JPH0223525B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to dentifrices having a high viscosity which is desirable from a rheological point of view. It is important that toothpastes, such as paste or gel toothpastes, have a high viscosity so that they do not become runny. Of course, the viscosity must not be so high that it becomes difficult to extrude from the toothpaste tube. Approximately 50,000~
A viscosity of 420,000 cp, for example about 60,000 to 240,000 cp, is considered to be a desirable high viscosity for a toothpaste-type dentifrice (viscosity is measured using a Bruckfield (Type B) viscometer, model RBF, using a No. 7 spindle). (measured at 22°C and 10 rpm). Toothpaste contains water and moisturizers (e.g. glycerin,
sorbit, polyethylene glycol 400, etc.)
This is combined with a solid phase containing a gelling agent (e.g., carboxymethyl cellulose, Irish moss, gum tragacanth, etc.) to produce a creamy or gel-like consistency, particularly with a viscosity of about 60,000 to 240,000 cp. It is generally manufactured as a toothpaste by mixing the following ratios: Humectants were sometimes considered optional ingredients in traditional formulations, but their absence would generally result in rapid drying of the product. An advantage of the present invention is that the anionic polyelectrolyte type carboxylic acid polymer (homopolymer or copolymer) used as a gelling agent or binder also imparts moisturizing properties to the dentifrice, resulting in a desirable high viscosity (e.g., about 50,000 to 420,000 cp). ) toothpaste will be provided. Other advantages will become apparent from the description below. US Pat. No. 3,429,963 (Shedlovsky) describes dental products containing polyelectrolyte-type polymers, including polyacrylic acid or polyacrylates, as anti-tartar agents. This patent also points out that some of the polyelectrolytes disclosed therein may also impart gelling properties. However, this polymer electrolyte is different from the polymer electrolyte specified in the present invention, which also exhibits a moisturizing effect. Other examples of U.S. patents disclosing polyacrylic compounds for toothpaste include No. 2798053;
(Brown), No. 2975102 (Matsumura et al.), No. 2980655
(Glass et al.), No. 3574822 (Shepard et al.), No. 3904747
(Cordon et al.), No. 3914405 (Shepard et al.), No.
No. 3934001 (Watson) and No. 4003971 (Mannara)
can be mentioned. In one aspect, the present invention provides a gelling agent that further imparts moisturizing properties to a dentifrice having a particle size in which at least about 90% of the particles are less than 500μ and about 99% of the particles are greater than 2μ. and a water-absorbing anionic polyelectrolyte polymer surface-treated with at least one type of polyvalent metal cation. Anionic polyelectrolyte polymers are disclosed in U.S. Pat.
4043952 (Ganslaw et al.). As described therein, there are three types of water-absorbing materials: water-soluble compositions, water-insoluble compositions crosslinked by covalent bonds, and water-insoluble compositions complexed by ionic bonds. . It is this last type of material that is used as a gelling agent in the present invention. Absorbent compositions of the first type (water-soluble) are characterized by substantial water solubility in aqueous media and the presence of anionic groups, preferably of the carboxyl, sulfonic, sulfate or phosphate type. It is a polyelectrolyte made of natural or synthetic polymers. Preferred natural polymers are anionic derivatives of starch or cellulose, and preferred synthetic polymers are carboxylic acid homopolymers or copolymers (eg polyacrylic acid) containing at least 20 mol % carboxylic acid units. Examples of carboxylic acid-containing polyelectrolytes are synthetic copolymers of ethylenically unsaturated monomers and monoethylenically unsaturated carboxylic acids or incompletely neutralized salts thereof. Examples of preferred α,β-monounsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid,
Itaconic anhydride, fumaric acid; half-esters and half-amides of maleic acid, fumaric acid and itaconic acid; crotonic acid, etc. Examples of preferred α,β-ethylenically unsaturated monomers include acrylamide or methacrylamide and N-alkyl and N,N-dialkyl derivatives of these amides with 1 to 18 carbon atoms in each alkyl group, acrylic acid and methacrylic acid. Examples include _C1 - _C18 alkyl esters of acids, vinyl esters, vinyl aromatic compounds, and dienes. Homopolymers of monoethylenically unsaturated carboxylic acids or copolymers of two or more monomers of this type can also be used. Examples are acrylic acid and methacrylic acid homopolymers and acrylic acid/methacrylic acid copolymers. Examples of sulfonic acid-containing polyelectrolytes are homopolymers of monoethylenically unsaturated sulfonic acids (or salts thereof) and copolymers of these with the ethylenically unsaturated monomers mentioned above. Suitable sulfonic acid-containing monomers include aromatic sulfonic acids (e.g.
