WO2004035012A1

WO2004035012A1 - The use of biomimic polymers in personal care compositions

Info

Publication number: WO2004035012A1
Application number: PCT/EP2003/011187
Authority: WO
Inventors: Jianwen Mao; Dietmar Ochs; Andrea Preuss; Jianzhao Wang; Werner Kaufmann
Original assignee: Ciba Specialty Chemicals Holding Inc.
Priority date: 2002-10-18
Filing date: 2003-10-09
Publication date: 2004-04-29
Also published as: AU2003301284A1

Abstract

The present invention relates to the use of biomimic polymeric and/or oligomeric peptides (also known as facially amphiphilic polymers) as antimicrobially active substances in home and personal care applications, i.e. in products that are used to clean, condition and/or enhance keratinic substrates such as human skin, hair, nails, etc., and formulations of various such products containing the subject antimicrobially active substances.

Description

THE USE OF BIOMIMIC POLYMERS IN PERSONAL CARE COMPOSITIONS

FIELD OF THE INVENTION

The present invention relates to the use of biomimic polymeric and or oligomeric peptides (also known as facially amphiphilic polymers) as antimicrobially active substances in home and personal care applications, i.e. in products that are used to clean, condition and/or enhance keratinic substrates such as human skin, hair, nails etc., and formulations of various such products containing the subject antimicrobially active substances.

BACKGROUND OF THE INVENTION

Today's consumers are well acquainted with the notion of germs and germ transmission. Daily, people come into contact with germs at eating establishments, the gym, while changing diapers or using portable toilet facilities (e.g., portapotties). Once in contact with human hands, these germs (i.e., micro-organisms such as bacteria, fungi and/or viruses) are quickly passed from individual to individual and, thus, contribute to the spread of contagious and/or infectious diseases. One of the best and easiest ways of preventing such germ and/or disease transmission is to routinely and conscientiously wash one's hands.

Therefore, the use of antimicrobials, i.e. substances that exhibit a pronounced antimicrobial action, especially against pathogenic gram-positive and gram-negative bacteria and also against bacteria of skin flora, e.g. Corynebacterium xerosis (bacteria that cause body odor), and also against yeasts and moulds, is widely practiced. Appropriately identified antimicrobials are especially suitable in the disinfection, deodorization and general antimicrobial treatment of keratinic surfaces such as skin, mucosa, nails and integumentary appendages (hair), more especially in the disinfection of the hands and of wounds.

On the other hand, the antimicrobials used in products that will be applied on human keratinic surfaces need to be toxicologicaliy acceptable and to not cause irritation and sensi- tization to the skin. They also need to be environmentally friendly and to biodegrade easily after use. There is also an increasing awareness that the antimicrobials used in killing or controlling microbial growth should not induce resistance of the microbes to antibiotics.

Plant and animal defense peptides have long been recognized as possessing antimicrobial properties since species from insects to mammals to certain plants use such peptides as part of their host-defense system to counter microbial infection. Many studies have been carried out to characterize the structure of such peptides. While there is no primary structure homology, the peptides are characterized by a preponderance of cationic and hydrophobic amino acids. Detailed investigations have indicated that a majority of these host-defense peptides exert their action on microorganisms by permeabilizing microbial membranes. From the point of view of minimizing the development of antibiotic resistance of microorganisms, substances that exert antimicrobial action via such a mechanism, i.e. that disrupt or cause leaking out of their membranes, are preferred because it is less likely that the microorganisms being attacked by such a mechanism would develop resistance.

Furthermore, one needs to make sure the antimicrobial substances being applied on human keratinic substrates such as skin, nails, hair etc., would not cause harmful effects. Often small organic molecules can penetrate the Stratum corneum, thereby increasing the likelihood of harmful effects. A polymeric substance, i.e. a high molecular weight substance comprising many repeated monomer units, is much less likely to penetrate skin due the larger size of the molecules.

Moreover, a lot of personal care preparations, for example, shampoos, soaps, etc., are washed away from the substrate after application. If one is to incorporate an antimicrobial substance into such preparations and want the antimicrobially active ingredient to remain on the substrate after the preparation is washed away, it is important that the antimicrobially active ingredient possess excellent substantivity to the substrate. Since many of the substrates of concern, i.e. skin, hair, and nails, are hydrophobic and slightly anionic, an antimicrobial substance that is also hydrophobic, of higher molecular weight and catatonically charged would be preferred in order to impart the required substantivity to the substrate.

Therefore, there is a need for antimicrobial substances that are effective against a wide spectrum of harmful microorganisms, are non-toxic, substantive to keratinic substrates, and non-penetrative to skin. Such antimicrobials can be incorporated into various personal care products, for example shampoos, bath additives, hair-care products, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, feminine hygiene cleansing products, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleansing cloths, oils or powders, to provide sanitizing, deodorizing, disinfecting and preservation benefits. Other benefits result- ing from the use of appropriate antimicrobial substances include control and prevention of dandruff formation on the scalp.

DESCRIPTION

Surprisingly, it is found that a class of biomimic polymers (also known as facially amphiphilic polymers) can fulfill all such requirements. The discovery of such polymers and their use in treating articles made of wood, plastic, paper, rubber and glass has recently been disclosed in PCT Application WO 02/072007 and Proc. Natl. Acad. Sci. USA, Vol. 99, Issue 8, 5110- 5114, April 16, 2002. The content of these two disclosures is incorporated herein in their entirety.

This present the invention therefore relates to the use of an antimicrobially effective amount of a biomimic antimicrobial polymer in personal care preparations and to personal care preparations comprising at least one biomimic antimicrobial polymer and cosmetically-functional carriers or agents.

In one aspect the personal care preparation comprises a biomimic antimicrobial polymer of formula I

wherein

A and B are independently optionally substituted o-, m-, p-phenylene or optionally substituted heteroarylene wherein either (i) A and B are both substituted with a polar (P) group and a nonpolar (NP) group, (ii) one of A or B is substituted with a polar (P) group and a non- polar (NP) group and the other of A or B is substituted with neither a polar (P) group nor a nonpolar (NP) group, or (iii) one of A or B is substituted with one or two polar (P) group(s) and the other of A or B is substituted with one or two nonpolar (NP) group(s) , or (iv) one of A or B is substituted at the 2-position with a polar (P) group and at the 5- or 6-position with a nonpolar (NP) group and the other of A or B is substituted with a non- polar group; or,

A is as defined above and substituted with a polar (P) group and a nonpolar (NP) group, and

B is a group -C≡C-(CH₂)_P-C≡C- wherein p is as defined below; s is a direct bond, or represents a single, double or triple bond, or the group VI wherein t is O or S, which is optionally substituted with polar (P) and nonpolar (NP) groups;

R¹ is (i) halo and R² is hydrogen; or (ii) C-s-B-s- and R² is C; or, (iii) C-s- and R² is -A-s-C wherein C is pyridine or phenyl, said pyridine or phenyl being optionally substituted with I or 2 substituents independently selected from the group consisting of halo, nitro, cyano, CrCβalkoxy, C Cealkoxycarbonyl, and benzyloxycarbonyl; or,

R¹ and R² together are s;

NP is a nonpolar group and independently selected from R⁴ or -U-(CH₂)_P-R⁴ wherein R⁴ is selected from the group consisting of hydrogen, Cι-Cι₀alkyl, C₃-C₁₈ branched alkyl, C₃-C₈cycloalkyl, monocyclic or polycyclic aryl optionally substituted with one or more CrC alkyl or halo groups and monocyclic or polycyclic heteroaryl optionally substituted with one or more d-C₄alkyl or halo groups and U and p are as defined below;

P is a polar group selected from the group consisting of the group

(III) — U — (CH-₂) — V . hydroxyethoxymethyl, methoxyethoxymethyl and poly- oxyethylene wherein;

U is a direct bond or is selected from the group consisting of O, S, S(=O), S(=O)₂, NH, -C(=O)O-, -C(=O)NH-, -C(=O)S-, -C(=S)N-H-, -S(=O)₂NH-, and C(=NO-) wherein groups with two chemically nonequivalent termini can adopt both possible orientations;

V is selected from the group consisting of amino, hydroxyl, CrC₆alkylamino, C Cβdialkyl- amino, NH(CH₂)_PNH2, N(CH₂CH₂NH₂)2, amidine, guanidine, semicarbazone, basic het- erocycle, and phenyl optionally substituted with an amino, Ci-Cβalkylamino, CrC₆dial- kylamino and lower acylamino optionally substituted with one or more amino, lower al- kylamino or lower dialkylamino; and the alkylene chain is optionally substituted with an amino or hydroxyl group or unsaturated; p is independently 0 to 8; and, m is 2 to at least about 500. with the proviso that if A and B are thiophene the polar groups cannot be 3-(propionic acid) or methoxy(diethoxy)ethyl and the nonpolar group cannot be n-dodecyl.

