearic acid,

soap base ad 100 %, e.g. of a sodium salt of tallow fatty acid or coconut fatty acid, or glyc- erol.

A shampoo has, for example, the following composition:

0.01 to 5 % by weight of of at least one of the benzotropolone derivative of formula (1 ), 12.0 % by weight of sodium laureth-2-sulfate,

4.0 % by weight of cocamidopropyl betaine,

3.0 % by weight of NaCI and

water ad 100 %.

A deodorant has, for example, the following composition:

0.01 to 5 % by weight of at least one of the benzotropolone derivative of formula (1 ), 60 % by weight of ethanol,

0.3 % by weight of perfume oil, and

water ad 100 %. The invention relates also to an oral composition containing from 0.01 to 15 % by weight, based on the total weight of the composition, of at least one of the benzotropolone derivative of formula (1 ), and orally tolerable adjuvants.

Example of an oral composition:

10 % by weight of sorbitol,

10 % by weight of glycerol,

15 % by weight of ethanol,

15 % by weight of propylene glycol,

0.5 % by weight of sodium lauryl sulfate,

0.25 % by weight of sodium methylcocyl taurate,

0.25 % by weight of polyoxypropylene/polyoxyethylene block copolymer,

0.10 % by weight of peppermint flavouring,

0.1 to 0.5 % by weight of at least one of the benzotropolone derivative of formula (1 ), and 48.6 % by weight water. The oral composition according to the invention may be, for example, in the form of a gel, a paste, a cream or an aqueous preparation (mouthwash).

The oral composition according to the invention may also comprise compounds that release fluoride ions which are effective against the formation of caries, for example inorganic fluoride salts, e.g. sodium, potassium, ammonium or calcium fluoride, or organic fluoride salts, e.g. amine fluorides, which are known under the trade name OLAFLUOR.

The antimicrobial compounds of this invention are also used in washing and cleaning formu- lations, e.g. in liquid or powder washing agents or softeners.

The antimicrobial compounds of this invention can also be used in household and general- purpose cleaners for cleaning and disinfecting hard surfaces. A cleaning preparation has, for example the following composition:

0.01 to 5 % by weight antimicrobial compound

3.0 % by weight octyl alcohol 4EO

1 .3 % by weight fatty alcohol C₈-Ci₀polyglucoside

3.0 % by weight isopropanol

water ad 100 %.

In the following examples for combinations of the compounds claimed in the present invention and biocides and/or preservatives are shown: Table 2: Examples of combinations of biocides and/or preservatives used as antimicrobial actives in cosmetic products and household products

