STABILISATION OF BODY-CARE AND HOUSEHOLD PRODUCTS

Abstract: A description is given of the use of phenolic antioxidants of formulae (1) and/or (2) and/or (3) for stabilising body-care and household products.

Description: Stabilisation of bodv-care and household products The present invention relates to the use of phenolic antioxidants for stabilising body-care and household products. The product trend of recent years towards increasingly using natural substances based on oil and fat in cosmetic formulations and household products also increases the problem of the oxidative degradation of fats and oils, resulting in rancidity. Natural oils or unsaturated fatty acids are hardly ever absent from emulsions. Oxidative changes may sometimes produce reactive metabolites, for example ketones, aldehydes, acids, epoxides and lipoper- oxides. As a result there is on the one hand an undesirable change in the smell of the products and on the other hand substances may be obtained which may alter the skin tolerance. The uncontrolled formation of free radicals on the skin contributes primarily to the initiation and progression of a multitude of pathophysical modulations, for example inflammation, canceroge- nesis and the like. However, oxidative degradation processes are not only found in the case of natural substances based on oil and fat. They are also found in a number of other cosmetic ingredients, such as fragrances and odoriferous substances, vitamins, colourants and the like. To prevent oxidative degradation processes (photooxidation, autooxidation), so-called antioxidants (AO) are therefore used in cosmetic and food products. These antioxidants may be classified into compounds which prevent oxidation (complex formers, reducing agents and the like) and into compounds which interrupt the free radical chain reactions, for example butylated hydroxytoluene (BHT), butylated hydroxyanisol (BHA), gallates, such as propyl- gallate (PG), or t-butylhydroquinone (TBHQ). However, the latter compounds often do not meet the requirements with respect to pH stability as well as to light and temperature stability. Surprisingly, it has been found that certain phenolic antioxidants meet these requirements. Accordingly, this invention relates to the use of phenolic antioxidants of formula wherein in formulae (1 ), (2) and (3) Ri is hydrogen; Cι-C 22 alkyl; C 1 -C 22 alkylthio; C 5 -C 7 cycloalkyl; phenyl; Cy-Cgphenylalkyl; or SO 3 M; R 2 is C r C 22 alkyl; C 5 -C 7 cycloalkyl; phenyl; or C 7 -C 9 phenylalkyl; Q is -C m H 2m -; -CH- ; -C m H m -NH; a radical of formula C m H 2m+1 O II T is -C n H 2n -; -(CH 2 ) n -O-CH 2 -; -C n H 2n — NH — C — ; or a radical of formula (1c) V is -O-; or -NH-; a is 0; 1 ; or 2; b, c and d are each independently of one another 0; or 1 ; e is an integer from 1 to 4; f is an integer from 1 to 3; and m, n and p are each independently of one another an integer from 1 to 3; if e = 1 , then R 3 is hydrogen; M; C C 22 alkyl; C 5 -C 7 cycloalkyl; C C 22 alkylthio; C 2 -C 1θ alkenyl; C r C 18 - phenylalkyl; a radical of formula (1 d) M is alkali; ammonium; if e = 2, then R 3 is a direct bond; -CH 2 -; — CH— (CH 2 2)'p-C v H" '„3 ; -O- ; or -S-; if e = 3, then R 3 is the radical of formula (1g) (1 i) if e = 4, then I R 3 is — C — ; or a direct bond; R 4 and R 5 are each independently of the other hydrogen; or CrC 22 alkyl; for stabilising body-care and household products. CrC 2 Alkyl is straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, iso- propyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl. C 1 -C 22 Alkylthio is straight-chain or branched alkylthio radicals, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, amylthio, heptylthio, octyl- thio, isooctylthio, nonylthio, decylthio, undecylthio, dodecylthio, tetradecylthio, pentadecyl- thio, hexadecylthio, heptadecylthio, octadecylthio or eicosylthio. C 2 -Cι 8 Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n- penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec- 2-enyl or n-octadec-4-enyl. C 5 -C 7 Cycloalkyl is cyclopentyl, cycloheptyl or, preferably, cyclohexyl. C 7 -C 9 Phenylalkyl is phenylpropyl, phenylethyl and, preferably, benzyl. It is preferred to use antioxidants of formula (1), wherein Q is -C m H 2m - and, preferably, a methylene or ethylene radical, and m has the meaning given in formula (1 ). V in formula (1 ) is preferably -O-. Particularly interesting compounds of formula (1) are those, wherein R, and R 2 are each independently of the other C Csalkyl and, in particular, d-C 5 