NL8202589A - TOOTHPASTE. - Google Patents

Description

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Toothpaste.

The invention relates to a foamable toothpaste, in particular a toothpaste in which the surfactant used is nonionic in nature.

Foaming is a desirable property of a dental paste since it spreads the latter into the oral cavity during brushing; thus contact of the toothpaste with the tooth surfaces is promoted and a characteristic mouthfeel is obtained.

Foam, in particular a thick foam, is generally formed by an anionic surfactant. Other surfactants, especially nonionic surfactants, do not foam as well as the anionic agents. Of the many existing anionic surfactants, some have been used commercially in toothpaste; most often sodium lauryl sulfate is used.

Anionic surfactants sometimes cause mild side effects that some users do not appreciate. Some, for example, when using such a toothpaste, may temporarily experience moderate irritation of the oral cavity, a certain bitter taste, a certain mouth mucus formation or an unpleasant taste reaction when drinking or eating fruits of the bristles shortly after brushing the teeth.

Although it is known to impart surfactant properties to the toothpaste by means of nonionic surfactants, such an agent has not been used heretofore since the foaming is lost unless an anionic surfactant is added.

It is an advantage of the invention that a toothpaste is provided which is easy to squeeze from a tube and which contains a non-ionic surfactant as well as a certain binder with which a desired stable complete foaming can be obtained.

It is a further advantage of the invention that the toothpaste is sweet without the need for a sweetening additive, nor is it 8202589 i * 2 non-irritating, while its users usually do not have oral mucus formation or an adverse taste reaction when consuming tropical fruits after use. of the toothpaste.

Further advantages of the invention will become apparent from the tape 5 of the following consideration.

In certain aspects, the invention relates to a toothpaste containing 20-80% by weight of a liquid wetting carrier, about 0.5-7% by weight of xanthan gum and about 1-10% by weight of a surfactant , which is a nonionic polyoxyethylene-poly-oxypropylene block copolymer. Preferably also up to 5% of bar-like poly (ethylene oxide) is present.

The nonionic surfactant used is a block copolymer containing polyoxyethylene and polyoxypropylene. Such a block copolymer is available from Wyandotte Chemicals 15 Corp.. under the band name 'Pluronic, f. These can be liquids, pastes or solids and are generally defined by the molecular weight of the hydrophobic polyoxypropylene duck and the weight percentage of the bydrophilic polyoxyethylene duck.

The following block polymers are available from Wyandotte:

Pluronic Physical% Hydrophilic Mol. hydro number character unit_ phobic unit L 121 liquid 10 U000 L 101 liquid 10 3250. 25 L 81 liquid 10 2250 L 61 liquid 10 1750 L 31 liquid 10 950 L 122 liquid 20 1 + 000 L 92 liquid 20 2750 30 L 72 liquid 20 2050 L 52 liquid 20 1750 L 1 + 2 liquid 20 1200 P 123 paste 30 1 + 000 P 103 pasta 30 3250 35 63 liquid 30 1750 L 1 + 3 liquid 30 1200 P 10l + pasta 1 + 0 3250 P 9 ^ pasta 1 + 0 2750 P 81+ pasta 1 + 0 2250 1 + 0 L 6h liquid 1 +0 1750 L 1 + 1 + liquid 1 + 0 1200 8202589 3 • r * * * »(Continued)

Pluronic Physical% Hydrophilic Mol. hydro number character unit_ phobe unit P 105 pasta 50 3250 P 85 pasta 50 2250 5 P- 75 pasta · 50 2050 P 6> 5 pasta 50 1750 L 35 liquid 50 950 P 127 solid 70 U000 P 87 solid 70 2250 10 P 77 solid 70 2050 P 108 solid 80 3250 F 98 'solid 80 2750 F 88 solid - 80. 2250 P 68 solid 80 1750 15 P 38 solid 80 950

The preferred nonionic block copolymers are solid (or flake) materials and most preferably these are Pluronic 108 {80% polyoxyethylene: molecular weight polyoxypropylene 3250) and F 87 (70 $ polyoxyethylene: molecular weight polyoxypropylene 20 2250).

The nonionic surfactant is used in a toothpaste in an amount of about 1-10% by weight 3 preferably about 2-5% and most preferably about 3%

The binding or gelling agent system of xanthan or xanthan and resinous poly (ethylene oxide) interacts with the nonionic surfactant to provide stable dense foaming (even though the only surfactant present is nonionic) while also desired mouthfeel properties are imparted to the toothpaste. Xanthan gum in the described concentrations allows a stable completely dense foam. In addition, according to a further aspect of the invention, the mouthfeel properties as described can be modified by adding a resinous poly (ethylene oxide). The toothpaste has a desired viscosity by which it can be pressed in the form of a strand from a toothpaste.

Resinous poly (ethylene oxide) is described in U.S. Patent 2,991,229 as a gelling agent or binder for toothpaste. Its presence softens the texture of the toothpaste.

The poly (ethylene oxide) 8202589 * k used in this invention includes solid, colorless water-soluble resins. These appear to form homogeneous systems in water in all amounts, although the ethylene oxide. polymers of relatively higher molecular weight at most swell when small amounts of water are added. The polymers dissolve when large amounts of water are added. The water solutions are viscous in which the viscosity increases directly in proportion to the concentration of the polymer in the solution and with the reduced viscosity of the polymer. The ethylene oxide polymers used in the invention show little change in melting point with increased reduced viscosity (an indication of increased molecular weight) and melting point, as measured by a change in stiffness depending on the temperature, which is about 65 ° C + 2 ° C appears to be in the entire range of the reduced viscosity from about 1.0 to about 10 and above. These polymers, upon X-ray examination, reveal a crystalline structure analogous to that of polyethylene. The crystallization temperature determined by measuring the interruption in the cooling curve is about 55 ° C.

Various terms will now be defined for a better understanding of the invention. It should first be noted that the word poly (ethylene oxide) as used herein refers to ethylene oxide polymers having a reduced viscosity in acetonitrile of at least 0.5 and up to 75 and above.

Unless otherwise indicated, the term "" reduced viscosity "as used herein includes a value obtained by dividing the specific viscosity by the concentration of the ethylene oxide polymer in the solution, which concentration is measured in grams of polymer per 100 ml of solvent at given temperature and which is considered as a measure of molecular weight. The specific viscosity is obtained by dividing the difference between the viscosity of the solution and the viscosity of the solvent by the viscosity of the solvent. The reduced viscosity as reported herein is measured at a concentration of 0.2 g of poly (ethylene oxide) in 100 ml of acetonitrile at 30 ° C (unless otherwise indicated).

