it has now been discovered that the rate of development of dental caries , as characterized by proximal , smooth surface , pit and fissure caries , can be prevented or substantially retarded by the daily application to the teeth of a composition comprising a pharmaceutically acceptable oral hygiene vehicle containing an effective concentration to prevent or inhibit dental caries of a pharmaceutically acceptable fluoride salt and a pharmaceutically acceptable alkyl phenoxy or oxydibenzene sulfonate salt . typical pharmaceutically acceptable fluoride compounds that are suitable for use in the compositions of this invention include sodium fluoride , potassium fluoride , lithium fluoride , aluminum fluoride , zinc fluoride , stannous fluoride , sodium monofluorophosphate , acidulated phosphate fluoride , ammonium fluoride , ammonium bifluoride and amine fluoride . the alkyl phenoxy and alkyl oxydibenzene sulfonate salts found useful in accordance with the present invention are selected from the group consisting of bis ( alkylphenoxy ) alkane sulfonate salts of the structure ( a ), ## str1 ## monoalkyldiphenyloxide monosulfonate salts of the structure ( b ), ## str2 ## dialkyldiphenyloxide monosulfonate salts of structure ( c ), ## str3 ## monoalkyldiphenyloxide disulfonate salts of the structure ( d ), ## str4 ## dialkyldiphenyloxide disulfonate salts of the structure ( e ), ## str5 ## monoalkyloxydibenzene monosulfonate salts of the structure ( f ), ## str6 ## dialkyloxydibenzene monosulfonate salts of structure ( g ), ## str7 ## monoalkyloxydibenzene disulfonate salts of the structure ( h ), ## str8 ## dialkyloxydibenzene disulfonate salts of structure ( i ), ## str9 ## wherein r is a linear or branched chain alkyl containing from 10 to 20 carbon atoms ; r 1 , r 2 , r 3 and r 4 are linear or branched chain alkyl containing from 8 to 20 carbon atoms , n is an integer from 2 to 4 ; and m is selected from the group consisting of hydrogen , lithium , sodium potassium , calcium , magnesium , zinc , aluminum , copper , ammonium and the substituted ammonium ions derived from pharmaceutically acceptable organic amines . the synthesis of the bis ( alkylphenoxy ) alkane sulfonate salts of structure a is essentially identical to that reported by m . j . rosen , m . baum , and f . kasher [ journal of the american oil chemists &# 39 ; society , volume 53 , pp . 742 - 745 ] for the synthesis of the corresponding symmetrical disodium sulfonates which contain no alkyl substituents on the phenyl rings . the compounds shown in structures ( b )-( i ) can be prepared in the same general manner as described above for the compounds of structure a and also according to the teachings in u . s . pat . no . 2 , 990 , 375 which teachings are incorporated herein by reference . some of the alkyl and dialkyl diphenyloxide and oxydibenzene monosulfonate and disulfonate salts are available from dow chemical company , midland , mich . under the general tradename of dowfax . some of the specific dowfax compounds useful include dowfax 2ai and dowfax xd 8390 . in connection with the above compositions , the fluoride ion concentration should be from about 0 . 005 to 2 . 00 % by weight of the total composition , preferably from about 0 . 01 to 1 . 00 % the concentration of the alkyl phenoxy and alkyl oxydibenzene sulfonate salts should be at least 0 . 0001 % by weight of the total composition , preferably from about 0 . 01 to 5 . 00 % and most preferably from about 0 . 05 to 3 . 00 %. in concentrate formulations , the sulfonated materials may have a concentration as high as 80 % by weight of the total composition . suitable pharmaceutically acceptable oral hygiene vehicles , that may be used alone or in any compatible combination , include glycerol , water , ethanol , polyethylene glycol , propylene glycol and sorbitol . alternatively , any pharmaceutically acceptable vehicle which is compatible with the sulfonated material and fluoride salts used may be employed . the compositions of this invention may be in the form of a mouthrinse , dentifrice , gel , powder , solution , varnish , lozenge , chewing gum , slow release device or concentrate to be diluted or other form suitable for oral application . any pharmaceutically acceptable materials , such as those ordinarily used in such oral compositions , that are compatible may be employed in the compositions of this invention . in accordance with the present invention , the compositions are applied to the teeth with an appliance , e . g ., toothbrush , swab , mechanical cleansing devices , impregnated dental floss or the like , by gently brushing the teeth at least once daily , more preferably twice daily . specific embodiments of the anticaries compositions prepared in accordance with the present invention are illustrated by the following representative examples . it will be understood , however , that the invention is not confined to the specific limitations set forth in the individual examples , but rather to the scope of the appended claims . a gel dentifrice is prepared as follows : the pluronic f - 127 surface active agent is dissolved in 50 ml . of deionized water with continuous stirring at 70 ° c . the sodium salt of a sulfonated 1 , 4 - bis ( dodecylphenoxy ) butane is then added with stirring until dissolved . the resultant solution is then cooled to 50 ° c . and the sodium fluoride , glycerol , sorbitol , sodium benzoate , sweetener , flavoring , dye and silicone dioxide are individually added . the ph of the solution is then adjusted to 5 . 5 to 6 . 0 with 1 . 0n hcl or 1 . 0n naoh as required and deionized water is added to bring the total weight to 100 g . the solution is permitted to gel overnight at 15 ° c . ______________________________________ % w / w______________________________________sodium fluoride 0 . 