SE464333B - PRE-PACKED DENTAL CREAM CONTAINING A SYNTHESIS PREVENTIVE ADDITIVES - Google Patents

Description

Alkaline earth metal salt or an alpha alumina trihydrate, has been successfully packaged in soft metal toothpaste containers, including aluminum tubes with an inner coating of an epoxy resin lacquer layer. However, it should be noted that when such toothpastes are packaged in containers with an inner polyolefin surface, such as plastic laminated toothpaste tubes, adversely affected toothpaste dispensers or soft pads, such impulses and liquids separate from solid particles, otherwise the pH of the toothpaste is reduced. materials that provide phosphate ion.

An advantage of the present invention is that phase separation of a toothpaste packaged in contact with a polyolefin material is substantially prevented. Other advantages will be apparent from the detailed description below.

More particularly, the invention relates to a packaged toothpaste comprising at least 20% by weight of a liquid vehicle comprising water and a moisture retaining system of glycerol and sorbitol in a weight ratio of glycerol to sorbitol of from about 0.25: 1 to 3: 1 and a solid vehicle of about 0.05 to 10% by weight of gelling agent and about 20 to 75% by weight of a dentally acceptable water-insoluble polishing material, at least a major proportion of which is a water-insoluble alkaline earth metal salt or alpha-alumina trihydrate, and when alpha- alumina trihydrate is present as a major proportion of said polishing material, in addition a water-soluble material for reducing the pH of the toothpaste to about 6 - 8, said pH reducing material providing phosphate ions. The packaged toothpaste is characterized in that it is in direct contact with a packaging surface of a polyolefin resin and that it contains polyethylene glycol as a syneresis-preventing additive, which has an average molecular weight of about 200-1000 and which is present in such an amount that the weight ratio of the total amount of glycerol and sorbitol to polyethylene glycol is about 60: 1-6: 1. 464 333 In toothpaste formulations, the liquid and solid materials are necessarily proportioned so that a creamy mass is formed with the desired consistency, which can be extruded from the package. Thus, the liquids in the present toothpaste comprise mainly water, glycerol and sorbitol together with a minor amount of polyethylene glycol having an average molecular weight of about 200 - 1000, preferably about 600 - 1000. The total amount of liquid vehicle comprises at least about 20% by weight of the preparation. . Preferably, a gelling agent is also used in toothpastes, such as natural and synthetic gum materials and gum-like materials, carrageenans, such as carrageenan or iota-caragenane, gum tragacanth, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, sodium alginate, guar gum, mixtures, starches, starches, starches, mixtures. Carrageenan, sodium carboxymethylcellulose and hydroxyethylcellulose and mixtures thereof are particularly compatible and are preferred gelling agents. When the majority of the polish is water-insoluble alkaline earth metal salt, iotacaragenan is also a preferred gelling agent. The rubber content is usually about 0.05% by weight and preferably about 0.05 - 5% by weight of the formulation.

Water is generally incorporated into the toothpaste in an amount of about 10 to 50 weight percent, preferably about 15 to 35 weight percent. glycerol and sorbitol together usually constitute about 15 - 50% by weight, preferably about 20 - 35% by weight of the toothpaste, the weight ratio of glycerol to sorbitol being about 0.25: 1 - about 3: 1, typically about 0.25: 1 - about 0.8: 1 and preferably about 0.6: 1 - about 0.8: 1. The amounts of sorbitol in the sense used herein refer to sorbitol syrup in a commercially available form, i.e. 70% by weight sorbitol in 30% by weight water. The low molecular weight polyethylene glycol, i.e. an average molecular weight of about 200 - 1000, preferably about 600 - 1000, disperses without difficulty in the liquid vehicle and effectively prevents the toothpaste from undergoing synthesis when in direct contact. contact with a polyolefin resin surface in a toothpaste package. To achieve efficient dispersion, grades of polyethylene glycol, which are normally solid at room temperature, are heated to transfer them to liquid form. The weight ratio of the total amount of glycerol and sorbitol to polyethylene glycol is in the stated range about 60: 1 - about 6: 1, preferably about 15: 1 - about 12: 1, in toothpaste with alkaline earth metal salt or about 10: 1 toothpaste with alpha-alumina trihydrate. Typically, at least 0.5% by weight of polyethylene glycol is present, preferably about 0.5-5%.