Styrenesulfonic acid, 2-vinyl-3-bromobenzenesulfonic acid, 2-vinyl-4-ethylbenzenesulfonic acid, 2-alkylbenzenesulfonic acid, vinylphenylmethanesulfonic acid, and 1
-sulfo-3-vinylphenylmethanesulfonic acid), heterocyclic sulfonic acid, (e.g., 2-sulfo-4-
vinylfuran and 2-sulfo-5-allylfuran), aliphatic sulfonic acids (e.g. ethylene sulfonic acid and 1-phenylethylene sulfonic acid), 2
Sulfonic acids containing the above acid groups (e.g., α-sulfoacrylic acid and α-sulfoethylenesulfonic acid), and sulfonic acid derivatives that can be hydrolyzed to the acid form (e.g., alkenylsulfonic acid compounds and sulfoalkyl acrylate compounds) There is. Examples of sulfuric acid-containing polyelectrolytes are those formed by reacting homopolymers or copolymers containing hydroxyl groups or residual polymeric unsaturation with sulfur trioxide or sulfuric acid. Examples are sulfated polyvinyl alcohol, sulfated hydroxyethyl acrylate, and sulfated hydroxypropyl methacrylate. Examples of phosphoric acid-containing polyelectrolytes are homopolymers and copolymers of ethylenically unsaturated monomers containing phosphoric acid moieties (eg, methacryloxyethyl phosphate). Examples of polyelectrolytes formed from natural polymers and their derivatives are carboxylated, sulfonated, sulfated and phosphorylated derivatives of cellulose and starch, such as carboxymethyl cellulose and carboxymethyl starch. natural anionic polyelectrolytes such as alginate, carrageenin, proteins (e.g. gelatin,
casein and soy protein), gum arabic,
Algin, gum chati, is also useful. The preparation of polyelectrolyte type polymers can be carried out by conventional polymerization methods such as solution, emulsion, suspension and precipitation polymerization methods. Polymers of this type are preferably prepared using a free radical polymerization mechanism, although other polymerization mechanisms can also be used, including anionic and cationic polymerization mechanisms. This polyelectrolyte generally has a molecular weight of 10,000 to 1,000,000. Absorbent compositions of the second type (water-insoluble, covalently crosslinked) contain the anionic polyelectrolyte of the first type, which is water-insoluble but covalently crosslinked. , and can be formed by modification so as to be water-swellable. Typically, a polyfunctional compound such as divinylbenzene is added to a polyelectrolyte such that it intercalates into multiple polyelectrolyte polymer chains or attaches to available side chain functionalities of multiple polymer chains. Copolymerize with a prepolymer of monomers to form a molecular electrolyte. Conventional polymerization methods can be used, including ultraviolet light and other radiation-initiated polymerization mechanisms. Examples of suitable polyfunctional compounds include divinyl compounds (e.g. divinylbenzene, divinyldiethylene glycol diether, divinylphenylsilane and divinyl sulfone), allyl compounds (e.g. triallyl cyanurate, trimethylolpropane diallyl ether,
allyl methacrylate, allyl acrylate, allyl crotonate, diallyl phthalate, diallyl succinate and diallyl sutucarose), polyfunctional acrylates and methacrylates (e.g., tetraethylene glycol diacrylate, triethylene glycol dimethacrylate, pentaerythritate tetra) acrylates, ethylidene dimethacrylate and trimethylolpropane trimethacrylate) and multifunctional acrylamides and methacrylamides (eg, N,N'-methylenebisacrylamide and N,N'-methylenebismethacrylamide). This second type of absorbent composition (similar to the third type described below) forms gelatinous aggregates of liquid-swollen particles in the presence of large amounts of body exudates; At least about its own weight