Granular poly (ethylene oxide) is formed by slurry polymerization of a stirred reaction mixture comprising ethylene oxide in contact with a polymerization catalyst and in the presence of an 8202589 W ~ 5 inert organic diluent, for example heptane, ethylene oxide soluble and the poly (ethylene oxide) obtained is insoluble. Granular poly (ethylene oxide) produced in this way is obtained in a finely divided solid particle state and is similar to finely divided sand vessel particle size. Unlike the granular poly (ethylene oxide) resulting from the slurry polymerization method, the bulk and solution polymerization methods yield a polymer that is substantially a homogeneous mass that either conforms to the shape of the reaction vessel or after the organic medium has drifted off. , predominantly by mechanical extrusion, as resembling sheets or plates with the Marshall mill (under vacuum and at slightly elevated temperature). This polymer can subsequently form into particles, for example into cubes and the like.

The term "granular or granular" refers to the particle size of the ethylene oxide polymers prepared by slurry polymerization. The granular product is a product that is in a free-flowing state and has particles of on average less than 1 + mm (5). mesh. US). If present, the poly (ethylene oxide) contains up to 5 parts by weight of the toothpaste, preferably about 0.1 -20 1.5 *.

Xanthan gum is a fermentation product prepared by the inking bacteria of the genus Xanthomonas onto carbohydrates. Four species of Xanthomonas, i.e. X. campetris, X * phaseoli, X. malvocearum and X. carotae have been reported in the literature as the most efficient gum products. How much the exact chemical structure. It has been generally accepted that the gum is a heteropolysaccharide with a molecular weight of several millions. It contains D. glucose, D. mannose and D. glucuronzutur in a molar ratio of 2.8: 3: 2.0. The molecule contains acetyl and about 3% pyruvate. The proposed chemical structure configurable can be found in McNeely and Kang, Industrial Gums, publisher R.L. Whistler, CH XXI, 2nd ed., Lev York, 1973. The procedure for culturing, isolating and purifying the xanthan gum is found in Manufacturing Chemist, May 1960, biz.

206-208 (including mention on biz. 208 of the potential use of the gums described therein in toothpaste compositions).

8202589 * * 4. * m 6

The application ran. special qualities of xanthan gum as disclosed in U.S. Patent No. 2,663,399 are within the scope of this invention. A certain quality described in U.S. Patent No. 2,663,399 is a xanthan gum containing up to 1.6% of the carboxyl groups are bound to calcium and the residual carboxyl groups are bound to sodium, potassium, a mixture. of sodium and potassium or other non-calcium cations.

The xanthan gelling agent is present in an amount of about 0.5-7% by weight of the toothpaste, preferably 1.5-3%. Since the surfactant used in the invention is nonionic in nature, the generally moderate bitterness caused by an anionic surfactant is caused by the. users were not encountered. Thus, sweeteners used thickly in toothpaste to at least partially overcome the bitter taste are less often needed in the toothpaste of the invention compared to the prior art. Thus, it is easy to obtain sufficient sweetness due to the low sweetening nature of many preservatives commonly used in toothpaste formulations. Such wetting agents are included in the liquid phase of the toothpaste, typically along with water. Typical preservatives include sorbitol (as 70% aqueous solution), glycerol, maltitol, xylitol, polyethylene glycol UOO and polyethylene glycol 600. The liquid phase comprises about 20-80% by weight of the toothpaste, preferably about 30-60%, wherein if water is present, it is typically present in an amount of up to 60% and the preservative typically up to about 20-60%. It is noted that in Japanese Patent Publications 73/102 and 65/15120 maltitol is described as a toothpaste component.

The liquid carrier and the gelling agent and the other 30 components of the toothpaste are mixed such that they form a cream or gel mass of the desired consistency extrudable from an aerosol or pump-binder or squeezable tube (for example, aluminum, lead or plastic) .

The toothpaste typically includes a dentifrice-acceptable polishing agent which is generally a substantially water-insoluble type as commonly used in toothpastes.

8202589 7 '.

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Representative polishing agents include, for example, dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide including hydrated alumina, calcined alumina, colloidal silica, magnesium carbonate, calcium carbonate. ____ 5 calcium pyrophosphate, bentonite, etc., including mixtures thereof. When used, it is preferred to use the water-insoluble phosphate salts as a polishing agent and more particularly insoluble sodium with phosphate and / or a calcium phosphate, such as dicalcium phosphate, dihydrate in dental creams. When visually clear gels or opaque gels are used, a colloidal silica polishing agent such as that sold under the band names Syloide 72 and 7 or under the trademark Santocel as well as Santocel 100 and synthetic alkali metal aluminosilicate complexes or silica is combined alumina contains particularly useful. When used, the polishing agent content is generally about 15-75% by weight. % in a dental cream and about 5-50 wt. % in a clear or un-. transparent gel.

A further aspect of the invention is a toothpaste containing a siliceous polishing material such as those mentioned in the aforementioned paragraph as well as poly (ethylene oxide) previously described.

Based on the prior art as described in U.S. Pat. No. 3,020,230, which discloses that silica material coagulates or flocculates in the presence of resinous poly (ethylene oxide) causing it to be precipitated from a liquid suspension, those skilled in the art In the field of toothpastes, it has not been possible to use silica materials in a toothpaste containing resinous poly (ethylene oxide). For example, U.S. Patent 2,991,229 discloses that the polishes or abrasives used in a toothpaste containing poly (ethylene oxide) include tricalcium phosphate, dicalcium phosphate, and calcium carbonate and the like, but not silica materials.

It is an advantage of this aspect of the invention that a toothpaste is provided with improved stain removal ability. . which has an acceptable cosmetic rheology and dentine cleansing properties. It is a further advantage that the desired foaming is achieved by incorporating a polyoxymethylene-polyoxypropylene block copolymer and xanthan into the toothpaste.

8202589 * »8

Further advantages will become apparent from the following description.