alkyl. Other important compounds of formula (1 ) are those, wherein a is 1. Very particularly interesting compounds are those of formula wherein R, and R 2 are each independently of the other CrC 5 alkyl, a is 1 or 2; and R 3 , Q, V, T, b, c, d and e have the meanings cited for formula (1). Preferred compounds are those of formula (1), wherein R, and R 2 are the tert-butyl radical; and a is 1. It is also preferred to use antioxidants of formula wherein R , and R 2 are each independently of the other C r C 5 alkyl; Q is -C m H 2m -; or -C m H 2 -NH- ; CH, R 3 is a direct bond; -O-; -S-; -CH 2 -; or — CH— ; a is 1 or 2; m is 1 to 5; and T has the meaning cited in formula (1 ). Interesting compounds of formula (1) are those, wherein CH- I Q is ethylene; or — CH— ; R 3 is a direct bond; and Ri, R 2 , T and a have the meanings given in formula (3). Likewise preferred are compounds of formula wherein T is -C n h ^n R T and R 2 are each independently of the other d-Csalkyl; R 3 is the radical of formula (1 g); (1 h); (1 i); or (1 k); m and n are each independently of the other 1 to 3; a is 1 or 2; and b and d are each independently of the other 0 or 1. Other antioxidants which are preferably used conform to formula wherein A is a radical of formula Ri, R 2 and R 3 are each independently of one another CrC 5 alkyl; and m is 1 to 3. Other preferred antioxidants are those of formula wherein B is a radical of formula Ri and R are each independently of the other Cι-C 5 alkyl; V is -O-; or -NH-; a is 1 ; or 2; m is 1 to 3; and n is 0 to 3. Examples of antioxidants used according to this invention are listed in Table 1 : The phenolic antioxidants of formulae (1), (2) and (3) can be used as individual compounds or as mixtures of several individual compounds. The antioxidants used according to this invention have pronounced reactivity and can therefore be advantageously used at low temperatures. They furthermore have good hydrolytic stability, in particular in alkaline medium. Owing to their good solubility, they can be easily incorporated into the respective formulations. The phenolic antioxidants of formulae (1), (2) and (3) can also be used together with toco- pherol and/or tocopherol acetate. The phenolic antioxidants of formulae (1 ), (2) and (3) can furthermore also be used together with light stabilisers. Suitable light stabilisers are, for example, sterically hindered amines. These include preferably a 2,2,6,6-tetraalkylpiperidine derivative containing at least one group of formula wherein G, Gi and G 2 are each independently of one another hydrogen or methyl, preferably hydrogen. Examples of tetraalkylpiperidine derivatives which can be used according to this invention are to be found in EP-A-356677, pages 3-17, paragraphs a) to f). The cited paragraphs of this EP-A are regarded as part of the present description. It is particularly useful to employ the following tetraalkylpiperidine derivatives: bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl)succi- nate, bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl- piperidin-4-yl)sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid-bis(1 ,2, 2,6,6- pentamethylpiperidyl)ester, the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexa- methylenediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-triazine, tris(2,2,6,6-tetrame- thyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-l,2,3,4-butanetetrao- ate, 1 ,1 '-(1 ,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl- piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl)-2- n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-tri- azaspiro[4.5]decane-2,4-dione, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 - octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,N-bis(2,2,6,6-tetrame- thyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di(4-n-butylamino- 1 ,2,2,6,6-pentamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, 8- acetyl-3-dodecyl-7J,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 - (2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1 -(1 ,2,2,6,6-pentamethyl-4- piperidyl)-pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearybxy-2,2,6,6-tetra- methylpiperidine, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene- diamine and 4-cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, the condensate of 1 ,2-bis(3-ami- nopropylamino)ethane and 2,4,6-trichloro-1 ,3,5-triazine and 4-butylamino-2,2,6,6-tetrame- thylpiperidine (CAS reg. No. [136504-96-6]); (2,2,6,6-tetramethyl-4-piperidyl)-n-dodecyl- succinimide, (1 ,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9- tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, the reaction product of 7,7,9,9-tetra- methyl-2-cycloundecyl-1 -oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin, tetra- (2,2,6,6-tetramethylpiperidin-4-yl)-butane-1 ,2,3,4-tetracarboxylate, tetra(1 ,2,2,6,6-pentame- thylpiperidin-4-yl)-butane-1 ,2,3,4-tetracarboxylate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21- oxo-dispiro[5.LH .2] -heneicosan, 8-acetyl-3-dodecyl-1 ,3,8-triaza-7,7,9,9-tetramethylspiro- [4,5] -decane-2,4-dione, or a compound of formulae wherein m has a value of 5-50, R = H or CH, or R = H or CH, It is also possible to use the inventive antioxidants of formulae (1), (2) and (3) together with benzotriazoles of formula In formula (42), R 6 is Ci-Csalkyl; Cι-C 5 alkoxy; Cι-C 5 alkoxycarbonyl ; C 5 -C 7 cycloalkyl; C 6 -Cι 0 aryl; aralkyl; -SO 3 M; a radical of formula (40a) R 8 is hydrogen; C r C 5 alkyl; C r C 5 alkoxy; halogen, preferably CI; or hydroxy R 9 and Rι 0 are each independently of the other hydrogen; or Cι-C 5 alkyl; m is 1 or 2; n is O or l ; if m = 1 , then R 7 is hydrogen; unsubstituted or phenyl-substituted d-C^alkyl; C 6 -C 0 aryl; A B if m = 2, then R 7 is a direct bond; -(CH 2 ) P -; and p is 1 to 3. The inventive antioxidants of formulae (1), (2) and (3) can also be used together with hydroxyphenyltriazine compounds of formula wherein i is Cι-C 22 alkyl, C 2 -C 22 alkenyl or C 5 -C 7 cycloalkyl; L 2 and L 6 are each independently of the other H, OH, halogen, CrC 22 alkyl, halomethyl; L 3 , L 5 and L 7 are each independently of one another H, OH, OLi, halogen, C C 22 alkyl, halo- methyl; U is H, OH, OLi, halogen, Cι-C 22 alkyl, phenyl, halomethyl; L 12 is CrC 22 alkyl, phenyl Cι-C 5 alkyl, C 6 -C 7 cycloalkyl, OLi or, preferably a group of formula is O, 1 , 2 or 3. If L-substituents are defined as alkyl or alkenyl, or if they are aromatic or aliphatic ring systems, then these contain within the scope of the cited meanings usually 1 to 50 carbon atoms and can be interrupted once or several times by O, S, NR', SO 2 , CO, phenylene, cyclohexylene, COO, OCO, -(SiR p R q O)- and/or substituted once or several times by OH, OR', NR'R", halogen, -CN, alkenyl, phenyl, -SiRpR q R r or COOH, where R' and R" are each independently of the other H, alkyl, alkenyl or acyl, and R p , R q and R r are each independently of the other H, alkyl, alkenyl, phenyl, alkoxy, acyl or acyloxy. The above groups can also carry further substituents. Dimers or polymers are also possible. Preferred 2-hydroxyphenyltriazines of this class are, for example, those of formulae wherein in formula (44) n is 1 or 2, and Li, where n = 1 , is alkyl or alkyl which is interrupted by one or several O and/or substituted by one or several of the radicals OH, glycidyloxy, alkenoxy, COOH, COOR e , O-CO-R f ; or alkenyl, cycloalkyl; phenylalkyl which is unsubstituted or substituted by OH, CI or CH 3 ; COR 9 ; SO 2 -R h ; CH 2 CH(OH)-R j ; where R e is alkyl; alkenyl; hydroxyalkyl; alkyl or hydroxyalkyl which is interrupted by one or several O; cycloalkyl; benzyl; alkylphenyl; phenyl; phenylalkyl; furfuryl; or CH 2 CH(OH)-R i ; R f , R 9 are each independently of the other alkyl, alkenyl or phenyl; R h is alkyl, aryl or alkylaryl; R' is aralkyl or CH 2 OR k ; R k is cyclohexyl, phenyl, tolyl, benzyl; and Li, where n = 2Js alkylene; alkenylene; xylylene; alkylene or hydroxyalkylene which is interrupted by one or several -O-; hydroxyalkylene; L 2 and L' 2 are each independently of the other H, alkyl or OH; U and L' are each independently of the other H, alkyl, OH, alkoxy, halogen and, where n = 1 , OLι; L 3 and L' 3 are each independently of the other H, alkyl or halogen. L,, L 2 , L' 2> L 3 , L' 3 , L 4 , L' can within the scope of the cited meanings carry additional substi- tuents, for example an ethylenically unsaturated polymerisable group. Dimers or polymers are also possible. Examples of such compounds are, inter alia, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5- triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5- triazine, 2-[2-hydroxy-4-(2-hydroxy-3-tridecyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5- triazine; and compounds of the following formulae: Abbreviations used in the above formulae: i = isomeric mixture; n = straight-chain radical; t = tertiary radical; o-, m-, p- designate the position of the radical relative to the triazine ring. Examples of benzotriazole compounds which may be used in accordance with this invention: In addition, the inventive antioxidants of formulae (1 ), (2) and (3) can also be used together with complex formers, in particular nitrogen-containing complex formers, for example ethy- lenediaminetetracetic acid (EDTA), nitrilotriacetic acid (NT A), β-alaninediacetic acid (EDETA) or ethylenediaminedisuccinic acid (EDDS). Other suitable complex formers conform to formula \ . .Q, N ' (96) Q wherein Qι, is Cart^; Carb 2, ; or a radical of formula -(CH 2 ) m -OH Q 2 is hydrogen or Carb 2 ; and Qo / Q 3 is Carb 3 ; an amino acid radical; or a radical of formula (96a) -N \ ' wherein Carbi, Carb 2 and Carb 3 are each independently of one another the radical of a C r C 8 mono- or dicarboxylic acid; and Particularly preferred compounds are those of formula (96), wherein Qi is a monocarboxylic acid; or a radical of formula (96b) -(CH 2 ) -OH ; Q 2 is hydrogen or a monocarboxylic acid; and Q 3 is formula (96b); or a monocarboxylic acid. Particularly interesting complex formers are those of formula (96), wherein Carb 2 and Carb 3 are each independently of the other the radical of formula (96c) -[(CH 2 )] n -COOH , wherein Complex formers which are important in practice are those conforming to formula or to formula HOOC— H 2 C (98) ^N-CH 2 -CH 2 -COOH HOOC CH 2 Nitrilotriacetic acid (NTA) is also suitable for use. Other examples of complex formers which may be used according to this invention are aminethmethylenephosphoric acid (ATMP) conforming to formula H 2 P0 3 CH 2 ^ CH 2 P0 3 H 2 (99) l CH 2 P0 3 H 2 serinediacetic acid (SDA) conforming to formula HOOC-CH 2 *\ H I (100) N-C-CH„-OH HOOC-CH /' C ' OOH asparaginediacetic acid conforming to formula methylglycinediacetic acid (MGDA) conforming to formula CH, (102) HOOC" CH - N- CH 2 - COOH I CH 2 -COOH Other suitable complex formers are polyanionically-derived natural polysaccharides, for example containing phosphate, phosphonate or methylphosphonate groups, such as chitin derivatives, e.g. sulfochitin, carboxymethylchitin, phosphochitin, chitosan derivatives, for example sulfochitosan, carboxymethylchitosan or, very particularly preferably, phosphochi- tosan, which conform to formula wherein R is hydrogen or a radical of formula O — X, R 12 is a radical of formula (1a); X, and X 2 are each independently of the other hydrogen, C^C^Ikyl or an alkali ion or ammonium ion; and n is 10 to 4000. The antioxidants of formulae (1), (2) and (3) as well as mixtures of these compounds with light stabilisers or complex formers are particularly suitable for stabilising body-care products, in particular used for skin-care products, bath and shower additives, preparations containing fragrances and odoriferous substances, hair-care products, dentifrices, deodorising and antiperspirant preparations, decorative preparations, light protection formulations and preparations containing active ingredients. Suitable skin-care products are, in particular, body oils, body lotions, body gels, treatment creams, skin protection ointments, shaving preparations, such as shaving foams or gels, skin powders, such as baby powder, moisturising gels, moisturising sprays, revitalising body sprays, cellulite gels and peeling preparations. Preparations containing fragrances and odoriferous substances are in particular scents, perfumes, toilet waters and shaving lotions (aftershave preparations). Suitable hair-care products are, for example, shampoos for humans and animals, in particular dogs, hair conditioners, products for styling and treating hair, perming agents, hair sprays and lacquers, hair gels, hair fixatives and hair dyeing or bleaching agents. Suitable dentifrices are in particular tooth creams, toothpastes, mouth-washes, mouth rinses, anti-plaque preparations and cleaning agents for dentures. Suitable decorative preparations are in particular lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions. Suitable cosmetic formulations containing active ingredients are in particular hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations. The cited body-care products can be in the form of creams, ointments, pastes, foams, gels, lotions, powders, make-ups, sprays, sticks or aerosols. They preferably contain the antioxidants of formulae (1) and/or (2) and/or (3) and, optionally, the above light stabilisers in the oil phase or in the aqueous or aqueous/alcoholic phase. This invention therefore also relates to a body-care product containing at least one phenolic antioxidant of formula (1 ) and/or (2) and/or (3). The antioxidant(s) are usually present in the