It is described as being able to absorb 15 times as much body exudate and still retain the absorbed exudate even when subjected to pressures that deform the aggregate. The third type (water-insoluble, complex salt formed by ionic bonding) of the absorbent composition (material used in the present invention) is an absorbent composition (material used in the present invention) in which the above-mentioned first type of anionic polyelectrolyte is formed by forming a complex salt by ionic bonding. Therefore, it can be formed by deforming it so that it is water-insoluble but water-swellable. Polyvalent metal cations are used in the complexation of polyelectrolyte polymers to modify the entire polymer complex to be substantially water-insoluble, but still highly swellable, in aqueous media. This cation has a valence of at least 3 and has a valence of at least 3, such as B, B,
Selected from cations of metals belonging to the B, B, B,, A, A, A, and A groups. Preferred metals are those that are orally acceptable such as aluminum, zirconium and iron. Aluminum is a particularly preferred metal. The metal compound used to supply this cation can be added to the polyelectrolyte solution before, during, and after polymerization of the polyelectrolyte monomers, the only restriction being that the polyelectrolyte The compound must be at least ionizable or soluble in the system. Polyvalent metals are basic,
They can be added to the composition as acidic or neutral salts, hydroxides, oxides or other compounds or complexes. However, these metal compounds or complexes still have at least some degree of solubility in water or organic solvents in which the polymer electrolyte and its constituent monomers are soluble at the time of cation introduction. Examples of inorganic salts include chlorides, nitrates, sulfates, borates, bromides, iodides, fluorides, nitrides,
There are perchlorates, phosphates and sulfides such as aluminum chloride, aluminum sulfate, ferric sulfate, ferric nitrate and zirconium chloride.
Examples of organic salts include carbonates and carboxylates such as formates, acetates, butyrates, hexanoates,
Adipates, citrates, lactates, oxalates, oleates, propionates, salicylates, glycinates, glycolates, and tartrates (e.g., aluminum formate, basic aluminum acetate, aluminum citrate) , aluminum diformate, aluminum triformate, ferric acetate, aluminum octoate, ferric oleate, zirconium lactate, and zirconium acetate). Ammonia and amine complex salts of these metals, especially those coordinated with ammonia, are particularly useful. Amines capable of forming such complexes include morpholine, monoethanolamine, diethylaminoethanol, and ethylenediamine.
Examples of such complex salts include ammonium zirconyl carbonate, ammonium zirconyl glycinate and ammonium zirconium chelate of nitrilotriacetic acid. Polyvalent metal complex salts of organic acids that can be solubilized in the alkaline PH range can also be used. Acetic acid, glutamic acid, formic acid, carbonic acid, salicylic acid, glycolic acid, octanoic acid, benzoic acid,
Anions such as gluconic acid, oxalate and lactate ions are advantageous. Particularly useful are polyvalent metal chelates in which the ligand is a bidentate amino acid such as glycine or alanine. Other organic compounds containing polyvalent metals are also useful, such as metal alkoxides, metal alkyls, and acetylacetone complexes (eg, aluminum isopropoxide, aluminum acetylacetonite, zirconium ethoxy, and triethylaluminum). The cation of one or more metals is 0.01 to 5.0 cation per gram of polymer electrolyte.