In one embodiment the personal care preparation comprises a biomimic antimicrobial polymer of formula (I), wherein

A and B are independently optionally substituted o-, m- or p-phenylene; s is a direct bond or represents a single, double; or a triple bond; NP is a nonpolar group independently selected from R⁴ or -U-(CH₂)_P-R⁴, wherein

R⁴ is selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₃-C₁₂ branched alkyl,C₃-

C₈ cycloalkyl, phenyl optionally substituted with one or more C₁-C₄alkyl groups and het- eroaryl optionally substituted with one or more CrC₄alkyl groups and U and p are as defined below; P is a polar group selected from the group consisting of (III) — U— (CH-₂)_p — V , hy- droxyethoxymethyl, methoxyethoxymethyl and polyoxyethylene , wherein

U is a direct bond, O, S, SO, SO₂, or NH;

V is selected from the group consisting of amino, hydroxyl, Cι-C₆alkylamino,

CrC₆dialkylamino, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, amidine, guanidine, semicarbazone, imidazole, piperidine, piperazine, 4-alkylpiperazine and phenyl optionally substituted with an amino, CrCβalkylamino, Cι-C₆dialkylamino and lower acylamino optionally substituted with one or more amino, lower alkylamino or lower dialkylamino; the alkylene chain being optionally substituted with an amino or hydroxyl group or unsaturated; p is independently 0 to 8; and, m is 2 to at least about 500.

In another embodiment the personal care preparation comprises a biomimic antimicrobial polymer of formula (I), wherein

A and B are independently optionally substituted m-phenylene wherein (i) A is substituted at the 5-position with a nonpolar (NP) group and B is substituted at the 5-position with a nonpolar (P) group, (ii) A is substituted at the 2-position with a polar (P) and at the 5-position with a nonpolar (NP) group and B is substituted at the 2-position with a nonpolar (NP) group and at the 5-position with a polar (P) group, (iii) one of A or B is substituted at the 2-position with a polar group and the 5-position with a nonpolar group and the other of A or B is substituted by neither a polar group nor a nonpolar group; or, (iv) one of A or B is substituted at the 5-position with a polar group and the 2-position with a nonpolar group and the other of A or B is substituted by neither a polar group nor a nonpolar group; s is a direct bond or represents a single, double or a triple bond;

NP is a nonpolar group independently selected from R₄ or -U-(CH₂)_P-R₄, wherein

R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and sec-pentyl and U and p are as defined below; is a polar group U-(CH )_P-V wherein U is a direct bond or selected from the group consisting of O and S, and V is selected from the group consisting of amino, lower al- kylamino, lower dialkylamino, imidazole, guanidine, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, piperidine, piperazine and 4-alkylpiperazine;

P is independently 0 to 8; and m is 2 to at least about 500.

In another embodiment the personal care preparation comprises a biomimic antimicrobial polymer of formula

wherein

NP is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-butyl, sec-butyl, tert-butyl, n- pentyl, isopentyl or sec-pentyl; P is a polar group U-(CH₂)_P-V wherein U is O or S, p is 0 to 8 and V is selected from the group consisting of amino, lower alkylamino, lower dialkylamino, guanidine, pyridine, piperazine and 4-alkylpiperazine; p is 0 to 8; and, m is 2 to at least about 30.

wherein

As mentioned earlier, the facially amphiphilic polymers of the above formulae and their preparation are known per se.

The antimicrobials as described above are found to be very useful in many personal care compositions and more particularly in hair care and skin care compositions. These compositions will generally comprise at least one cosmetically-functional agent used in an amount effective to impart desired cosmetic properties to the personal care composition. The term "cosmetically-functional agent", as used herein, means any material, compound or composition applied to the hair or skin for cosmetic application thereof. -Exemplary agents include emollients, humectants, lubricants, UV-light inhibitors, preservatives, pigments, dyes, colorants, alpha-hydroxy acids, aesthetic enhancers such as starch, perfumes and fragrances, film formers (water proofing agent), antiseptics, antifungal, antimicrobial and other medicaments, solvents, surfactants, natural or synthetic polymers, hair conditioning agents and hair fixatives. Such cosmetically-functional agents include mineral oils, glycerin, beeswax, lanolin, acetylated lanolin, stearic acid, palmitic acid, cetyl alcohol, sodium salts of olefin sulfonates, various proteins, polymeric sugars, conditioning agents such as polyquaternium and hair fixatives such as poly(vinyl pyrrolidone) and N-vinyl formamide or polyvinyl formamide.

The cosmetically-functional agent may be present in the personal care composition in an amount of up to 60 weight percent based on the total weight of the personal care composition.

The personal care preparation according to the invention comprises from 0.01 to 15% by weight, preferably from 0.5 to 10% by weight, based on the total weight of the composition, of the facially amphiphilic biomimic antimicrobial polymer and cosmetically tolerable adjuvants.

Personal care compositions are for example shampoos, bath- and shower additives, hair- care products, wax fat compositions, liquid soaps, lotions, gels, cremes, deodorants, stick preparations, powders, ointments, other aqueous or alcoholic or aqueous/alcoholic solutions, for example cleaning solutions for the skin, moist cleaning sheets and oils.

Personal care compositions include a very wide range of products. Suitable products are, for example, especially the following: skin-care products, for example skin washing and cleansing products in the form of bars of soap or liquid soaps, syndets or washing pastes, bath products, for example liquid (foam baths, milks, shower products) or solid bath products, such as bath pearls and bath salts; skin-care products, such as skin emulsions, multiple emulsions or skin oils; decorative body-care products, for example face make-ups in the form of day or powder creams, face powders (lose and compressed), rouge or cream make-ups, eye-care products, for example eye shadow products, mascara, eyeliners, eye creams or eye-fix creams; lip-care products, for example lipstick, lip gloss, lip liner, nail-care products, such as nail varnish, nail varnish remover, nail hardeners or cuticle removers; feminine hygiene products, such as feminine hygiene washing lotions or sprays; foot-care products, for example foot baths, foot powders, food creams or foot balms, special deodorants and antiperspirants or products for scrubbing off callouses; sunscreens, such as sun milks, lotions, creams, oils, sunblockers or tropicals, pre-sun products or after-sun products; suntanning products, for example self-tanning creams; depigmenting products, for example products for bleaching or lightening skin; insect repellents, for example insect oils, lotions, sprays or sticks; deodorants, for example deodorant sprays, non-aerosol sprays, deodorant gels, sticks or roll-ons; antiperspirants, for example antiperspirant sticks, creams or roll-ons; products for cleansing and treating impure skin, for example syndets (solid or liquid), peeling or scrubbing products or peeling masks; chemical depilatory products, for example depilatory powders, liquid depilatory products, creamy or pasty depilatory products, depilatory gels or aerosol foams; shaving products, for example shaving soap, foaming shaving creams, non-foaming shaving creams, shaving foams and gels, preshaving products for dry shaving, aftershaves or aftershave lotions; scents, for example perfumes (Eau de Cologne, Eau de Toilette, Eau de Parfum, Parfum de Toilette, perfume), perfume oils or perfume creams; products for oral and dental hygiene as well as for dentures, for example toothpastes, tooth gels, tooth powders, mouth-wash concentrates, anti-plaque mouth-washes, denture cleaning products or denture adhesion products; cosmetic formulations for hair treatment, for example hair washes in the form of shampoos, hair conditioners, hair-care products, for example pretreatment products, hair tonics, hair styling creams and gels, pomades, hair rinses, deep conditioning treatments, intensive hair care treatments, hair setting products, for example waving agents for perms (hot wave, mild wave, cold wave), hair straightening products, liquid hair fixatives, hair foams, hair sprays, bleaching agents, for example hydrogen peroxide solutions, bleaching shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-temporary or permanent hair dyes, products containing self-oxidizing dyes, or natural hair dyes, such as henna or camomile.