novel body-care product in a concentration of 50 to 1000 ppm. Creams are oil-in-water emulsions containing more than 50 % of water. The oil-containing base used therein is usually mainly fatty alcohols, for example lauryl, cetyl or stearyl alcohol, fatty acids, for example palmitic or stearic acid, liquid to solid waxes, for example isopropyl- myristate or beeswax and/or hydrocarbon compounds, such as paraffin oil. Suitable emulsi- fiers are surfactants having primarily hydrophilic properties, such as the corresponding non- ionic emulsifiers, for example fatty acid esters of polyalcohols of ethylene oxide adducts, such as polyglycerol fatty acid ester or polyoxyethylenesorbitan fatty acid ether (Tween trademarks); polyoxyethylene fatty alcohol ether or their esters or the corresponding ionic emulsifiers, such as the alkali metal salts of fatty alcohol sulfonates, sodium cetyl sulfate or sodium stearyl sulfate, which are usually used together with fatty alcohols, such as cetyl alcohol or stearyl alcohol. In addition, creams contain agents which reduce water loss during evaporation, for example polyalcohols, such as glycerol, sorbitol, propylene glycol, and/or polyethylene glycols. Ointments are water-in-oil emulsions which contain up to 70 %, preferably not more than 20 to 50 %, of water or of an aqueous phase. The oil-containing phase contains predominantly hydrocarbons, such as paraffin oil and/or solid paraffin which preferably contains hydroxy compounds, for example fatty alcohol or their esters, such as cetyl alcohol or wool wax for improving the water absorption. Emulsifiers are corresponding lipophilic substances, such as sorbitan fatty acid ester. In addition, the ointments contain moisturisers such as polyalcohols, for example glycerol, propylene glycol, sorbitol and/or polyethylene glycol as well as preservatives. Rich creams are anhydrous formulations and are produced on the basis of hydrocarbon compounds, such as paraffin, natural or partially synthetic fats, for example coconut fatty acid triglycerides or, preferably, hardened oils and glycerol partial fatty acid esters. Pastes are creams and ointments containing powdered ingredients which absorb secretions, for example metal oxides, such as titanium dioxide or zinc oxide, and also tallow and/or aluminium silicates which bind the moisture or the absorbed secretion. Foams are liquid oil-in-water emulsions in aerosol form. Hydrocarbon compounds are used, inter alia, for the oil-containing phase, for example paraffin oil, fatty alcohols, such as cetyl alcohol, fatty acid esters, such as isopropylmyristate and/or waxes. Suitable emulsifiers are, inter alia, mixtures of emulsifiers having predominantly hydrophilic properties, for example polyoxyethylenesorbitan fatty acid ester, and also emulsifiers having predominantly lipophilic properties, for example sorbitan fatty acid ester. Commercially available additives are usually additionally employed, for example preservatives. Gels are, in particular, aqueous solutions or suspensions of active substances in which gel formers are dispersed or swelled, in particular cellulose ethers, such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose or vegetable hydrocolloids, for example sodium alginate, tragacanth or gum arabic. The gels preferably additionally contain also polyalcohols, such as propylene glycol or glycerol as moisturisers and wetting agents, such as polyoxyethylenesobitan fatty acid ester. The gels furthermore contain commercially available preservatives, such as benzyl alcohol, phenethyl alcohol, phenoxyethanol and the like. The following Table lists typical examples of body-care products of this invention and their ingredients: Bodv-care product Ingredients moisturising cream vegetable oil, emulsifier, thickener, perfume, water, antioxidant shampoo surfactant, emulsifier, preservatives, perfume, antioxidant toothpaste cleaning agent, thickener, sweetener, flavour, colourant, antioxidant, water lip-care stick vegetable oil, wax, TiO 2 , antioxidant The novel body-care products have high stability towards colour changes and chemical degradation of the ingredients present in these products. This is to be attributed to the effectiveness, colour stability, ease of incorporation and hydrolytic stability of the antioxidants used. The phenolic antioxidants are also used in household cleaning and treatment agents, for example in liquid scouring agents, glass detergents, neutral cleaners (all-purpose cleaners), acid household cleaners (bath), WC cleaners, preferably