GB1603027A - Anticariogenic additives and comestibles containing them - Google Patents

Abstract

The cariostatic additive consists of a soluble salt containing an aluminium ion and of a constituent chosen from adipic acid, ascorbic acid and mixtures thereof. It can be used in particular in the manufacture of anticariogenic confectionaries.

Description

(54) ANTICARIOGENIC ADDITIVES AND COMESTIBLES CONTAINING THEM (71) We, INDIANA UNIVERSITY FOUNDATION, Indiana Memorial Union, P.O.

Box 500, Bloomington, Indiana 47401 United States of America do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to the production of anticariogenic additives and comestibles containing them. More specifically, it is concerned with a candy product which is rendered anticariogenic through the use of a novel cariostatic additive.

For a long time, attempts have been made to compensate for the cariogenic potential of comestibles, particularly foods containing a high preponderance of sweeteners such as sucrose and other sugars. It has been suggested that, when sugars are placed in the mouth, they give rise to the production of acids which promote dental caries.

A contributing cause of dental caries in children is the adherence of highly refined sugars and their decomposition products to the dental plaque after ingestion, coupled with the slow rate of oral clearance, or the ability to produce high amounts of acid, or combinations of such factors.

A number of cariostatic agents have been evaluated in the past in systems wherein the agent is applied or consumed topically, i.e., directly on the teeth, in the form of a dentrifice, e.g., a toothpaste or a toothpowder. However, knowledge gained of the effectiveness of cariostatic agents used in such topical applications has not permitted a prediction of efficacy for these cariostatic agents in other applications, such as in foods, and particularly in foods containing a substantial proportion of sugars.

Unfortunately, known cariostatic agents have not in general provided any substantial degree of protection when used in foodstuffs. Thus, known cariostatic agents such as fluorides, phosphates, vitamin K, nitrofurans, ammonium compounds and iodoacetic acid, when added separately to a foodstuff containing a high percentage of sugar, have little direct topical effect in a foodstuff environment.

For these and other reasons, dental researchers have continued their efforts to develop new anticariogenic agents which not only demonstrate a high level of anticariogenic effectiveness but which are non4oxic, stable, and widely available. It has been suggested that aluminium salts may have a beneficial effect in reducing dental caries, or in facilitating the uptake of fluoride by the dental enamel (see, e.g., Manly et al., "Substances Capable of Decreasing the Acid Solubility of Tooth Enamel", J. Dent Res. 28: 160 (1948): Regolati, et al., "Effects of Aluminium and Fluoride on Caries, Fluorine Content and Dissolution of Rat Molars", Hel. Odon. Acta. 13: 59 (1969); and Kelada, "Electrochemical Characteristics of Free and Complexed Fluorides in Drinking Water and the Effects of Aluminium and Iron on Fluoride Incorporation Into Tooth Enamel, "Univ. Michigan Thesis (1972).

In vitro studies have shown that pretreatment of enamel with aluminium solutions resulted in increased fluoride uptake when followed by treatment with a fluoride solution; however, treatment with combinations of aluminium and fluoride did not show any added benefit over that of fluoride alone. These studies are described by McCann, "The Effects of Fluoride Complex Formation on Fluoride Uptake and Retention in Human Enamel", Archs. Oral Biol. 14:521 (1969) and Gerhardt, et al., "Fluoride Uptake in Natural Tooth Surfaces Pretreated with Aluminium Nitrate", J. Dent. Res. 51:870 (1972). Moreover, the foregoing techniques have dealt primarily with the use of aluminium in combination with fluorides and have not focussed on the effect of aluminium in the absence of fluoride.

It has heretofore been suggested that the addition of a source of aluminium to the diet may reduce the cariogenic potential thereof. However, studies have to date suggested that aluminium is ineffective as a dietary anticariogenic agent. Thus, Van Reen, et al., "Trace Elements and Dental Carries: Molybdenum, Aluminum, and Titanium", Helv, Odont.