According to these aspects, the invention relates to a toothpaste containing 20-8 -. of a liquid wetting carrier, about 5-50 parts by weight of a siliceous polishing material and about 0.05 - 5 parts of a resinous poly (ethylene oxide) comprising toothpaste flocculated particles of said siliceous polishing agent in the presence of said poly (ethylene oxide). As mentioned above, particularly with respect to a clear or opaque gel, the amount of the siliceous polishing agent is in the range of 5-50 parts by weight of the toothpaste, preferably 10-30% such as. 10 - 25 # · Such a polishing agent is, for example, a complex al-potassium aluminum aluminosilicate with a refractive index of 1, W + - 1 containing at least 70 # silica, up to 10 # alumina, such as 1-10 #, preferably 0.1 - 3 #, preferably up to about 20 # moisture, such as about 0.5-10 # and up to 10 # of an alkali metal oxide. This material typically has a particle size in the range of up to mic0 micrometer, preferably 1 - k micrometer. The preferred moisture content is 5 - 20 # as measured by combustion at 1000 ° C and the typical alkali metal oxide is 5 - 10 #.

In general. the polishing agent has a bulk density of up to 0.2 g / em at most, such as 0.07 - 0.12 g / cm. Another suitable type of polishing agent is porous amorphous silica anhydride with an average particle size preferably below 20 micrometers and above 1 micrometer, a specific surface area of at least 200 m / µg, preferably at least 100 m / g, and a mass density of at least 3 0.15 g / cm, preferably 0.30 g / cm, such as a dehydrated silica hydrogel (that is, say a xerogel), preferably of the known regular density or intermediate density type. Examples of such amorphous silicic anhydride polishing agents are Syloid 63, Syloid 72, and Syloid 7 (Syloid is a trademark) described in "The

Davison Family of Syloid Silicas ”published by the producer,

Grace, Davison Chemical Company. "Santocel 100" from Monsanto (Santocel is a trademark) is also a suitable tooth abrasive. "Syloid 72" 35 has an average particle size of about U micrometre, a specific surface area of about 3 ^ 0 m / g, a mass density of approximately 3 spring 1.77 g / cm. For "Syloid 63", the corresponding numbers are about 8202589 9 spring 9 µm, about 675 m / g and about .0 g / cm. A quality of, fSantocel 100 "has a specified surface area of approximately 329 m / g eh and a mass density of approximately 0.2¾ g / cm. These amorphous silicic anhydrides can be used individually or mixed.

As mentioned above, the poly (ethylene oxide) contains about 0.05-5% of the toothpaste, preferably about 0.1-1.5 *.

In the toothpaste, the silicic acid polishing agent flocculates in situ in the presence of the poly (ethylene oxide). The flocculated-TO particles can typically. agglomerate with each other to have an apparent particle size of up to about 250 microns or more, typically about 1 to 177 microns, with other for the flocculated particles being passed through a U.S. Pat. screen No. 80 and held on a U.S. sieve No. 325.

Despite the presence of the flocculated particles, the toothpaste is readily formulated to provide a giving appearance and a rheological texture without an excessive "grainy" appearance or a "gritty" feel.

The liquid carrier of the toothpaste according to this aspect of the invention may be a carrier, as indicated above, wherein the components of the toothpaste are again aligned to form a crane or gel mass of the given consistency formed from a spray tube or pump holder or compressible tube (for example aluminum, lead or plastic) can be pressed.

In addition to the resinous (polyethylene oxide), further gelling or binders may be added, such as sodium carboxymethyl cellulose, Irish mass, xanthan, and the like, in amounts of about 0.5-7 * Xanthan is preferred. The total amount of gelling and binder in the toothpaste can be about 0.1-12% by weight.

[The toothpaste according to this aspect of the invention may contain an anionic, nonionic, cationic or amphoteric surfactant to obtain increased polylactic distillation, the thorough and complete dispersion of the present compositions in the oral cavity. and make the present compositions more cosmetically acceptable.

A preferred surfactant is the non-ionic block copolymer of polyoxyethylene and polyoxypropylene as described above.

Other useful nonionic surfactants include condensates of sorbitan monostearate with approximately 5 moles of ethylene oxide. Amphoteric agents include quaternized imidazole derivatives available under the trademark "Miranol" such as Miranol CgM.

Suitable types of anionic solids are water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monosulfated monoglyceride of hydrogenated coconut oil fatty acids, higher alkyl sulfate and, such as sodium inlauryl sulfate, alkyl lauryl sulfonate, such as sodium rhinodonodyl sulfonate sulfonate containing the olefin group 1.2-21 carbon atoms, higher alkyl sulfoacetates, higher fatty acid esters of 1,2-15 dihydroxypropane sulfonates and the substantially saturated higher aliphatic acylamides of lower aliphatic amino carboxylic acids, such as those having 12-16 carbon atoms in the fatty acid, alkyl or acyl groups and the like. Examples of the latter amines are β-lauroyl sarcosine. and the sodium, potassium and ethanolamine salts of ΙΓ-lauryl, K-20 myristoyl and ΙΓ-palmitoyl sarcosine, which may be substantially free of soap or a similar higher fatty acid material which tends to significantly enhance the effect of these compounds Reduce. The use of these sarcosine compounds in toothpaste compositions of the invention is particularly advantageous since these materials have long-lasting and highly elastic properties, counteracting acid formation in the oral cavity caused by carbohydrate degradation and also a certain reduction in the solubility of create the tooth enamel in the acid solution.

Cationic surfactant germicides and antibacterial compounds, such as diisobutylphenoxyethoxyethyl dimethylbenzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, tertiary amine with a fatty acid alkyl group (of 12-18 carbon atoms) and two (poly) oxyethylene groups attached to the nitrogen ( typically containing in total 2 - 50 ethanoxy groups per molecule) and salts thereof with 35 acids, and the compounds of the structure of formula 1 of the fonmile sheet, wherein R is a fatty acid alkyl group having 12-18 carbon atoms 8202589 t - --——................ — ..........

· 11 contains X, Y and X in total 3 or higher, and salts thereof with inorganic or organic acids can also be used. It is preferred to use about 0.05-5 wt.% Of the aforementioned surfactants in the present toothpaste.

Another aspect of the invention is a toothpaste in which the wetting agent present is maltitol and the polishing material. is a complex alkali metal aluminosilicate. Such toothpaste is visually clear.

In recent years, visually clear toothpastes * 10 have developed, comprising a dentifrice or polish. Such dental cleaning or polishing agents are generally siliceous. of nature with refractive indices of about 1.44-1, b-T- By using such materials, it is possible to prepare toothpastes in which the refractive index of the liquid carrier corresponds to that of the siliceous polishing agent. This is typically accomplished by using glycerol and / or sorbitol as wetting agents in the. liquid carrier, since glycerol has a refractive index of 1.73 and sorbitol (70% water solution) of 1.60, since real water. :. -..-- having a refractive index of 1.33, only very little pharmaceutical water-20 (i.e. separated from that associated with other components such as sorbitol) could be used without significantly lowering the refractive index and reducing or losing clarity cause.

