except in the operating and comparative examples , or where otherwise explicitly indicated , all numbers in this description indicating amounts of material or conditions of reaction , physical properties of materials and / or use are to be understood as modified by the word “ about .” all amounts are by weight of the oil - in - water emulsion , unless otherwise specified . cosmetic compositions within the scope of the invention are generally personal care compositions including but not limited to skin care compositions ( leave - on or rinse - off ), hair care compositions ( shampoos and conditioners and hair tonics ), dentifrices ( toothpastes and mouthwashes ), and lipsticks and color cosmetics . inventive compositions may be in the form of lotions , creams , gels , soap bars , shower gels , toners , and face masks . the preferred compositions are skin care compositions , in order to deliver anti - sebum benefit to the skin . the term “ skin ” as used herein includes the skin on the face , neck , chest , back , arms , hands , legs and scalp . selected from the group consisting of compounds a through h as follows : the substituted iminodibenzyl or fluorine compounds are employed in the present invention in an amount of from 0 . 0001 % to 50 %, preferably from 0 . 0001 % to 10 %, most preferably from 0 . 0001 % to 5 %. the substituted iminodibenzyl or fluorine compounds can be obtained from new chemical entities , inc . ( bothell , wash .). the compositions according to the invention comprise a cosmetically acceptable vehicle to act as a diluant , dispersant or carrier for the substituted iminodibenzyl or fluorine compounds in the composition , so as to facilitate its distribution when the composition is applied to the substrate . the vehicle may be aqueous , anhydrous or an emulsion . preferably , the compositions are aqueous or an emulsion , especially water - in - oil or oil - in - water emulsion . water when present will be in amounts which may range from 5 to 99 %, preferably from 40 to 90 %, optimally between 60 and 90 % by weight . besides water , relatively volatile solvents may also serve as carriers within compositions of the present invention . most preferred are monohydric c 1 - c 3 alkanols . these include ethyl alcohol , methyl alcohol and isopropyl alcohol . the amount of monohydric alkanol may range from 1 to 70 %, preferably from 10 to 50 %, optimally between 15 and 40 % by weight . emollient materials may also serve as cosmetically acceptable carriers . these may be in the form of silicone oils and synthetic esters . amounts of the emollients may range anywhere from 0 . 1 to 50 %, preferably between 1 and 20 % by weight . silicone oils may be divided into the volatile and non - volatile variety . the term “ volatile ” as used herein refers to those materials which have a measurable vapor pressure at ambient temperature . volatile silicone oils are preferably chosen from cyclic or linear polydimethylsiloxanes containing from 3 to 9 , preferably from 4 to 5 , silicon atoms . linear volatile silicone materials generally have viscosities less than about 5 centistokes at 25 ° c . while cyclic materials typically have viscosities of less than about 10 centistokes . nonvolatile silicone oils useful as an emollient material include polyalkyl siloxanes , polyalkylaryl siloxanes and polyether siloxane copolymers . the essentially non - volatile polyalkyl siloxanes useful herein include , for example , polydimethyl siloxanes with viscosities of from about 5 to about 25 million centistokes at 25 ° c . among the preferred non - volatile emollients useful in the present compositions are the polydimethyl siloxanes having viscosities from about 10 to about 400 centistokes at 25 ° c . ( 1 ) alkenyl or alkyl esters of fatty acids having 10 to 20 carbon atoms . examples thereof include isoarachidyl neopentanoate , isononyl isonanonoate , oleyl myristate , oleyl stearate , and oleyl oleate . ( 3 ) polyhydric alcohol esters . ethylene glycol mono and di - fatty acid esters , diethylene glycol mono - and di - fatty acid esters , polyethylene glycol ( 200 - 6000 ) mono - and di - fatty acid esters , propylene glycol mono - and di - fatty acid esters , polypropylene glycol 2000 monooleate , polypropylene glycol 2000 monostearate , ethoxylated propylene glycol monostearate , glyceryl mono - and di - fatty acid esters , polyglycerol poly - fatty esters , ethoxylated glyceryl monostearate , 1 , 3 - butylene glycol monostearate , 1 , 3 - butylene glycol distearate , polyoxyethylene polyol fatty acid ester , sorbitan fatty acid esters , and polyoxyethylene sorbitan fatty acid esters are satisfactory polyhydric alcohol esters . ( 4 ) wax esters such as beeswax , spermaceti , myristyl myristate , stearyl stearate and arachidyl behenate . ( 5 ) sterols esters , of which cholesterol fatty acid esters are examples thereof . fatty acids having from 10 to 30 carbon atoms may also be included as cosmetically acceptable carriers for compositions of this invention . illustrative of this category are pelargonic , lauric , myristic , palmitic , stearic , isostearic , hydroxystearic , oleic , linoleic , ricinoleic , arachidic , behenic and erucic acids . humectants of the polyhydric alcohol type may also be employed as cosmetically acceptable carriers in compositions of this invention . the humectant aids in increasing the effectiveness of the emollient , reduces scaling , stimulates removal of built - up scale and improves skin feel . typical polyhydric alcohols include glycerol , polyalkylene glycols and more preferably alkylene polyols and their derivatives , including propylene glycol , dipropylene glycol , polypropylene glycol , polyethylene glycol and derivatives thereof , sorbitol , hydroxypropyl sorbitol , hexylene glycol , 1 , 3 - butylene glycol , 1 , 2 , 6 - hexanetriol , ethoxylated glycerol , propoxylated glycerol and mixtures thereof . for best results the humectant is preferably propylene glycol or sodium hyaluronate . the amount of humectant may range anywhere from 0 . 