Acta., 11:53-59 (1967), concluded at page 57 that "Aluminium potassium sulphate when added to the drinking water of rats to provide 10, 50, or 100 ppm of aluminium did not afford any protection against dental caries " The same conclusion was reached with aluminium added to the dietary ration fed rats, as reported by Wynn et al., "Dental Caries in the Albino Rat on High Sucrose Diets Containing Different Amounts of Aluminium", J.

Nutrition, 54:285-290 (1954), and with parenterally injected aluminium, as reported by Kurger, "The Effect of "Trace Elements" on Experimental Dental Caries in the Albino Rat", Univ. of Queensland Papers, 1:1-28 (1959).

Nor has the use of aluminium salts in dentifrices demonstrated a desirable result. Thus, while French Patent No. 3610M describes a specific combination of aluminium lactate, aluminium fluoride and calcium pyrophosphate, the abrasive interferes with the aluminium by reacting therewith to form insoluble aluminium phosphate. Similarly, U.S. Patent No.

3,095,356 uses aluminium salts such as aluminium fluoride to coact with insoluble sodium metaphosphate abrasives to reduce the solubility of such abrasives and to increase fluoride uptake, but without independent therapeutic advantage being taken of the aluminium.

U.S. Patent No. 3,282,792 describes low pH stannous fluoride dentirices stabilized against precipitation and oxidation of stannous tin ions through the use of hydroxylsubstituted di- and tri-carboxylic acids. However, nothing is said in the latter Patent regarding the use of aluminium in systems which do not contain fluoride. Similarly, while U.S. Patent No. 3,937,806 teaches oral compositions comprising indium and fluoride to which malic acid is added to stabilize the indium, the Patent does not recognize that beneficial results may be achieved with aluminium and carboxylic acids without incorporating fluoride.

Canadian Patent No. 829,272 describes acidic dentifrices comprising a combination of surface-active substances and albumen-coagulating substances such as certain carboxylic acid salts of aluminium and other metals. However, this Patent likewise fails to teach that significant dental health benefits can be achieved with aluminium-containing comestibles.

Thus, while some elements are known to inhibit dental caries, e.g., F, Mo, Sr and V, and while others are known to promote caries, e.g., Se, Mg and Cd, the preponderance of data on aluminium indicates that it is inert to dental caries, as classified by Navia, "Effect of Minerals on Dental Caries", in Dietary Chemicals v. Dental Caries, A.C.S., Washington, D.C. (1970).

U.S. Patent No. 3,772,431 relates to a mouthwash tablet containing an effervescent couple, e.g., a solid basic material and a solid organic acid such as fumaric, citric or tartaric and which produces carbon dioxide when dissolved in water, in combination with an astringent-desensitizing agent, which may, but need not, be an aluminium compound. In addition, the Patent discloses the optional use of Vitamin C (ascorbic acid) as a mucin-precipitating agent in combination with an anti-microbial agent and a chelating agent. The Patent, does not, however, suggest that any anticariogenic, therapeutic effect is achieved as a result of the aluminium compounds in such compositions. Furthermore, the other essential constituents in the tablets namely, the constituents forming the effervescent couple, are incompatible with any anticariogenic, therapeutic effect of aluminium ions, in that they prevent the aluminium ions from being therapeutically available to exert an anticariogenic effect.

On review, the prior art has not previously suggested a therapeutically effective system which provides bilogically available aluminium in a comestible in the absence of fluoride.

Accordingly, an object of the present invention is to provide a means for reducing or substantially overcoming the disadvantages of the prior art approaches to reducing the dental caries potential of sugar-containing foodstuffs.

A further object of the invention is to provide an effective aluminium-containing cariostatic additive for use in sweetened comestibles such as candy.

The invention therefore provides a cariostatic additive for incorporation in comestibles, which additive comprises at least one soluble aluminium ion-containing salt in which the aluminium ion is present in anticariogenically effective form, and adipic acid, ascorbic acid, or a mixture thereof. Where such an additive is provided in a candy product, even very low levels of additive, e.g., amounts of aluminium as low as about 100 ppm, are effective since repeated ingestion of small amounts of the anticariogenic agent has been shown to have an accumulative effect.