It is present in the absorbent composition in an amount of milliequivalents, preferably 0.1 to 1.0 milliequivalents. If the amount of cation is lower than this, the polymer composition will not become water-insoluble;
On the other hand, if the amount of cations is greater than the above, the polymer composition will become water-insoluble, but will also lose its water-swellable properties. When the polyelectrolyte has a relatively high molecular weight, the lower cation amounts within the above range are particularly effective. Irrespective of the pH, the higher cation content within the above range contributes to the permanence of the gel formed by exposing the dried complex to the liquid to be absorbed. In general, it has been found that the optimal cation amount varies depending on the ionic size (ionic radius) of the cation. As those skilled in the art of complex formation will appreciate, not all of the available ionic bonds of a given polyvalent cation necessarily bind to different polyelectrolyte polymer chains. Particularly for cations with valences or oxidation states greater than 3, such as zirconium, the formation of intramolecular salts (i.e., when one cation carries one polymer chain or a number of polymer chains less than its valency) (binding) occurs to an unspecified degree depending on the spatial geometric relationships, relative concentrations, etc. of the reactants. This third type of composition has good absorbency when the molecular weight of the polyelectrolyte is in the significantly higher range of 10,000 to 1,000,000 as mentioned above. Therefore,
Various difunctional monomers such as allyl methacrylate may be used to chain extend the polyelectrolyte prior to exposure to cations. However, of course, the amount of chain extender must not be so great as to render the polyelectrolyte insoluble in the aqueous medium. When the chain length of the polyelectrolyte is increased, the number of polymer chains available for complex salt formation is reduced, so the amount of cations used can be reduced. The absorption properties of the composition are improved by incorporating up to about 95%, preferably 40-85%, of the anionic groups of the polyelectrolyte with a suitable base (e.g., alkali metal oxide, primary, secondary or tertiary amine, etc.). This can also occur when neutralized by This neutralization acts to uncoil and straighten the polymer chains in the aqueous liquid,
As a result, the final complex salt thus becomes more swellable in the presence of liquid. Polyelectrolytes need to be substantially water-soluble at a pH between 2.0 and 8.5 in order to utilize complex salt formation with metals to form the desired water-insoluble absorbable complex salts. It is. However, the reversibility of ionic complex formation (different from covalent bonding in this respect)
It is well known in the field of chemistry that when the pH of a complex salt rises above a certain level (i.e., the reversible pH), the complex salt decomposes and returns to its original water-soluble, non-absorbable polyelectrolyte. . The acid strength of acid-type polyelectrolytes has a significant effect on the reversible PH. The higher the acid strength (ie, the lower the dissociative PH), the lower the reversible PH. For example, polyacrylic acid, a weak polymeric acid, decomplexes at pH 8.5-9.0, while styrene sulfonic acid, a very strong polymeric acid, decomplexes at a pH of 8.5-9.0.
The complex salt is resolved at a pH of 3.5 to 5.0. A preferred composition is polyaluminum acrylate cation complex salt. Aluminum cations are typically added (as aluminum acetate) during the free radical catalyzed precipitation polymerization of acrylic acid in an amount of approximately 0.3 milliequivalents of aluminum per gram of polymer according to the composition table below. . Ingredient parts by weight Potassium acrylate 73.07 Acrylic acid 27.74 Allyl methacrylate 0.19 Basic aluminum acetate 1.49 Absorbent compositions of the second and third types described above (those that are water-insoluble) have a mild to moderate amount of water between the polymer chains. The formation of a network of bonds (covalent bonds in one case, ionic bonds in the other case) renders the composition water-insoluble but water-swellable. The dry absorbent composition becomes a gelatinous aggregate of liquid-swollen particles in the presence of large amounts of body exudates or other water-containing materials. The composition is capable of absorbing at least 15 times its own weight in body exudates, generally at least about 40 times its own weight. Additionally, the composition can be applied at a pressure sufficient to deform the resulting aggregates, typically about 2.5 psi (0.175 Kg/cm ² ).