Table 2: A B C D E F G H I K L M N O P Q R S T u V w

Combination name

BIOCIDE/PRESERVATIVE 1

BIOCIDE/PRESERVATIVE 2

BIOCIDE/PRESERVATIVE 3

BIOCIDE/PRESERVATIVE 4

BIOCIDE/PRESERVATIVE 5

BIOCIDE/PRESERVATIVE 6

BIOCIDE/PRESERVATIVE 7

BIOCIDE/PRESERVATIVE 8

BIOCIDE/PRESERVATIVE 9 Table 2: A B c D E F G H I K L M N 0 P Q R s T u V w

Combination name

BIOCIDE/PRESERVATIVE 10

BIOCIDE/PRESERVATIVE 1 1

BIOCIDE/PRESERVATIVE 12

BIOCIDE/PRESERVATIVE 13

BIOCIDE/PRESERVATIVE 14

BIOCIDE/PRESERVATIVE 15

BIOCIDE/PRESERVATIVE 16

BIOCIDE/PRESERVATIVE 17

BIOCIDE/PRESERVATIVE 18

BIOCIDE/PRESERVATIVE 19

BIOCIDE/PRESERVATIVE 20

BIOCIDE/PRESERVATIVE 21

BIOCIDE/PRESERVATIVE 22

BIOCIDE/PRESERVATIVE 23

BIOCIDE/PRESERVATIVE 24

BIOCIDE/PRESERVATIVE 25

BIOCIDE/PRESERVATIVE 26

BIOCIDE/PRESERVATIVE 27

BIOCIDE/PRESERVATIVE 28

BIOCIDE/PRESERVATIVE 29

BIOCIDE/PRESERVATIVE 30

BIOCIDE/PRESERVATIVE 31

BIOCIDE/PRESERVATIVE 32

BIOCIDE/PRESERVATIVE 33

BIOCIDE/PRESERVATIVE 34

BIOCIDE/PRESERVATIVE 35

BIOCIDE/PRESERVATIVE 36

BIOCIDE/PRESERVATIVE 37

BIOCIDE/PRESERVATIVE 38

BIOCIDE/PRESERVATIVE 39

BIOCIDE/PRESERVATIVE 40

BIOCIDE/PRESERVATIVE 41

BIOCIDE/PRESERVATIVE 42

BIOCIDE/PRESERVATIVE 43

BIOCIDE/PRESERVATIVE 44

BIOCIDE/PRESERVATIVE 45

BIOCIDE/PRESERVATIVE 46

BIOCIDE/PRESERVATIVE 47

BIOCIDE/PRESERVATIVE 48

BIOCIDE/PRESERVATIVE 49

BIOCIDE/PRESERVATIVE 50

BIOCIDE/PRESERVATIVE 51

BIOCIDE/PRESERVATIVE 52 Table 2: A B c D E F G H I K L M N 0 P Q R s T u V w

Combination name

BIOCIDE/PRESERVATIVE 53

BIOCIDE/PRESERVATIVE 54

BIOCIDE/PRESERVATIVE 55

BIOCIDE/PRESERVATIVE 56

BIOCIDE/PRESERVATIVE 57

BIOCIDE/PRESERVATIVE 58

BIOCIDE/PRESERVATIVE 59

BIOCIDE/PRESERVATIVE 60

BIOCIDE/PRESERVATIVE 61

BIOCIDE/PRESERVATIVE 62

BIOCIDE/PRESERVATIVE 63

BIOCIDE/PRESERVATIVE 64

BIOCIDE/PRESERVATIVE 65

BIOCIDE/PRESERVATIVE 66

BIOCIDE/PRESERVATIVE 67

BIOCIDE/PRESERVATIVE 68

BIOCIDE/PRESERVATIVE 69

BIOCIDE/PRESERVATIVE 70

BIOCIDE/PRESERVATIVE 71

BIOCIDE/PRESERVATIVE 72

BIOCIDE/PRESERVATIVE 73

BIOCIDE/PRESERVATIVE 74

BIOCIDE/PRESERVATIVE 75

BIOCIDE/PRESERVATIVE 76

BIOCIDE/PRESERVATIVE 77

BIOCIDE/PRESERVATIVE 78

BIOCIDE/PRESERVATIVE 79

BIOCIDE/PRESERVATIVE 80

BIOCIDE/PRESERVATIVE 81

BIOCIDE/PRESERVATIVE 82

BIOCIDE/PRESERVATIVE 83

BIOCIDE/PRESERVATIVE 84

BIOCIDE/PRESERVATIVE 85

BIOCIDE/PRESERVATIVE 86

BIOCIDE/PRESERVATIVE 87

BIOCIDE/PRESERVATIVE 88

BIOCIDE/PRESERVATIVE 89

BIOCIDE/PRESERVATIVE 90

BIOCIDE/PRESERVATIVE 91

BIOCIDE/PRESERVATIVE 92

BIOCIDE/PRESERVATIVE 93

BIOCIDE/PRESERVATIVE 94

BIOCIDE/PRESERVATIVE 95 Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w

Combination name

BIOCIDE/PRESERVATIVE 96

BIOCIDE/PRESERVATIVE 97

BIOCIDE/PRESERVATIVE 98

BIOCIDE/PRESERVATIVE 99

BIOCIDE/PRESERVATIVE 100

BIOCIDE/PRESERVATIVE 101

BIOCIDE/PRESERVATIVE 102

BIOCIDE/PRESERVATIVE 103

BIOCIDE/PRESERVATIVE 104

BIOCIDE/PRESERVATIVE 105

BIOCIDE/PRESERVATIVE 106

BIOCIDE/PRESERVATIVE 107

BIOCIDE/PRESERVATIVE 108

BIOCIDE/PRESERVATIVE 109

BIOCIDE/PRESERVATIVE 1 10

BIOCIDE/PRESERVATIVE 1 1 1

BIOCIDE/PRESERVATIVE 1 12

BIOCIDE/PRESERVATIVE 1 13

BIOCIDE/PRESERVATIVE 1 14

BIOCIDE/PRESERVATIVE 1 15

BIOCIDE/PRESERVATIVE 1 16

BIOCIDE/PRESERVATIVE 1 17

BIOCIDE/PRESERVATIVE 1 18

BIOCIDE/PRESERVATIVE 1 19

BIOCIDE/PRESERVATIVE 120

BIOCIDE/PRESERVATIVE 121

BIOCIDE/PRESERVATIVE 122

BIOCIDE/PRESERVATIVE 123

BIOCIDE/PRESERVATIVE 124

BIOCIDE/PRESERVATIVE 125

BIOCIDE/PRESERVATIVE 126

BIOCIDE/PRESERVATIVE 127

BIOCIDE/PRESERVATIVE 128

BIOCIDE/PRESERVATIVE 129

BIOCIDE/PRESERVATIVE 130

BIOCIDE/PRESERVATIVE 131

BIOCIDE/PRESERVATIVE 132

BIOCIDE/PRESERVATIVE 133

BIOCIDE/PRESERVATIVE 134

BIOCIDE/PRESERVATIVE 135

BIOCIDE/PRESERVATIVE 136

BIOCIDE/PRESERVATIVE 137

BIOCIDE/PRESERVATIVE 138 Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w

Combination name

BIOCIDE/PRESERVATIVE 139

BIOCIDE/PRESERVATIVE 140

BIOCIDE/PRESERVATIVE 141

BIOCIDE/PRESERVATIVE 142

BIOCIDE/PRESERVATIVE 143

BIOCIDE/PRESERVATIVE 144

BIOCIDE/PRESERVATIVE 145

BIOCIDE/PRESERVATIVE 146

BIOCIDE/PRESERVATIVE 147

BIOCIDE/PRESERVATIVE 148

BIOCIDE/PRESERVATIVE 149

BIOCIDE/PRESERVATIVE 150

BIOCIDE/PRESERVATIVE 151

BIOCIDE/PRESERVATIVE 152

BIOCIDE/PRESERVATIVE 153

BIOCIDE/PRESERVATIVE 154

BIOCIDE/PRESERVATIVE 155

BIOCIDE/PRESERVATIVE 156

BIOCIDE/PRESERVATIVE 157

BIOCIDE/PRESERVATIVE 158

BIOCIDE/PRESERVATIVE 159

BIOCIDE/PRESERVATIVE 160

BIOCIDE/PRESERVATIVE 161

BIOCIDE/PRESERVATIVE 162

BIOCIDE/PRESERVATIVE 163

BIOCIDE/PRESERVATIVE 164

BIOCIDE/PRESERVATIVE 165

BIOCIDE/PRESERVATIVE 166

BIOCIDE/PRESERVATIVE 167

BIOCIDE/PRESERVATIVE 168

BIOCIDE/PRESERVATIVE 169

BIOCIDE/PRESERVATIVE 170

BIOCIDE/PRESERVATIVE 171

BIOCIDE/PRESERVATIVE 172

BIOCIDE/PRESERVATIVE 173

BIOCIDE/PRESERVATIVE 174

BIOCIDE/PRESERVATIVE 175

BIOCIDE/PRESERVATIVE 176

BIOCIDE/PRESERVATIVE 177

BIOCIDE/PRESERVATIVE 178

BIOCIDE/PRESERVATIVE 179

BIOCIDE/PRESERVATIVE 180

BIOCIDE/PRESERVATIVE 181 Table 2: A B C D E F G H I K L M N 0 P Q R s T u V w

Combination name

BIOCIDE/PRESERVATIVE 182

BIOCIDE/PRESERVATIVE 183

BIOCIDE/PRESERVATIVE 184

BIOCIDE/PRESERVATIVE 185

BIOCIDE/PRESERVATIVE 186

BIOCIDE/PRESERVATIVE 187

BIOCIDE/PRESERVATIVE 188

BIOCIDE/PRESERVATIVE 189

BIOCIDE/PRESERVATIVE 190

BIOCIDE/PRESERVATIVE 191

BIOCIDE/PRESERVATIVE 192

BIOCIDE/PRESERVATIVE 193

BIOCIDE/PRESERVATIVE 194

BIOCIDE/PRESERVATIVE 195

BIOCIDE/PRESERVATIVE 196

BIOCIDE/PRESERVATIVE 197

BIOCIDE/PRESERVATIVE 198

BIOCIDE/PRESERVATIVE 199

BIOCIDE/PRESERVATIVE 200

BIOCIDE/PRESERVATIVE 201

BIOCIDE/PRESERVATIVE 202

BIOCIDE/PRESERVATIVE 203

BIOCIDE/PRESERVATIVE 204

BIOCIDE/PRESERVATIVE 205

BIOCIDE/PRESERVATIVE 206

BIOCIDE/PRESERVATIVE 207

BIOCIDE/PRESERVATIVE 208

BIOCIDE/PRESERVATIVE 209

BIOCIDE/PRESERVATIVE 210

BIOCIDE/PRESERVATIVE 21 1

BIOCIDE/PRESERVATIVE 212

BIOCIDE/PRESERVATIVE 213

BIOCIDE/PRESERVATIVE 214

BIOCIDE/PRESERVATIVE 215

BIOCIDE/PRESERVATIVE 216

BIOCIDE/PRESERVATIVE 217

BIOCIDE/PRESERVATIVE 218

BIOCIDE/PRESERVATIVE 219

BIOCIDE/PRESERVATIVE 220

BIOCIDE/PRESERVATIVE 221

BIOCIDE/PRESERVATIVE 222

BIOCIDE/PRESERVATIVE 223

BIOCIDE/PRESERVATIVE 224 Table 2: A B C D E F G H I K L M N O P Q R s T u V w

Combination name

BIOCIDE/PRESERVATIVE 225

BIOCIDE/PRESERVATIVE 226

BIOCIDE/PRESERVATIVE 227

BIOCIDE/PRESERVATIVE 228

BIOCIDE/PRESERVATIVE 229

BIOCIDE/PRESERVATIVE 230

BIOCIDE/PRESERVATIVE 231

BIOCIDE/PRESERVATIVE 232

BIOCIDE/PRESERVATIVE 233

BIOCIDE/PRESERVATIVE 234

BIOCIDE/PRESERVATIVE 235

BIOCIDE/PRESERVATIVE 236

BIOCIDE/PRESERVATIVE 237

BIOCIDE/PRESERVATIVE 238

BIOCIDE/PRESERVATIVE 239

BIOCIDE/PRESERVATIVE 240

BIOCIDE/PRESERVATIVE 241

BIOCIDE/PRESERVATIVE 242

BIOCIDE/PRESERVATIVE 243

BIOCIDE/PRESERVATIVE 244

BIOCIDE/PRESERVATIVE 245

BIOCIDE/PRESERVATIVE 246

BIOCIDE/PRESERVATIVE 247

BIOCIDE/PRESERVATIVE 248

BIOCIDE/PRESERVATIVE 249

BIOCIDE/PRESERVATIVE 250

BIOCIDE/PRESERVATIVE 251

BIOCIDE/PRESERVATIVE 252

BIOCIDE/PRESERVATIVE 253

INCI Name CAS No.

A Benzoic acid or/and its salts 65-85-0

B 2-bromo-2-nitropropane-1 ,3-diol 52-51 -7

c Benzyl alcohol 100-51 -6

D Benzisothiazolinone 2634-33-5

E Dehydroacetic acid 16807-48-0

F Dichlorobenzyl alcohol 12041 -76-8

G DMDM hydantoin 6440-58-0

H Diazolidinyl urea 78491 -02-8

I Ethylparaben 120-47-8

K lodopropynyl butylcarbamate 55406-53-6

L Imidazolidinyl urea 39236-46-9

M Methylchloroisothiazolinone 26172-55-4 INCI Name CAS No.

N Methyldibromo glutaronitrile 35691 -65-7

0 Methylparaben 99-76-3

P Methylisothiazolinone 2682-20-4

Q 2-phenoxyethanol 122-99-6

R Propylparaben 94-13-3

S Salicylic acid or/and its salts 69-72-7

T Sorbic acid and/or its salts 1 10-44-1

u Triclosan 3380-34-5

V Undecylenic acid and/or its salts 1333-28-4

w Silver Citrate and Citric acid 36701 -38-9

In all of the biocide combinations listed before in Table 2, "X" represents a specific biocide and/or preservative. The concentrations of these biocidal/preservative substances in the blends are between 1 % and 99%, preferably between 10% and 90%. The use concentration of these blends in household and personal care products is typically in the range of 0.1 % to 5% and preferred 0.2% to 2%.

Further biocide combination examples are the following:

In all the biocide combinations listed before the weight ratio of the biocides and or preserva- tives (based on the weight of all biocides/preservatives in the combination) is for combinations of two biocides/preservatives 1 :1 or 1 :2 or 2:1 or 1 :3 or 3:1 .

Formulation examples

The compounds of the present invention from table 1 can be componed with the

BIOCIDES/PRESERVARTIVES from Table 2 as shown in the following formulation exam- pies:

„BIOCIDE/PRESERVATIVE" may be (as described in Table 2) BIOCIDE/PRESERVATIVE 1 , or BIOCIDE/PRESERVATIVE 2, or BIOCIDE/PRESERVATIVE 3, or BIOCIDE/PRESERVATIVE 4, or BIOCIDE/PRESERVATIVE 5, or BIOCIDE/PRESERVATIVE 6, or BIOCIDE/- PRESERVATIVE 7, or BIOCIDE/PRESERVATIVE 8, or BIOCIDE/PRESERVATIVE 9, or BIOCIDE/PRESERVATIVE 10, or BIOCIDE/PRESERVATIVE 1 1 , or BIOCIDE/PRESERVATIVE 12, or BIOCIDE/PRESERVATIVE 13, or BIOCIDE/PRESERVATIVE 14, or BIOCIDE/- PRESERVATIVE 15, or BIOCIDE/PRESERVATIVE 16, or BIOCIDE/PRESERVATIVE 17, or BIOCIDE/PRESERVATIVE 18, or BIOCIDE/PRESERVATIVE 19, or BIOCIDE/PRESERVATIVE 20, or BIOCIDE/PRESERVATIVE 21 , or BIOCIDE/PRESERVATIVE 22, or BIOCIDE/- PRESERVATIVE 23, or BIOCIDE/PRESERVATIVE 24, or BIOCIDE/PRESERVATIVE 25, or BIOCIDE/PRESERVATIVE 26, or BIOCIDE/PRESERVATIVE 27, or BIOCIDE/PRESERVA- TIVE 28, or BIOCIDE/PRESERVATIVE 29, or BIOCIDE/PRESERVATIVE 30, or BIOCIDE/- PRESERVATIVE 31 , or BIOCIDE/PRESERVATIVE 32, or BIOCIDE/PRESERVATIVE 33, or BIOCIDE/PRESERVATIVE 34, or BIOCIDE/PRESERVATIVE 35, or BIOCIDE/PRESERVATIVE 36, or BIOCIDE/PRESERVATIVE 37, or BIOCIDE/PRESERVATIVE 38, or BIOCIDE/- PRESERVATIVE 39, or BIOCIDE/PRESERVATIVE 40, or BIOCIDE/PRESERVATIVE 41 , or BIOCIDE/PRESERVATIVE 42, or BIOCIDE/PRESERVATIVE 43, or BIOCIDE/-PRESER- VATIVE 44, or BIOCIDE/PRESERVATIVE 45, or BIOCIDE/PRESERVATIVE 46, or BIOCIDE/PRESERVATIVE 47, or BIOCIDE/PRESERVATIVE 48, or BIOCIDE/PRESERVATIVE 49, or BIOCIDE/PRESERVATIVE 50, or BIOCIDE/PRESERVATIVE 51 , or BIOCIDE/PRE- SERVATIVE 52, or BIOCIDE/PRESERVATIVE 53, or BIOCIDE/PRESERVATIVE 54, or

BIOCIDE/PRESERVATIVE 55, or BIOCIDE/PRESERVATIVE 56, or BIOCIDE/PRESERVATIVE 57, or BIOCIDE/PRESERVATIVE 58, or BIOCIDE/PRESERVATIVE 59, or BIOCIDE/- PRESERVATIVE 60, or BIOCIDE/PRESERVATIVE 61 , or BIOCIDE/PRESERVATIVE 62, or BIOCIDE/PRESERVATIVE 63, or BIOCIDE/PRESERVATIVE 64, or BIOCIDE/PRESER- VATIVE 65, or BIOCIDE/PRESERVATIVE 66, or BIOCIDE/PRESERVATIVE 67, or BIOCIDE/PRESERVATIVE 68, or BIOCIDE/PRESERVATIVE 69, or BIOCIDE/PRESERVATIVE 70, or BIOCIDE/PRESERVATIVE 71 , or BIOCIDE/PRESERVATIVE 72, or BIOCIDE/PRESERVATIVE 73, or BIOCIDE/PRESERVATIVE 74, or BIOCIDE/PRESERVATIVE 75, or BIOCIDE/PRESERVATIVE 76, or BIOCIDE/PRESERVATIVE 77, or BIOCIDE/PRESER- VATIVE 78, or BIOCIDE/PRESERVATIVE 79, or BIOCIDE/PRESERVATIVE 80, or BIO-