Such additive-containing comestibles also preferably incorporate a noncariogenic nutritive sweetener comprising a mixture of at least one first sweetening agent which is sorbitol, xylitol and/or a mixture thereof and at least one second sweetening agent which is dextrose, fructose or a mixture thereof. The mixture preferably contains at least 75% of the first sweetening agent by weight of the mixture where dextrose is the second agent and at least 60% of the first agent where fructose is the second agent. The sweetener is provided in the comestible in an amount effective to sweeten it. Such sweeteners are described and claimed in our copending Application No. 3508/77 (now Serial No. 1,574,848).

Use of the cariostatic additive of this invention reduces the acid solubility of dental enamel and, where the sweetening system of this invention is also employed, products are obtained which, when introduced into the mouth, exhibit little or no harmful lowering of the dental plaque pH (indicating that the formation of decay causing oral acids has been minimized); little or no harmful decalcification of the dental enamel decalcification being a precursor of dental caries formation) and rapid oral clearance.

In accordance with this invention, comestibles, especially sweetened comestibles such as candy, have incorporated therein anticariogenically effective and nontoxic amounts of an additive comprising a mixture of one or more soluble aluminium ion-containing salts in which the aluminium ion is present in anticariogenically effective form, and adipic acid, ascorbic acid, or a mixture thereof.

As used herein, the term "comestible" should be understood to mean substantially any of the wide range of food products suitable for ingestion by humans, including without limitation candies, bakery products, chewing gum, prepared beverages and fruit preparations.

As used herein, the term "ascorbic acid" should be understood to encompass its isomeric epimer, isoascorbic acid, also known as erythorbic acid and D-erthro-hex-2-enomic acid gamma-lactone, which may be substituted for it for purposes of this invention.

The adipic and/or ascorbic acid is preferably present at any convenient level greater than 0 to 6% by weight of the comestible. The acid is more preferably a level of about 3% by weight.

The particular soluble aluminium salt employed is not critical, and substantially any nontoxic water - soluble aluminium ion-containing salt may be used, provided the aluminium ion is present in anticariogenically effective form. Suitable aluminum salts include aluminium potassium sulphate, AlK(SO4)2.12H2O; aluminium chloride, AlC13.6H2O; aluminium sodium sulphate, AlNa(SO4)2.12H2O; aluminium ammonium sulphate, AlNH4(SO4)2.12H2O; aluminium sodium phosphate, NaAl3H14 (PO4)8.4H2O; aluminium sulphate, Al2(SO4)3. 18H2.0; aluminium nitrate, Al(NO3)3 and sodium aluminate, NaAlO2. Aluminium potassium sulphate and aluminium sodium sulphate are preferred by reason of their wide availability and established safety.

The anticariogenically effective and nontoxic amount of the soluble aluminium salt should preferably lie in the range capable of supplying from 100 ppm to 1000 ppm aluminium ions, (0.01 - 0.10 weight percent, calculated as aluminium ion). Thus, where aluminium potassium sulphate dodecahydrate and aluminium chloride hexahydrate are employed, the salts are present in the range of 0.2 up to 2% and 0.1 up to 1.0% by weight respectively.

The cariostatic additive of this invention may be used in all types of sweetened comestibles such as hard candies, toffees and caramels, chocolates and chocolate coatings and in other candy products. However, the additive is preferably provided in tableted and cooked hard candies. Where candy products are produced from a variety of individual consitutents, as in candies in which a cooked sugar based centre may be coated with chocolate, the additive of this invention may be employed in one or more of the constituents or in all of them.

An important feature of this invention is the discovery that, in comparison with other conventionally used carboxylic acids such as citric acid and malic acid, ascorbic and adipic acids are relatively safe and do not decalcify the teeth when present in the mouth during the rapid oral clearance period achieved with the candies of this invention. In addition, these acids (1) do not interfere with aluminium ions as do many other carboxylic acids; (2) help temporarily to reach pH of 3,5-4.5 in the mouth at which aluminium ions are most actively incorporated into dental enamel; and (3) open the enamel apatite crystal lattice somewhat so that aluminium ions may better react with the enamel.

Candy products produced in accordance with this invention are essentially the same as prior art candy products with the exception that, by virtue of the addition of the cariostatic additive of this invention, the candy products hereof may be safely consumed without causing or promoting dental caries.