in washing, rinsing and dishwashing agents, clear rinsing agents, dishwasher detergents, shoe polishes, polishing waxes, floor detergents and polishes, metal, glass and ceramic cleaners, textile-care agents, agents for removing rust, colour and stains (stain remover salt), furniture and multipurpose polishes and leather dressing agents (leather sprays). Typical examples of novel household cleaning and treating agents are: Household Ingredients cleaners/household treating agents detergent concentrate surfactant mixture, ethanol, antioxidant, water shoe polish wax, wax emulsifier, antioxidant, water, preservative wax-containing floor emulsifier, wax, sodium chloride, antioxidant, water, cleaning agent preservative The antioxidant(s) are usually incorporated by dissolution in an oil phase or alcoholic or water phase, where required at elevated temperature. Details can be found in the Examples. The phenolic antioxidants of formulae (1 ), (2) and (3) also have pronounced antimicrobial action. The following Examples illustrate the invention. Preparation of stabilised formulations of body-care products Example i 1a: Preparation of a moisturiser cream Phase Ingredients (w/w) % A passionflower oil 8 glyceryl dioleate 4 dicapryl ether 4 isopropylisostearate 4 antioxidant of formula (31) 0.05 B water, demin. ad. 100 EDTA 0.1 C carbomer 0.15 D sodium hydroxide 10% 0.20 E perfume; preservative q.s. Preparation: The components (A) are thoroughly mixed in a homogeniser for 10 min at 75-80°C. The water (B), likewise heated to 75-80°C beforehand, is slowly added and the mixture is homogenised for 1 min. The mixture is cooled, with stirring, to 40°C and then (C) and (E) are added and the mixture is homogenised for 1 min. Subsequently, (D) is added and the mixture is homogenised for 1/2 min and cooled, with stirring, to room temperature. Alternatively to the antioxidant of the formulae (31) the following antioxidants can be applied (0.05 %): Example 1 b: antioxidant of the formula (7) Example 1c: antioxidant of the formula (32) Example 1 d: antioxidant of the formula (33) Example 2: Preparation of a toilet water (w/w) % Ingredients (w/w) % ethanol, 96% 60 d-iimonene 5 cedrene 1.5 citronellol 0.5 savin 0.5 antioxidant of formula (29) 0.08 UV absorber of formula (91 ) 0.1 S.S-EDDS 0.005 colourant (D&C Yellow No.5) 0.02 water ad. 100 Preparation: The components are thoroughly mixed in the cited sequence at 50°C, a clear homogeneous solution being obtained. Example 3: Preparation of a hair styling spray Ingredients , . . „. (w/w) % alcohol, anhydrous 96.21 octylacrylamide/acrylate butylaminoethylmethacrylate copolymer 2.52 hydroxypropyl cellulose 0.51 aminomethylpropanol (95%) 0.46 antioxidant of formula (33) 0.05 benzophenone-4 0.05 perfume oil 0.20 Preparation: The hydroxypropyl cellulose is first predissolved in half of the alcohol (Vortex mixer) and is charged with the aminomethylpropanol. The other components - with the exception of the acrylate resin - are dissolved in alcohol and this solution is added, with stirring, to the hydroxypropyl cellulose. Subsequently, the acrylate resin is added and stirred until completely dissolved. Example 4: Preparation of a shampoo for oreasv hair Ingredients (w/w) % sodium myreth sulfate 50.00 TEA abietoyl collagen hydrolysate 3.50 laureth-3 3.00 colourant (D&C Red No. 33) 0.20 antioxidant of formula (29) 0.05 UV absorber of formula (92) 0.15 phosphonomethylchitosan, sodium salt 0.01 perfume oil 0.10 water ad. 100 Preparation: The components are mixed, with stirring, at room temperature until they are completely dissolved. The pH is 6.5. Preparation of stabilised household products Example 5: Preparation of a leather dressing and cleaning agent Ingredients (w/w) % synthetic soap (Zetesap 813) 7.85 glycerol 6.00 anionic surfactant (Lumorol 4192; Mulsifan RT 13) 22.00 Vaseline 11.00 paraffin 52/54 20.00 talcum 2.00 orange terpene 4.00 antioxidant of formula (33) 0.02 water 27.13 Preparation: The antioxidant is predissolved in the terpene. The components are then stirred in the cited sequence at about 65°C until homogeneous. The mixture is then cooled to room temperature. Example 6: Preparation of a glass detergent Ingredients (w/w) % anionic / amphoteric sur actants (Lumorol RK) 0.7 butyl glycol 5.0 isopropanol 20.0 d-limonene 4.00 antioxidant of formula (32) 0.02 water, demin. ad. 100 Preparation: The antioxidant is predissolved in the terpene. The components are then dissolved in the cited sequence until a clear homogeneous mixture is obtained.