CIDE/PRE-SERVATIVE 81 , or BIOCIDE/PRESERVATIVE 82, or BIOCIDE/PRESERVATIVE 83, or BIOCIDE/PRESERVATIVE 84, or BIOCIDE/PRESERVATIVE 85, or BIOCIDE/PRESERVATIVE 86, or BIOCIDE/PRESERVATIVE 87, or BIOCIDE/PRESERVATIVE 88, or BIOCIDE/PRESERVATIVE 89, or BIOCIDE/PRESERVATIVE 90, or BIOCIDE/PRESERVATIVE 91 , or BIOCIDE/PRESERVATIVE 92, or BIOCIDE/PRESERVATIVE 93, or BIOCIDE/PRESERVATIVE 94, or BIOCIDE/PRESERVATIVE 95, or BIOCIDE/PRESERVATIVE 96, or BIOCIDE/PRESERVATIVE 97, or BIOCIDE/PRESERVATIVE 98, or BIOCIDE/PRE-SERVA- TIVE 99, or BIOCIDE/PRESERVATIVE 100, or BIOCIDE/PRESERVATIVE 101 , or BIOCIDE/PRESERVATIVE 102, or BIOCIDE/PRESERVATIVE 103, or BIOCIDE/PRESER- VATIVE 104, or BIOCIDE/PRESERVATIVE 105, or BIOCIDE/PRESERVATIVE 106, or BIOCIDE/PRESERVATIVE 107, or BIOCIDE/PRESERVATIVE 108, or BIOCIDE/PRESERVATIVE 109, or BIOCIDE/PRESERVATIVE 1 10, or BIOCIDE/PRESERVATIVE 1 1 1 , or BIOCIDE/PRESERVATIVE 1 12, or BIOCIDE/PRESERVATIVE 1 13, or BIOCIDE/PRESERVATIVE 1 14, or BIOCIDE/PRESERVATIVE 1 15, or BIOCIDE/PRESERVATIVE 1 16, or BIO- CIDE/PRESERVATIVE 1 17, or BIOCIDE/PRESERVATIVE 1 18, or BIOCIDE/PRESER- VATIVE 1 19, or BIOCIDE/PRESERVATIVE 120, or BIOCIDE/PRESERVATIVE 121 , or BIOCIDE/PRESERVATIVE 122, or BIOCIDE/PRESERVATIVE 123, or BIOCIDE/PRESERVATIVE 124, or BIOCIDE/PRESERVATIVE 125, or BIOCIDE/PRESERVATIVE 126, or BIOCIDE/PRESERVATIVE 127, or BIOCIDE/PRESERVATIVE 128, or BIOCIDE/PRESERVA- TIVE 129, or BIOCIDE/PRESERVATIVE 130, or BIOCIDE/PRESERVATIVE 131 , or BIOCIDE/PRESERVATIVE 132, or BIOCIDE/PRESERVATIVE 133, or BIOCIDE/PRE-SERVA- TIVE 134, or BIOCIDE/PRESERVATIVE 135, or BIOCIDE/PRESERVATIVE 136, or BIOCIDE/PRESERVATIVE 137, or BIOCIDE/PRESERVATIVE 138, or BIOCIDE/PRESERVATIVE 139, or BIOCIDE/PRESERVATIVE 140, or BIOCIDE/PRESERVATIVE 141 , or BIO- CIDE/PRESERVATIVE 142, or BIOCIDE/PRESERVATIVE 143, or BIOCIDE/PRESERVATIVE 144, or BIOCIDE/PRESERVATIVE 145, or BIOCIDE/PRESERVATIVE 146, or BIOCIDE/PRESERVATIVE 147, or BIOCIDE/PRESERVATIVE 148, or BIOCIDE/PRESERVATIVE 149, or BIOCIDE/PRESERVATIVE 150, or BIOCIDE/PRESERVATIVE 151 , or BIOCIDE/PRESERVATIVE 152, or BIOCIDE/PRESERVATIVE 153, or BIOCIDE/PRESERVA- TIVE 154, or BIOCIDE/PRESERVATIVE 155, or BIOCIDE/PRESERVATIVE 156, or BIOCIDE/PRESERVATIVE 157, or BIOCIDE/PRESERVATIVE 158, or BIOCIDE/PRESERVATIVE 159, or BIOCIDE/PRESERVATIVE 160, or BIOCIDE/PRESERVATIVE 161 , or BIOCIDE/PRESERVATIVE 162, or BIOCIDE/PRESERVATIVE 163, or BIOCIDE/PRESERVATIVE 164, or BIOCIDE/PRESERVATIVE 165, or BIOCIDE/PRESERVATIVE 166, or BIO- CIDE/PRESERVATIVE 167, or BIOCIDE/PRESERVATIVE 168, or BIOCIDE/PRESERVATIVE 169, or BIOCIDE/PRESERVATIVE 170, or BIOCIDE/PRESERVATIVE 171 , or BIOCIDE/PRESERVATIVE 172, or BIOCIDE/PRESERVATIVE 173, or BIOCIDE/PRESERVATIVE 174, or BIOCIDE/PRESERVATIVE 175, or BIOCIDE/PRESERVATIVE 176, or BIOCIDE/PRESERVATIVE 177, or BIOCIDE/PRESERVATIVE 178, or BIOCIDE/PRESERVA- TIVE 179, or BIOCIDE/PRESERVATIVE 180, or BIOCIDE/PRESERVATIVE 181 , or BIOCIDE/PRESERVATIVE 182, or BIOCIDE/PRESERVATIVE 183, or BIOCIDE/PRESERVATIVE 184, or BIOCIDE/PRESERVATIVE 185, or BIOCIDE/PRESERVATIVE 186, or BIOCIDE/PRESERVATIVE 187, or BIOCIDE/PRESERVATIVE 188, or BIOCIDE/PRESERVATIVE 189, or BIOCIDE/PRESERVATIVE 190, or BIOCIDE/PRESERVATIVE 191 , or BIO- CIDE/PRESERVATIVE 192, or BIOCIDE/PRESERVATIVE 193, or BIOCIDE/PRESERVATIVE 194, or BIOCIDE/PRESERVATIVE 195, or BIOCIDE/PRESERVATIVE 196, or BIOCIDE/PRESERVATIVE 197, or BIOCIDE/PRESERVATIVE 198, or BIOCIDE/PRESERVATIVE 199, or BIOCIDE/PRESERVATIVE 200, or BIOCIDE/PRESERVATIVE 201 , or BIOCIDE/PRESERVATIVE 202, or BIOCIDE/PRESERVATIVE 203, or BIOCIDE/PRESERVA- TIVE 204, or BIOCIDE/PRESERVATIVE 205, or BIOCIDE/PRESERVATIVE 206, or BIO- CIDE/PRESERVATIVE 207, or BIOCIDE/PRESERVATIVE 208, or BIOCIDE/PRESERVATIVE 209, or BIOCIDE/PRESERVATIVE 210, or BIOCIDE/PRESERVATIVE 21 1 , or BIOCIDE/PRESERVATIVE 212, or BIOCIDE/PRESERVATIVE 213, or BIOCIDE/PRESERVATIVE 214, or BIOCIDE/PRESERVATIVE 215, or BIOCIDE/PRESERVATIVE 216, or BIO- CIDE/PRESERVATIVE 217, or BIOCIDE/PRESERVATIVE 218, or BIOCIDE/PRESERVATIVE 219, or BIOCIDE/PRESERVATIVE 220, or BIOCIDE/PRESERVATIVE 221 , or BIOCIDE/PRESERVATIVE 222, or BIOCIDE/PRESERVATIVE 223, or BIOCIDE/PRESERVATIVE 224, or BIOCIDE/PRESERVATIVE 225, or BIOCIDE/PRESERVATIVE 226, or BIOCIDE/PRESERVATIVE 227, or BIOCIDE/PRESERVATIVE 228, or BIOCIDE/PRESERVA- TIVE 229, or BIOCIDE/PRESERVATIVE 230, or BIOCIDE/PRESERVATIVE 231 , or BIOCIDE/PRESERVATIVE 232, or BIOCIDE/PRESERVATIVE 233, or BIOCIDE/PRESERVATIVE 234, or BIOCIDE/PRESERVATIVE 235, or BIOCIDE/PRESERVATIVE 236, or BIOCIDE/PRESERVATIVE 237, or BIOCIDE/PRESERVATIVE 238, or BIOCIDE/PRESERVATIVE 239, or BIOCIDE/PRESERVATIVE 240, or BIOCIDE/PRESERVATIVE 241 , or BIO- CIDE/PRESERVATIVE 242, or BIOCIDE/PRESERVATIVE 243, or BIOCIDE/PRESERVATIVE 244, or BIOCIDE/PRESERVATIVE 245, or BIOCIDE/PRESERVATIVE 246, or BIOCIDE/PRESERVATIVE 247, or BIOCIDE/PRESERVATIVE 248, or BIOCIDE/PRESERVATIVE 249, or BIOCIDE/PRESERVATIVE 250, or BIOCIDE/PRESERVATIVE 251 , or BIOCIDE/PRESERVATIVE 252, or BIOCIDE/PRESERVATIVE 253.

In the following some examples of formulations combining the compounds of the present invention with other cosmetic and household product ingredients including the

BIOCIDES/PRESERVATIVES of table 2 are shown:

Sun Milk A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part C12-15 Alkyl Benzoate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 A

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Tridecyl Trimellitate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Isohexadecane 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Cyclopentasiloxane 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Stearic Acid 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

PEG-100 Stearate (and) Glyc0,80 0,80 0,80 0,80 0,80 0,80 0,80 0,80 0,80 eryl Stearate Sun Milk A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Potassium Cetyl Phosphate 1,30 1,30 1,30 1,30 1,30 1,30 1,30 1,30 1,30

PVP/Eicosene Copolymer 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Bis-Ethylhexyloxyphenol Meth- 0,00 2,50 5,00 10.0C 0,00 2,50 5,00 10.0C 0,00 oxyphenyl Triazine (Tinosorb S)

Butyl Methoxydibenzoylmetha- 0,00 5,00 2,50 0,00 5,00 2,50 0,00 5,00 2,50 ne

Part Methylene Bis-Benzotriazolyl 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 B Tetramethylbutylphenol (and)

water (and) decyl glucoside

(and) propylene glycol (and)

xanthan gum (Tinosorb M)

Water Qs Qs Qs Qs Qs Qs Qs Qs Qs to to to to to to to to to 100 100 100 100 100 100 100 100 100

Propylene Glycol 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Xanthan Gum 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Acrylates/C 10-30 Alkyl Acrylate 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 Crosspolymer

Disodium EDTA 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15

Part Triethanolamine Qs Qs Qs Qs Qs Qs Qs Qs Qs C

Dimethicone 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40

Tocopheryl Acetate 0,90 0,90 0,90 0,90 0,90 0,90 0,90 0,90 0,90

Part Benzotropolone according to the 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 D present inveniton (Table 1)

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Water resistant Sunscreen Emulsion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Polyglyceryl-10 Pentastearate 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50

A (and) Behenyl Alcohol (and)

Sodium Stearoyl Lactylate

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Triisodecyl Trimellitate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

VP/Eicosene Copolymer 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50

Stearyl Alcohol 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50

Squalane 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50

C12-15 Alkyl Benzoate 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 Water resistant Sunscreen Emulsion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Bis-Ethylhexyloxyphenol 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 Methoxyphenyl Triazine (Ti- nosorb S)

Diethylamino Hydroxy Benzoyl 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00 Hexyl Benzoate

water (and) decyl glucoside

(and) propylene glycol (and)

xanthan gum (Tinosorb M)

Glycerin 1,80 1,80 1,80 1,80 1,80 1,80 1,80 1,80 1,80

Steareth-10 Allyl 0,80 0,80 0,80 0,80 0,80 0,80 0,80 0,80 0,80 Ether/Acrylates Copolymer

VP/Hexadecene Copolymer 2,70 2,70 2,70 2,70 2,70 2,70 2,70 2,70 2,70

Part Cyclomethicone 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 C

Water (and) Tocopheryl Ace3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 tate (and) Caprylic/Capric

Triglyceride (and) Polysorbate

80 (and) Lecithin

Fragrance qs qs qs qs qs qs qs qs qs

Water (and) Sodium Hydroxiqs qs qs qs qs qs qs qs qs de

Part Benzotropolone according to 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 D the present inveniton (Table 1)

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Every Day Lotion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Stearyl Phosphate 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 A

Phenethyl Benzoate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Triisodecyl Trimellitate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Tricontanyl PVP 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Ethoxydiglycol Oleate 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50 1,50

Squalane 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

C12-15 Alkyl Benzoate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Glyceryl Stearate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Cetyl Alcohol 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Bis-Ethylhexyloxyphenol Me- 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00

Even /dav Moisturizing Cream A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Water qs. qs. qs. qs. qs. qs. qs. qs. qs. A 100 100 100 100 100 100 100 100 100

Part Hydroxyethylcellulose 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 B

Part Panthenol 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 C

Preservative 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Part Tocopheryl acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 D

Grape seed oil 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Almond 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Caprilyc/Capric triglyceride 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00

Caprylyl methicone 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Dimethicone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Glyceryl stearate (and) ce- 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Gel A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Alcohol Denatured Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to

100 100 100 100 100 100 100 100 100

Phenethyl Benzoate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Triisodecyl Trimellitate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Hydroxypropyl Cellulose 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Acrylates/Octylacrylamide Co- 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Emulsifierfree lotion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Ceteareth-20 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Xanthan Gum 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Bis-Ethylhexyloxyphenol Meth- 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 oxyphenyl Triazine (Tinosorb S)

Homosalate 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00

Methylene Bis-Benzotriazolyl 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 Tetramethylbutylphenol (and)

water (and) decyl glucoside

(and) propylene glycol (and)

xanthan gum (Tinosorb M)

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Tridecyl Trimellitate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Dimethyl Capramide 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

C12-15 Alkyl Benzoate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Butylenglycol Dicapry- 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 latDicaprate

Cyclomethicone 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

PVP Hexadecene Copolymer 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Glycerin 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Vitamin E Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Polyethylene Terephthalate 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40

Ethanol 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Parfume 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 Emulsifier free lotion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Benzotropolone according to the 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 present inveniton (Table 1 )

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50

(Table 2)

Water ad. ad. ad. ad. ad. ad. ad. ad. ad.