Thus, anticariogenic candy products produced in accordance with this invention may contain usual and customary complementary ingredients conventionally found in candy products such as colorings, flavorings, dairy and vegetable fats, foaming agents, texturing agents such as crisped rice, nuts, and the like. However, certain conventional candy ingredients are undesirable from a dental standpoint. For example, significant amounts of fats and texturing agents such as crisped rice may adversely affect the oral clearance of the candy. Nonetheless, by employing the additive of this invention, the candies may be rendered less harmful to the teeth.

Candies produced in accordance with this invention may be prepared using the manufacturing techniques heretofore employed. The additive may be added at any convenient point so long as it is present in the final product at the desired level.

The compositions of exemplary anticariogenic candies produced in accordance with this invention are given in the following examples.

Example I - Tableted Candy Constituent Parts by weight Sucrose 95.0 Adipic Acid 3.0 Aluminium Potassium Sulphate 0.2 Magnesium Stearate 1.0 Flavorings, Colours, etc. 0.8 Example II - Cooked Hard Candy Constituent Parts by weight Sucrose 98.0 Adipic Acid 1.0 Aluminium Chloride 0.5 Flavorings, Colours, etc. 0.5 Desirably, the cariostatic additive of this invention is employed in sweetened comestibles containing, in place of the sucrose or other cariogenic sweetener, a noncariogenic nutritive sweeting system comprising a mixture of at least one first sweetening agent which is sorbitol, xylitol or a mixture thereof and at least one second sweetening agent which is dextrose, fructose or a mixture thereof, with the mixture preferably containing at least 75% first agent by weight of the mixture where dextrose is the second agent and at least 60% of the first agent where fructose is the second agent.

Sorbitol is the preferred first agent, with dextrose being the preferred second agent on the basis of cost and availability. Desirably, homogeneous mixtures of the first and second agents are employed.

Where sorbitol-dextrose or xylitol-dextrose mixtures are employed, a 75% sorbitol and/or xylitol - 25% dextrose mixture is preferred. Where fructose is employed, somewhat greater amounts of the second sweetening agent may be employed. Thus, about 40% fructose is preferred in the case of sorbitol-fructose and xylitol-fructose mixtures.

Generally, the sweetening mixtures of this invention are employed at the same levels that the sugar or other cariogenic sweetening systems have been employed. Thus, where noncariogenic nutritive sweetening systems are employed in accordance with this invention in a candy product they are preferably used at a level of about 40-100% by weight of the candy produced.

Candy products produced in accordance with this invention are essentially the same as prior art candy products with the exception that, by virtue of the addition of the cariostatic additive and the substitution of the noncariogenic nutritive sweetening system, they may be safely consumed with a reduction of the incidence and severity of dental caries.

Candies produced in accordance with this invention may be prepared using the foregoing noncariogenic nutritive sweetening system heretofore employed. Manufacturing techniques are generally the same although certain modifications must be made by reason of the use of sorbitol or xylitol as the principle constituent of the sweetening system.

Thus, in the case of tableted candies, the same techniques of mixing the ingredients and forming them into tablets are used, but somewhat greater humidity control must be exerted because sorbitol and xylitol are dessiccants. An agent such as magnesium stearate may also be added at low levels to facilitate removal of the tablets from the mould.

With knowledge of these properties of the sorbitol and/or xylitol containing sweetening agents, one skilled in the art can readily adapt existing candy processing techniques to the preparation of other candy products pursuant to this invention.