The personal care compositions listed above can be in a very wide range of forms of presentation, for example in the form of liquid formulations as an oil-in-water (O/W) emulsion, in the form of a gel, in the form of an oil, cream, milk or lotion, in the form of a powder, lacquer, pellets or make-up, in the form of a stick or bar, in the form of a spray (spray with propellant or pumping spray) or an aerosol, in the form of a foam, or in the form of a paste.

When the personal care composition is a liquid formulation in the form of an oil-in-water (O/W) emulsion, the oil phase (oil-component) can be chosen from the following substance groups without limiting the kind of lipophilic ingredient to those substances:

Fattv alcohols:

Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoates of C₁₂-C₁₅ alcohols, acetylated lanolin alcohol, etc. Esters of fatt acids:

Esters of linear C₆-C₂₄ fatty acids with linear C₃-C₂₄ alcohols, esters of branched C₆-C₁₃carbo- xylic acids with linear C₆-C₂₄ fatty alcohols, esters of linear C₆-C₂₄ fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C₆-C₂₂ fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2- ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, pet- roselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, ga- doleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxo-synthesis and as monomer fractions in the dimerization of unsaturated fatty alcohols).

Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooc- tylstearate, iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, eru- cylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc.

Further oil components that can be used are dicarboxylic acid esters, such as diethylhexyl 2,6-naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelate, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C₆-C₂₄ fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C₂-Cι₂dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups.

Natural or synthetic triglycerides including glyceryl esters and derivatives: Di- or tri-glycerides, based on C₆-C₁₈ fatty acids, modified by reaction with other alcohols (caprylic capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil (Ricinus Communis), hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, etc.

Waxes:

This includes esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., camauba wax (Copernicia Cerifera), beeswax (white or yellow), lanolin wax, candellila wax (Euphorbia Cerifera), ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax.etc; also, hydrophilic waxes as cetearyl alcohol or partial glycerides.

Pearlescent waxes:

Alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyc- eride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof. Hvdrocarbon oils:

Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes, and polybu- tene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from the plant and animal kingdom.

Silicones or siloxanes (orqanosubstituted polvsiloxanes):

Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear polvsiloxanes: dimethicone such as Dow Corning^® 200 fluid, Mirasil^® DM (Rhodia), dimethiconol. Cyclic silicone fluids: cyclopentasiloxanes, volatiles such as Dow Corning^® 345 fluid, Sil- bione^® grade, Abil^® grade. Phenyltrimethicones; Dow corning^® 556 fluid. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).

Fluorinated or perfluorinated oils:

Perfluorhexane, dimethylcyclohexane, ethylcyclopentane (Flutec^® grades), polyperfluoro- methylisopropyl ether (Fomblin^® grades).

In an OAW-formulation the oil component is preferably present in an amount of from 5 wt-% to 50 wt-% and more preferably from 10 wt-% to 35 wt-%, based on the total weight of the personal care composition.

Emulsifiers:

Any conventionally usable emulsifier can be used for the personal care compositions. Emul- sifier systems may comprise for example: Carboxylic acids and their salts:

Alkaline soaps of sodium, potassium and ammonium; metallic soaps of calcium or magnesium; organic basis soaps such as lauric, palmitic, stearic and oleic acid, etc. Alkyl phosphates or phosphoric acid esters: acid phosphate, diethanolamine phosphate, potassium cetyl phosphate; ethoxylated carboxylic acids or polyethyleneglycol esters (PEG-n Acylates). Linear fatty alcohols having from 8 to 22 carbon atoms, products from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polygly- colethers such as Laureth-n, Ceteareth-n, Steareth-n, Oleth-n. Fatty acid polyglycol ethers such as PEG-n Stearate, PEG-n Oleate, PEG-n Cocoate; monoglycerides and polyol esters. C^-C^ fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols; fatty acid and polyglycerol esters such as monostearate glycerol, diisostearoyl polyglyceryl-3- diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2- sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycol esters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters; fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides; sorbitol and sorbitan: sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products; polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)- isostearate sorbitan, PEG-(10)-laurate sorbitan, PEG-17- dioleate sorbitan; glucose derivatives: Cβ-C∞ alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as Methyl Gluceth- 20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate.

Sulfates and sulfonated derivatives:

Dialkylsulfosuccinates (DOSS: dioctyl succinate), alkyl lauryl sulfonate, linear sulfonated paraffins, sulfonated tetrapropylene sulfonate, sodium lauryl sulfates, ammonium and ethanola- mine lauryl sulfates, lauryl ether sulfates, sodium laureth sulfates, sulfosuccinates, acetyl isothionates, alkanolamide sulfates such as taurines, methyl taurines, imidazole sulfates; Amine derivatives:

Amine salts, ethoxylated amines such as Oxide amine, with chains containing a heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinolines, cetyl pyridinium chloride, cetyl pyridinium bromide, quaternary ammoniums such as cetyltrimethylammonium bromide, Stearylalkonium; Amide derivatives: alkanolamides such as acylamide DEA, ethoxylated amides, such as PEG-n acylamide, oxydeamide;

Polysiloxane/polyalkyl/polyether copolymers and derivatives: dimethicone, copolyols, silicone polyethylene oxide copolymers and silicone glycol copolymers; Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block- poly(oxypropylene)_n-block(oxyethylene) copolymers;

Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N- dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethyl-carboxy- methylglycinate, N-alkylbetaine and N-alkylaminobetaines; Alkylimidazolines, alkylopeptides and lipoaminoacids;

Self emulsifying bases (see K.F. DePolo - A Short Textbook Of Cosmetology, Chapter 8, Table 8-7, p 250-251);

Non ionic bases such as PEG-6 Beeswax (and) PEG-6 Stearate (and) polyglyceryl -2 iso- stearate [Apifac], Glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 Glyceryl stearate [Arlatone 983 S], Sorbitan oleate (and) Polyglyceryl-3 Ricinoleate [Arlacel 1689], sorbitan stearate and sucrose cocoate [Arlatone 2121], Glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and Ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and Polysorbate 60 and PEG-150 and stearate-20 [Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and Ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl Alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and Steareth-7 and Steareth-10 [Emulgator E 2155], cetearyl Alcohol and Steareth-7 and Steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate [Hetester PCS], propylene glycol iso- ceth-3 acetate [Hetester PHA], cetearyl alcohol and Ceteth-12 and Oleth-12 [Lanbritol Wax N 21], PEG -6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and Ceteth-20 and Steareth-20 [Tefose 2000], PEG-6 Stearate and ceteth-20 and Glyceryl Stearate and steareth-20 [Tefose 2561], glyceryl stearate and Ceteareth-20 [Teginacid H, C, X]; Anionic alkaline bases such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD] and propylene glycol stearate [Tegin P];

Anionic acid bases such as cetearyl alcohol and sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], Trilaneth-4 phosphate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl sulfate [Teginacid Special]; and Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.

The emulsifiers may be used in an amount of, for example, from 1 wt-% to 30 wt-%, especially from 4 wt-% to 20 wt-% and preferably from 5 wt-% to 10 wt-%, based on the total weight of the composition.