100 100 100 100 100 100 100 100 100

Emulsifier free face care A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Sodium Carbomer 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Xanthan Gum 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30

Isoamyl p-Methoxycinnamate 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00

water (and) decyl glucoside

(and) propylene glycol (and)

xanthan gum (Tinosorb M)

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

C12-15 Alkyl Benzoate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Dicaprylyl Carbonate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Dimethicone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Shea Butter 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Ethylhexylglycerine 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Glycerin 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50

Glycine Soja 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50

Vitamin E Acetate 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 oc-Glycosil Rutin 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30

Polyethylene Terephthalate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Trisodium EDTA 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30

Ethanol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50

(Table 2)

Water ad. ad. ad. ad. ad. ad. ad. ad. ad.

100 100 100 100 100 100 100 100 100

Skin care spray A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w Skin care spray A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Butylene Glycol Dicapryla- 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 A te/Dicaprate

C18-36 Acid Triglyceride 0,70 0,70 0,70 0,70 0,70 0,70 0,70 0,70 0,70

Ceteareth-20 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

C12-15 Alkyl Benzoate 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00

Taurine 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40

PVP/Hexadecene Copoly0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 mer

Polysilicone-15 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00

Part Methylene Bis-Benzotria- 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 B zolyl Tetramethylbutylphe- nol (and) water (and) decyl

glucoside (and) propylene

glycol (and) xanthan gum

(Tinosorb M)

Water qs. qs. qs. qs. qs. qs. qs. qs. qs.

To To To To To To To To To 100 100 100 100 100 100 100 100 100

Glycerin 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00

Methylpropanediol 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Acrylates/C 10-30 Alkyl 0,18 0,18 0,18 0,18 0,18 0,18 0,18 0,18 0,18 Acrylate Crosspolymer

Trisodium EDTA 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10

Part Alcohol Denatured 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 C

Tocopheryl Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Benzotropolone according 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 to the present inveniton

(Table 1 )

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

O/W -oarming Lotion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Decyl Cocoate 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 A

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

O/W Lotion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Stearic Acid 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Phenethyl Benzoate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Tridecyl Trimellitate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Myristyl Alcohol 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50

Cetearyl Alcohol 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

PEG-100 Stearate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Kaolin 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

Hydroxyethylcellulose 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

Magnesium Aluminium Silicate 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Mineral Oil 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00

Cyclomethicone 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Dimethicone 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

PEG-180/Laureth-50/TMMG Co0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 polymer O/W Lotion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Glycerin 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Zinc Oxide 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00

water (and) decyl glucoside (and)

propylene glycol (and) xanthan

gum (Tinosorb M)

Hydrogenated Coco-Glycerides 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Parfume q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

Water ad ad ad ad ad ad ad ad ad

100 100 100 100 100 100 100 100 100

Propellent Qs Qs Qs Qs Qs Qs Qs Qs Qs

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50

(Table 2)

pH-value adjusted to 5.0-6.5

W/O mulsion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w W/O mulsion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Butylen Glycol Dicapryla- 5,50 5,50 5,50 5,50 5,50 5,50 5,50 5,50 5,50 A te/Dicaprate

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

C18-36 Acid Triglyceride 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Isopropyl Stearate 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50

C12-15 Alkyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Polyglyceryl-2 Dipoly- 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 hydroxystearate

Diethylhexyl Butamido 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 Triazone

Cetyl Dimethicone 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Bis-Ethylhexyloxyphenol 0,00 2,50 5,00 10,00 0,00 2,50 5,00 10,00 0,00 Methoxyphenyl Triazine

(Tinosorb S)

Ethylhexyl Methoxycin- 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00 namate

Part Tris-Biphenyl Triazine 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 B

Butylene Glycol 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50

Glycerin 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50

Aluminum Starch Octe- 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 nylsuccinate

Magnesium Sulfate Hep- 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 tahydrate

Part Alcohol Denatured 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 C

BHT 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

Tocopheryl Acetate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Benzotropolone accord0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 ing to the present inveni- ton (Table 1 )

BIOCIDE/PRESERVATIV 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 E (Table 2)

Exfoliating w/o lotion with AHA A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Water qs. qs. qs. qs. qs. qs. qs. qs. qs.

A 100 100 100 100 100 100 100 100 100

Quaternium-82 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

PEG-12 laurate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Lipstick A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Caprylic/Capric Triglyceride 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00

Octyldodecanol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Pentaerythrityl Tetraisostearate 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00

Polyglyceryl-3 Diisostearate 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50

Bis-Diglyceryl Polyacyladipate-2 9,00 9,00 9,00 9,00 9,00 9,00 9,00 9,00 9,00

Cetearyl Alcohol 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00

Myristyl Myristate 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50

Beeswax 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Copernicia Cerifera (Carnauba) 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 Wax

Cera Alba 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Tocopheryl Acetate 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Tocopherol; Ascorbyl Palmitate 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

Simmondsia Chinensis (Jojoba) 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 Seed Extract

Parfum. BHT q.s q.s q.s q.s q.s q.s q.s q.s q.s

Ricinus Communis QS QS QS QS QS QS QS QS QS to to to to to to to to to 100 100 100 100 100 100 100 100 100

Benzotropolone according to 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 the present inveniton (Table 1 )

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Lipstick A B C D E F G H I INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Octyldodecanol 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Phenethyl Benzoate 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Triisodecyl Trimellitate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Dimethyl Capramide 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Butylene Glycol Dicaprylate/ 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 Dicaprate

Pentaerythrityl Tetraisostearate 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00

Bis-Diglyceryl Polyacyladipate- 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 2

Cetearyl Alcohol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00

Myristyl Myristate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Beeswax 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00

Cera Alba 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

C20-40 Alkyl Stearate 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50

Tocopheryl Acetate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Tocopherol; Ascorbyl Palmitate 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

Simmondsia Chinensis (Jojoba) 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 Seed Extract

Parfum. BHT q.s q.s q.s q.s q.s q.s q.s q.s q.s

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Lip balm SPF 15 A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Petrolatum 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 A

Beeswax 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00 8,00

Candelilla wax 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00

Cocoa seed butter 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Benzophenone-3 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

(Table 1 )

BIOCID (Table 2) 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50

Carrot extract 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Aloe barbadensis oil 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00

Chamomile oil 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00 6,00

Caprylic/capric triglyceride Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs.

To To To To To To To To To Lip balm SPF 15 A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

100 100 100 100 100 100 100 100 100

Jojoba oil 14,20 14,20 14,20 14,20 14,20 14,20 14,20 14,20 14,20

Ethylhexyl Methoxycinna- 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 mate

Peppermint oil 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

W/O/W Multiple Emulsion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

I. Primary emulsion W/O:

Part Isohexadecane 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 A

Phenethyl Benzoate 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

Tridecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Triisodecyl Trimellitate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 W/O/W Multiple Emulsion A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Dimethyl Capramide 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Caprylic/capric triglyceri4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 des

PPG-15 stearyl ether 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50 7,50

PEG-30 Dipolyhydro- 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 xystearate

(Tinosorb S)

Octocrylene 0,00 5,00 10,00 0,00 5,00 10,00 0,00 5,00 10,00

Part Methylene Bis-Benzo- 10,00 5,00 0,00 10,00 5,00 0,00 10,00 5,00 0,00 B triazolyl Tetramethylbutyl- phenol (and) water (and)

decyl glucoside (and) propylene glycol (and) xan- than gum (Tinosorb M)

Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to

100 100 100 100 100 100 100 100 100

Sodium chloride 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40

Preservative q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

II. Secondary emulsion

W/O/W:

Primary emulsion (W/O) 70,00 70,00 70,00 70,00 70,00 70,00 70,00 70,00 70,00

Part Water Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to Qs to C 100 100 100 100 100 100 100 100 100

Poloxamer 407 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

(2-{4-[2-(4-Diethylamino-2- 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 hydroxy-benzoyl)-benzoyl]- piperazine-1 -carbonyl}- phenyl)-(4-diethylamino-2- hydroxy-phenyl)-metha- none

Carbomer 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Sodium chloride 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Part Triethanolamine 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 D

(Table 1 )

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Alcohol-free anti-acne cleansing wet A B C D E F G H I wipes

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

A BIOCIDE/PRESERVATIVE 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 (Table 2)

B Disodium laureth sulfosuccinate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 Alcohol-free anti-acne cleansing wet A B C D E F G H I wipes

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Lauryl glucoside 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

PEG-7 glyceryl cocoate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

C Water Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs.

To To To To To To To To To

100 100 100 100 100 100 100 100 100

D Fragance Qs Qs Qs Qs Qs Qs Qs Qs Qs

Benzotropolone according to the 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 present inveniton (Table 1 )

Anti-Acne Stick A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Octyldodecanol 32.00 32.00 32.00 32.00 32.00 32.00 32.00 32.00 32.00 A

Caprylic/Capric Triglyceride 21.40 21.40 21.40 21.40 21.40 21.4C 21.40 21.40 21.40

Bis-Diglycerylcaprylate/Ca- 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 prate/l sostearate/Stea rate/H yd r

oxystearate Adipate

Butyrospermum Parkii (Shea 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Butter)

Caprylic/Capric/Myristic/Stearic 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Triglyceride Anti-Acne Stick A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Tetradibutyl Pentaerithrityl 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 B Hydroxyhydrocinnamate

Euphorbia Cerifera (Candelilla) 6.50 6.50 6.50 6.50 6.50 6.50 6.50 6.50 6.50 Wax

Carnauba Wax 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50

Beeswax 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00 12.00

Hydrogenated Coco-Glycerides 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00

Benzotropolone according to 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 the present inveniton (Table 1 )

Foaming antibacterial Hand soap A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

A Sodium lauryl sulfate 23,7 23,7 23,7 23,7 23,7 23,7 23,7 23,7 23,7

0 0 0 0 0 0 0 0 0

B PEG-16 macadamia glycerides 3,40 3,40 3,40 3,40 3,40 3,40 3,40 3,40 3,40

C Cocamidopropyl betaine 4,70 4,70 4,70 4,70 4,70 4,70 4,70 4,70 4,70

D Triclosan 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Benzophenone-4 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

E Water Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs. Qs.

100 100 100 100 100 100 100 100 100

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

F Hydrolyzed jojoba esters (and) 9,00 9,00 9,00 9,00 9,00 9,00 9,00 9,00 9,00 water

G Jojoba wax PEG-120 esters 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50

H Color qs qs qs qs qs qs qs qs qs

Fragance qs qs qs qs qs qs qs qs qs

Deodorant shower gel A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

A BIOCIDE/PRESERVATIVE 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 (Table 2)

B Sodium laureth sulfate 28,60 28,60 28,60 28,60 28,60 28,60 28,60 28,60 28,60

Decyl glucoside 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00

Cocamidopropyl betaine 7,90 7,90 7,90 7,90 7,90 7,90 7,90 7,90 7,90

C Water qs qs qs qs qs qs qs qs qs

100 100 100 100 100 100 100 100 100

D Glycerin 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Polyquaternium-7 1 ,25 1 ,25 1 ,25 1 ,25 1 ,25 1 ,25 1 ,25 1 ,25 1 ,25

Panthenol 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30

Color 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05 0,05

Skin Liquid A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Water qs qs qs qs qs qs qs qs qs A to to to to to to to to to

100 100 100 100 100 100 100 100 100

Sodium Lauryl Sulfate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00

Part PPG-2 Methyl Ether 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 B

Propylene Glycol 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0

Color and Perfume qs qs qs qs qs qs qs qs qs

Part Ethanolamine ad ad ad ad ad ad ad ad ad C pH pH pH pH pH pH pH pH pH

5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 Mild Deodorant Bar Soap A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Citric Acid 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 A

Perfume qs qs qs qs qs qs qs qs qs

Benzotropolone according to 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 the present inveniton (Table 1)

(Table 1)

Part Disodium Lauryl Sulfosuccinate 93.20 93.20 93.20 93.20 93.20 93.20 93.20 93.20 93.20 B (and) Sodium Coco-Sulfate

(and) Corn Starch (and) Cete- aryl Alcohol (and) Paraffin (and)

Titanium Dioxide

Hand Scrub A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Sodium Laureth Sulfate 17.9 17.9 17.9 17.9 17.9 17.9 17.9 17.9 17.9 A