Capable of retaining absorbed exudate even when exposed to pressures up to Polyvalent metal cations useful in this invention are those with a valence of at least 3, preferably ammonia, zirconium or iron. Aluminum is a particularly preferred metal. The polyvalent metal compound that provides the polyvalent metal cation can be added to the dispersion medium either before, after, or with the absorbent composition. The only restriction on the selection of the polyvalent metal compound is that it must be at least ionizable or soluble in the dispersion medium used. Therefore, polyvalent metal cations can be added to the dispersion medium as basic, acidic or neutral salts, hydroxides, oxides or other compounds or complexes that have at least limited solubility in the dispersion medium. . Examples of suitable inorganic salts include chlorides, nitrates, sulfates, borates, bromides, molides, fluorides, nitrides, perchlorates, phosphates and sulfides, such as aluminum chloride, aluminum sulfate. , ferric sulfate, ferric nitrate and zirconium chloride. Examples of suitable organic salts include carbonates and carboxylic acids such as formates, acetates, butyrates, hexanoates, adipates, citrates, lactates, oxalates, oleates, propionates. , salicylates, glycinates, glycolates and tartrates (e.g. zinc acetate, aluminum acetate formate, basic aluminum acetate, aluminum citrate,
aluminum diformate, aluminum triformate, ferric acetate, aluminum octoate, zirconium lactate, and zirconium acetate). Basic aluminum acetate is a particularly preferred organic salt. Ammonia and amine complex salts of these metals, especially those coordinated with ammonia, are particularly useful. Amines capable of forming such complexes include morpholine, monoethanolamine, diethylaminoethanol, and ethylenediamine.
Examples of such complex salts include ammonium zirconyl carbonate, ammonium zirconyl glycinate and ammonium zirconium chelate of nitrilotriacetic acid. Organic polyvalent metal complex salts that can be solubilized in the dispersion medium can be used. Anions such as acetic acid, glutamic acid, formic acid, carbonic acid, salicylic acid, glycolic acid, octanoic acid, benzoic acid, gluconic acid, oxalic acid and lactate ions are advantageous. Particularly useful are polyvalent metal chelates in which the ligand is a bidentate amino such as glycine or alanine. Other organic compounds containing polyvalent metals are also useful, such as metal alkoxides, metal alkyls, and acetylacetone complexes (eg, aluminum isopropoxide, aluminum acetylacetonate, zirconium ethoxide, and triethylaluminum). The amount of such one or more metal cations ranges from 0.05 to 1 g of the absorbent composition on a dry basis.
It is present in an amount of 10.0 meq, preferably 0.1 to 2.0 meq. Generally, the finer the particle morphology of the dry absorbent composition, the more cation should be used. The most preferred anionic polyelectrolyte is a polyacrylate surface treated or cross-linked with aluminum, particularly from National Starch and Chemical Corp., New Jersey, USA.
It is commercially available under the trademark Permasorb.
590 μ (300 mesh) with this kind of polyacrylate
Smaller particles, with about 99% of the particles larger than 2 microns, are effective as gelling agents that also impart substantial moisturizing properties to the dentifrice. To provide optimal cream properties without complicating wetting of the dentifrice, it is preferred that the particles be substantially within the range of about 74-15 microns. The preferred particle size distribution of the polyacrylate according to the invention is shown in Table 1 below.

[Table] The gelling agent of the present invention is about 0.5 of the weight of toothpaste.
-20%, preferably about 0.5-3%. Generally, the gelling agent is comprised solely of the water-absorbing polyelectrolyte polymer described above. However, if desired, the rheological properties of the dentifrice can be improved by coexisting a small amount (e.g., about half or less of the amount of polyelectrolyte) of another gelling agent (e.g., sodium carboxymethylcellulose, Irish moss, gum tragacanth, etc.). It can be changed. Typical anionic polyelectrolytes have particle size distributions shown in Table 2 below.