When formulated in O/W emulsions, the amount of the emulsifier system preferably represents 5% to 20% by weight of the oil phase.

Adjuvants and additives.

The personal care compositions, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, super-fatting agents, consistency regulators, additional thickeners, polymers, stabilizers, bio- genic active ingredients, deodorizing active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilizers, perfume oils, colourants, bacteria-inhibiting agents and the like.

The adjuvants and additives may optionally be present in the personal care composition in an amount of, for example, from 0.1 wt-% to 25 wt-% based on the total weight of the composition.

Super-fatting agents:

Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilizers. Surfactants:

Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isothionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.

Consistency regulators/Additional Thickeners and Rheology modifiers: As additional thickeners and rheology modifiers, there come into consideration the groups of silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof, for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, Car- raghenan, gellan, pectins, or modified cellulose such as hydroxycellulose and hydroxypropyl- methylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and polyacrylamides, e.g. the Carbopol range (e.g. Carbopol types 980, 981 , 1382, EΞTD 2001, ETD2020, Ultrez 10; INCI: Carbomer) or the Ciba Salcare^® range such as Salcare^® SC80 (Steareth-10 allyl ether/acrylates copolymer), Salcare^® SC81 (acrylates copolymer), Salcare^® SC91 and Salcare^® AST (sodium acrylates copolymer/PPG-1 trideceth-6), Sepigel 305 (polyacrylamide/laureth-7), Simulgel NS and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates/vinyl isodecanoate crosspoly- mer), Pemulen TR-1 (acrylates/C₁₀-C₃o alkyl acrylate crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylate copolymer), etc.

Polymers:

Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternized hydroxymethyl cellulose obtainable under the name Polymer JR 400^® from Amer- chol, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinyl imidazole polymers, for example Luviquat^® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat^®lJGrϋnau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Car- taretin^®/Clariant), copolymers of acrylic acid with dimethyldiallylammonium chloride (Mer- quat^® 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2252 840, and the cross-linked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternized chitosan, optionally distributed as microcrystals; condensation products of di- haloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino- 1,3-propane, cationic guar gum, for example Jaguar^® C-17, Jaguar^® C-16 from Celanese, quaternized ammonium salt polymers, for example Mirapol^® A-15, Mirapol^® AD-1 , Mirapol^® AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids cross linked with polyols, acrylamidopropyltrimethylammonium chlo- ride/acrylate copolymers, octyl acrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, v ylpyrrolidone/dimethyl-aminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatized cellulose ethers and silicones. Furthermore the polymers as described in EP 1093796 (pages 3 - 8, paragraphs 17 - 68) may be used.

Bioqenic active ingredients:

Biogenic active ingredients are to be understood as meaning, for example, tocopherol, toco- pherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Deodorizing active ingredients:

As deodorizing active ingredients there come into consideration, for example, antiperspirants, for example aluminum chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® of Clariant, there is available commercially, for example, an aluminum chlorohydrate corresponding to formula AI₂(OH)₅CI x 2.5 H₂O, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminum hydroxyacetates and acidic aluminum/zirconium salts. Es- terase inhibitors may be added as further deodorizing active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen^® CAT, Henkel KGaA, Dϋsseldorf/GER), which inhibit enzyme activity and hence reduce odor formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Additional antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in deodorant stick preparations). -Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-Chloro-2- (2,4-dichlorophenoxy)-phenol (Irgasan^® DP 300, Ciba Specialty Chemicals Inc.) has proved especially effective.

Anti-dandruff agents:

As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc py- rithione.

Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.

Antioxidants:

The personal care product can optionally contain one or more antioxidants. Any common an- tioxidant can be used. Typical examples of such antioxidants are 4,4'-di-α-cumyl-diphenyl- amine, mono- and dialkylated tert-butyl/tert-octyl-diphenylamines, n-octadecyl 3,5-di-tert-bu- tyl-4-hydroxyhydrocinnamate, tetradibutyl pentaerythrityl-4-hydroxyhydrocinnamate, neo- pentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octa-decyl 3,5-di- tert-butyl-4-hydroxybenzylphosphonate, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)iso- cyanurate thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydro-cinnamate), 1 ,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5- tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert- butylphenol), 1 ,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocynurate, 1 ,1 ,3-tris(2- methyl-4-hydroxy-5-tert-butyl-phenyl)butane, 1 ,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydro- cinnamoyloxy)ethyl] iso-cyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexa- methylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1 -(3,5-di-tert-butyl-4-hydroxy- anilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydro- cinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmer- captoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hydrazide, N,N'-bis[2-(3,5-di- tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]oxamide, and N,N-dialkylhydroxylamine prepared from di(hydrogenated tallow)amine by direct oxidation.

Further suitable antioxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), ca- rotinoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and derivatives thereof, chloro- genic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmi- toyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. γ-hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), β-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hy- droxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionyl]-sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO₄), selenium and derivatives thereof (e.g. selenium methionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lip- ids) of HALS (="Hindered Amine Light Stabilizers") compounds may also be mentioned.

The amount of antioxidants present is usually from 0.001 wt-% to 25 wt-%, preferably from 0.01 wt-% to 3 wt-%, based on the weight of the personal care product.

Hvdrotropic agents:

To improve the flow behavior of the compositions it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of C-atoms or their ethers (e.g. ethanol, isopropanol, 1 ,2-dipropanediol, propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol mono- butyl ether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monobutyl ether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutyl ether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, al- kylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Daltons; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 wt-% to 50 wt-%; methylol compounds, such as, especially trimethylol- ethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower al- kyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanola- mine or 2-amino-1 ,3-propanediol.

Preservatives and Bacteria-inhibiting agents:

Suitable preservatives include, for example, methyl-, ethyl-, propyl-, butyl- parabens, ben- zalkonium chloride, 2-bromo-2-nitro-propane-1 ,3-diol, dehydroacetic acid, diazolidinyl urea, 2-dichloro-benzyl alcohol, DMDM hydantoin, formaldehyde solution, methyldibromoglutani- trile, phenoxyethanol, sodium hydroxymethylglycinate, imidazolidinyl urea and triclosan, and further substance classes listed in the following reference: K.:F.DePolo - A Short Textbook Of Cosmetology, Chapter 7, Tables 7-2, 7-3, 7-4 and 7-5, pp 210-219.

Bacteria-inhibiting agents:

Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Irgasan^® DP 300/Ciba), chlorhexidine (1 ,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-tri- chlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorizing agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent.

The amount of the additional bacteria-inhibiting agents present is usually from 0.1 wt-% to 2 wt-%, based on the solids content of the preparations.

Perfume oils:

There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petit- grain), from fruit (aniseed, coriander, caraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, scotch pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and cas- toreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citron- ellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeo- nal; the ketones include, for example, the ionones^ isomethylionone and methyl cedryl ke- tone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, li- nalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, α-hexyl cinnamal- dehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, am- broxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, ally) amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, α-damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.

Colorants:

There may be used as colorants any substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. The colorants are usually used in concentrations of from 0.001 wt-% to 0.1 wt-%, based on the total mixture.

Other adjuvants:

It is furthermore possible for the personal care composition to contain, as adjuvants, anti- foams, such as silicones, structurants, such as maleic acid, solubilizers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N₂O, dimethyl ether, CO₂, N₂ or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cys- teamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidizing agents, such as hydrogen peroxide, potassium bromate or sodium bromate. There come into consideration as insect repellents, for example, N,N-diethyl-m-toluamide, 1 ,2-pentanediol or insect repellent 3535; suitable self-tanning agents are, for example, dihy- droxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.

Ultraviolet Light Absorber:

Ultraviolet Light Absorbers (UV absorbers) are employed in cosmetics to protect the product from chemical or physical deterioration induced by ultraviolet light. Sunscreen Agents are OTC drug ingredients, which protect the skin from ultraviolet light. UV absorbers, like sunscreen agents, have the ability to convert incident ultraviolet radiation into less damaging infrared radiation (heat).