Attempts have been made am visually. develop clear toothpastes in which less glycerol and / or sorbitol can be tolerated. For example: (1) In U.S. Patent 3,842,167, maltodextrin is recommended as a non-wetting component of the liquid phase to reduce the amount of glycerol and / or sorbitol; (2) U.S. Patent 3,927-202 discloses various non-siliceous phosphate polishing agents that allow modification of the refractive index range of the liquid carrier; U.S. Patent 4,007-260 discloses a silica polishing agent having a refractive index of about 1,410-1,440.

It is an advantage of this aspect of the invention that a visually clear toothpaste can be obtained which contains a liquid carrier 8202589 * 12 containing a wetting agent with a brewing index of about 1.1 * 8 (eg about 1.1 * 750 - about 1.1 * 81 * 9) and water.

It is a verier advantage that an increased amount of free water can be used over those previously used in visually clear toothpastes containing an alkali metal aluminosilicate polishing agent having a refractive index of about 1.1 * 1 * to about 1.1 * 7 and a wetting agent having a refractive index of about 1.1 * 8. The amount of water is not so high that it leads to undesired drying of the toothpaste due to a significant evaporation of the water, especially in view of the presence of maltitol. Other advantages will become apparent upon consideration of the following examples and description.

In accordance with this aspect, the invention relates to a visually clear toothpaste containing a carrier containing about 0.5-10% by weight of a solid part of a gelling agent and about 50-5% by weight of a liquid portion comprising (a) a wetting agent in which maltitol having a refractive index of about 1.1 * 8 is present as the sole or substantially non-water component of said liquid carrier and (b) water in an amount to add to said liquid a refractive index between about 1.1 * 1 * and about 1.1 * 7, which visually clear toothpaste also contains about 5-50% by weight of a complex alkali metal aluminosilicate polishing agent having a refractive index between 1.1 * 1 * and 1.1 * 7.

The liquid portion of the carrier comprises about 50-91 +, 5% by weight of the visually clear toothpaste, preferably about 55-80%. It contains a humectant consisting wholly or mainly (i.e. more than about 50%) of maltitol. Maltitol is essentially a glycosyl sorbitol, ie, 1-D-alpha-D-glycolpyranosyl-D-glucitol, of the formula 2 of the formula sheet.

It is prepared by hydrogenation of maltose. In almost pure form, it is a glassy solid. It readily dissolves in small amounts of water, and its solutions containing at least about 13% maltitol and up to 27% water are found to have refractive indices of about 1.1 * 8 (ie 8202589 ^ ~~~ - - - · ** '“* ^ * ............" "" —r · *' ** · ι 'll - 13 about 1.4750 to 1.4849 Included in a toothpaste along with separately added water with a refractive index of about 1.333, the liquid carrier can be adjusted to provide a refractive index of about 1.44 to about 1.48 Typically, about 5-25 wt.% Water provide such a refractive index, with lower quantities of water (e.g., about 1.1 + 7) giving a higher refractive index and higher amounts of water (e.g., about .15-23 $) giving a lower refractive index (e.g., about 1.44) Preferably, the refractive index of the liquid carrier is about 1.4¾ to 1.47 and is achieved by about 10 5-10% by weight of formula water. part of the toothpaste refers to water that has been separated from or not associated with water used to dissolve the wetting agent.

Maltitol does not have to be pure in the sense that the sugar alcohol derivative is of pure maltose. Commercial maltitol consisting of maltitol with appropriate amounts of sugar alcohols derived from. maltotriose ,. maltotetrosis and related lower-maltodextrin portions of corn syrup and with. mini- ......

male quantities of D-sorbitol. Thus, a commercial "hydrogenated starch hydrolyzate" tasted from corn syrup with arc maltose content-20 will also be suitable for practicing the invention.

Maltitol is recommended for use in toothpaste • or bean bean is not used as the main preservative for visually better toothpastes * containing a polishing agent.

In this regard reference may be made to "Caries Re-25 search", vol. 14, No. 2, 19S0, biz. 67-74, Rundegren et al (observed that maltitol does not contribute to demineralization); "Sbigaku", vol. 60, No. 6, 1973, biz. 760-765, Matsuo (observed that maltitol is not fermented by Streptococcus salivarius, S); "Acta Odont. Scand.", Vol. 37, No. 2, 1979, biz. 103-115, Birkbed et al and "Caries Research" 30 vol. 2, No. 3 (1978), biz. 128-136, Birkbed (observations made on attack) "Acta Odont. Scand., Vol. 35, no. 5 (1976) biz. 257-263,

Edwardsson et al (observations made on oral bacteria); Japanese patent publication 73 10241 to Sunstar (discloses maltitol as a mouthwashing agent component). Furthermore, maltitol may be a component of a variant of sorbitol known as "non-crystallizing sorbitol" which can be used as a toothpaste moisturizer. The actual 8202589 * »

However, the amount of sorbitol in a non-crystallizing sorbitol is such that a refractive index of about 1 · U8 is not reached, thereby reducing the possibility of variation of the water-wetting carrier formulation compared to that of the invention. It is also noted that fatty acid esters of maltitol and other sugar alcohols as toothpaste flavor components are described in British Patent 2,038,182 of the Lion Dentrifice Company.

Optionally, the liquid phase of the visually clear toothpaste of the present invention in addition to maltitol may contain a small amount (ie, less than about 50%) of the wetting agent or even a non-wetting liquid carrier component, such as maltodextrin. , contain. Humectants as indicated previously, for example, glycerol, sorbitol (typically 70% sorbitol solution), polyethylene glycol U00, polyethylene glycol 600 and the like. .

15. can be applied. " Preferably, maltitol comprises more than 50% by weight of the non-water portion of the Liquid carrier, preferably about 65-100%, Maltitol is typically supplied in about -3-85% solution and is available from manufacturers with including Aldrich Chemical. Company, Merck and Co., Inc., Imperial Chemicals Industries, 20 Pfizer Inc., Lonza, Roquette Freres and Hayashibara Chemical Laboratories.