Cocamidopropyl Betaine 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00

Sodium Cumene Sulfonate 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

Benzotropolone according to 0,10 0,25 0,50 1,00 1,50 2,00 3,00 4,00 5,00 the present inveniton (Table 1)

(Table 1)

Part Hydroxypropyl Methylcellulose 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 B

Part Water qs qs qs qs qs qs qs qs qs C to to to to to to to to to

100 100 100 100 100 100 100 100 100

Sodium Benzotriazolyl Butyl- 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 phenol Sulfonate (and) Buteth- 3 (and) Tributyl Citrate

D&C Red No.33 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

Part Ethanolamine ad ad ad ad ad ad ad ad ad D pH pH pH pH pH pH pH pH pH

5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5

Clear shampoo A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Sodium Lauryl Sulfate 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

Sodium Polyoxyethylene lauryl 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 12,00 sulfate

Lauroamidopropyl betaine 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00

POE(16) lauryl ether 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 Clear shampoo A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Glyceryl monoisodecyl ether 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Cationized cellulose 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Polyvinyl Alcohol 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

Glycerin 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00

Tocopherol Acetate 0,24 0,24 0,24 0,24 0,24 0,24 0,24 0,24 0,24

Sodium Sulfate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Perfume 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10

Sodium Hydroxide q.s q.s q.s q.s q.s q.s q.s q.s q.s pH= pH= pH= pH= pH= pH= pH= pH= pH= 7 7 7 7 7 7 7 7 7

Water Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp Qsp

100 100 100 100 100 100 100 100 100

Benzotropolone according to 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1 ,00 the present inveniton (Table 1 )

(Table 1 )

Sclerotium Gum 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10

Anti-Dandruff shampoo A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Magnesium Aluminium Silica2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 te

Part Ammonium Lauryl Sulfate 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00 B

Ammonium Laureth Sulfate 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00

Cocamidopropyl hydroxysul- 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 10,00 taine

Sodium Lauryol Sarcosinate 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00

Di-PPG-2 Myreth-10 Adipate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

PEG-150 Pentaerythrityl Tet- 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 rastearate and PEG-6 Ca- priliy/Capric Glycerides and

water

Dimethicone 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20

DMDM Hydantoin 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30 0,30

Part Zinc Pyrithion, 48% 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 C

Part Citric Acid, 30% qs. qs. qs. qs. qs. qs. qs. qs. qs. D

Benzotropolone according to 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 the present inveniton (Table

1 ) (Table 1 )

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2) Liquid Dentrifrice formulation A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Sodium Lauryl Sulfate 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 A

Water 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00

Part Benzotropolone according to 0,01 0,02 0,05 0,08 0,10 0,15 0,20 0,30 0,50 B the present inveniton (Table 1 )

(Table 1 )

Propylene Glycol 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50

Glycerin 23,40 23,40 23,40 23,40 23,40 23,40 23,40 23,40 23,40

Part Water Qs Qs Qs Qs Qs Qs Qs Qs Qs C to to to to to to to to to

100 100 100 100 100 100 100 100 100

Sodium Fluoride 0,24 0,24 0,24 0,24 0,24 0,24 0,24 0,24 0,24

Sorbitol 70% 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00

Mout 1 Rinse formulation A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Sodium Lauryl Sulfate 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60 0,60 A

Water 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00 20,00

Part Ethanol 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 B

Benzotropolone according to 0,01 0,02 0,05 0,08 0,10 0,15 0,20 0,30 0,50 the present inveniton (Table

1 ) (Table 1 )

Propylene Glycol 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00 7,00

Glycerin 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70 1 1 ,70

Part Water Qs Qs Qs Qs Qs Qs Qs Qs Qs C to to to to to to to to to

100 100 100 100 100 100 100 100 100

Sorbitol 70% 10,0 10,0 10,0 10,0 10,0 10,0 10,0 10,0 10,0

0 0 0 0 0 0 0 0 0

Sodium Saccharine 0,03 0,03 0,03 0,03 0,03 0,03 0,03 0,03 0,03

Mout nwash A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Benzotropolone according to 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 A the present inveniton (Table

1 ) (Table 1 )

Part Glycerin 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 B

SD Alcohol 39-C 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00

Flavour qs qs qs qs qs qs qs qs qs Part Poloxamer 407 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 C

Part Sodium Saccharin 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 D

Sodium Fluoride 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

Sodium Benzoate 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10

BIOCIDE/PRESERVATIVE 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,10 0,15 (Table 2)

Mild transparent Toothgel A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Sorbitol 23.5 23.5 23.5 23.5 23.5 23.5 23.5 23.5 23.5 A 0 0 0 0 0 0 0 0 0

Sodium Saccharin 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20

Sodium Citrate 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20

Betaine 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00

Glycerin 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00

Part PEG-8 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 1 .75 B

Gellan Gum 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25

Xanthan Gum 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25

Part Hydrated Silica 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 15,00 C

Part FD&C Blue No.1 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 D

Part Propylene Glycol (and) Olaflur 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 E

Aroma 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75

Benzotropolone according to 0,05 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 the present inveniton (Table

1 ) (Table 1 )

Part Sodium Lauroyl Sarcosinate 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 F

Feminine Hygiene cleansing formula A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Chamomile extract 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50 1 ,50

Lactic acid (80% solution) 0,01 0,01 0,01 0,01 0,01 0,01 0,01 0,01 0,01

Disodium laureth sulfoccinate 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

PEG 150 disterarate 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00 1 ,00

Water deioniz. qs. qs. qs. qs. qs. qs. qs. qs. qs.

Mild Feminine Hygiene Wash A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Water qs to qs qs qs qs qs qs qs qs A 100 to to to to to to to to

100 100 100 100 100 100 100 100

Part Sodium Laureth Sulfate 20.0 20. 20. 20. 20. 20. 20. 20. 20. B 0 00 00 00 00 00 00 00 00

Cocamidopropyl Betaine 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00

Laureth 02 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25

Sodium Laureth-11 Carboxylate 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25

PEG-7 Glyceryl Cocoate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Propylene Glycol 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

Benzotropolone according to the 0,10 0,20 0,30 0,40 0,50 0,50 0,50 0,50 0,50

Deoc orant Pump spray A B C D E F G H 1

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

(Table 2)

Antiperspirant roll-on A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part PEG 60 Hydrogenated Castor 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 2,50 A Oil

PEG-6 Caprylic Capric Glyceri- 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 de

Part Hydroxyethylcellulose 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 0,50 B

Benzotropolone according to 0,10 0,25 0,50 0,10 0,25 0,50 0,25 0,50 0,10 the present inveniton (Table 1 )

(Table 1 )

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Part Aluminum Chlorohydrate 30,0 30,0 30,0 30,0 30,0 30,0 30,0 30,0 30,0 C 0 0 0 0 0 0 0 0 0

Glycerin 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00

Propylene Glycol 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 2,00 Alcohol-free Deodorant roll-on A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 A (Table 2)

Part PEG 60 Hydrogenated Castor 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 B Oil

PEG-6 Caprylic Capric Glyceri- 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 3,00 de

Propylene Glycol 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00

(Table 1 )

Part Steareth-10 allyl ether/acrylates 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 5,00 C copolymer

Part Ethanolamine qs qs qs qs qs qs qs qs qs D

Part Water Qs Qs Qs Qs Qs Qs Qs Qs Qs E to to to to to to to to to

100 100 100 100 100 100 100 100 100

Deodorant and Antiseptic Foot A B C D E F G H I Cream

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Polyglyceryl-3 Diisostearate 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 A

Glyceryl Oleate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00

Zinc Stearate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00

Caprylic/Capric Triglyceride 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00

Hexyldecanol 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00

Beeswax 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

Benzotropolone according to 0,30 0,30 0,30 0,30 0,10 0,25 0,20 0,30 0,30 the present inveniton (Table

1 ) (Table 1 )

Part BIOCIDE/PRESERVATIVE 0,10 0,25 0,20 0,30 0,30 0,30 0,30 0,30 0,00 B (Table 2)

Glycerin 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00

Part Magnesium Sulfate 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 C

Deod orant Footsprav A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Benzotropolone according to the 0,1 0,2 0,3 0,4 0,5 0,6 0,75 1 1 ,5 A present inveniton (Table 1 ) (Table 1 ) Deod orant Footspray A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part PEG-40 Hydrogenated Castor 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 4.50 B Oil

PEG-8 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Glyceryl La urate 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50

Cetearyl Ethylhexanoate (and) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Isopropyl Myristate

SD Alcohol 39-C 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0

Perfume qs qs qs qs qs qs qs qs qs

Part Water qs qs qs qs qs qs qs qs qs C to to to to to to to to to

100 100 100 100 100 100 100 100 100

Liquid Hand Soap A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Benzotropolone according to 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1,00 A the present inveniton (Table

1) (Table 1)

Part Sodium Laureth Sulfate 28.60 28.60 28.60 28.60 28.60 28.60 28.60 28.60 28.60 B

Lauryl Glucoside 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Phenoxyethanol (and) Methyl- 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 paraben (and) Ethylparaben

(and) Butylparaben (and) Propylparaben (and) Isobutylpa- raben

Part Polyquaternium-7 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 C

FD&C Green No.8 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

Sodium Benzotriazolyl Butyl- 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 phenol Sulfonate (and)

Buteth-3 (and) Tributyl Citrate

Laureth 02 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50

Sodium Chloride 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Part Citric Acid ad ad ad ad ad ad ad ad ad D pH pH pH pH pH pH pH pH pH

6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0

Mois turizing liquid Hand Soap A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Water 18.20 18.20 18.20 18.20 18.20 18.20 18.20 18.20 18.20 Mois turizing liquid Hand Soap A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

A

Sodium C14-16 Olefin Sul30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 fonate (and) Sodium Laureth

Sulfate (and) Lauramide DEA

Cocamidopropyl Betaine 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00

Glycerin 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Aloe Vera 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50

Lauramide DEA 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

Part Water 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 30.00 B

Acrylamidopropyltrimonium 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Chloride/Acrylamide Copolymer

Part Polysorbate 20 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 C

1 ) (Table 1 )

Part Sodium Chloride 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 D

Part Citric Acid 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 0.65 E

Liquid Laundry Deterqent A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

100 100 100 100 100 100 100 100 100

Antibacterial Dishwashinq Paste A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Water 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 24.00 A

Sodium Carbonate 16.00 16.00 16.00 16.00 16.00 16.00 16.00 16.00 16.00

Calcium Carbonate 28.00 28.00 28.00 28.00 28.00 28.00 28.00 28.00 28.00

Sodium Silicate 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00

Part Nonoxynol-10 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B

Fragrance 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20

Benzotropolone according to 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 1 ,00 the present inveniton (Table

1 ) (Table 1 )

C.I.15510 (Acid Orange 7) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10

Glycerin 85% 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00

Part Dodecylbenzene Sulfonic A- 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 25.00 C cid

Bactericidal Dishwashinq Liquid A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Benzotropolone according to 0,10 0,25 0,50 0,10 0,25 0,50 0,10 0,25 0,50 A the present inveniton (Table

Dishwashing liquid and AntiA B C D E F G H I bacterial Hand Soap

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

1 ) (Table 1 )

Part Lauryl-myristyl sulfate Na-salt 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 B

Sodium Myreth Sulfate 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00 7.00

Lauryl Glucoside 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00

Coco Betaine 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1 1 .1

SD Alcohol 39-C 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00

Part Sodium Chloride 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 C

Part Citric Acid ad ad ad ad ad ad ad ad ad D pH pH pH pH pH pH pH pH pH

6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5

BIOCIDE/PRESERVATIVE 0,10 0,10 0,10 0,25 0,25 0,25 0,50 0,50 0,50 (Table 2)

Part Water qs qs qs qs qs qs qs qs qs E to to to to to to to to to

100 100 100 100 100 100 100 100 100

All Purpose Cleaner A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w Part Hydoxydichlorodiphenyl Ether 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 A

Part Alkoxylated Alcohol 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 B

Sodium C14-17 Alkyl Sec Sul14.00 14.00 14.00 14.00 14.00 14.00 14.00 14.00 14.00 fonate

Lauryl-myristyl sulfate Na-salt 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00