The compositions of exemplary anticariogenic candies produced employing the nutritive sweetening system in accordance with this invention are given in the following examples: Example III - Table ted Candy Constituent Parts by Weight Sorbitol 71.3 Dextrose 23.8 Flavorings, Color, Etc. 0.7 Adipic Acid 3.0 Aluminium Potassium Sulphate 0.2 Example IV - Tableted Candy Constituent Parts by Weight Sorbitol 81.0 Dextrose 14.0 Ascorbic Acid 3.0 Flavoring, Colour, etc. 0.5 Aluminium Chloride 0.5 Magnesium Stearate 1.0 Example V - Tableted Candy Constituent Parts by Weight Sorbitol 57.2 Fructose 38.1 Adipic Acid 1.5 Ascorbic Acid 1.5 Flavoring, Colour, etc. 0.5 Magnesium Stearate 1.0 Aluminium Potassium Sulphate 0.2 Example VI - Tableted Candy Constituent Parts by Weight Xylitol 72.0 Dextrose 24.0 Adipic Acid 3.0 Flavoring, Colour, etc. 0.2 Magnesium Stearate 1.0 Aluminium Chloride 0.5 Example VII - Tableted Candy Constituent Parts by Weight Sorbitol 64.1 Dextrose 15.5 Fructose 15.5 Adipic Acid 1.5 Ascorbic Acid 1.5 Flavoring, Colour, etc. 0.5 Magnesium Stearate 1.0 Aluminium Chloride 0.5 Example VIII - Tableted Candy Constituent Parts by Weight Sorbitol 35.7 Xylitol 35.7 Dextrose 23.8 Adipic Acid 3.0 Flavoring, Colours, etc. 0.2 Magnesium Stearate 1.0 Aluminium Chloride 0.5 Example IX - Cooked Hard Candy Constituent Parts by Weight Sorbitol (70% solution) 81.8 Dextrose 17.3 Adipic Acid 0.8 Flavoring, Colour, etc. 0.2 Aluminium Potassium Sulphate 0.2 Example X - Taffy Constituent Parts by Weight Sorbitol (70% solution) 70.1 Dextrose 16.3 Egg albumin (45.27% solution) 2.4 92 degree coconut oil 8.9 Adipic Acid 1.7 Sodium Alginate 0.3 Calcium Acetate 0.3 Calcium Acetate 0.1 Emulsifier 0.1 Flavoring, Color, etc. 0.2 Aluminium Chloride 0.5 Example XI - Chocolate Candy Coating Constituent Parts by Weight Sorbitol 42.0 Dextrose 14.0 Kaomel (hard butter) 30.9 Cocoa Powder 7.8 Non-Fat Dry Milk 4.2 Lecithin 0.3 Salt 0.1 Vanilla Powder 0.9 Aluminium Potassium Sulphate 0.2 EXPERIMENTAL EVALUATIONS The anticariogenic attributes of the products produced in accordance with this invention have been verified by the following experimental studies.

A primary criterion in evaluating an anticariogenic agent is its ability to reduce the solubility of dental enamel, namely, enamel solubility reductions ("ESR"). In vitro, "ESR" studies are carried out in the following manner. Sound bovine incisors are mounted in self-curing acrylic resin, with the labial surface exposed, and given a thorough prophylaxis with flour of pumice. A "window" is then formed on the labial surface by dripping wax over a 1.0 cm diameter aluminium foil circle. A sharp stylus is then used to circumscribe the foil window which is then pulled off exposing a round area of enamel of reproducible size.

The windowed teeth are decalcified 4 consecutive times over 20-minute intervals with 25 ml aliquots of a 0.2 N acetic acid solution (buffered to a pH of 4.0) at a stirring rate of 60 rpm using an ESR stirring apparatus. By the 4th decalcification, the amount of calcium and phosphorus being demineralized from the teeth has reached a constant level. The teeth are then treated with 25 mls of candy supernatant (1 part candy diluted with 3 parts redistilled water to simulate the dilution that occurs in the mouth upon ingestion) stirred at a rate of about 60 rpm.

After treatment, the teeth are decalcified again with 25 ml portions of the acetic acid buffer for four additional 20-minute intervals. The 5th and 8th decalcification solutions are referred to as the first post-treatment decalcification (1st DTD) and 4th post-treatment decalcification (4th PTD), respectively.

The difference in the amount of calcium and phosphorus in the 4th decalcification solution before treatment and that present in the 5th and 8th decalcification solutions after treatment, divided by the amount of the 4th decalcification, times 100 is used to determine the 1st PTD and 4th PTD ESR values. Calcium is determined using atomic absorption spectroscopy, and phosphorus using the Fiske-Subbarow method.