Claims: What is claimed is: 1. Use of phenolic antioxidants of formulae (a 2 ) an antioxidant of formula wherein in formulae (1), (2) and (3) Ri is hydrogen; C r C 22 alkyl; Cι-C 22 alkylthio; C 5 -C 7 cycloalkyl; phenyl; (VCgphenylalkyl; or SO 3 M; R 2 is C C 22 alkyl; C 5 -C 7 cycloalkyl; phenyl; or C 7 -C 9 phenylalkyl; Q is -C m H 2m -; -CH- ; -C m H 2m -NH; a radical of formula C m H 2m + l O II T is -C n H 2n -; -(CH 2 ) n -O-CH 2 -; -C n H 2n — H — C — ; or a radical of formula (1c) V is -O-; or -NH-; a is 0; 1 ; or 2; b, c and d are each independently of one another 0; or 1 ; e is an integer from 1 to 4; f is an integer from 1 to 3; and m, n and p are each independently of one another an integer from 1 to 3; if e = 1 , then R 3 is M; hydrogen; Cι-C 2 alkyl; C 5 -C 7 cycloalkyl; CrC 22 alkylthio; C 2 -C 18 alkenyl; C C 18 - phenylalkyl; a radical of formula (1d) is alkali; ammonium; if e = 2, then is a direct bond; -CH 2 -; — CH— (CHJ-CH, ; -O- ; or if e = 3, then R 3 is the radical of formula (1g) (1 i) if e - 4, then R 3 is — C — ; or a direct bond; R 4 and R 5 are each independently of the other hydrogen; or C r C 22 alkyl; for stabilising body-care and household products. 2. Use according to claim 1 , wherein in formula (1) Q is -C m H 2m - , wherein m has the meaning cited in claim (1). 3. Use according to either claim 1 or claim 2, wherein Q is a methylene or ethylene radical. 4. Use according to any one of claims 1 to 3, wherein V is -O- . 5. Use according to any one of claims 1 to 4, wherein Ri and R 2 are each independently of the other C C 18 alkyl. 6. Use according to claim 5, wherein Ri and R 2 are each independently of the other Cι-C 5 alkyl. 7. Use according to either claim 1 , claim 5 or claim 6, wherein a is 1. 8. Use according to claim 1 , which comprises using an antioxidant of formula wherein Ri and R 2 are each independently of the other CrC 5 alkyl, a is 1 or 2; and R 3 , Q, V, T, b, c, d and e have the meanings cited in claim 1. 9. A composition according to claim 8, wherein R, and R 2 are the tert-butyl radical; and a is 1. 10. Use according to claim 1 , which comprises using an antioxidant of formula wherein R. and R 2 are each independently of the other d-Cs-alkyl; Q is -C m H 2m -; or -C m H 2 -NH- ; C I H 3, R 3 is a direct bond; -O-; -S-; -CH 2 -; or — CH— a is 1 or 2; m is 1 to 5; and T has the meaning cited in claim 1. 11. Use according to claim 10, wherein the antioxidant is a compound of formula (3), wherein CH, Q is ethylene; or — C IH— ; R 3 is a direct bond; and Ri, R 2 , T and a have the meaning given in claim 10. 12. Use according to claim 1 , wherein the antioxidant is the compound of formula wherein Q is -C m H 2m -; Ri and R 2 are each independently of the other Cι-C 5 -alkyl; R 3 is the radical of formula (1g); (1 h); (1 i); or (1k) ; m and n are each independently of the other 1 to 3; a is 1 or 2; and b and d are each independently of the other 0 or 1. 13. Use according to claim 12, wherein the antioxidant is a compound of formula wherein A is a radical of formula Ri , R 2 and R 3 are each independently of one another d-Csalkyl; and m is 1 to 3. 14. Use according to claim 12, wherein the antioxidant is a compound of formula wherein B is a radical of formula Ri and R 2 are each independently of the other C C 5 alkyl; V is -O-; or -NH-; a is 1; or 2; m is 1 to 3; and n is 0 to 3. 15. Use according to any one of claims 1 to 14, which comprises using the phenolic antioxidants of formulae (1), (2) and (3) as individual compounds or as a mixture of several individual compounds. 16. Use according to any one of claims 1 to 15, which comprises using the antioxidant or the sum of the antioxidants in a concentration of 50 to 1000 ppm. 17. Use according to any one of claims 1 to 16, which comprises using the antioxidants together with tocopherol and/or tocopherol acetate. 