Diethylene Glycol Monobutyl 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 Ether

Part Benzotropolone according to 0,05 0,1 0,2 0,3 0,4 0,5 0,75 0,85 1 C the present inveniton (Table

1 ) (Table 1 )

Citric Acid ad ad ad ad ad ad ad ad ad pH pH pH pH pH pH pH pH pH 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5

Acid Blue 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

Benzotriazole Derivative 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

Perfume qs qs qs qs qs qs qs qs qs

Part Water qs qs qs qs qs qs qs qs qs D to to to to to to to to to

100 100 100 100 100 100 100 100 100

Antibacterial All Purpose Cleaner A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Benzotropolone according to 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 A the present inveniton (Table

1 ) (Table 1 )

Part Lauryl-myristyl sulfate Na-salt 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 B 0 0 0 0 0 0 0 0 0

Alkyl Polyglycoside 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

Sodium Cumene Sulfonate 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00 5.00

Part BIOCIDE/PRESERVATIVE 0 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,1 C (Table 2)

Citric Acid ad pH ad pH ad pH ad ad pH ad pH ad ad pH ad pH

3.0 3.0 3.0 pH 3.0 3.0 pH 3.0 3.0

3.0 3.0

Water qs to qs to qs to qs to qs to qs to qs to qs to qs to

100 100 100 100 100 100 100 100 100

Surface disinfectant sprav A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

1 ) (Table 1 )

Part Isopropyl Alcohol 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 B

Sodium Lauryl Sulfate 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 1 .00 Surface disinfectant spray A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Citric Acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

BIOCIDE/PRESERVATIVE 0 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,1

(Table 2)

Part Water (and) Sodium Hydroxiad ad ad ad ad ad ad ad ad

C de pH pH pH pH pH pH pH pH pH

5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0

Part Water qs qs qs qs qs qs qs qs qs

D to to to to to to to to to

100 100 100 100 100 100 100 100 100

Wet wipes A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

Part Benzotropolone according to 0,1 0,1 0,1 0,1 0,1 0,1 0,1 0,1 0,1 A the present inveniton (Table

1) (Table 1)

Part PEG-5 Glyceryl Stearate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 B

Steareth-20 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Steareth-21 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Mineral Oil 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Isopropyl Myristate 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Part Perfume qs qs qs qs qs qs qs qs qs C

Propylene Glycol 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Glycerin 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50

BIOCIDE/PRESERVATIVE 0 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,1 (Table 2)

Part Water qs qs qs qs qs qs qs qs qs D to to to to to to to to to

100 100 100 100 100 100 100 100 100

Anti-bacterial Fabric Softener A B C D E F G H I

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

1) (Table 1)

Part C12-15 Pareth-7 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 B

Quaternium 18 (and) Isopro4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 pyl Alcohol

Part Water qs qs qs qs qs qs qs qs qs D to to to to to to to to to

100 100 100 100 100 100 100 100 100

BIOCIDE/PRESERVATIVE 0,00 0,00 0,00 0,25 0,25 0,25 0,50 0,50 0,50 Anti-bacterial Fabric Softener A B C D E F G H 1

INCI-Name % % % % % % % % % w/w w/w w/w w/w w/w w/w w/w w/w w/w

(Table 2)

Perfume qs qs qs qs qs qs qs qs qs

Uses of benzotropolones in other technical applications outside home and personal care The benzotropolone derivatives of formula (1 ) are also suitable for treating, especially pre- serving, textile fibre materials. Such materials are undyed and dyed or printed fibre materials, e.g. of silk, wool, polyamide or polyurethanes, and especially cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, as well as cellulose and regenerated cellulose. The benzotropolone derivatives of formula (1 ) are suitable also for treating, especially imparting antimicrobial properties to or preserving, plastics, e.g. polyethylene, polypropylene, poly- urethane, polyester, polyamide, polycarbonate, latex etc. Fields of use therefore are, for example, floor coverings, plastics coatings, plastics containers and packaging materials;

kitchen and bathroom utensils (e.g. brushes, shower curtains, sponges, bathmats), latex, fil- ter materials (air and water filters), plastics articles used in the field of medicine, e.g. dressing materials, syringes, catheters etc., so-called "medical devices", gloves and mattresses.

The benzotropolone derivatives of formula (1 ) are suitable also for treating, especially imparting antimicrobial properties to or preserving industrial formulations such as coatings, lubri- cants etc.

Paper, for example papers used for hygiene purposes, may also be provided with antimicrobial properties using the present anti-microbial compounds. It is also possible for nonwovens, e.g. nappies/diapers, sanitary towels, panty liners, and cloths for hygiene and household uses, to be provided with the benzotropolone derivatives of formula (1 ).

In addition to preserving cosmetic and household products, the preservation of technical products, the provision of technical products with antimicrobial properties and use as a bio- cide in technical processes are also possible, for example in paper treatment, especially in paper treatment liquors, printing thickeners of starch or cellulose derivatives, surface- coatings and paints. The benzotropolone derivatives of formula (1 ) are also suitable for the antimicrobial treatment of wood and for the antimicrobial treatment of leather, the preserving of leather and the provision of leather with antimicrobial properties.

Preservative uses The benzotropolone derivatives of formula (1 ) are also suitable for the protection of cosmetic products and household products from microbial damage.

The benzotropolone derivatives of formula (1 ) can be combined with biocides used as antim- icrobial actives in cosmetic products and household products and/or preservatives used in cosmetic products or houseold products in order to improve the antimicrobial activity of the cosmnetic product or household product.

In addition, the benzotropolone derivatives of formula (1 ) are capable of penetrating biofilms on living and non-living surfaces, of preventing the adhesion of bacteria to surfaces and any further build-up of the biofilm, of detaching such biofilm and/or inhibiting the further growth of the biofilm-forming micro-organisms in the biological matrix, or of killing such microorganisms. Biofilms are understood, very generally, to be aggregations of living and dead micro-organisms, especially bacteria, that adhere to living and non-living surfaces, together with their metabolites in the form of extracellular polymeric substances (EPS matrix), e.g. polysaccharides. The activity of antimicrobial substances that normally exhibit a pronounced growth- inhibiting or lethal action with respect to planktonic cells may be greatly reduced with respect to microorganisms that are organized in biofilms, for example because of inadequate penetration of the active substance into the biological matrix.

In the present invention, this may relate to biofilms on human tooth surfaces and oral mucosa, which play a crucial role in the onset of degenerative diseases in the oral cavity, e.g. caries or periodontitis, as a result of the biofilm-forming micro-organisms or their metabolites.

Action against bio-films in the present invention also relates to biofilms on non-human surfaces. The antimicrobial compounds of this invention are useful in coatings or films in protecting surfaces from bio-fouling. Such surfaces include surfaces in contact with marine envi- ronments (including fresh water, brackish water and salt water environments), for example, the hulls of ships, surfaces of docks or the inside of pipes in circulating or pass-through water systems. Other surfaces are susceptible to similar biofouling, for example walls exposed to rain water, walls of showers, roofs, gutters, pool areas, saunas, floors and walls exposed to damp environs such as basements or garages and even the housing of tools and outdoor furniture. The benzotropolone derivatives of formula (1 ) are also useful in preventing bio-fouling, or eliminating or controlling microbe accumulation on the surfaces either by incorporating the antimicrobial compounds into the article or surface of the article in question or by applying the antimicrobial to these surfaces as part of a coating or film.

When applied as a part of a film or coating, the benzotropolone derivatives of formula (1 ) are part of a composition which also comprises a binder. The binder may be any polymer or oligomer compatible with the present antimicrobials. The binder may be in the form of a polymer or oligomer prior to preparation of the anti-fouling composition, or may form by polymerization during or after preparation, including after application to the substrate. In certain applications, such as certain coating applications, it will be desirable to crosslink the oligomer or polymer of the anti fouling composition after applica- tion.

The term binder as used in the present invention also includes materials such as glycols, oils, waxes and surfactants commercially used in the care of wood, plastic, glass and other surfaces. Examples include water proofing materials for wood, vinyl protectants, protective waxes and the like.

The composition may be a coating or a film. When the composition is a thermoplastic film which is applied to a surface, for example, by the use of an adhesive or by melt applications including calendaring and co-extrusion, the binder is the thermoplastic polymer matrix used to prepare the film.

When the composition is a coating, it may be applied as a liquid solution or suspension, a paste, gel, oil or the coating composition may be a solid, for example a powder coating which is subsequently cured by heat, UV light or other method.

As the composition may be a coating or a film, the binder can be comprised of any polymer used in coating formulations or film preparation. For example, the binder is a thermoset, thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer. Thermoset, thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers include polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polycarbonate, polystyrene, polyvinyl acetates, polyvinyl alcohols, polyester, halogenated vinyl polymers such as PVC, natural and synthetic rubbers, alkyd resins, epoxy resins, unsaturated polyesters, unsaturated polyamides, polyimides, silicon containing and carbamate polymers, fluorinated polymers, crosslinkable acrylic resins derived from substituted acrylic esters, e.g. from epoxy acrylates, urethane acrylates or polyester acrylates. The polymers may also be blends and copolymers of the preceding chemistries. Biocompatible coating polymers, such as, poly[-alkoxyalkanoate-co-3-hydroxyalkenoate]

(PHAE) polyesters, Geiger et. al. Polymer Bulletin 52, 65-70 (2004), can also serve as binders in the present invention.

Alkyd resins, polyesters, polyurethanes, epoxy resins, silicone containing polymers, polyacry- lates, polyacrylamides, fluorinated polymers and polymers of vinyl acetate, vinyl alcohol and vinyl amine are non-limiting examples of common coating binders useful in the present invention. Other coating binders, of course, are part of the present invention.

Coatings are frequently crosslinked with, for example, melamine resins, urea resins, isocy- anates, isocyanurates, polyisocyanates, epoxy resins, anhydrides, poly acids and amines, with or without accelerators.

The compositions of present invention are for example a coating applied to a surface which is exposed to conditions favorable for bioaccumulation. The presence of the antimicrobial compounds of this invention in said coating will prevent the adherence of organisms to the surface.

The benzotropolone derivatives of formula (1 ) may be part of a complete coating or paint formulation, such as a marine gel-coat, shellac, varnish, lacquer or paint, or the anti fouling composition may comprise only a polymer of the instant invention and binder, or a polymer of the instant invention, binder and a carrier substance. It is anticipated that other additives encountered in such coating formulations or applications will find optional use in the present applications as well. The coating may be solvent borne or aqueous. Aqueous coatings are typically considered more environmentally friendly.

The coating is, for example, aqueous dispersion of a polymer of the instant invention and a binder or a water based coating or paint. For example, the coating comprises an aqueous dispersion of a polymer of the instant invention and an acrylic, methacrylic or acrylamide polymers or co-polymers or a poly[-alkoxyalkanoate-co-3-hydroxyalkenoate] polyester.

The coating may be applied to a surface which has already been coated, such as a protec- tive coating, a clear coat or a protective wax applied over a previously coated article.

Coating systems include marine coatings, wood coatings, other coatings for metals and coatings over plastics and ceramics. Exemplary of marine coatings are gel coats comprising an unsaturated polyester, a styrene and a catalyst.

The coating is, for example a house paint, or other decorative or protective paint. It may be a paint or other coating that is applied to cement, concrete or other masonry article. The coating may be a water proofer as for a basement or foundation. The coating composition is applied to a surface by any conventional means including spin coating, dip coating, spray coating, draw down, or by brush, roller or other applicator. A drying or curing period will typically be needed.

Coating or film thickness will vary depending on application and will become apparent to one skilled in the art after limited testing.

The composition may be in the form of a protective laminate film.

Such a film typically comprises thermoset, thermoplastic, elastomeric, or crosslinked poly- mers. Examples of such polymers include, but are not limited to, polyolefin, polyamide, poly- urethane, polyacrylate, polyacrylamide, polycarbonate, polystyrene, polyvinyl acetates, polyvinyl alcohols, polyester, halogenated vinyl polymers such as PVC, natural and synthetic rubbers, alkyd resins, epoxy resins, unsaturated polyesters, unsaturated polyamides, polyim- ides, fluorinated polymers, silicon containing and carbamate polymers. The polymers may also be blends and copolymers of the preceding chemistries. When the anti-fouling composition is a preformed film it is applied to the surface by, for example, the use of an adhesive, or co-extruded onto the surface. It may also be mechanically affixed via fasteners which may require the use of a sealant or caulk wherein the esters of the instant invention may also be advantageously employed.