Dentally compatible water-insoluble polish is present in the toothpaste in the stated amount of about 20-75% by weight, preferably about 35-60% by weight. At least the main part, ie about 50 - 100%, of the polishing material is water-insoluble alkaline earth metal salt or alpha-alumina trihydrate.

Typical water-insoluble alkaline earth metal salts include dicalcium phosphate dihydrate, anhydrous dicalcium phosphate, calcium carbonate, tricalcium phosphate, calcium pyrophosphate, dimagnesium phosphate trihydrate and magnesium carbonate and mixtures thereof. Most preferred is calcium salt, especially dicalcium phosphate dihydrate or mixture of dicalcium phosphate dihydrate and anhydrous dicalcium phosphate.

Dentally compatible water-insoluble alpha-alumina polishing material is typically used with a small particle size, for example where at least about 85% of the particles are smaller than μm and preferably hydrated, such as that classified as gibbsite (alpha-alumina trihydrate) and normally chemically referred to as Al2O33H2O or Al (OH) 3. The average particle size of the gibbet usually amounts to about 6 - 9 Pm. However, alpha alumina trihydrate with larger particle size, for example where 20-70% of the particles have a size exceeding 20 μm, can also be used. A particularly desirable grade of alpha alumina trihydrate, available from Alcoa as C-333, is a fine grade of gibbsite having the following size distribution: Em Percent <30 94 - 99 <20 85 - 93 <5 28 - 40 As long as the pH of the toothpaste not adjusted, toothpaste containing a substantial amount of alpha alumina trihydrate is usually strongly alkaline, for example about 9 to 10.5. Thus, acidic materials are often added to such toothpastes to reduce the pH, typically to about 6 to 8. Water-soluble phosphate materials, especially inorganic phosphate materials, effectively effect such a reduction in alkalinity. Such materials include orthophosphates, especially orthophosphoric acid and alkali metal or ammonium monoacid orthophosphates or diacid orthophosphates. Sodium diacid orthophosphate and hydrates thereof are preferred. The amount of these materials sufficient to adjust the pH to about 6 to 8, for example sodium diacid orthophosphate monohydrate or anhydrous liquid, is typically present in an amount of about 0.15 to 0.50% by weight. Such phosphate pH adjusting materials make the toothpastes prone to syneresis when in contact with a polyolefin resin surface, unless an additive is present which prevents syneresis. 464 333 When water-insoluble alkaline earth metal salt constitutes the main component of the polishing material, alpha alumina trihydrate, calcined alumina or other additional polishing material may optionally be present in a minor amount, for example in a weight ratio of alkaline earth metal salt to alumina material of about 2 , 5: 1 - approx. 4: 1, whereby the total amount of polishing material in the toothpaste amounts to 25 - 75% by weight.

When alpha alumina trihydrate is the major component of the polishing material, the minor proportion of polishing material, if present, typically constitutes about 5 to 20% by weight of the polishing material, and may be dicalcium phosphate dihydrate, aqueous uric acid dicalcium phosphate, calcium carbonate, phosphate calcium, calcium phosphate, calcium phosphate. , dimagnesium phosphate trihydrate, magnesium carbonate, calcined alumina, zirconium silicate and insoluble sodium metaphosphate.

Organic surfactants can be used in the toothpaste of the present invention to achieve increased prophylactic action, contribute to the achievement of consistent and complete dispersion of the present compositions throughout the oral cavity and make the toothpastes cosmetically more tolerable. The organic surfactant material may be anionic, nonionic, ampholytic or cationic in nature, but preferably a detergent material is used as the surfactant which imparts to the composition detersive and foaming properties. Suitable types of such detergents are water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monosulfated monoglyceride of hydrogenated coconut oleic fatty acids, higher alkyl sulfates such as sodium lauryl sulfate, alkylaryl sulfonates such as sodium sulphonate sulfate olefins; 22 carbon atoms, higher alkyl sulfoacetates, 464,333 higher fatty acid esters of 1,2-dihydroxypropanesulfonates and the substantially saturated higher aliphatic acylamides of lower aliphatic aminocarboxylic acid compounds such as those having 12 to 16 carbon atoms in the fatty acid, alkyl or acyl radicals. Examples of the latter amides are the N-lauroyl sarcosine and the sodium, potassium and ethanolamine salts of the N-lauroyl, N-myristoyl or N-palmitoyl sarcosine, which are to be substantially free of soap or similar higher fatty acid materials. which tend to significantly reduce the effect of these compounds in the composition of the present invention. The amides are particularly advantageous because they show a prolonged and marked effect in inhibiting acid formation in the oral cavity due to carbohydrate degradation in addition to achieving some reduction in the solubility of tooth enamel in acidic solutions. Another desirable material is a long chain fatty acid sodium monoglyceride sulfonate used alone or in combination with sodium lauryl sulfate.