Suitable UV absorbers are, for example:

Acetaminosalol, allantoin PABA, Benzalphthalide, benzophenone, Benzophenone-1 , Benzo- phenone-2, Benzophenone-3, Benzophenone-4, Benzophenone-5, Benzophenone-6, Ben- zophenone-7, Benzophenone-8, Benzophenone-9, Benzophenone-10, Benzophenone-11 , Benzophenone-12, benzotriazolyl dodecyl p-cresol, 3-benzylidene camphor, benzylidene- camphor hydrolyzed collagen sulfonamide, benzylidene camphor sulfonic acid, benzyl salicy- late, bis-ethylhexyloxyphenol methoxyphenyl triazine, bornelone, bumetrizole, butyl meth- oxydibenzoylmethane, Butyl PABA, Callophyllum Inophyllum seed oil, Camellia Sinensis leaf extract, carotenoids, Ceria/Silica, Ceria/Silica talc, Cinoxate, DEA-methoxycinnamate, diben- zoxazoyl naphthalene, di-t-butyl hydroxybenzylidene camphor, diethylhexyl butamido tria- zone, diethylhexyl 2,6-naphthalate, digalloyl trioleate, diisopropyl methyl cinnamate, 1 -(3,4- dimethoxyphenyl)-4,4-dimethyl-1 ,3-pentanediene, dimethyl PABA, ethyl cetearyldimonium tosylate, dimorpholinopyridazinone, diphenyl carbomethoxy acetoxy naphthopyran, disodium bisethylphenyl triaminotriazine stilbenedisulfonate, disodium distyrylbiphenyl disulfonate, disodium phenyl dibenzimidazole tetrasulfonate, Drometrizole, Drometrizole Trisiloxane, Es- culin, ethyl dihydroxypropyl PABA, ethyl diisopropylcinnamate, ethylhexyl dimethoxybenzyli- dene dioxoimidazolidine propionate, ethylhexyl dimethyl PABA, ethylhexyl Ferulate, ethylhexyl methoxycinnamate, ethylhexyl salicylate, ethylhexyl triazone, ethyl methoxycinnamate, ethyl PABA, ethyl urocanate, Etocrylene, Ferulic Acid, 4-(2-beta-glucopyranosiloxy) propoxy- 2-hydroxybenzophenone, glyceryl ethylhexanoate dimethoxycinnamate, glyceryl PABA, glycol salicylate, hexanediol salicylate, homosalate, hydrolyzed lupine protein, isoamyl p- methoxycinnamate, isopentyl trimethoxycinnamate trisiloxane, isopropylbenzyl salicylate, isopropyl dibenzoylmethane, isopropyl methoxycinnamate, menthyl anthranilate, menthyl salicylate, 4-methylbenzylidene camphor, methylene bis-benzotriazolyl tetramethylbutylphe- nol, octocrylene, octrizole, PABA, PEG-25 PABA, pentyl dimethyl PABA, phenylbenzimida- zole sulfonic acid, Pinus Pinaster bark extract, polyacrylamidomethyl benzylidene camphor, Polysilicone-15, potassium methoxycinnamate, potassium phenylbenzimidazole sulfonate, red petrolatum, sodium benzotriazolyl butylphenol sulfonate, sodium isoferulate, sodium phenylbenzimidazole sulfonate, sodium urocanate, Spirulina Platensis Powder, TEA-phenyl- benzimidazole sulfonate, TEA-salicylate, terephthalylidene dicamphor sulfonic acid, tetrabu- tyl phenyl hydroxybenzoate, titanium dioxide, tocotrienols, TriPABA Panthenol, urocanic acid, VA/crotonates/methacryloxybenzophenone-1 copolymer and Vitis Vinifera (grape) seed extract.

Sunscreen compositions may contain polymeric beads or hollow spheres as SPF enhancers. The combination of UV-absorbers as described above, with SPF enhancers, such as non- active ingredients like styrene/acrylate copolymers, silica beads, spheroidal magnesium silicates, spherical polyamide powders such as n-lactam polymers (Orgasol^® range, Elf Ato- chem) cross linked polymethyl methacrylates (PMMA; Micopeari M305 Seppic), can enhance the UV protection of the sun products. Holosphere additives (Sunspheres^® ISP, Silica Shells Kobo.) deflect radiation, and the effective path length of a photon is therefore increased (see EP0893119). Some beads provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g. Micropearl M305, can modulate skin shine by eliminating reflection phenomena and indirectly may scatter UV light. When formulated in O W sunscreen emulsions, preferably the amount of such SPF enhancers should represent 1 wt-% to 10 wt-% of the total amount of the personal care composition.

A typical O/W- based antimicrobial personal care composition comprises:

0.05 to 10 wt-% of at least one biomimic antimicrobial polymer,

0.5 - 10 wt-% of other suitable non-antimicrobial polymers or copolymers,

2 - 25 wt-% of at least one oil-component,

0 - 25 wt-% of at least one other adjuvant and/or additive, water up to 100 wt-%.

A typical oil-based antimicrobial personal care composition comprises: 0.05 to 10 wt-% of at least one biomimic antimicrobial polymer 0.5 - 10 wt-% of other suitable non-antimicrobial polymers or copolymers,

50 - 99 wt-% of at least one oil-component,

0 - 25 wt-% of at least one other adjuvant and or additive.

An antimicrobial soap has, for example, the following composition:

0.05 to 10 wt-% of at least one biomimic antimicrobial polymer,

0.5 - 10 wt-% of other suitable non-antimicrobial polymers or copolymers,

0.3 to 1 % wt-% of titanium dioxide,

1 to 10% wt-% of stearic acid, to 100 wt-% of soap base, for example the sodium salts of tallow fatty and coconut fatty acid or glycerols.

An antimicrobial shampoo has, for example, the following composition:

0.05 to 10 wt-% of at least one biomimic antimicrobial polymer,

0.5 - 10 wt-% of other suitable non-antimicrobial polymers or copolymers,

12.0% wt-% of sodium laureth-2-sulfate,

4.0% wt-% of cocamidopropylbetaine,

3.0% wt-% of NaCl and water to 100 wt-%.

An antimicrobial deodorant has, for example, the following composition:

0.05 to 10 wt-% of at least one biomimic antimicrobial polymer

0.5 - 10 wt-% of other suitable non-antimicrobial polymers or copolymers,

60% by weight of ethanol,

0.3% by weight of perfume oil and water to 100%.

The invention relates also to an oral care composition containing from 0.01 to 15 % by weight, based on the total weight of the composition, of a at least one biomimic antimicrobial polymer and orally tolerable adjuvants.

The oral hygiene composition may comprise an additional antibacterial enhancing agent, for example an anionic polymeric polycarboxylate, a dehydrated polyphosphate salt, a compound which provides a source of fluoride ions, a polishing material, including siliceous mate- rial or sodium bicarbonate, an orally acceptable vehicle, including a water-phase with humec- tants, thickeners, surface-active agents and a flavoring or sweetening material.

An oral antimicrobial composition has, for example, the following composition:

10 % by weight sorbitol,

10 % by weight glycerol,

15 % by weight ethanol,

15 % by weight propylene glycol,

0.5 % by weight sodium lauryl sulfate,

0.25 % by weight sodium methylcocyl taurate,

0.25 % by weight polyoxypropylene/polyoxyethylene block copolymer,

0.10 % by weight peppermint flavoring,

0.1 to 0.5 % by weight of a biomimic antimicrobial polymer, 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 polymer is also useful in washing and cleaning formulations, e.g. in liquid or powder washing agents or softeners, and 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 of at least one biomimic antimicrobial polymer,

3.0 % by weight octyl alcohol 4EO,

1.3 % by weight fatty alcohol C₈-C₁₀polyglucoside,

3.0 % by weight isopropanol, and water ad 100 %. ln addition to preserving cosmetic and household products, the preservation of technical products, the provision of technical products with antimicrobial properties and use as a biocide 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 biomimic antimicrobial polymers are also suitable for the antimicrobial treatment of leather, the preserving of leather and the provision of leather with antimicrobial properties.