A plastic film may also be applied with heat which includes calendaring, melt applications and shrink wrapping. The composition may be part of a polish, such a furniture polish, or a dispersant or surfactant formulation such as a glycol or mineral oil dispersion or other formulation as used in for example wood protection.

Examples of useful surfactants include, but are not limited to, polyoxyethylene-based sur- face-active substances, including polyoxyethylene sorbitan tetraoleate (PST), polyoxyethyl- ene sorbitol hexaoleate (PSH), polyoxyethylene 6 tridecyl ether, polyoxyethylene 12 tridecyl ether, polyoxyethylene 18 tridecyl ether, TWEEN RTM surfactants, TRITON RTM surfactants, and the polyoxyethlene-polyoxypropylene copolymers such as the PLURONIC RTM and POLOXAMER RTM product series (from BASF). Other matrix-forming components in- elude dextrans, linear PEG molecules (MW 500 to 5,000,000), star-shaped PEG molecules, comb-shaped and dendrimeric, hyperbrached PEG molecules, as well as the analogous linear, star, and dendrimer polyamine polymers, and various carbonated, perfluorinated (e.g., DUPONT ZONYL RTM fluorosurfactants) and siliconated (e.g, dimethylsiloxane-ethylene oxide block copolymers) surfactants.

Given the wide array of applications for the present anti-microbial compositions, the composition may contain other additives such as antioxidants, UV absorbers, skin protective agents, hindered amines, phosphites or phosphonites, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifi- ers, emollients, pigments, dispersants, thickening or solidifying agents (consistency regulators), , , perfume oils, sequestering agents, other optical brighteners, flame retardants, antistatic agents, blowing agents and the like, such as the materials listed below, or mixtures thereof additives that improve the mechanical properties, such as dicarboxylic acids and/or aluminium, zinc, calcium or magnesium salts of Ci₄-C₂2fatty acids, and preservatives. The substrate can be an inorganic or organic substrate, for example, a metal or metal alloy; a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer as described above; a natural polymer such as wood or rubber; a ceramic material; glass; leather or other textile.

The substrate may be, for example, non-metal inorganic surfaces such as silica, silicon dioxide, titanium oxides, aluminum oxides, iron oxides, carbon, silicon, various silicates and sol- gels, masonry, and composite materials such as fiberglass and plastic lumber (a blend of polymers and wood shavings, wood flour or other wood particles).

The inorganic or organic substrate is, for example, a metal or metal alloy, a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer, a ceramic material or a glass.

The substrate may be a multi-layered article comprised of the same or different components in each layer. The surface coated or laminated may be the exposed surface of an already applied coating or laminate.

The inorganic or organic substrate to be coated or laminated can be in any solid form.

For example, polymer substrates may be plastics in the form of films, injection-molded articles, extruded workpieces, fibres, felts or woven fabrics.

For example molded or extruded polymeric articles used in construction or the manufacture of durable goods such as siding, fascia and mailboxes can all benefit from the present method for stabilizer replenishment.

Plastics which would benefit from the present method include, but are not limited to, plastics used in construction or the manufacture of durable goods or machine parts, including outdoor furniture, boats, siding, roofing, glazing, protective films, decals, sealants, composites like plastic lumber and fiber reinforced composites, functional films including films used in displays as well as articles constructed from synthetic fibers such as awnings, fabrics such as used in canvas or sails and rubber articles such as outdoor matting and other uses cited in this disclosure. Exemplary of such plastics are polypropylene, polyethylene, PVC, POM, polysulfones, styrenics, polyamides, urethanes, polyesters, polycarbonate, acrylics, butadi- ene, thermoplastic polyolefins, ionomers, unsaturated polyesters and blends of polymer resins including ABS, SAN and PC/ABS.

The benzotropolone derivatives of formula (1 ) are also effective in protecting useful plants, such as plants in agriculture, in horticulture and in forests, plant parts and seeds from disease and spoilage. For example, the present invention also provides a method which comprises applying to useful plants, the locus thereof or propagation material thereof a composition which comprises at least one of the polyglycerol polymers and co-polymers of the invention. Said compositions can be used as foliar, soil and seed treatment fungicides.

The compositions comprising the benzotropolone derivatives of formula (1 ) can inhibit or destroy the phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different useful plants. The present compositions are applied by treating the fungi, the useful plants, the locus thereof, the propagation material thereof, the natural substances of plant origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials threatened by fungus attack with the compositions in an effective amount.

The compositions comprising the benzotropolone derivatives of formula (1 ) may be applied before or after infection of the useful plants, the propagation material thereof, the natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, or the industrial materials by the fungi.

The compositions comprising the benzotropolone derivatives of formula (1 ) are of particular interest for controlling a large number of fungi in various useful plants or their seeds, especially in field crops such as potatoes, tobacco and sugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane, fruit and ornamentals in horticulture and viticulture, in vegetables such as cucumbers, beans and cucurbits.

When applied to plants, the benzotropolone derivatives of formula (1 ) are applied at a rate of 1 to 5000 g a.i./ha, for example 2 to 2000 g a.i./ha, for example, 5 to 2000 g a.i./ha, for example, 10 to 1000 g a.i./ha, e.g. 50, 75, 100, 200, 250, 500, 800, 1000, 1500 g a.i./ha of polymer or co-polymers. In agricultural practice the application rates depend on the type of effect desired, and typically range from 20 to 4000 g of total antimicrobials per hectare.

When treating seed, rates of 0.001 to 50g of the present benzotropolone derivatives of for- mula (1 ), for example 0.01 to 10g, per kg of seed, are generally sufficient.

The composition comprising benzotropolone derivatives of formula (1 ) may be employed in any conventional form, for example in the form a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants. Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners and compounds that provide adjuvancy effects). For example, formulations to be applied in spraying forms, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, typically contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects.

A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g. as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g. as slow release capsules or microcapsules. In general, the formulations include from 0.01 to 90% by weight of at least one of the antimicrobial compounds, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts and adjuvant(s), and optionally other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions gener- ally contain in between about 2 and 80%, for example, between about 5 and 70% by weight of total active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, for example from 0.01 to 5% by weight of active agent.

Methods of preparing the above plant protection formulations are well known, for example, US Published Pat. Appl. 20070265267, already incorporated by reference.

Examples

Example 1 : Antimicrobial Efficacy

The bactericidal activity of the benzotropolone derivatives of formula (1 ) is measured in a suspension test according to trivial modifications of the European Standard method EN 1040.

Test samples B-21 , B-9, B-17, B-20, B-43, B-28, B-37, B-32, B-25, B-26 and B-36 are dissolved in dimethly sulfoxid (DMSO) resulting in 1 % stock solutions of the compounds. The test bacteria are incubated for 24 hours at 37°C and the suspensions are then diluted with 0.85% sodium chloride to the following final cell densities (cfu = colony forming units):

Staphylococcus aureus ATCC 6538 3,3 x 10⁸ cfu/ml

Escherichia coli ATCC 10536 4,7 x 10⁸ cfu/ml

For the suspension tests, an appropriate concentration of the test compound is incubated with a bacterial suspension resulting in a final cell count of about 10⁷ cfu/ml in the mixture with the test compound. These test mixtures are incubated at room temperature (22°C +/- 2°C) and aliquots of 1 ml test mixture containing the test bacteria were taken after 24 hours for determination of the residual cell count. For determination of the residual cell count, dilutions of the 1 ml aliquots are prepared in

TSbroth special and plated on CASO agar Agar with neutralizer (Merck # 18360). The plates are incubated for 24 hours until the residual cells have developed colonies. The result of the determination of residual cell counts are given in the Table below. The fungicidal activity of the compounds of the present invention is measured in a suspension test according to trivial modifications of the European Standard method EN 1275.

Test samples B-21 , B-9, B-6, B-20, B-43, B-28, B-37, B-32, B-25, B-26 and B-36 are dissolved in dimethly sulfoxid (DMSO) resulting in 10% stock solutions of the compounds. Can- dida albicans ATCC 10231 was grown on Sabouraud 4% Glucaose Agar with neutralizer (Merck # 18359) and Aspergillus niger ATCC 6275 on Sabouraud 4% Glucose Agar with neutralizer (Merck # 18359).

The fungal spore suspension of Aspergillus niger ATCC 6275 used as inoculum for the sus- pension tests is 4.4 x 10⁷ cfu/ml. The cell density of Candida albicans ATCC 10231 used as inoculum for the suspension test was 2.4 x 10⁷ cfu/ml. Malassezia furfur DSM 6171 is cultivated on Medium 472 (i.e. 40g malt extract, 20g ox-bile (desiccated), 10g Tween 40, 2.5g glycerol mono-oleate, 15g agar and 1000 ml distilled water) for 4 days at 30°C. For the preparation of the inoculum, the suspension is then diluted with 0.85% sodium chloride to a final cell concentration of 10⁶ cfu/ml.

For the suspension tests, an appropriate concentration of the test compound is incubated with the Candida albicans suspension, the Malassezia furfur suspension or the spore suspension of Aspergillus niger resulting in a final cell count of about 10⁵ cfu/ml (for Malassezia furfur and Aspergillus niger) or 10⁶ cfu/ml (for Candida albicans) in the mixture with the test compounds. These mixtures are incubated at room temperature (22°C +/- 2°C) and aliquots of 1 ml test mixture are taken after 24 hours for determination of the residual cell count.

For the determination of the residual cell counts, the 1 ml aliquots taken after 24 hours are diluted in TSbroth special and the determination of the cell counts is done on CASO AgarAgar (Merck # 18360) for Candida albicans, Sabouraud 4% Glucose Agar with neutralization (Merck #18539) for Aspergillus niger and Medium 472 for Malassezia furfur.

The result of the determination of residual cell counts are given in the below table. Results of the suspension tests conducted to determine bactericidal and fungicidal activities:

Test Compound

(concentration Test Organism

tested) (cfu/ml and log reduction after set contact time are given in the table)

C. albiA. niger M. furfur

S. aureus E. coli cans

Contact Time -> 24 h 24 h 24 h 24 h 24 h

B-21

(1000 ppm) < 1 < 1 < 1

B-9

(1000 ppm) 2,6 < 1 < 1

B-17

(1000 ppm) 4,8 < 1 < 1 2.3

B-20

(1000 ppm) < 1 < 1 < 1

B-43

(1000 ppm) < 1 < 1 < 1

B-28

(1000 ppm) < 1 < 1 < 1

B-37

Compounds B-9, B-17, B-37, B-32 and B-25 show a microbicidal activity against at least one of the test microorganisms. For determination of the microbistatic activity, the Minimum Inhibitory Concentrations (MIC) of the test compounds are determined.

The compounds B-17, B-32 and B-25 which show good activities in the suspension test, are tested in an agar incorporation test in order to determine their minimum inhibitory concentra- tions (MIC) against various tests organisms.

For B-17, B-32 and B-25, 1 % stock solutions are prepared in DMSO.

A dilution series of the test compounds is done in 15 ml still liquid Mijller Hinton Agar (for bacteria and Candida albicans) or Sabouraud 4% Glucose Agar (for Aspergillus niger) or

Medium 472 (for Malassezia furfur) with the following final concentrations of test compounds in the agar: 400 ppm, 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, 6,25 ppm, 3.125 ppm and 1.56 ppm of test compound. The molten agar is poured into petri dishes and after solidification of the agar, all agar plates containing the test compounds are stored over night in the laboratory (at about 22°C) for drying. The test bacteria Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 10536, Pseu- domonas aeruiginosa ATCC 15442 and the yeast Candida albicans ATCC 10231 are grown in Casein Soymeal Peptone Broth at 37°C for 24 hours. The test fungi Aspergillus niger ATCC 6275 is grown on the surface of Sabouraud 4% Glucose agar for 3 days at 30°C and the spores are removed with 0.85% sodium chloride solution.