【table】

[Table] ○R
Permasorb 10 (200 mesh passes) is preferred.
The liquid phase of the dentifrice may be up to about 85.9% water by weight. If it is desired to change the rheological properties of the dentifrice, humectants may be used in addition to the moisturizing effect provided by the anionic polyelectrolytes. Such humectants may include glycerin, sorbitate, polyethylene glycol 400, and the like, which may be present in amounts up to about 20% by weight of the dentifrice. Although such humectants may not be present, they are preferably present in an amount of about 2-10% by weight of the dentifrice. A preferred humectant is glycerin. A normally water-insoluble, orally acceptable abrasive is dispersed in the dentifrice vehicle. Abrasives are particularly important ingredients in toothpastes and serve an important mechanical cleaning function. Typically, the abrasive is a water-insoluble powder material of a fine particle size that passes through a 140 mesh sieve on the American Standard Sieve Series. Preferably, the particle size is 1 to 40 μm, particularly 2 to 20 μm, and the particle size distribution is a normal distribution within this range. Abrasives useful in the manufacture of toothpastes include dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, crystalline silica, colloidal silica, complex aluminosilicates, aluminum hydroxide (alpha-alumina trihydrate), ), magnesium phosphate, magnesium carbonate, calcium carbonate, calcium pyrophosphate, bentonite, talc, calcium silicate, calcium aluminate,
Included are aluminum oxide, aluminum silicate, and silica xerogel. This list of abrasives and the list of other components of the dentifrice composition mentioned herein are illustrative and not all-inclusive. Therefore, for materials other than those listed for each component, please refer to standard handbooks, such as Sagarin, Cosmetic Science.
and Technology, 2nd edition (1963), Interscience
See Pub., Inc. The content of abrasives in the final product of toothpaste can vary widely. For example, in the manufacture of extrudable toothpastes with commercially acceptable shape retention, 20-75% abrasives (eg, dicalcium phosphate) are typically present. The preferred content of this component is 40-60%. Suitable surfactants or detergent substances may also be present in the dentifrice composition. Compatible materials of this type desirably provide additional cleaning, foaming and antimicrobial properties, depending on the type of surfactant, and the selection criteria are similar. Such detergents are usually water-soluble compounds, and may be of any type, anionic, nonionic, or cationic in structure. It is usually preferred to use water-soluble, non-stick type or synthetic organic detergents. Suitable cleaning agents are known, and include, for example, water-soluble higher fatty acid monoglyceride monosulfates, higher alkyl sulfates (eg, sodium lauryl sulfate), alkylaryl sulfonates (eg, sodium dodecylbenzenesulfonate), 1, Examples include 2-dihydroxypropanesulfonic acid higher fatty acid ester salts. Various surfactant materials may be used in any suitable amount, generally from about 0.05 to 10%, preferably from about 0.5 to 5% by weight of the dentifrice composition. It is another embodiment of the present invention to use a substantially saturated higher aliphatic acylamide (eg, one in which the acyl group has 12 to 16 carbon atoms) of a lower aliphatic aminocarboxylic acid compound. The amino acid moiety is generally derived from a lower aliphatic saturated monoaminocarboxylic acid having about 2 to 6 carbon atoms, usually a monocarboxylic acid compound. Preferred compounds are glycerin, sarcosine,
Aliphatic amides of alanine, 3-aminopropanoic acid, and valine in which the acyl group has about 12 to 16 carbon atoms. However, for optimal effect, N−
Preference is given to using lauroyl, myristoyl and palmitoyl sarcoside compounds. Although the amide compounds can be used in the free acid form, they are preferably used as their water-soluble salts, such as alkali metal, ammonium, amine and alkanolamine salts. Specific examples are sodium and potassium N-lauroyl, myristoyl and palmitoyl sarcoside, ammonium and ethanolamine N-lauroyl sarcoside, N-lauroyl sarcosine, and sodium N-lauroylglyside and alanine. In this specification, for convenience, terms such as "aminocarboxylic acid compound" and "sarcoside" are used to refer to
Refers to such compounds having free carboxylic acid groups or water-soluble carboxylic acid groups. The compositions of the invention may also suitably contain fluorine-containing compounds that have beneficial effects on the protection and hygiene of the oral cavity, such as reducing the acid solubility of enamel and preventing dental caries. Examples include sodium fluoride, stannous fluoride, potassium fluoride, potassium stannous fluoride ( _SnF2KF ), sodium hexafluorostannate, stannous fluoride chloride, sodium fluorozirconate and There is sodium fluorophosphate. Dissociate in water or
Such fluorine-containing ion liberating materials are suitably present in effective but non-toxic amounts, usually within the range of about 0.01 to 1% by weight of their water-soluble fluorine content. A preferred fluorine-containing compound is sodium monofluorophosphate, which is typically present in an amount of 0.076 to 7.6% by weight, preferably about 0.76%.