Other particularly suitable surfactants include nonionic agents such as sorbitan monostearate condensate with approximately 20 moles of ethylene oxide, ethylene oxide condensate with propylene glycol ("Pluronic material") and amphoteric agents such as long chain (alkyl) aminoalkylene alkylated amine derivatives. which are available under the brand name "Miranol" such as Miranol CZM. Cationic surfactants and antibacterial compounds such as di-isobutylphenoxyethoxyethyldimethylbenzylammonium chloride, benzyldimethylstearylammonium chloride, benzyldiethylstylstylylammonium chloride, tertiary amines having a fatty alkyl group (having 12 to 18 carbon atoms) or 2 - 50 ethanoxy groups per molecule) and salts thereof with acids, and compounds having the structure 464 333 (CH 2 CH 2 O) 2 H (CH 2 CH 2 O) XH RN-CH 2 CH 2 CH 2 N- (CH 2 CH 2 O) yH where R is a fatty alkyl group containing about 12 to 18 carbon atoms and x, y and z total 3 or higher, as well as salts thereof with mineral or organic acids, can also be used. Preferably, about 0.05 - 5% by weight of the above surfactant is used in the toothpaste. It is most preferred that the surfactant be an anionic material, especially sodium lauryl sulfate.

The toothpaste may suitably also contain a fluorine-containing compound which has a beneficial effect on the care and hygiene of the oral cavity, for example reduction of enamel solubility in acid and protection of the teeth against decay.

Examples include sodium fluoride, stannous fluoride, potassium fluoride, potassium stannous fluoride (SnF2 KF), sodium hexafluorostannate, stannous chlorofluoride, sodium fluorosirconate and sodium monofluorophosphate. These materials, which dissociate or release fluorine-containing ions into water, may conveniently be present in an effective but non-toxic amount, which is usually in the range of about 0.01 to 1% by weight of the water-soluble fluorine content therein.

The preferred fluorine-containing compound is sodium monofluorophosphate which is typically present in an amount of about 0.076-7.6% by weight, preferably 0.76%. A mixture of sodium monofluorophosphate and sodium fluoride is also suitable, for example in a weight ratio of about 2: 1 based on fluoride.

Any suitable flavoring or sweetening material may be used for the composition of a flavor for the composition of the present invention. Examples of suitable 464 333 flavoring ingredients include the aromatic oils, for example oils of spearmint, peppermint, evergreens, sassafras, cloves, sage, eucalyptus, marjoram, cinnamon, lemon and orange as well as methyl salicylate. Suitable sweeteners include sucrose, lactose, maltose, xylitol, sodium 6-methyl-3,4-dihydro-1,2,3-oxathiazin-4-one, sodium cyclamate, perillartine and sodium saccharin. Suitably, flavoring and sweetening agents together comprise about 0.0l to 5% by weight or more of the compositions of the present invention.

Various other materials can also be incorporated into the toothpaste.

Examples are color or whitening agents or dyes, anticorrosives, silicones, chlorophyll compounds, ammonia-treated materials such as urea, diammonium phosphate and mixtures thereof and other constituents. Whitening agents such as titanium dioxide, typically in amounts of about 0.5 - 2%, can be beneficial for the appearance of the dental composition, as in aging some discoloration may occur.

The additives are incorporated into the present compositions in amounts which do not substantially adversely affect the properties and characteristics which are sought and selected and used in the proper amounts depending on the particular type of particular composition.