5 to 30 %, preferably between 1 and 15 % by weight of the composition . thickeners may also be utilized as part of the cosmetically acceptable carrier of compositions according to the present invention . typical thickeners include crosslinked acrylates ( e . g . carbopol 982 ), hydrophobically - modified acrylates ( e . g . carbopol 1382 ), cellulosic derivatives and natural gums . among useful cellulosic derivatives are sodium carboxymethylcellulose , hydroxypropyl methylcellulose , hydroxypropyl cellulose , hydroxyethyl cellulose , ethyl cellulose and hydroxymethyl cellulose . natural gums suitable for the present invention include guar , xanthan , sclerotium , carrageenan , pectin and combinations of these gums . amounts of the thickener may range from 0 . 0001 to 5 %, usually from 0 . 001 to 1 %, optimally from 0 . 01 to 0 . 5 % by weight . collectively , the water , solvents , silicones , esters , fatty acids , humectants and / or thickeners will constitute the cosmetically acceptable carrier in amounts from 1 to 99 . 9 %, preferably from 80 to 99 % by weight . an oil or oily material may be present , together with an emulsifier to provide either a water - in - oil emulsion or an oil - in - water emulsion , depending largely on the average hydrophilic - lipophilic balance ( hlb ) of the emulsifier employed . surfactants may also be present in cosmetic compositions of the present invention . total concentration of the surfactant will range from 0 . 1 to 40 %, preferably from 1 to 20 %, optimally from 1 to 5 % by weight of the composition . the surfactant may be selected from the group consisting of anionic , nonionic , cationic and amphoteric actives . particularly preferred nonionic surfactants are those with a c 10 - c 20 fatty alcohol or acid hydrophobe condensed with from 2 to 100 moles of ethylene oxide or propylene oxide per mole of hydrophobe ; c 2 - c 10 alkyl phenols condensed with from 2 to 20 moles of alkylene oxide ; mono - and di - fatty acid esters of ethylene glycol ; fatty acid monoglyceride ; sorbitan , mono - and di - c 8 - c 20 fatty acids ; block copolymers ( ethylene oxide / propylene oxide ); and polyoxyethylene sorbitan as well as combinations thereof . alkyl polyglycosides and saccharide fatty amides ( e . g . methyl gluconamides ) are also suitable nonionic surfactants . preferred anionic surfactants include soap , alkyl ether sulfate and sulfonates , alkyl sulfates and sulfonates , alkylbenzene sulfonates , alkyl and dialkyl sulfosuccinates , c 8 - c 20 acyl isethionates , acyl glutamates , c 8 - c 20 alkyl ether phosphates and combinations thereof . various types of additional active ingredients may be present in cosmetic compositions of the present invention . actives are defined as skin benefit agents other than emollients and other than ingredients that merely improve the physical characteristics of the composition . although not limited to this category , general examples include additional anti - sebum ingredients and sunscreens . sunscreens include those materials commonly employed to block ultraviolet light . illustrative compounds are the derivatives of paba , cinnamate and salicylate . for example , avobenzophenone ( parsol 1789 ®) octyl methoxycinnamate and 2 - hydroxy - 4 - methoxy benzophenone ( also known as oxybenzone ) can be used . octyl methoxycinnamate and 2 - hydroxy - 4 - methoxy benzophenone are commercially available under the trademarks , parsol mcx and benzophenone - 3 , respectively . the exact amount of sunscreen employed in the compositions can vary depending upon the degree of protection desired from the sun &# 39 ; s uv radiation . a preferred additional anti - sebum agent is a retinoid . it has been found that compounds e through h had improved sebum suppressive activity in the presence of a retinoid . retinoids ( e . g . retinol / retinyl ester / retinal / retinoic acid ) are present in the epidermis , so compounds e through h will have the improved sebum suppressive activity when applied to the skin . the preferred compositions , however , include a retinoid as an additional ingredient . the term “ retinol ” includes the following isomers of retinol : all - trans - retinol , 13 - cis - retinol , 11 - cis - retinol , 9 - cis - retinol , 3 , 4 - didehydro - retinol . preferred isomers are all - trans - retinol , 13 - cis - retinol , 3 , 4 - didehydro - retinol , 9 - cis - retinol . most preferred is all - trans - retinol , due to its wide commercial availability . retinyl ester is an ester of retinol . the term “ retinol ” has been defined above . retinyl esters suitable for use in the present invention are c1 - c30 esters of retinol , preferably c2 - c20 esters , and most preferably c2 , c3 , and c16 esters because they are more commonly available . examples of retinyl esters include but are not limited to : retinyl palmitate , retinyl formate , retinyl acetate , retinyl propionate , retinyl butyrate , retinyl valerate , retinyl isovalerate , retinyl hexanoate , retinyl heptanoate , retinyl octanoate , retinyl nonanoate , retinyl decanoate , retinyl undecandate , retinyl laurate , retinyl tridecanoate , retinyl myristate , retinyl pentadecanoate , retinyl heptadeconoate , retinyl stearate , retinyl isostearate , retinyl nonadecanoate , retinyl arachidonate , retinyl behenate , retinyl linoleate , retinyl oleate , retinyl lactate , retinyl glycolate , retinyl hydroxy caprylate , retinyl hydroxy laurate , retinyl tartarate . the preferred ester for use in the present invention is selected from retinyl palmitate , retinyl acetate and retinyl propionate , because these are the most commercially available and therefore the cheapest . retinyl ester is also preferred due to its efficacy . the retinoid is employed in the inventive composition in an amount of from about 0 . 