18. Use according to any one of claims 1 to 17, which comprises using the phenolic antioxidants together with light stabilisers. 19. Use according to claim 18, wherein the light stabilisers used are sterically hindered amines. 20. Use according to claim 18, wherein the light stabilisers used are benzotriazoles of formula wherein R 6 is CrC 12 alkyl; C C 5 alkoxy; Cι-C 5 alkoxycarbonyl ; C 5 -C 7 cycloalkyl; C 6 -C 10 aryl; aralkyl; -SO 3 M; a radical of formula (...a) R 8 and R 9 are each independently of the other hydrogen; or C C 5 alkyl; m is 1 or 2; n is O or l ; if m = 1 , R 7 is hydrogen; unsubstituted or phenyl-substituted Ci-Csalkyl; C 6 -Cι 0 aryl; if n = 2, R 2 is a direct bond; -(CH 2 ) P -; and p is 1 to 3. 21. Use according to claim 18, wherein the light stabilisers used are 2-hydroxyphenyltri- azines of formula wherein Li is C C 22 alkyl, C 2 -C 22 alkenyl or C 5 -C 7 cycloalkyl; L 2 and L 6 are each independently of the other H, OH, halogen, Cι-C 22 alkyl, halomethyl; L 3 , L 5 and L 7 are each independently of one another H, OH, OLi, halogen, Cι-C 22 alkyl, halomethyl; U is H, OH, OLi, halogen, C 1 -C 22 alkyl, phenyl, halomethyl; L 12 is Cι-C 22 alkyl, phenyl Cι-C 5 alkyl, C 5 -C 7 cycloalkyl, OLi or, preferably, a group of formula j is 0, 1 , 2 or 3. 22. Use of the phenolic antioxidant according to claim 1 in body-care products for the skin and its adnexa. 23. Use according to claim 22, wherein the body-care products are selected from skin-care products, bath and shower additives, preparations containing fragrances and odoriferous substances, hair-care products, dentifrices, deodorising and antiperspirant preparations, decorative preparations, light protection formulations and preparations containing active ingredients. 24. Use according to claim 23, wherein the skin-care products are selected from body oils, body lotions, body gels, treatment creams, skin protection ointments, shaving preparations and skin powders. 25. Use according to claim 23, wherein the preparations containing fragrances and olfactory substances are selected from scents, perfumes, toilet waters and shaving lotions. 26. Use according to claim 23, wherein the hair-care products are selected from shampoos, hair conditioners, agents for styling and treating hair, perming agents, hair sprays and lacquers and hair dyeing or bleaching agents. 27. Use according to claim 23, wherein the decorative preparations are selected from lipsticks, nail varnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders, depilatory agents and suntan lotions. 28. Use according to claim 23, wherein the active ingredient-containing cosmetic formulations are selected from hormone preparations, vitamin preparations, vegetable extract preparations and antibacterial preparations. 29. Use of the phenolic antioxidant according to claim 1 in household cleaning and treating agents. 30. Use according to claim 29, wherein the household cleaning and treating agents are selected from washing, rinsing and dishwashing agents, shoe polishes, polishing waxes, floor detergents and polishes, metal, glass and ceramic cleaners, textile care agents, agents for removing rust, colour and stains (stain remover salt), furniture and multipurpose polishes. 31. A body-care product, which comprises at least one phenolic antioxidant according to claim 1. 32. A household cleaning and treating agent, which comprises a phenolic antioxidant according to claim 1.

Inventors: EHLIS THOMAS, HUEGLIN DIETMAR, KRAMER ERICH, LUPIA JOSEPH ANTHONY, EHLIS, THOMAS, HUEGLIN, DIETMAR, KRAMER, ERICH, LUPIA, JOSEPH, ANTHONY
Applicants: CIBA SC HOLDING AG, EHLIS THOMAS, HUEGLIN DIETMAR, KRAMER ERICH, LUPIA JOSEPH ANTHONY, CIBA SPECIALTY CHEMICALS HOLDING INC., EHLIS, THOMAS, HUEGLIN, DIETMAR, KRAMER, ERICH, LUPIA, JOSEPH, ANTHONY
Application year: 1999
Main classification: A61K7
IPC codes: A61K8, A61Q3, A61Q5, A61Q11, C09K15, C11D3