The biomimic antimicrobial polymers are also suitable for the protection of cosmetic products and household products from microbial damage.

The following examples describe certain embodiments of this invention, but the invention is not limited thereto. It should be understood that numerous changes to the disclosed embodiments could be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. These examples are therefore not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. In these examples all parts given are by weight unless otherwise indicated.

Example 1 : Preparation of polymer (A):

Biomimic antimicrobial polymers can be prepared as disclosed in PCT/US02/06899 and other related disclosures. The preparation of poly (phenylene ethynylene) is typical of the procedure for such a preparation and has been described as follows:

A dried air-free flask is charged with m-diethynyl-benzene (0.037 g, 0.284 mmole), amyl-2,6- diiodo-4-cyanophenyl ether (0.157 g, 0.275 mmole, 1.00 eq), 3 mol % Pd(PPh₃)₄ (0.009g), Cul (0.003 g, 0.017 mmole), 5 ml toluene, and 2 ml diisopropylamine. The solution is flushed under nitrogen with stirring, and then placed in an oil bath at 70° C for 12 hours. The solution is poured into rapidly stirring methanol and the precipitate collected. After drying overnight in vacuum oven, the molecular weight of the protected polymer 5 is determined.

1a: NP= CH₂CH₂CH₂CH₂CH₃. P = benzyl amine, Mn = 17,400, PDI = 2.2.

1b:NP= (S)-CH₂CH(CH₃)CH₂CH₃, P = benzyl amine, Mn = 9,780, PDI= 1.4.

The polymer (50 mg) is taken up in 4M HCI/dioxane at 0 °C and then allowed to warm to room temperature for 12 h. The solvent is removed in vacuuo and the solid triturated with ether three times before drying overnight.

Examples 2-13:

The following examples describe typical non-limiting formulations of personal care products containing biomimic antimicrobial polymer (A). All percents are by weight.

Example 2: Preparation of a Svndet (detergent formulation)

Components:

15.7% of alkylarylsulfonate,

3.7% of fatty alcohol sulfonate,

2.7% of fatty acid monoethanolamide,

39% of tripolyphosphate,

4% of sodium silicate,

2% of magnesium silicate,

1% of carboxymethylcellulose,

0.5% of EDTA,

2% of biomimic antimicrobial polymer and

4.7% of water. Preparation:

The ingredients are stirred with equivalent amounts of water to form a slurry. The resultant paste is dried at 50° C and finally pressed through a sieve with a mesh diameter of 0.8 mm. Particles <0.3 mm are discarded.

Example 3: Preparation of a Dishwashing Product

Components:

7 parts of sodium lauryl sulfate,

7 parts of sodium myreth sulfate,

4 parts of lauryl glucoside,

1 parts of cocamidopropylbetaine,

1 parts of the biomimic antimcirobial polymer,

1 parts of sodium chloride,

0.02 parts of dibromodicyanobutane,

0.08 parts of phenoxyethanol and

78.9 parts of water.

Preparation:

Sodium lauryl sulfate is mixed with sodium myreth sulfate and lauryl glucoside and dissolved in 30 parts of water. The biomimic antimicrobial polymer (A) is added and homogenized. Cocamidopropylbetaine, sodium chloride, dibromodicyanobutane and phenoxyethanol are added. The pH is adjusted to 6.0 with citric acid. Water is added to give 100 parts.

Example 4: Preparation of a Hand Disinfectant

Components:

4 parts of sodium lauryl sulfate,

0.5 parts of hydroxyethylcellulose,

3 parts of the biomimic antimicrobial polymer, to 100 parts with water.

Preparation:

Sodium lauryl sulfate is dissolved in 20 parts of water and the biomimic antimicrobial polymer is added. Hydroxyethylcellulose is dissolved in 60 parts of water at 60° C. The mixture is cooled down and added to the surfactant mixture. The pH is adjusted to 5.5 with monoetha- nolamine. Water is added to give 100 parts.

Example 5: Preparation of a Shower Gel

Components:

6% of sodium laureth-2 sulfate,

3% of cocamidopropylbetaine,

1.5% of hydrolysed protein,

1.5% of laureth-9,

0.3% of polyquaternium-7,

1% of biomimic antimicrobial polymer,

1.0% of glycol distearate,

0.2% of sodium chloride, to 100% with water.

Example 6: Antimicrobial Facial Moisturizer

Example 8: Antimicrobial Spray Moisturizer

Example 9: Antimicrobial Leave-On Hair Conditioner (without silicone)

Example 10: Antimicrobial Hair Conditioner (with Silicone)

Example 11 : Antimicrobial Rinse-Off Hair Conditioner

Example 12: Anti-Acne Skin Cream

Example 13: Detection of the Microbicidal Activity of Biomimic Antimicrobial Polymers 1a and 1 b in a Suspension Test

13-a. Evaluation of the Polymers as Disinfectants

These tests are designed to show that the biomimic polymer as prepared according to Example 1 has microbicidal activity. These properties are important for personal care applications where disinfection is of importance.

Procedure

0.5 ml of the polymer formulation is diluted with 8.5 ml of water and the dilution is subsequently treated with 1 ml of a 1:10 dilution of a culture of the test bacteria which is incubated for 16 to 24 hours at 37° C.

The concentration of the test organisms in the batch is 10⁸ microorganisms/ml. The batch is mixed thoroughly and subsequently incubated for 5 minutes at room temperature with gentle stirring. After 30 minutes, 1 ml of the batch is removed and the live bacterial count is determined. To this end, dilutions are performed in dilution medium, and 0.1 ml each of these dilutions are plated onto agar media.

The live bacterial count is determined after the plates have been incubated for 24 to 48 hours at 37° C by counting the colonies taking into consideration the dilution factor.

13-b. Liquid Soap with a Concentrated Formulation Comprising the Polymer The tests of -Example 13-b are designed to show that soap formulations to which the biomimic antimicrobial polymers 1 a and 1b are added have microbicidal activity, which is required for use as a disinfectant or decontaminant for hands. Test formulation: 4 parts of sodium lauryl sulfate, 10 parts of biomimic antimicrobial polymer 1a or 1b, and to 100 parts with water.§

The pH of the mixture is brought to 5.5 using ethanolamine.

Procedure:

9 ml of the test formulation are mixed with 1 ml of a 1:10 dilution of a bacterial suspension which has been incubated at 37° C for 16 to 24 hours, and the mixture is subsequently incubated at room temperature with stirring.

After an incubation time of 1 minute, 1 ml of the test batch is removed, diluted in dilution medium, and 0.1 ml each of the dilutions are plated onto agar media.

After the plates have been incubated for 24 to 48 hours at 37° C, the live microbial count is determined by counting the colonies taking into consideration the dilution factor.

A log reduction of test microorganisms of >5 after 1 minute shows a very powerful microbicidal activity against the microorganisms tested.

Example 14: Preservative Stress Tests with Liouid Soaps

Repetitive preservative stress tests (triple stress) are designed to demonstrate that compositions comprising the biomimic antimicrobial polymer are highly suitable for the preservation of cosmetics and household articles. Soap formulation:

6% of sodium laureth-2 sulfate, to 100% with water.

The pH is brought to 5.5 with monoethanolamine.

The soap formulation is preserved with 2% and 3% of a biomimic antimicrobial polymer respectively :

Test microorganisms: Staphylococcus aureus ATCC 9144 Escherichia coli ATCC 10536 Enterobacter gergoviae ATCC 33028 Klebsiella oxytoca DSM 30106 Pseudomonas aeruginosa CIP A-22 Pseudomonas fluorescens ATCC 17397 Candida albicans ATCC 10231 Aspergillus niger ATCC 6275

Nutrient media:

Casein soy flour peptone agar with 3% polyoxyethylene(20) sorbitan monooleate; 0.3% lecithin; 0.1% L-histidine for bacteria and yeasts.