In order to demonstrate that repeated ingestion of candy incorporating the cariostatic additive of this invention over short periods of time has an accumulative effectiveness in reducing the solubility of dental enamel, the teeth are treated a number of times relatively short duration (e.g., 5 minutes, the typical oral clearance time of candies of this type).

Using this technique, a grape flavored tableted candy having the formulation given in Example III was evaluated. For comparative purposes a candy of the same formulation but without the aluminium salt was tested as a control. The ESR data for the Example III candy was measured after 10 five minute treatments and also after 20 five minute treatments. The ESR data, which are given in Table I, show that repeated 5-minute treatments with this dissolved candy causes an accumulated significant ESR effect. After 20 such treatments an ESR of 70% is obtained.

TABLE I No. of 5-min. CA ESR (%) P ESR (%) Treatment Solution Treatments 1st PTD 4th PTD 1st PTD 4th PTD Example III, but no AlK(SO4)2.12H2O (pH adjusted to 4.0) (Average of 3 readings) 20 9 5 12 3 Example III (pH adjusted to 4.0) (Average of 3 readings) 10 41 30 44 25 Example III (pH adjusted to 4.0) (Average of 3 readings) 20 69 43 74 43 While ESR evaluations are indicative of the effectiveness of an anticariogenic agent, it is also very desirable to determine the amount of the agent actually taken up by the dental enamel in order to further establish its efficacy. Six windowed sound bovine incisors were treated with the candy of Example III diluted 1:3 with redistilled water. the teeth were treated 20 consecutive times over separate 5 minute intervals with 25 mls of the candy solution. After treatment the teeth were decalcified for 30 seconds in 15.0 mls of 2.0 HC104, and the amount of calcium and aluminium was determined. Calcium was determined by atomic absorption, and aluminium the Aluminon method.

The data which are reported in Table II unequivocally demonstrate that a substantial amount of aluminium ion reacts with and is taken up into the tooth enamel. Treatment of teeth with redistilled water in a similar manner resulted in a zero aluminium uptake score.

These accumulative aluminium uptake values correspond to and should be associated with the accumulative ESR values reported in Table I. Collectively they demonstrate the cariostatic effectiveness of the additives of this invention.

TABLE II Calcium Total g Aluminium Total g g Aluminium Tooth Ion ppm Calcium Ions ppm Aluminium g Calcium x1O 1 1.14 1710 0.79 11.85 6.93 2 0.89 1335 0.50 7.50 5.62 3 0.68 1020 0.54 8.10 7.95 4 1.22 1830 0.88 13.20 7.21 5 0.97 1455 0.88 13.20 9.07 6 1.00 1500 0.97 14.55 9.70 The anticariogenic effectiveness of the addtives has also been shown in an in vivo rat study conducted as follows. Ten 35-day old Wistar strain rats were randomly distributed into two equal groups according to sex, body weight, and littermates. Group 2 rats served as the control and were fed a low fluoride corn meal diet and fluoride free water ad libitum.

Group 1 rats were maintained on the same regimen except that their corn diet was supplemented with 3% adipic acid and 1% AlCl3.6H2O. At the end of 1 month, the rats were sacrificed, and the acid solubility of their mandibular molars was measured. The data are reported in Table III.

TABLE III Phosphorus ESR Calcium ESR Group Reps. Mean + % Mean + No. (N) S.D. (ppm) Reduction -S.D. (ppm) Reduction 1 10 2.05+0.20 40.2 4.40+0.40 35.8 - (p .005) - (p .005) 2 10 3.43+0.20 ---- 6.85+0.68 These data show phosphorus and calcium ESR's of 40% and 35%, respectively, for rats fed a diet incorporating the cariostatic additive of this invention.

The anticariogenic effectiveness of the anticariogenic candies of this invention has also been demonstrated in rats using the method described by Francis, "The Effectiveness of Anticaries Agents in Rats Using an Incipient Carrious Lesion Method", Arch, Oral Biol., 11:141-148 (1966).