Antibacterial agents may also be used in the oral compositions of the present invention in an amount of about 0.01 to 5% by weight. Typical antibacterial agents include: N1- (4-chlorobenzyl) -N5- (2,4-dichlorobenzyl) biguanide; p-chlorophenyl biguanide; 4-chlorobenzyhydryl biguanide; 4-chlorobenzhydrylguanylurea; N-3-lauroxypropyl-N5-chlorobenzyl biguanide; 1,6-dichlorophenylbiguanidohexane; 1,6-bis- (2-ethylhexyl biguanide) hexane; 1- (lauryl dimethylammonium) -8- (p-chlorobenzyldiemethylammonium) octane dichloride; 6-dichloro-2-guanidinobenzimidazole; N-β-chlorophenyl-N3-lauryl biguanide; -amino-1,3-bis (2-ethylhexyl) -5-methylhexahydropyrimidine and their non-toxic acid addition salts.

In toothpaste containing alkaline earth metal salt polish, various calcium and magnesium suppressants can also be used to adjust the physical properties of the compositions.

Suitable agents are the water-soluble inorganic polyphosphate salts such as tetrasodium pyrophosphate or disodium diacid phosphate, with the partially neutralized or acidic polyphosphate being preferred. Other suitable agents are the alkali metal, preferably sodium, salts of citric acid.

In general, such compounds constitute a minor amount or proportion of the formulation. The exact amount depends on the specific preparation, ie. the physical properties of the toothpaste, but generally amount to about 0.1 - 3% by weight.

The toothpastes should have a pH suitable for use.

A pH range of 5 - 10 is particularly desirable for toothpaste containing water-insoluble alkaline earth metal salt. The pH discussed refers to the pH determined directly on the toothpaste. If desired, materials such as citric acid can be added to adjust the pH to, for example, 6 - 7. For V! (J) Q 464 333 11l toothpaste containing alpha alumina trihydrate is a pH of about 6 to 8, obtained by adjusting with a water-soluble material which provides phosphate ion, particularly desirable.

The package in which the toothpaste is incorporated can be any polyolefin laminate toothpaste tube. For example, the tube may be as simple as described in U.S. Patent No. 3,260.410. As described in an example therein, an aluminum foil having a thickness of about 0.003 cm is heated to a temperature of approximately 170 ° C and a surface of the heated foil is contacted with an extrudable film of a random copolymer of ethylene and acrylic acid (acid). content 3i0.5% and melt index 8i1), while a deee opposite surface is placed against a film of low density polyethylene.

Using driven rollers, a laminated base is obtained in which the copolymer layer is about 15 μm and the polyethylene layer is approximately 13 μm in thickness. The base is then formed into a tube shape and glass tube.

After dividing the formed tubular structure into tube bodies, the tubes can be packed with toothpaste according to the present invention.

Polyolefin laminate toothpaste tubes containing several intermediate layers can also be successfully used for the toothpaste of the present invention without syneresis occurring. For example, the soft multilayer structure of toothpaste tubes described as "prior art" in U.S. Patent No. 4,418,84l can be used as well as the more crack resistant structures described therein. Toothpastes of the present invention packaged in tubes of sheet material according to prior art A and A-1 of U.S. Patent No. 4,418,841 are very satisfactory and undergo substantially no syneresis. These tubes UI 464 353 12 A and A-1 are composed of layers as below, in the order from the outermost to the innermost layer. _¿L_ A-1 3.8pmLDPE 3.8pm LDPE, 1 pm LDPE with pigment 5.1 pm LDPE with pigment 4.1 pm paper 4.1 pm paper 1.8 pm LDPE 5, lpmLDPE 8.4 pm EAA 2 , 5 pm UP 1.8 pm foil 2.5 pm EAA, 1 pm EAA 1.8 pm foil 3.0 pm LDPE 5.1 pm EAA 3.0 pm LDPE, 5 pm Total, 5 pm Total In Tables A and A-1 has the abbreviations the following meanings: LDPE - low density polyethylene EAA - ethylene acrylic acid OPP - oriented polypropylene.

Mechanically actuated dispensers, such as the dispenser for particularly pasty substances described in U.S. Patent No. 4,437.591, may also be used in the practice of the present invention. The container in such dispensers is usually composed of a polyolefin resin such as polypropylene. Thus, the container material is essentially formed as a layer, and its inner surface is in contact with the toothpaste. When the toothpaste of the present invention is packaged in such a mechanical dispenser of polypropylene, it undergoes substantially no syneresis. The benefits of the present invention are also achieved when the toothpaste is packaged in a soft pad with a polyolefin surface, typically of low density or medium density polyethylene.