Dilution media:

Trypticase soy flour peptone broth with 10% polyoxyethylene(20)sorbitan monooleate;

3% lecithin; 0.1% L-histidine and 0.5% sodium thiosulfate.

Procedure:

20 g of the soap formulation in question are inoculated with 0.2 ml of a microorganism suspension in such a way that the resulting microbial stress of the product is 10⁵ to 10⁶ microor- ganisms/g of product. ln order to determine the total microbial count at a particular point in time, 1 g of material is removed, and a dilution series is established in dilution medium. The total microbial count is determined by pipetting 0.1 ml of the dilutions onto agar media after incubation at 37° C for 24 hours (bacteria and yeasts) or incubation at 28° C for 5 days (Aspergillus).

The total bacterial count in the product is determined after inoculation and also after 1 and 2 weeks. After 2 and 4 weeks, the product is again inoculated in the same manner with test microorganisms, and the total microbial counts are determined after a further 1 and 2 weeks in each case.

A reduction of total bacterial count of at least 99% in the course of 2 weeks after inoculation indicates high antimicrobial effectiveness.

Claims

WHAT IS CLAIMED IS:

1. A personal care composition which provides antimicrobial surface protection to hair, skin or teeth, comprising an antimicrobially effective amount of a biomimic antimicrobial polymer and at least one cosmetically-functional agent.

2. A composition according to claim 1 , wherein the biomimic antimicrobial polymer is a compound of formula

(I) (vi). wherein

A is as defined above and substituted with a polar (P) group and a nonpolar (NP) group, and B is a group -C≡C-(CH₂)_P-C≡C- wherein p is as defined below; s is a direct bond, or represents a single, double or triple bond, or the group VI wherein t is O or S, which is optionally substituted with polar (P) and nonpolar (NP) groups;

R¹ is (i) halo and R² is hydrogen; or (ii) C-s-B-s- and R² is C; or, (iii) C-s- and R² is -A-s-C wherein C is pyridine or phenyl, said pyridine or phenyl being optionally substituted with I or 2 substituents independently selected from the group consisting of halo, nitro, cyano, CrCβalkoxy, Cι-C₆alkoxycarbonyl, and benzyloxycarbonyl; or, R¹ and R² together are s;

NP is a nonpolar group and independently selected from R⁴ or -U-(CH₂)_P-R⁴ wherein R⁴ is selected from the group consisting of hydrogen, Cι-C₁₀alkyl, C₃-C₁₈ branched alkyl, C₃-C₈cycloalkyl, monocyclic or polycyclic aryl optionally substituted with one or more Cι-C₄alkyl or halo groups and monocyclic or polycyclic heteroaryl optionally substituted with one or more C C^lkyl or halo groups and U and p are as defined below;

P is a polar group selected from the group consisting of the group (III),

— U-(CH-₂)_p — V (III) hydroxyethoxymethyl, methoxyethoxym ethyl and polyoxyethylene wherein;

U is a direct bond or is selected from the group consisting of O, S, S(=O), S(=O) , NH, -C(=O)O-, -C(=O)NH-, -C(=O)S-, -C(=S)N-H-, -S(=O)₂NH-, and C(=NO-) wherein groups with two chemically nonequivalent termini can adopt both possible orientations;

V is selected from the group consisting of amino, hydroxyl, C Cealkyiamino, C

C₆dialkylamino, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, amidine, guanidine, semicarbazone, basic heterocycle, and phenyl optionally substituted with an amino, Cι-C₆alkylamino, C Cβdialkylamino and lower acylamino optionally substituted with one or more amino, lower alkylamino or lower dialkylamino; and the alkylene chain is optionally substituted with an amino or hydroxyl group or unsaturated; p is independently 0 to 8; and, m is 2 to at least about 500. with the proviso that if A and B are thiophene the polar groups cannot be 3-(propionic acid) or methoxy(diethoxy)ethyl and the nonpolar group cannot be n-dodecyl.

3. A composition according to claim 1 , wherein the biomimic antimicrobial polymer is a compound of formula (l), wherein

A and B are independently optionally substituted o-, m- or p-phenylene; s is a direct bond or represents a single, double; or a triple bond; NP is a nonpolar group independently selected from R⁴ or -U-(CH₂)_P-R⁴, wherein R⁴ is selected from the group consisting of hydrogen, C C alkyl, C₃-C₁₂ branched alkyl,C₃- C₈ cycloalkyl, phenyl optionally substituted with one or more CrC₄alkyl groups and het- eroaryl optionally substituted with one or more C dalkyl groups; and U and p are as defined below; P is a polar group selected from the group consisting of (III) — U — (CH-₂)_p — V , hy- droxyethoxymethyl, methoxyethoxymethyl and polyoxyethylene wherein

U is a direct bond, O, S, SO, SO₂, or NH;

V is selected from the group consisting of amino, hydroxyl, CrC₆alkylamino,

CrCβdialkylamino, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, amidine, guanidine, semicarbazone, imidazole, piperidine, piperazine, 4-alkylpiperazine and phenyl optionally substituted with an amino, d-Cβalkylamino, C_rC₆dialkylamino and lower acylamino optionally substi- tuted with one or more amino, lower alkylamino or lower dialkylamino; the alkylene chain being optionally substituted with an amino or hydroxyl group or unsaturated; p is independently 0 to 8; and, m is 2 to at least about 500.

4. A composition according to claim 1 , wherein the biomimic antimicrobial polymer is a compound of formula (i), wherein

A and B are independently optionally substituted m-phenylene wherein (i) A is substituted at the 5-position with a nonpolar (NP) group and B is substituted at the 5-position with a nonpolar (P) group, (ii) A is substituted at the 2-position with a polar (P) and at the 5- position with a nonpolar (NP) group and B is substituted at the 2-position with a nonpolar (NP) group and at the 5-position with a polar (P) group, (iii) one of A or B is substituted at the 2-position with a polar group and the 5-position with a nonpolar group and the other of A or B is substituted by neither a polar group nor a nonpolar group; or, (iv) one of A or B is substituted at the 5-position with a polar group and the 2-position with a nonpolar group and the other of A or B is substituted by neither a polar group nor a nonpolar group; s is a direct bond or represents a single, double or a triple bond;

NP is a nonpolar group independently selected from R₄ or -U-(CH₂)_P-R₄ wherein

R₄ is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and sec-pentyl and U and p are as defined below;

P is a polar group U-(CH₂)_P-V wherein U is a direct bond or selected from the group consisting of O and S, and V is selected from the group consisting of amino, lower alkylamino, lower dialkylamino, imidazole, guanidine, NH(CH₂)_PNH₂₎ N(CH₂CH₂NH₂)₂, piperidine, piperazine and 4-alkylpiperazine;

P is independently 0 to 8; and m is 2 to at least about 500.

5. A composition according to claim 1, wherein the biomimic antimicrobial polymer is a com¬

pound of formula (XIX) , wherein

6. A composition according to claim 1 , wherein the biomimic antimicrobial polymer is a compound of formula

wherein

7. A composition according to claim 1 , which is selected from the group consisting of skin washing and cleansing products in the form of bars of soap or liquid soaps, syndets or wash- ing pastes; liquid and solid bath auxiliary products; skin-care products; decorative body-care products in the form of powder or cream facial make-up, eye-care products, lip-care products or nail-care products; feminine hygiene products, foot-care products, sunscreen products, self-tanning creams and lotions, depigmenting products, insect repellents, deodorants and antiperspirants in the form of aerosol sprays, non-aerosol sprays, gels, creams, sticks or roll- ons; products for treating skin, in the form of peeling or scrubbing products or peeling masks; chemical depilatory products, shaving products in the form of shaving soaps, foaming shaving creams, non-foaming shaving creams, shaving foams and gels, preshaving products for dry shaving, aftershaves or aftershave lotions; fragrances; products for oral and dental hygiene as well as for dentures, in the form of toothpastes, tooth gels, tooth powders, mouth- wash concentrates, anti-plaque mouth-washes, denture cleaning products or denture adhesion products, and hair treatment products in the form of shampoos, hair conditioners, hair pretreatment products, hair tonics, hair styling creams and gels, pomades, hair rinses, deep conditioning treatments, intensive hair care treatments, hair setting products in the form of waving agents for hair permanents, hair straightening products, liquid hair fixatives, hair foams, hair sprays, hair bleaching agents in the form of bleaching shampoos, bleaching creams, bleaching powders, bleaching pastes or oils and temporary, semitemporary or permanent hair dyes.