A total of 100 weanling (21 day old) Wistar strain rats were randomly divided into five equal groups according to sex, body weight, and litter mates. The parents of the weanlings were placed on a noncariogenic low fluoride corn diet and fluoride-free redistilled drinking water one week prior to mating. The dames were maintained on this same regimen during the pups' 21-day gestation period, birth, and 21-day weaning period in order to avoid exposure of the pups to any exogeneous sources of fluoride during their development. After weaning, the 21-day old rats were placed on a high sucrose caries inducing diet and fluoride-free redistilled water ad libitum. Once daily, five days per week, for a 4 week period, both the right and left molars of the mandibular were each swabbed for 60 seconds with the respective topical anticariogenic candy solution. A stick cotton swab was used to apply the solution to the molars by freshly dipping into the candy solution at 15 second intervals. The topical candy solutions used for treatment were prepared by dissolving the various experimental candes 1 part by weight with 3 parts redistilled water. The basic candy formula Example III was employed wit the following variations: Group 1 - Control group - Example III without the AlK(SO4)2. 12H2O Group 2 - Example III Group 3 - Example III with 6% AlK(SO4)2.12H2O Group 4 - Example III substituting dextrose for all of the sorbitol Group 5 - Same as Group 3, substituting dextrose for all the sorbitol The rats were housed in an air-conditioned room in cages with raised screen floors, and the usual sanitary measures in the care of laboratory animals were strictly followed. The lights were time regulated to insure 12 hours of light and 12 hours of darkness.

The weight of the rats was determined initially and then at the end of the one-month study. There were no statistical differences in weight gain between the experimental groups and the control group. In addition, not one single animal died during the course of the study.

At the termination of the experiment the animals were sacrificed by chloroform inhalation, and the teeth were stained with 1% silver nitrate, sectioned in half and graded for incipient lesions. The data are reported in Table IV.

TABLE IV Incipient Lesions Group No. Incidence Reduction Severity Reduction 1 (Control) 27.3+1.6 ---- 58.4+5.8 2 24+4+2.5 10.6% 52.6+5.5 9.9% 3 22.4+2.5 17.9% 49.7+6.1 14.9% 4 24.5+3.5 10.3% 57.0+10.2 3.0% 5 25.4+3.6 7.0% 57.6+ 12.2 1.4% A statistical analysis of the data showed that the 11% caries incidence reduction noted for Group 2 (3:1 sorbitol-dextrose candy containing .2% AlK(SO4)2,12H2O) was significant at the 98% c

TABLE V Phosphorus ESR (%) Calcium ESR (%) 37 ppm aluminium Mean (+ S.D.) Mean (+S.D.) with 1% of 1st PTD 4th PTD 1st PTD 4th PTD No acid 92.1 (#5.0) 72.2 (#18.5) 90.4(#6.0) 75.7 (#15.5) Adipic Acid 85.7 (#5.8) 72.7 (#8.9) 81.7 (#4.0) 70.7 (#8.6) Ascorbic Acid 80.7 (#6.8) 70.7 (#12.8) 78.7 (#6.7) 72.1 (#10.3) Glutaric Acid 77.9 (#5.2) 65.1 (#5.7) 70.0 (#5.8) 64.1 (#5.7) Succinic Acid 71.5 (#12.5) 54.4 (#11.5) 64.3 (#10.8) 57.5 (#7.5) Fumaric Acid 65.6 (#2.9) 52.5 (#5.6) 60.9 (#5.8) 52.4 (#8.4) Tartaric Acid 7.9 (#34.7) -25.2 (#54.0) 3.5 (#23.8) -15.5 (#41.4) Citric Acid 11.4 (#6.8) -10.9 (#10.7) 7.5 (#8.7) -8.8 (#10.3) Malic Acid -12.5 (#26.6) -11.3 (#17.7) -16.0 (#22.4) -6.3 (#16.0) Control-Redistilled H2O -12.5 (#8.1) -26.4 (#21.9) -2.6(#8.4) -4.7 (#5.9) While the foregoing invention has been described with respect to candy products in particular, these techniques are intended to have utility in relation to other food products in which the additive according to the invention may be employed.

Claims (24)

WHAT WE CLAIM IS

1. A cariostatic additive for comestibles comprising at least one soluble aluminium ion-containing salt in which the aluminium ion is present in anticariogenically effective form, and adipic acid, ascorbic acid or a mixture thereof.