The solid part of the carrier is a gelling agent as previously indicated, for example, the natural and synthetic gums and gum-like materials, such as Irish moss, alkali metal (eg sodium) carboxymethyl cellulose and xanthan, as well as gum treagacanth, hydroxymethyl carboxymethyl cellulose, polyvinylpyrrolidone, starch, guar gum, sodium alginate, hydrophilic colloidal carboxyvinyl polymers such as those sold under the trademarks Carbopol 93 and 9 ^ 0 and synthetic inorganic silicate clays such as. which sold under the trade names Laponite CP and Laponite SP. These qualities of Laponite have the formula (SigMg ^ ^ Li ^. ^ 0 ^) 0.6 - ^ +. The solid portion of the carrier is typically present in an amount of up to 10% by weight of the toothpaste, and preferably about 0.25-5% by weight. Qualities of

Laponite are typically used in amounts of about 1-5% by weight.

The complex alkali metal aluminosilicate is as described above. It is typically basic in nature, typically a sodium salt and effectively promotes oral cavity hygiene. It is an amorphous powder which contains 8202589? - ..— ---: - “--------------- ................— -------- -: - 15 »15 der & e has the property that when incorporated in the carrier it makes its particles virtually invisible.

- -. . The amount of alumina in the aluminosilicate is typically about 0.1-3% by weight and preferably about 1% by weight. The refractive index of the aluminosilicate is usually between about 0.005 and -...

presently, typically within about 0.001 unit of that of the liquid carrier.

As mentioned, the polishing agent typically constitutes about 5 to 50% by weight of the toothpaste composition and preferably 10 to 30% by weight.

The complex alkali alumino silicate salt has been found to contain interlinked silica to alumina, with Al-O-Si bonds, as described by Temele "Chemistry of the Surface and the Activity of Alumina-Silica Cracking Catalyst" discussions of the Faraday Society 15, no. 8, biz. 270 - 279 (1950) and in particular on biz. 273, figure 1, curve 3, in which the interaction between silica and aluminum ions has been potentiometrically detected. type complex, writes Milliken et al., "The Chemical Characteristics and Structure. res of Cracking Catalysts ", Discussion of the Faraday Society, no. 8, 20 biz. 279-290 (1950) and in particular the phrase connecting pages 28! + and 285. These complexes are clearly different from silica gel as described by Plank et al, "Differences Between Silica and Silica-Alumina Gels I. Factors Affecting the Porous Structure of These Gels",

Journal of Colloid Science, 2, p. 399 - * + 12 (19 ^ 7) and Plank, "Diffe-25 rences Between Silica and Silica-Alumina Gels II. A Proposed Mechanism for the Gelation and Syneresis of These Gels", Journal of Colloid Science 2 ,. pn. 1 + 13 - * + 27, (19 ^ 7), in which the formation of the Al-O-Si bond is described on p. i + 19 -! +22. The aluminosilicate can be described as a silica containing combined alumina.

As mentioned above, the use of maltitol in toothpastes is described in Japanese Patent Publications 15120/65 (Patent No. + 6l 281) and 73/1021 + 1. The first does not describe a siliceous polishing agent; the latter discloses silicic anhydride as a polishing agent. However, it has been found that when silica anhydridide, such as colloldale silicaxerogel available from Grace Davison as Sylold 7! + Is applied in a visually clear toothpaste containing maltitol, 8202589 mm 16-the toothpaste quickly dulls in appearance and dries out on contact with air and forms a cured opaque product. When the aluminosilicate complex of the invention is used, the toothpaste substantially retains its brightest appearance and rheology. Organic surfactants can be used in the compositions of this aspect of the invention to achieve improved prophylactic dilation, promoting the thorough and complete dispersion of the present compositions in the oral cavity. and making the present compositions cosmetically more acceptable. The organic surfactant can be anionic, nonionic, ampholytic or cationic in nature. as indicated above, and it is most appreciable that the surfactant used is a material with solid fork which imparts detersive and foaming properties to the composition.

An alkali metal fluorine-providing compound can be used in the described toothpastes. The alkali metal-fluorine-providing. compound includes sodium fluoride, stannous fluoride, stannous chlorofluoride, potassium stannous fluoride (Sg-KF), lithium fluoride, ammonium fluoride and complex fluorides, such as. potassium fluorosirconate, sodium hexafluorostannate 20 and alkali metal monofluorophosphates. These compounds have a beneficial effect on the care and hygiene of the oral cavity, for example, reduction of the tooth enamel solubility in acid, protection of the teeth against caries and satisfactory retention of the soluble fluoride in the toothpastes of the invention. In particular, the retention level of 25 monofluorophosphate ions as fluoride within the alkali metal monofluorophosphates is very high. The fluorine-containing compound is used in an amount that provides an effective amount of non-toxic fluorine-containing ions to the toothpaste; typically about 0.01-1% by weight, preferably about 1% fluorine. Thus, sodium fluoride is usually used in an amount of about 0.02-2%, preferably about 0.2%, and sodium monofluorophosphate, HagPO2 F, in an amount of 0.1-6.6%. , preferably about 0.76 $.

The useful alkali metal monofluorophosphates include sodium monofluorophosphate, lithium monofluorophosphate, potassium monofluorophosphate, and ammonium monofluorophosphate. The preferred salt is sodium monofluorophosphate, HagPO ^ F which, being commercially available, significantly 8202589 ppu --π - <r »

IT

can vary in purity. It can be used in any suitable purity provided that the impurity does not adversely affect the desired properties. Generally, it is desired that the purity be at least about 80 #. For the best results this should be at least 85 # and preferably at least 90 #, based on the weight of. the sodium monofluorophosphate, the remainder consisting essentially of impurities or by-products of the pipeline such as sodium fluoride, water-soluble sodium phosphate salts and the like.

In other words, the sodium monofluorophosphate used should have a total fluoride content of about 12 #, he. preferably about 12, T #; a content of not more than 1.5 #, preferably not more than 1.2 # of free sodium fluoride; and a sodium monofluorophosphate content of at least 12 #. he prefers to include at least 12.1 #, all recalculated as fluorine.

Other monofluorophosphate salts that can be used in the invention include monofluoropolyphosphates such as Ha ^ P ^ OpF, K4P309F, (HH ^ P ^ F, Na3KP309F, (HHj ^ HaP ^ F, and Li ^ P ^ F.

Any suitable flavoring or sweetening agent can be used ... to impart flavor to the compositions of the invention. Examples of suitable flavor components include the aromatic oils, such as, for example, spearmint, peppermint, wintergreen, sassefiras, marjoram, clover, sago, eucalyptus, cinnamon, lemon and orange as well as methyl salicylate. Suitable sweeteners include sucrose, lactose, maltose, sorbitol, sodium cyclamate, perillartine and saccharin. It is convenient to include the flavors and sweeteners together in an amount of about 0.1-5% or more of the compositions of the invention. Chloroform can also be used. Sweeteners are less necessary when anionic surfactants are not present since anionic surfactants impart low heat to the toothpaste.