8. A composition according to claim 1, which is a liquid formulation in the form of an oil-in- water emulsion, a gel, oil, cream, milk, lotion, foam; an aerosol or non-aerosol spray, or is in the form of a paste, a powder or a solid stick or bar.

9. A composition according to claim 1 , which is an oral hygiene composition.

10. A composition according to claim 9, wherein the oral hygiene composition comprises at least one of an additional antibacterial enhancing agent in the form of an anionic polymeric polycarboxylate or a dehydrated polyphosphate salt; a compound which provides a source of fluoride ions or a polishing material, in an orally acceptable vehicle which includes a water phase with humectants, thickeners, surface-active agents and a flavoring or sweetening material.

11. A composition according to claim 1 , which comprises 0.01 to 15% by weight of an antimicrobially effective biomimic antimicrobial polymer.

12. A composition according to claim 1, wherein the cosmetically-functional agent comprises at least one emollient, humectant, lubricant, UV-light inhibitor, preservative, pigment, dye, colorant, alpha-hydroxy acid, aesthetic enhancer, film former, antiseptic, antifungal, antimicrobial or other medicament, solvent, surfactant, natural or synthetic polymer, hair conditioning agent or hair fixative.

13. A method of providing antimicrobial protection to surfaces selected from the group consisting of hair, skin or teeth, which comprises contacting said surfaces with a personal care preparation comprising an antimicrobially effective amount of a biomimic antimicrobial polymer and at least one cosmetically-functional agent.

14. A method according to claim 13, wherein the biomimic antimicrobial polymer is a compound of formula I

(I) (VI) . wherein

A is as defined above and substituted with a polar (P) group and a nonpolar (NP) group, and B is a group -C≡C-(CH₂)_P-C≡C- wherein p is as defined below;

S is a direct bond, or represents a single, double or triple bond, or the group VI wherein t is O or S, which is optionally substituted with polar (P) and nonpolar (NP) groups;

R¹ is (i) halo and R² is hydrogen; or (ii) C-s-B-s- and R² is C; or, (iii) C-s- and R² is -A-s-C wherein C is pyridine or phenyl, said pyridine or phenyl being optionally substituted with I or 2 substituents independently selected from the group consisting of halo, nitro, cyano, C-ι-C₆alkoxy, C C₆alkoxycarbonyl, and benzyloxycarbonyl; or, R¹ and R² together are s; NP is a nonpolar group and independently selected from R⁴ or -U-(CH₂)_P-R⁴ wherein R⁴ is selected from the group consisting of hydrogen, CrCι₀alkyl, C₃-C₁₈ branched alkyl, C₃-C₈cycloalkyl, monocyclic or polycyclic aryl optionally substituted with one or more Cι-C₄alkyl or halo groups and monocyclic or polycyclic heteroaryl optionally substituted with one or more C C alkyl or halo groups and U and p are as defined below;

P is a polar group selected from the group consisting of the group

(III) U (CH-₂)_p — V , hydroxyethoxymethyl, methoxyethoxymethyl and polyoxyethylene, wherein

V is selected from the group consisting of amino, hydroxyl, d-Cβalkylamino, C_r

C₆dialkylamino, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, amidine, guanidine, semicarbazone, basic heterocycle, and phenyl optionally substituted with an amino, Cι-C₆alkylamino, C C₆dialkylamino and lower acylamino optionally substituted with one or more amino, lower alkylamino or lower dialkylamino; and the alkylene chain is optionally substituted with an amino or hydroxyl group or unsaturated;

P is independently 0 to 8; and, m is 2 to at least about 500. with the proviso that if A and B are thiophene the polar groups cannot be 3-(propionic acid) or methoxy(diethoxy)ethyl and the nonpolar group cannot be n-dodecyl.

15. A method according to claim 13, wherein the biomimic antimicrobial polymer is a compound of formula (I), wherein

A and B are independently optionally substituted o-, m- or p-phenylene; s is a direct bond or represents a single, double; or a triple bond; NP is a nonpolar group independently selected from R⁴ or -U-(CH₂)_P-R⁴, wherein R⁴ is selected from the group consisting of hydrogen, C C₄ alkyl, C₃-C₁₂ branched alkyl,C₃- C₈ cycloalkyl, phenyl optionally substituted with one or more Cι-C₄alkyl groups and heteroaryl optionally substituted with one or more d-C-talkyl groups and U and p are as defined below;

P I s a polar group selected from the group consisting of formula

(III) U (CH^" ₂)_p — V , hydroxyethoxymethyl, methoxyethoxymethyl and polyoxyethylene , wherein U is a direct bond, O, S, SO, SO₂, or NH;

V is selected from the group consisting of amino, hydroxyl, CrC₆alkylamino,

Cι-C₆dialkylamino, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, amidine, guanidine, semicarbazone, imidazole, piperidine, piperazine, 4-alkylpiperazine and phenyl optionally substituted with an amino, CrC₆alkylamino, d-Cedialkylamino and lower acylamino optionally substituted with one or more amino, lower alkylamino or lower dialkylamino; the alkylene chain being optionally substituted with an amino or hydroxyl group or unsaturated;

P is independently 0 to 8; and, m is 2 to at least about 500.

16. A method according to claim 13, wherein the biomimic antimicrobial polymer is a compound of formula (I), wherein

A and B are independently optionally substituted m-phenylene wherein (i) A is substituted at the 5-position with a nonpolar (NP) group and B is substituted at the 5-position with a nonpolar (P) group, (ii) A is substituted at the 2-position with a polar (P) and at the 5- position with a nonpolar (NP) group and B is substituted at the 2-position with a nonpolar (NP) group and at the 5-position with a polar (P) group, (iii) one of A or B is substituted at the 2-position with a polar group and the 5-position with a nonpolar group and the other of A or B is substituted by neither a polar group nor a nonpolar group; or, (iv) one of A or B is substituted at the 5-position with a polar group and the 2-position with a nonpolar group and the other of A or B is substituted by neither a polar group nor a nonpolar group; s is a direct bond or represents a single, double or a triple bond; NP is a nonpolar group independently selected from R₄ or -U-(CH₂)_P-R₄, wherein R₄ is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and sec-pentyl and U and p are as defined below; P is a polar group U-(CH₂)_P-V wherein U is a direct bond or selected from the group consisting of O and S, and V is selected from the group consisting of amino, lower alkylamino, lower dialkylamino, imidazole, guanidine, NH(CH₂)_PNH₂, N(CH₂CH₂NH₂)₂, piperidine, piperazine and 4-alkylpiperazine; P is independently 0 to 8; and m is 2 to at least about 500.

17. A method according to claim 13, wherein the biomimic antimicrobial polymer is a compound of formula

(XIX) , wherein

18. A method according to claim 13, wherein the biomimic antimicrobial polymer is a compound of formula

(XX) wherein

19. A method according to claim 13, wherein the personal care preparation comprises 0.01 to 15% by weight of an antimicrobially effective biomimic antimicrobial polymer.

20. A method according to claim 13, wherein the cosmetically-functional agent comprises at least one emollient, humectant, lubricant, UV-light inhibitor, preservative, pigment, dye, colorant, alpha-hydroxy acid, aesthetic enhancer, film former, antiseptic, antifungal, antimicrobial or other medicament, solvent, surfactant, natural or synthetic polymer, hair conditioning agent or hair fixative.