Malassezia furfur DSM 6171 is cultivated in Media 472 at 30°C.

The cell suspensions (in case of Aspergillus niger, the spore suspension) of the test organ- isms are diluted in 0.85% sodium chloride as follows:

1 :1000 dilution of Staphylococcus saureus ATCC 6538

1 :1000 dilution of Escherichia coli ATCC 10536

1 :1000 dilution of Pseudomonas aeruginosa ATCC 15442

1 :10 dilution of Candida albicans ATCC 10231

1 :10 dilution of Aspergillus niger ATCC 6275

1 :10 Malassezia furfur DSM 6171 , CIP 1636-86

10 μΙ of these cell or spore dilutions are then dotted onto the surface of the agar plates containing various concentrations of the test compounds. The so inoculated agar plates are then incubated for 24 hours at 37°C (for bacteria), 48 hours at 37°C for Canidda albicans, 3 days at 30°C (for Aspergillus niger) and 4 days at 30°C for Malassezia furfur and then the highest dilution of the test compound at which no more growth is observed (corresponds to the MIC) is determined.

MIC- values [in ppml

The lower the MIC the stronger is the microbistatic activity of the test compound. Best mi- crobistatic activities are observed with B-17 and B-32.

Claims

Claims:

1. f benzotropolone derivatives of formula

, wherein

R₂, R3, R₄, R5 and R₆ independently of one another are hydrogen; OH; CrC₃oalkyl, C₂-C₃₀al- kenyl, CrC₃oalkoxy, C₃-Ci₂cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆-C2oaryl, which may be substituted by one or more G; C₄-C2oheteroaryl, which may be substituted by one or more G, C₂- Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C₂₅aralkyl, or -CO-Ri₇; Ci-C₃₀mono- or dialkylamino; COR₉; COORg; CONR₉R₁₀; CN; S0₂R₉; OCOOR₉; OCOR₉; NHCOOR₉; NR₉CORi₀; NH₂; sulphate; sulphonate; phosphate; phosphonate;

Ri, R₇ and R₈ independently of one another are hydrogen; Ci-Ci₂alkyl or C₃-Ci₂-cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆- C₂₀aryl, which may be substituted by one or more G; C₄-C₂oheteroaryl, which may be substituted by one or more G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C₂₅aralkyl, or COOR₉;

R₇ and R₈ together form a five or six membered ring; or

R₆ and R₇ together form a five or six membered ring; or

C₂₀aryl, which may be substituted by one or more G; C₄-C₂oheteroaryl, which may be substituted by one or more G; organosilanyl; or

R₉ and R₁₀ together form a five or six membered ring;

D is -CO-; -COO-; -S-; -SO-; -S0₂-; -0-; -NR₁₄-; -SiR_i9R₂o-; -PORn-;

or

-C≡C-; and

E is -OR_i8; -SR_i8; -NR₁₄R₁₅; -NR₁₄CORi₅; -COR_i7; -COORi₆; -CONR₁₄R₁₅; -CN; halogen; or OS0₃Ri₈; S0₃Ri₈; S0₂Ri₈; P0₃(Ri₈)₂; OP0₃(Ri₈)₂;

G is E; CrCi₈alkyl, which is optionally interrupted by D; Ci-Ci₈perfluoroalkyl; CrCi₈alkoxy, which is optionally substituted by E and/or interrupted by D; wherein Ri2, R₁₃, R₁₄ and Ri₅ independently of each other are hydrogen; C₆-Ci₈aryl which is optionally substituted by OH, CrCi₈alkyl or CrCi₈alkoxy; CrCi₈alkyl, which is optionally interrupted by -0-; or

Ri₄ and R₁₅ together form a five or six membered ring,

Ri6 is hydrogen; C₆-Ci₈aryl which is optionally substituted by OH, Ci-Ci₈alkyl or d- Ci₈alkoxy; Ci-Ci₈alkyl which is optionally interrupted by -O-;

Ri7 is H; C₆-Ci₈aryl which is optionally substituted by OH, Ci-Ci₈alkyl or Ci-Ci₈alkoxy; or d- Ci₈alkyl which is optionally interrupted by -0-;

Ri₈ is hydrogen; C₆-Ci₈aryl, which is optionally substituted by OH, Ci-Ci₈alkyl or d- Ci₈alkoxy; Ci-Ci₈alkyl, which is optionally interrupted by -O-; and

Rig and R₂₀ independently of each other are hydrogen; Ci-Ci₈alkyl; C₆-Ci₈aryl which is optionally substituted by Ci-Ci₈alkyl;

as antimicrobial and/or preserving agents.

2. Use the benzotropolones correspond to formula

(1 a) , wherein

R21 and R22 independently of one another are hydrogen; OH; CrC₃oalkyl or CrC₃oalkoxy, which may be substituted by one or more E and/or interrupted by one or more D; and Ri , R3, R3, R₄, R5, Re, E and D are defined as in claim 1 .

3. Use according to claim 2, wherein in formula (1 b)

R21 is hydrogen or CrC₃oalkyl;

R22 is hydrogen; CrC₃₀alkyl or CrC₃₀alkoxy; and

Ri , R3, R3, R₄, R5, Re, E and D are defined as in claim 1 .

4. Use according to claim 1 , wherein the benzotropolones correspond to formula

R21 and R22 independently of one another are hydrogen; OH; d-C₃oalkyl or CrC₃oalkoxy, which may be substituted by one or more E and/or interrupted by one or more D;

Ri, R3, R3, R₄, R5, R6, E and D are defined as in claim 1 .

5. Use according to claim 4, wherein in formula (1 b)

R21 and R22 independently of one another are hydrogen; OH; CrC₃oalkyl or CrC₃oalkoxy, which may be substituted by one or more E and/or interrupted by one or more D;

Ri, R3, R3, R₄, R5, R6, E and D are defined as in claim (1 ).

6. Use according to any of claims 1 to 5, wherein

Ri, R₇ and R₈ are hydrogen; and

R₂, R3, R₄, R5 and R₆ are defined as in claim (1 ).

7. Use according to any of claims 1 to 6, wherein

R₂, R₃, R₄, R5 and R₆ independently of one another are hydrogen; OH; CrC₃₀alkyl, C₂-C₃₀al- kenyl, CrC₃₀alkoxy, C₃-Ci₂cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; COR₉; COOR₉; CONR₉R₁₀; SO2R₉; OCOORg; NHCOORg; NRgCORio;

Ri, R₇ and R₈ independently of one another are hydrogen; d-C^alkyl or C₃-Ci₂-cycloalkyl, which may be substituted by one or more E and/or interrupted by one or more D; COR₉; CONR₉R₁₀; S0₃R₉; S0₂R₉; P0₃(R₉)₂; P0₂(R₉)₂;

R₉ and R₁₀ independently from each other are hydrogen; CrCi₈alkyl or C₃-Ci₂-cycloalkyl which may be substituted by one or more E and/or interrupted by one or more D; C₆- C₂oaryl, which may be substituted by one or more G; or

R₉ and R₁₀ together form a five or six membered ring,

D is -CO-; -COO-; -S-; -SO-; -S0₂-; -0-; -NR₁₄-; -SiRi₉R₂₀-; -PORn-;

or

-C≡C-; and E is -OR_i8; -SRi₈; -NR₁₄Ri₅; -NR₁₄CORi₅; -CORi₇; -COORi₆; -CONR₁₄R₁₅; -CN; halogen; or OS0₃Ri₈; S0₃Ri₈; S0₂Ri₈; P0₃(Ri₈)₂; OP0₃(Ri₈)₂;

G is E; CrCi₈alkyl, which is optionally interrupted by D; CrCi₈alkoxy, which is optionally substituted by E and/or interrupted by D; wherein

R12, Ri3, Ri₄ and Ri₅ independently of each other are hydrogen; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl or CrCi₈alkoxy; CrCi₈alkyl, which is optionally interrupted by

-0-; or

R-I4 and R₁₅ together form a five or six membered ring,

R16 is hydrogen; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl or CrCi₈alkoxy; C Ci₈alkyl which is optionally interrupted by -0-;

Ri7 is H; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl or CrCi₈alkoxy; or d-

Ci₈alkyl which is optionally interrupted by -0-;

R18 is hydrogen; C₆-Ci₈aryl, which is optionally substituted by CrCi₈alkyl or CrCi₈alkoxy; CrCi₈alkyl, which is optionally interrupted by -0-; and

Rig and R₂₀ independently of each other are hydrogen; CrCi₈alkyl; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl.

8. Use according to any of claims 1 to 7, wherein

R₅ is hydrogen; substituted or unsubstituted CrCi₈alkyl;

R₂ and R₄ independently from each other are hydrogen; or substituted or unsubstituted C Ci₈alkyl;

R₃ is hydrogen; or carboxylate COOX; wherein

X is Na, K or NH₄; and

D and E are defined as in claim 1 .

9. Use according to any of claims 1 to 8, wherein

R₂, R₃, R₄, R5 and R₆, independently of one another are hydrogen; d-C^alkyl, CrC₃₀alkoxy or CrCi₂alkenyl substituted by E;

E is carboxylate; OCOR₉; sulphate; sulphonate; phosphonate; or phosphate; and

R₉ is defined as in claim 1.

10. Use according to any of claims 1 to 9, wherein in formula (1 ) R₃ is a radical of formula , wherein

R22 is hydrogen; d-C^alkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆-C2oaryl, which may be substituted by one or more G; C₄- C₂oheteroaryl, which may be substituted by one or more G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, C₇-C25aralkyl, or -CO-Ri₇;

Ri₇ is H; C₆-Ci₈aryl which is optionally substituted by CrCi₈alkyl or Ci-Ci₈alkoxy; or d-

Ci₈alkyl which is optionally interrupted by -O-; and

Ri, R2, R₄, R5, R6, R7 and R₈, D, G and E are defined as in claim 1.

1 1. Use according to any of claims 1 to 10, wherein

R₂, R3, R₄, R5, R6, R9, RIO_> RI I _> and R12 independently of one another are sulphate; sulpho- nate; phosphate; or phosphonate and/or R-i, R₇ and R₈ together with the adjacent oxygen independently of one another form a sulphate, sulphonate, phosphate or phosphonate group.

12. Use according to any of claims 1 to 11 , wherein

R₂ is CrC₃oalkyl, C₂-C₃oalkenyl, CrC₃oalkoxy, C₃-Ci₂-cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆- C₂oaryl, which may be substituted by one or more G; COR₉; COOR₉; CONR₉R₁₀;

Ri, R₃, R₄, R₅, R6, R7, Re, E, D and G are defined as in claim 1.

13. Use according to any of claims 1 to 12, wherein

R₂ and R₅ is CrC₃₀alkyl, C₂-C₃₀alkenyl, CrC₃₀alkoxy, C₃-Ci₂-cycloalkyl or CrC₃₀hydroxyalkyl, which may be substituted by one or more E and/or interrupted by one or more D; C₆- C₂₀aryl, which may be substituted by one or more G; COR₉; COOR₉; CONR₉R₁₀; and

Ri, R₃, R₄, R₆, R7, R₈, E, D and G are defined as in formula (1 ).

14. Use according to any of claims 1 to 13, wherein

15. A method for protecting skin, mucosa and integumentary appendages against the action of microbes including protecting the scalp from dandruff, which comprises applying a prepa- ration comprising an effective amount of the benzotropolone derivative of formula (1 ) according to claim 1 .

16. A method for protecting paper, wood, leather, synthetic textile materials or natural textile materials against the action of microbes comprising incorporating or applying an effective amount of the benzotropolone derivative of formula (1 ) according to claim 1.

17. A method for cleaning and disinfecting hard surfaces which comprises applying a preparation comprising an effective amount of the benzotropolone derivative of formula (1 ) accord- ing to claim 1 .

18. A method for preventing bio-fouling of an article comprising incorporating the benzotropolone derivative of formula (1 ) according to claim 1 into the article or surface of the article or by applying the benzotropolone derivative of formula (1 ) according to claim 1 to these sur- faces either directly or as part of a coating or film.