Antibacterial agents can be used in the described toothpaste in an amount of about 0.01-5% by weight.

Typical antibacterial agents include: 1 H - (chlorobenzyl) -IT- (2, dichlorhenzyl) higuanide; P-chlorophenyl biguanide; 3/5 H-chlorobenzhydryl biguanide; 5 k-chlorohenzhydrylguanylurea; 8202589 * 18 H-3-lauroxypropyl-Ir-p-chlorobenzyrbiguanide; 1,6-di-p-chlorophenylbiguanidohexane; 1j 6-bis (2-ethylhexylbiguanido) hexane; 1- (lauryl dimethylammonium) -8- (p-chlorobenzyldimethylammoniim) octane dichloride; 5,6-dichloro-2-guanidinobenzimidazole; ......

p-chlorophenyl ir * lauryl biguanide; 5-amino-1,3-bis (2-ethylhexyl) -5-methylhexahydropyrimicLine; as well as its non-toxic acid addition salts.

Various other materials can be included in the compositions of the invention and examples thereof are colorants or whiteners or dyes, preservatives, silicones or chlorophylls, ammonia materials such as urea, diammonium phosphate and mixtures thereof, and other ingredients. Auxiliaries can be included in the present composition in amounts which have substantially no deleterious effect on the desired properties and characteristics and are selected and used in the appropriate amounts depending upon the particular. type of preparation concerned. .

Synthetic finely divided fumed silica, such as sold under the tradename Cab-O-Sil M5, Syloid 2kk, Syloid 266 and

Aerosil D-20Q can also be used in amounts of about 1-5 wt / 5 to aid in thickening or gelling the disclosed toothpaste.

The toothpastes should have a pH which is favorable for practical use. A moderate to alkaline pH is preferred.

The following specific examples further illustrate the nature of the toothpaste of the invention. although the invention is not limited thereto. All amounts are by weight unless otherwise indicated.

Examples I - II

The following opaque gel toothpastes were prepared: I '8202589; -----------—------------------------- --------------------------------------.

η T9 - ___ Examples - _JL xi

Glycerol 10.0 10.0

Maltitol 15.0 15.0 5 Sodium aluminosilicate (silica combined with approximately \% combined alumina) Zeo 49B (Huber) 18.0 18.0

Pluronic 108 block copolymer - 3.0

Sodium lauryl sulfate 1.0 10 Xanthan 2.0 2.0

Polyox ¥ SR 301 0.2 0.2

Sodium monofluorophosphate Ο, Τβ Ο, Τβ

Titanium dioxide 0, ¾ 0, ¾

Minor menthol flavor - 0.5 15 Peppermint oil flavor 0.5 -

Sodium saccharine 0.2 · -

Color solution (1 $) 0.05 0.05 -

Water q..s. up to 100 qs. to 100

The toothpaste Tan example I with sodium lauryl sulfate 20 has a desirable foamy character. The toothpaste of Example II also exhibits a very good stable scalp forming character, even though no anionic surfactant has been used. The foam remains in the yellow mouth cavity, with a desirable feel in the mouth when the toothpaste is brushed onto the teeth. Moreover, it does not have a bitter navy even though a slight menthol taste is present and no sweetener is added. The toothpastes have a fine smooth texture and appearance, effectively remove stains and have an acceptable dentine abrasive character. They contain flocculated particles of sodium aluminosillcate.

Similarly desired results are obtained when xanthan of example II is replaced by the low calcium xanthan of example I of the U.S. Pat. No. 2,663,399.

A similar foam and feel is obtained when other block copolymers of polyoxyethylene and polyoxypropylene replace Pluronic P-108, particularly Pluronic F-8T

Polyox WSR-301 is available from Union Carbide Corp.

8202589 · 20 as granules of water-soluble poly (ethylene oxide) resin with a molecular weight of about b,000,000 and a Brookfield viscosity of 1650-3850 cps. (25 ° C, axis 1, speed 2 ppm) in water in an amount of 1 wt. %. Likewise, a similar foaming and feel is obtained when other water-soluble poly (ethylene oxide) resins from Union Carbide Corp. such as Polyox WSR-W-10, W5R-N-80, WSR-W-750, WSR-W-3000, WSR-205 and WSR-1105 which replace Polyox WSR-301 in different conentrations.

The silica with combined alumina as indicated in the examples is obtained from J.M. Huber, Corp. Havre de Grace, Maryland, as Zeo b9 (A or B).

The following clear gel (ill and IV) and opaque gel (V and VI) toothpastes are prepared:

Examples III-VI

15 III · II I VI

Glycerol. 10.0 - 10.0 - '

Sorbitol 16.0 - 15.0 -

Maltitol (active) 16.0. 35.0 15.0 30.0

Hatrium aluminosilicate 20 (silica with combined alumina) 22.0 18.0 18.0 18.0

Pluronic F-108 3.0 3.0 5.0

Pluronic F- 8j - - - 3.0

Xanthan 1.5 2.0 2.0 2.0 25 Polyox WSR-301 0.2 0.2 0.2 0.2

Examples

III IV V VI

Hat r ium mono fluo rf0 s phate 0.76 0.76 0.76 0.76

Titanium dioxide - - 0, U 0, ¼ 30 Mild bulb flavor 0.5 0.5 0.5 0.5

Color solution (1%) 0.05 0.05 0.05 0.05

Water q.s. to 100 q.s. to 100 q.s. to q, .s. to 100 100

The toothpastes of Examples III and IV are belder 35 and those of V and VI opaque. They have a smooth texture. All four have a very good stable dense foam, that of the toothpaste of Example V being fuller than that of the toothpastes of Examples 8202589 * 21 den III and IV. A larger amount of foam is produced with the toothpastes of Example VI. All foams provide desired feel throughout the oral cavity during brushing. There are no bitter notes. The toothpastes effectively remove deposits and stains 5 and have an acceptable dentin-abrasion effect. They included flocculated deals of sodium aluminosilicate.