22sodium salt of a sulfonated 1 , 4 - bis - 1 . 00 ( dodecylphenoxy ) butanesilicon dioxide 1 . 00pluronic f - 127 ( wyandotte chemicals 18 . 00corporation &# 39 ; s tradename for a nonionicsurface active agent prepared by theaddition of ethylene oxide to polypropy - lene glycol ) sweetener 0 . 80sodium benzoate 0 . 30glycerol 10 . 00sorbitol solution , 70 % 2 . 00flavoring 0 . 80dye ( 0 . 5 % aq . soln .) 0 . 70deionized water q . s . to 100______________________________________ an abrasive paste dentifrice is prepared as follows : the sodium fluoride , sodium benzoate , sweetener , pluronic f87 and dowfax xd 8390 are dissolved in 25 ml . of water at 50 ° c . with continuous stirring . in separate vessels , the xanthan gum is mixed with the glycerol and the natrosol 250h is mixed with the sorbitol and then each of these mixtures is added to the solution . the zeothix 265 , titanium dioxide , and hydrous silica gel are then individually added to the solution with stirring . the ph of the solution is then adjusted to 5 . 0 to 6 . 0 with 1 . 0n hcl or 1 . 0n naoh as required and the flavoring is then added as well as enough deionized water to bring the solution to 100 g . the resultant product is mixed and placed in containers and permitted to stand at 20 ° c . overnight . ______________________________________ % w / w______________________________________sodium fluoride 0 . 22dowfax xd 8390 ( dow chemical company &# 39 ; s tradename 1 . 00for the disodium 4 - hexadecylated oxydibenzenesulfonate ) sodium benzoate 0 . 20sweetener 0 . 50titanium dioxide 0 . 50flavoring 1 . 00glycerol 10 . 00sorbitol soln . 70 % 12 . 00hydrous silica gel 15 . 00zeothix 265 9 . 00natrosol 250h ( hercules inc . tradename for 1 . 00nonionic water soluble cellulose ether ) xanthan gum 1 . 00pluronic f87 ( wyandotte chemical corporation &# 39 ; s 3 . 00tradename for a nonionic surface active agentprepared by the addition of ethylene oxide topolypropylene glycol ) deionized water q . s . to 100______________________________________ a mouthrinse solution is prepared as follows : the flavoring is dissolved in ethanol in a suitable stainless steel vessel . the pluronic f - 108 , water , glycerol , sorbitol , sweetener , dowfax 2a1 and sodium fluoride are individually added with continuous stirring . the ph is adjusted to 5 . 5 to 6 . 0 with 1 . 0n hcl as required and the entire solution is strained through a 400 mesh stainless steel screen . ______________________________________ % w / w______________________________________sodium fluoride 0 . 05dowfax 2al ( dow chemical company &# 39 ; s tradename 0 . 02for the sodium salt of a dodecyl diphenoxydisulfonate ) ethanol , usp 7 . 0pluronic f108 ( wyandotte chemical corporation &# 39 ; s 2 . 00tradename for a nonionic surface active agentprepared by the addition of ethylene oxide topolypropylene glycol ) glycerol 10 . 00sorbitol soln . 70 % 10 . 00sweetener 0 . 20flavoring 0 . 20deionized water q . s . to 100______________________________________ an in vitro assay technique is utilized to demonstrate the enhancing properties of the sulfonated polymeric material on fluoride ion activity . this technique is based on the titrametric measurement of organic acids produced from sucrose by the cariogenic bacterium s . mutans . a fresh cell suspension of streptococcus mutans 6715 , grown in trypticase soy broth for 16 - 18 hrs . at 35 ° c ., centrifuged and the cells then resuspended in buffer containing dithiothreitol is used in the assay system . the cell suspension is stored under anaerobic conditions at 4 ° c . until used . the assay utilizes a ph - stat and the reaction is carried out under a nitrogen atmosphere at 37 ° c . the production of acid is monitored with the automatic addition of 0 . 005n potassium hydroxide solution . the cells are initially activated with glucose at ph 7 . 5 . after the exhaustion of glucose , the ph of the reaction mixture is manually dropped to 5 . 5 with 0 . 01n hcl . sucrose is added and after 4 minutes of acid production , the test compound is added . the rate of acid production is recorded as ml of potassium hydroxide consumed per minute to maintain a ph of 5 . 5 . antiacidogenic activity is reported as that amount of compound which reduces the acid production by a given percent as compared to a control containing no test compound . the higher the percent reduction of acid production of a composition containing the sulfonated materials and fluoride ion compared to a composition containing the sulfonated material alone , the better the anticaries activity of such a composition . the following table shows the results when various compounds falling within the scope of this invention are tested : ______________________________________ % reduction of acid product compound plus concen - compound fluoride fluoridecompound tration alone alone ion______________________________________sodium salt of a 0 . 001 23 20 67sulfonated 1 , 4 - bis - 0 . 002 65 20 93 ( dodecylphenoxy ) butanedowfax 2al 0 . 001 27 20 70 0 . 002 64 20 100dowfax xd 8390 0 . 0005 27 20 63 0 . 001 41 20 100______________________________________ in addition to the preferred embodiments described herein , other embodiments , arrangements , and variations within the spirit of the invention and the scope of the appended claims will occur to those skilled in the art .
compositions providing improved protection against dental caries consisting of a pharmaceutically acceptable fluoride compound and a pharmaceutically acceptable alkyl phenoxy or oxydibenzene sulfonate in a suitable vehicle are described .