The following examples further illustrate the present invention, but the invention is of course not limited thereto. All amounts and proportions express by weight unless otherwise indicated.

Example 1 The following toothpastes are prepared to a creamy consistency and packaged in tubes of the laminated structures A and Al, as indicated above: Parts 1 2 3 4 Glycerol 8,000 8,000 8,000 8,000 Sorbitol (70%) 16,000 15,000 15,500 14,000 Sodium carboxymethylcellulose 1,000 1,000 1,000 1,000 Sodium saccharin 0.200 0.200 0.200 0.200 Sodium monofluorophosphate 0.760 0.760 0.760 0.760 Sodium diacid orthophosphate monohydrate 0.250 0.250 0.250 0.250 Deionized water irradiated 19,700 19,700 19,700 19,700 Alpha-alumina 52 0.890 Polyethylene glycol Average molecular weight - 1,000 0.500 2,000 pH 7.0 7.0 7.0 7.1 464 333 14 After aging for at least 13 weeks at 25 ° C, toothpastes (2), (3) and (4) remain creamy in the consistency of laminate tubes of laminate structures A and A-1, while the dental cream (1) separates into liquid and solid phases within one week at 25 ° C in both tubes with structures A and A-1.

Example 2 Toothpastes (1) - (4) are incorporated into a mechanical dispenser in accordance with U.S. Patent No. 4,437,591 with polypropylene containers. Toothpastes (2), (3) and (4) retain their creamy consistency while the dentifrice (1) separates into liquid and solid phases.

Example 3 Results similar to those described above in Examples 1 and 2 are observed when: (i) the relative amounts of glycerol, sorbitol (70%) and polyethylene glycol having an average molecular weight of 600 are: 6: 24: 2 versus 6: 24: 0 and 18 : 6: 2 versus 18: 6: 0, (ii) polyethylene glycol having average molecular weights 200 and 1000 was used instead of polyethylene glycol having an average molecular weight of 600. Toothpastes are packaged in laminated tubes according to U.S. Patent No. 3,260.410, (iii) (iv) The toothpastes are packaged in crack-resistant laminated tubes according to U.S. Patent No. 4,418,84l.

(V) (vi) (vii) (viii) (iX) 464 335 The toothpastes are packaged in soft pads with the following structure from the outermost to the innermost layer: 12.2 μm polyethylene terephthalate 21.3 μm white ethylene acrylic acid 9.0 Pm foil 3.3 Pm ethylene acrylic acid, 4 Fm medium density polyethylene, Mixture of 0.3 parts sodium carboxymethylcellulose and 0.6 parts xanthan was used instead of sodium carboxymethylcellulose as the only gelling material, 3,000 parts calcined alumina replaces 3,000 parts alpha-alumina trihydrate, parts 10,000 parts of alpha alumina trihydrate, and sodium cyclamate replaces sodium saccharin.

Example 4 The following toothpastes are prepared to a creamy consistency and packaged in tubes made from each of the laminated structures A and A-1 as above: 464 333 16 in E1 L Glycergl 10,000 10,000 Sodium monofluorophosphate 0.760 0.760 Sodium carboxymethylcellulose 0.950 0.9250 Sorbitol - 70% solution 15,000 17,000 Polyethylene glycol - average molecular weight 600 2,000 - Deionized water - irradiated 20,090 20,090 Dicalcium phosphate dihydrate 48,760 48,760 Flavor 0.890 0.890 Sodium lauryl sulphate 1,100 1,100 After aging for at least 20 weeks, creamy in consistency in toothpaste tubes of the two structures A and A-1, while toothpaste (2) separates into liquid and solid phases within 4 - 10 days at 25 ° C in tubes of the two structures A and A -1.

Example 5 Toothpastes (1) and (2) are incorporated into a mechanical dispenser according to U.S. Patent No. 4,437.59l, with polypropylene containers.

Toothpaste (1) retains its creamy consistency while toothpaste (2) separates into liquid and solid phases.