The following toothpastes were prepared:

Examples VII-XI

VII VIII IX X XI

Maltisol (active) 30.0 30.0 30.0 30.0 30.0

Sodium aluminosilicate (silica with combined alumina) 12.0 12.0 12.0 18.0 15.0

Calcined alumina 5.0 5.0 5.0 5.0 2.0 15 Plnronic P-108 3.0 3.0 3.0 3.0 3.0

Xanthan 2.0 2.0 2.0 1, T 2.0

Polyox WSR-301 0.2 - - 0.2 0.2 W5R-1105 - 0.2 - - - -.

WSR-N-750 - - 1.0 - - 20 Sodium monofluorophosphate 0.76 0.76 0.76 0.76 0.76

Titanium dioxide 0.4 0.4 0.4 0.4 0.4

Mild bulb flavor 0.5 0.5 0.5 0.5 0.5

Water q, .to qto q, .s.to q, .s.to q, .s.to 100 100 100 100 100 25 The toothpastes of Examples VII - XI have better cleaning properties and provide good, stable, thick foam.

They have a smooth structure, with the toothpastes VII, X and XI containing polyox-WSR-301 having the best texture. They all foam and provide a desired mouthfeel throughout the oral cavity during brushing. There are no bitter notes. They effectively remove stains and have an acceptable dentin abrasion effect. They contain flocculated particles of sodium aluminosilicate.

The following toothpastes were prepared: 8202589 * 22

. "..... --.- Examples XII - XV

m mi χιν xv

Glycerol 10.0 10.0 10.0 10.0

Sorbitol 15.0 15.0 15.0 15.0 5 Maltitol (active) 15.0 15.0 15.0 15.0

Di c alium phosphate-dihydrate 30.0 30.0 15.0 15.0

Anhydrous dicalcium phosphate - - 10.0

Calcined alumina - - - 10.0. Pluronic F-108 3.0 3.0 3.0 3.0 10 Xanthan 2.0 2.0 2.0 2.0

Polyox WSR-301 - 0.2 0.2 0.2

Sodium monofluorophosphate 0.76 0.76 0.76 0.76

Titanium dioxide 0, ¾ 0, ¾ 0, ¾ 0, ¾. Slight hollow taste 0.5 0.5 0.5 0.5 15 Water q... To q...,. To...,. 100 · 100

The toothpastes of Examples XII-XV provide a good stable dense foam. Those of Examples XIII-XV (containing the Polyox material) have a particularly fine smooth texture. The foam. 20 of all toothpastes * give an acceptable feel in the entire oral cavity during brushing. Even though no sweetener is used, the toothpastes have a sweet taste.

Examples XVI-XVII

The following clear gel toothpastes were prepared: ^ Share

XVI XVII

Maltitol {75% 1 s solution) 0.00.00

Hatrium aluminum silsilate (silica containing approximately \% combined alumina -30 Zeo ¾9B-Huber) 18.00 18.00

Pluronic F 108 block copolymer 3.00 3.00

Xanthan 1.70 1.70

Polyox WSH 301 (Union Carbide) 0.20

Titanium dioxide 0 ^ 0 Q, kQ

35 Taste 0.50 0.50

Hatria accharine 0.20 0.20

Deionized water q..s. up to 100 q..s. up to 100 8202589 * »ρρ, ..„ ·, - »- - * ·. - -. - - - 23

Both toothpastes give a stable dense foam and a good mouthfeel; feeling in the mouth of this toothpaste. XVI is very satisfying.

By comparison, the ability to remove tooth stains and to sand the dentine clean, the toothpaste of Example XVT, which contains the Polyox material, removes more stains with less dentine abrasion than the toothpaste of Example XVII without Polyox material. In the toothpaste of Example XVII, flocculated particles of sodium trinminosilicate are formed in situ.

10 The results are as follows:

Toothpaste Percentage of stains - Radioactive dentine - ________ .. "removal removal. .....__ XVI 35 1¾ XVII 22 39 15 In a stain removal test, parts of the human tooth enamel are etched for 2 minutes with 0.1 IT HCl, rinsed .. with water, then attached with a dilute solution of stannous oil. ride, rubbed dry and finally exposed to a flow of hydrogen sulfide gas, which leads to the deposition of a brown stannous sulfide scale. The surface stains are measured with a Gardner Automatic Color Difference Meter. The surface is then brushed with a mechanical brushing machine for 500 leg and spring strokes with a suspension of a toothpaste, after which the remaining stains were measured with the meter. Finally, the remaining stains are completely removed with dental pumice and the reflection is read from this surface. The ability of the '. toothpaste to remove the stains is expressed by the following equation:

Percentage of stains removed * (Rd cnn, - Rd..) 100 ..... ....... 500 strokes_start_

Rd. . - Rd. .

Thumb toe in the early 30s Ed Hd 50Q Slagm and Ed roejevetly the reflectivity values were measured of the initially stained surfaces, after brushing for 500 leg and spring strokes and after removal of the residual stains by pumice treatment.

The RDA values are advancing. obtained by a procedure 8202589 * 2k

based on a radioactive technique as described in the literature; Stookey C.K. and Muhler J.C., J. Dental Research 1 + 7 521 + -538 (1968). Example XVIII

The following toothpaste is prepared and compared to the toothpaste of Example X.

Share

Maltitol (75 $ solution) 1 + 0.00 (30.00 active)

Sodium aluminosilicate (silica, containing approx. Combined alumina-Zeo 1 + 9B-- Huber) 10 18.00

Calcined alumina 5.00

Pluronic F-108 ^ 3.00

Xanthan 1.70

Titanium dioxide 0.1 + 0 15 Taste 0.50

Sodium saccharin 0.10

Deionized water ¢. 3. to 100

The toothpastes of Examples X and XVIII both provide a stable dense foam with a good mouthfeel; the mouthfeel of toothpaste X is particularly satisfactory.

The following results of stain removal and radioactive dentine abrasion were obtained with the toothpastes of Examples X and XVIII, demonstrating the superiority of the toothpaste of Example X containing the Polyox material by the stronger stain removal with an analogous dentine abrasion.

Toothpaste Percentage stain removal RDA

10 65 18 1 + 1 + 1 + 1

Examples XIX - XX

30 The following toothpastes * are prepared:

Share

XIX XX

Maltitol ($ 80) 59l 59.0

Deionized water 10.71+ 10.71+ 35 Sodium monofluorophosphate 0.76 0.76 8202589 pw.j ', II __------ 7 --..- ·, ______________________-— _________— --- --------- - - * »25

Share (Continued)

m XX

Sodium saccharin 0.25 0.25

Sodium carboxymethyl cellulose 0r35 0j35.