2. An additive, as claimed in claim 1, in which the acid is adipic acid.

3. An additive as claimed in claim 1 or 2, in which the aluminium salt is aluminium potassium sulphate dodecahydrate, AlK(SO4)2.12H2O.

4. An additive as claimed in claim 1 or 2, in which the aluminium salt is aluminium chloride hexahydrate, AlCl3.6H2O.

5. An additive as claimed in claim 1, substantially as herein described with reference to any of the examples.

6. An anticariogenic comestible comprising an anticariogenically effective and nontoxic amount of at least one soluble aluminium ion - containing salt in which the aluminium ion is present in anticariogenically effective form, and adipic acid, ascorbic acid or a mixture thereof.

7. A comestible as claimed in claim 6, in which the aluminium salt is present at a level of from 0.01 to 0.10%, calculated as aluminium ion, by weight of the comestible.

8. A comestible as claimed in claim 6 or claim 7, in which the acid is present at a level of up to 6% by weight of the comestible.

9. A comestible as claimed in any of claims 6 to 8, in which the acid is adipic acid.

10. A comestible as claimed in any of claims 6 to 9, in which the aluminium salt is aluminium potassium sulphate dodecahydrate, AlK (SO4)2.12H2O.

11. A comestible as claimed in any of claims 6 to 9, in which the aluminium salt is aluminium chloride hexahydrate, AlCl3.6H2O.

12. A comestible as claimed in any of claims 6 to 9, which further comprises, as a nutritive sweetening agent, a mixture of at least one first sweetening agent which is sorbitol, xylitol or a mixture thereof and at least one second sweetening agent which is dextrose, fructose, or a mixture thereof, the mixture being present in an amount effective to sweeten the comestible.

13. A comestible as claimed in claim 12, in which the mixture contains at least 75% of the first agent by weight of the mixture where dextrose is the second agent and at least about 60% of the first agent by weight where fructose is the second agent.

14. A comestible as claimed in claim 12 or claim 13 in which the first agent is sorbitol and the second agent is dextrose.

15. A comestible as claimed in claim 12 or claim 13 in which the first agent is sorbitol and the second agent is fructose.

16. A comestible as claimed in claim 12 or claim 13 in which the first agent is xylitol and the second agent is dextrose.

17. A comestible as claimed in claim 12 or claim 13, in which the first agent is xylitol and the second agent is fructose.

18. A comestible as claimed in claim 6 substantially as herein described with reference to any of the examples.

19. An anticariogenic candy product comprising: from 0.1 to 1.0% by weight, based on the weight of the product, of a soluble aluminium ion - containing salt in which the aluminium ion is present in anticariogenically effective form; up to 6.0% by weight of adipic acid, ascorbic acid or a mixture thereof; and at least 40% by weight of a nutritive sweetening mixture of sorbitol and dextrose comprising at least 75% sorbitol by weight of the mixture.

20. An anticariogenic candy product as claimed in claim 19 substantially as herein described with reference to any of the Examples.

21. A process for rendering a sweetened comestible anticariogenic comprising the step of incorporating therein an anticariogenically effective and nontoxic amount of at least one soluble aluminium ion - containing salt in which the aluminium ion is present in anticariogenically effective form, and adipic acid, ascorbic acid or a mixture thereof.

22. A process as claimed in claim 21, which further comprises the step of incorporating in the comestible, as a nutritive sweetening agent, a mixture of at least one first sweetening agent which is sorbitol, xylitol or a mixture thereof, and at least one second sweetening agent which is dextrose, fructose or a mixture thereof, with the mixture containing at least 75% of the first agent by weight of the mixture where dextrose is the second agent and at least 60% of the first agent by weight of the mixture where fructose is the second agent, the mixture being incorporated into the comestible in an amount effective to sweeten the comestible.

23. A process as claimed in claim 21 substantially as herein described with reference to any of the Examples.

24. A comestible or candy product as claimed in any of claims 6 to 19 when prepared by a process as claimed in any of claims 21 to 23.