Results consistent with the above are obtained when: (i) calcium carbonate replaces dicalcium phosphate dihydrate, (ii) (iii) (iv) (v) (Vi) (vii) (viii) 464 333 dimagnesium phosphate trihydrate replaces dicalcium phosphate dihydrate, the glycerol constituents , sorbitol (70%) and polyethylene glycol with an average molecular weight of 600 are: 6: 24: 2 versus 6: 24: 0 and l8: 6: 2 versus l8: 6: 0, polyethylene glycol with an average molecular weight of 200 and 1000 was used instead of polyethylene glycol with an average molecular weight of 600, the toothpastes are packaged in laminated tubes according to U.S. Patent No. 3,260.410, the toothpastes are packaged in crack-resistant laminated tubes according to U.S. Patent No. 4,418.84l, (the toothpastes are packaged in soft pads with the following structural pads). to the innermost layer: 12.2 Pm polyethylene terephthalate 21.3 Fm white ethylene acrylic acid 9.0 Pm foil 3.3 Pm ethylene acrylic acid, 4 Fm medium density polyethylene, and mixture of 0.3 parts sodium carboxymethylcellulose and 0.6 parts iotacar agenane replaces sodium carboxymethylcellulose as the only gelling material.

Claims (15)

10 15 20 25 30 464 333 18 P a t e n t k r a v Packaged toothpaste comprising at least 20% by weight of a liquid vehicle comprising water and a moisture retention system of glycerol and sorbitol in a weight ratio of glycerol to sorbitol of from about 0.25: 1 to 3: 1 and a solid vehicle of about 0.05 to 10% by weight of gelling agent and about 20 to 75% by weight of a dentally compatible water-soluble polishing material, at least a major proportion of which is a water-insoluble alkaline earth metal salt or alpha alumina trihydrate, and when alpha alumina tri hydrate is present as the major component of said polishing material, in addition a water-soluble material for reducing the pH of the toothpaste to about 6-8, said pH-reducing material providing phosphate ions, characterized in that it is in direct contact with a packaging surface of a polyolefin resin and that it contains polyethylene glycol as a syneresis-preventing additive, which has an average molecular weight of about 200 - 1000 and which is present in such an amount that the weight ratio of the total amount of glycerol and sorbitol to polyethylene glycol is about 60: 1-6: 1. Packaged toothpaste according to claim 1, characterized in that the weight ratio of glycerol to sorbitol amounts to about 0.25: 1 - 0.8: 1 and that the weight ratio of the total amount of glycerol and sorbitol to said polyethylene glycol amounts to about l5: 1 - l0: l. Packaged toothpaste according to claim 2, characterized in that the weight ratio of glycerol to sorbitol amounts to about 0.6: 1 - 0.8: 1. lO 15 20 25 30 464 333 19 Packaged toothpaste according to any one of the preceding claims, characterized in that the average molecular weight of said polyethylene glycol is about 600 - 1000. Packaged toothpaste according to claim 4, characterized in that the average molecular weight of said polyethylene glycol is about 600. Packaged toothpaste according to any one of the preceding claims, characterized in that said polyethylene glycol is present in an amount of at least about 0.5% by weight. Packaged toothpaste according to claim 6, characterized in that said polyethylene glycol is present in an amount of about 0.5 - 5% by weight. Packaged toothpaste according to any one of the preceding claims, characterized in that said alpha-alumina trihydrate is present as the sole polish. Packaged toothpaste according to any one of the preceding claims, characterized in that said material, which reduces the pH value, is inorganic. Packaged toothpaste according to claim 9, characterized in that said inorganic material which reduces the pH value provides orthophosphate ion. Packaged toothpaste according to claim 10, characterized in that said material containing orthophosphate ion is selected from the group consisting of orthophosphoric acid, alkali metal diacid orthophosphate, ammonium diacid orthophosphate, alkali metal monoacid orthophosphate and ammonium monoacid orthophosphate. 10 464 333 20 12. k ä n n e t e c k - n a d Packaged toothpaste according to claim ll, in that said material containing orthophosphate ion is a sodium diacid orthophosphate. Packaged toothpaste according to claim 12, characterized in that said sodium diacid orthophosphate is sodium diacid orthophosphate monohydrate. 14. a package of toothpaste according to any one of claims 1 to 7, in that said water-insoluble alkaline earth metal salt is present and is a calcium salt. 15. Know that said calcium salt is dicalcium phosphate dihydrate. Packaged toothpaste according to claim 14,