5 Polyethylene glycol (Carbovax 600) 3.0 3.0

Silica xerogel (Syloid 74) 18.0 ..-

Sodium aluminosilicate (silica containing approximately 1 * combined alumina -; Zeo 49B-Huber) - 18.0 10 Sodium lauryl sulfate 1 »2 1.2

Taste 1 * 2 1 * 2

The refractive index of Syloid 74 in the toothpaste of Example XIX and Zeo 49B in the toothpaste of Example XX is within about 0 * 005 unit of that of the liquid carrier of each tape paste.

sHfr -yan the toothpastes. is clear and shining in the beginning. After 1 week at room temperature, the toothpaste of example XIX, • containing the silica xerogel, becomes dull in appearance and after exposure to lucid opaque turns whitish and particularly bard.

Under these same conditions, the toothpaste of Example XX remains shiny and clear and retains desired flow properties.

Examples XXI - XXIII _

The following visually better toothpastes were. prepared in which the refractive index of the polishing agent is within 0.005 one-bit of that of the liquid carrier.

Share XXI XXII XXIII Maltitol (73 *) ¢ 2.0

Maltitol (80 *) - 60.0 48.0 30 Deionized water J, 2k 16.6 22.6

Sodium monofluorophosphate 0.76 0.76 0.76

Sodium saccharin 0.25 0.2 * + 0.24

Sodium benzoate 0.50

Sodium carboxymethyl cellulose 0.35 0.4 35 Xanthan - - 1.4

Polyethylene Glycol (Carbowax 600) 3.00 82 () 2 5 8 9 26

Share (Continued) m xxii xxiii

Nat riumaluminosilicate (silica containing approximately \% combined alumina- Zeo b9A 5 in example XXI and Zeo kg / B in examples XXII and XXIII (Huber) 18.00 20.00 20.00

Silica thickener (Syloid 2hk) 5.50

Sodium lauryl sulfate 1.20 1.20 1.20

Taste. 1.20, 0.80, 0.80, 8202589

Claims (19)

1. Toothpaste comprising about 20-80% by weight of a liquid moisturizing carrier, about 0.5-7% by weight of xanthan gum. and. about 1 to 10% by weight of a surfactant, well: surfactant is a surfactant nonionic polyoxyethylene-5-polyoxypropylene block copolymer. Toothpaste according to claim 1, characterized in that resinous poly (ethylene oxide) is present in an amount of about 0.1-5% by weight. Toothpaste according to claim 1 or 2, characterized in that said block copolymer is a solid material. k. Toothpaste according to claim 3, characterized in that said solid block copolymer contains about 80% by weight polyoxyethylene with a molecular weight of said polyoxypropylene of about .3250 or about 70% of polyoxyethylene with a molecular weight of said poly-. Oxypropylene of about 2250. Toothpaste according to claim 2. characterized in that about 1.5-3% by weight of xanthan and about 0.1-1.5% by weight of said resinous poly (ethylene oxide) is present, 6. -. Toothpaste according to claim 1 or 2, characterized in that said liquid moisturizing carrier comprises glycerol, sorbitol, maltiol and mixtures thereof. Toothpaste according to claim 6, characterized in that the maltitol is present as a wetting agent and said toothpaste contains about 5-50% by weight of a complex alkali metal aluminosilicate polishing agent and said toothpaste is visually clear. Toothpaste according to claim 2, characterized in that the toothpaste comprises about 5-50% by weight of the siliceous polishing material. 9. Toothpaste according to claim 8, characterized in that said siliceous polishing material is complex alkali metal aluminosilicate. 10. Toothpaste comprising about 20-80% by weight of a liquid wetting carrier, about 5-50% by weight of a silica 8202589 Λ. Polishing material containing about 0.05-5 wt.% Of a resinous poly (ethylene oxide) containing toothpaste flocculated particles formed by the siliceous polishing material in the presence of said poly-. (ethylene oxide). Toothpaste according to claim 10, with. characterized in that said resinous poly (ethylene oxide) has a reduced viscosity of 0.5 s measured at a concentration of 0.2 g of said poly (ethylene oxide) in 100 ml of acetonitrile at 30 ° C. Toothpaste according to claim 11, characterized in that said resinous poly (ethylene oxide) is present in an amount of 0.1-1.5 wt.%. Toothpaste according to claim 10, characterized in that said siliceous polishing material is a complex alkali metal aluminum silicate with a refractive index of 1.1 u-15 µl. Toothpaste according to claim 13, characterized in that said alkali metal aluminosilicate is sodium aluminosilicate, in which the silica is combined with about 0.1-3% alumina. Toothpaste according to claim 10, characterized in that said flocculated particles have an apparent particle size of about W-ITT micrometer. Toothpaste according to claim 10, characterized in that maltitol is present as a preservative. 1T. Toothpaste containing a carrier comprising 0.5-10 wt.% Of a solid portion of a gelling agent and about 50-9.5 wt.% Of a liquid portion comprising (a) a preservative comprising mannitol having a refractive index of about 1.1 * 8 is present as the sole or predominant non-water component of said liquid carrier and (b) water in an amount around a refractive index to said liquid carrier of between about 1.1 * 1 * and about 1 1 * 7, which toothpaste also contains about 5-50% by weight of a complex alkali metal-aluminosilicate polishing agent having a refractive index of between about 1.1 * 1 * -1 bT and is visually better. Toothpaste according to claim 17, characterized in that maltitol is present in an aqueous solution containing at least about 73% by weight of maltitol. 8202589 * » Toothpaste according to claim 18, characterized in that the maltitol is present in an aqueous solution containing about T3 -85% by weight of maltitol. , 20. Toothpaste according to claim 19, characterized in that the maltitol solution contains about 75-100% by weight of the non-aqueous portion. of said liquid carrier and the water portion of said liquid carrier comprises about 5-25 wt.% of said toothpaste, the water in said water portion being not combined with wetting agent. 21. Toothpaste according to claim 1T, characterized in that said alkali metal mpta-a / l «1 ηττηnnilatrate is wet aluminum aluminosilicate. 22. Toothpaste according to claim 21, characterized in that said sodium aluminosilicate contains about 0.1-3% alumina in combination with silica. Toothpaste according to claim 22, characterized in that said sodium aluminosilicate contains about 1% alumina in combination with silica. 2k. A clear toothpaste according to claim 17, characterized in that the refractive index of said sodium aluminosilicate 20 is within 0.005 units of that of said liquid carrier, 8202589