001 % to about 10 %, preferably in an amount of from about 0 . 01 % to about 1 %, most preferably in an amount of from about 0 . 01 % to about 0 . 5 %. many cosmetic compositions , especially those containing water , must be protected against the growth of potentially harmful microorganisms . preservatives are , therefore , necessary . suitable preservatives include alkyl esters of p - hydroxybenzoic acid , hydantoin derivatives , propionate salts , and a variety of quaternary ammonium compounds . particularly preferred preservatives of this invention are methyl paraben , propyl paraben , phenoxyethanol and benzyl alcohol . preservatives will usually be employed in amounts ranging from about 0 . 1 % to 2 % by weight of the composition . the composition according to the invention is intended primarily as a product for topical application to human skin , especially as an agent for controlling or preventing excessive sebum secretion . in use , a quantity of the composition , for example from 1 to 100 ml , is applied to exposed areas of the skin , from a suitable container or applicator and , if necessary , it is then spread over and / or rubbed into the skin using the hand or fingers or a suitable device . the cosmetic composition of the invention can be in any form , e . g . formulated as a toner , gel , lotion , a fluid cream , a soap bar or a cream . the composition can be packaged in a suitable container to suit its viscosity and intended use by the consumer . for example , a lotion or fluid cream can be packaged in a bottle or a roll - ball applicator or a propellant - driven aerosol device or a container fitted with a pump suitable for finger operation . when the composition is a cream , it can simply be stored in a non - deformable bottle or squeeze container , such as a tube or a lidded jar . the invention accordingly also provides a closed container containing a cosmetically acceptable composition as herein defined . the composition may also be included in capsules such as those described in u . s . pat . no . 5 , 063 , 057 , incorporated by reference herein . the following specific examples further illustrate the invention , but the invention is not limited thereto . compounds a through h were tested for their potential to suppress sebum expression , alone or in the presence of a retinoid . secondary cultures of human sebocytes obtained from an adult male were grown in 48 - well tissue culture plates ( costar corp . ; cambridge , mass .) or 96 - well tissue culture plates ( packard co . ; meriden , conn .) until confluent . sebocyte growth medium consisted of clonetics keratinocyte basal medium ( kbm ) supplemented with 14 μg / ml bovine pituitary extract , 0 . 4 μg / ml hydrocortisone , 5 μg / ml insulin , 10 ng / ml epidermal growth factor , 1 . 2 × 10 − 10 m cholera toxin , 100 units / ml penicillin , and 100 μg / ml streptomycin . all cultures were incubated at 37 ° c . in the presence of 7 . 5 % co2 . medium was changed three times per week . on the day of experimentation , the growth medium was removed and the sebocytes washed three times with sterile dulbecco &# 39 ; s modified eagle medium ( dmem ; phenol red free ). fresh dmem was added to each sample ( duplicates , triplicates , or quadruplicates depending on the experiment ) with 5 microliter of test agent solubilized in ethanol either alone or in the presence of one or 10 micromolar of retinol . controls consisted of addition of ethanol alone , retinol alone , or phenol red , which has estrogen - like activity and is included as a positive control . each plate was returned to the incubator for 20 hours followed by the addition of 14c - acetate buffer ( 5 mm final concentration , 56 mci / mmol specific activity ). sebocytes were returned to the incubator for four hours after which each culture was rinsed three times with phosphate buffered saline to remove unbound label . radioactive label remaining in the sebocytes was harvested and counted using a beckman scintillation counter . it can be seen from the results in tables 1 - 17 , that compounds a through h had sebum suppressive activity . retinol alone was inactive , but compounds c , and e through h had improved activity when combined with retinol . it should be understood that the specific forms of the invention herein illustrated and described are intended to be representative only . changes , including but not limited to those suggested in this specification , may be made in the illustrated embodiments without departing from the clear teachings of the disclosure . accordingly , reference should be made to the following appended claims in determining the full scope of the invention .
cosmetic methods and compositions containing selected iminodibenzyl or fluorene derivatives . when used for skin or hair care , the inventive compositions provide control of sebum secretion from sebocytes , improved oil control and improved feel , and prevent shine and stickiness .