If the fluorine-containing compound is present, the anionic polyelectrolyte type carboxylic acid polymer is preferably present in an amount of about 0.5 to 2% by weight. Various other materials can also be incorporated into the oral products of the present invention. Examples of this are coloring or brightening agents, preservatives such as sodium benzoate, silicones, chlorophyll compounds and ammonia source materials such as urea, diammonium phosphate and mixtures thereof. Such adjuvants or additives are incorporated into the compositions of the present invention in amounts that do not materially adversely affect the appropriately selected properties and properties thereof, and in amounts appropriate to the type of product. used. For some applications, it may be preferable to have an antimicrobial agent present in the compositions of the invention. Antimicrobial agents can be used in amounts of about 0.01 to 5%, preferably about 0.05 to 1.0%, by weight of the dentifrice composition, representative examples of which include: N ¹ -4-(chlorobenzyl)-N ⁵ -(2,4-
dichlorobenzyl) biguanide; N-chlorophenyl biguanide; 4-chlorobenzylhydryl biguanide; 4-chlorobenzhydrylguanylurea; N-3-lauroxypropyl- ^N5 -P-chlorobenzyl biguanide; 1,6-dichlorobenzyl biguanide; -P-chlorophenyl biguanidohexane; 1-(lauryldimethylammonium)-8-
(P-chlorobenzyldimethylammonium)octane dichloride; 5,6-dichloro-2-guanidinobenzimidazole; ^N1 -P-chlorophenyl- ^N5 -lauryl biguanide; 5-amino-1,3-bis(2-ethylhexyl) -5-methylhexahydropyrimidine; and non-toxic acid addition salts thereof. Suitable flavors or sweeteners may also be used to impart flavor to the compositions of the invention. Suitable fragrances are those that are less volatile than chloroform. Examples of suitable fragrance ingredients include fragrance essential oils (e.g., spearmint oil, peppermint oil, wintergreen oil, satsafras oil, stew oil, sage oil, eucalyptus oil, marjolan oil, cinnamon oil, lemon oil, and orange oil) and salicylic acid. There is methyl. Saccharic acid imparts sweetness to toothpaste. Suitable sweeteners include saccharin, sucrose, lactose, maltose, sorbitate, sodium cyclamate, the dipeptides of US Pat. No. 3,939,261 and the oxathiazone salts of US Pat. No. 3,932,606. The total amount of flavoring and sweetener is approximately 0.01 to 5.
It is appropriate to account for the weight. The pH of toothpaste is 5.0-9.0, preferably about 6.0-
Should be 7.5. Here, PH means the PH value directly measured with toothpaste before it changes over time. The manufacture of the dentifrice of the present invention involves preparing a premix of water, anionic polyelectrolyte and additional gelling agent (if used), adding humectant (if used), and then polishing. This can be done by mixing the agents (if used). The system is then thoroughly mixed in a planetary mixer under vacuum to completely swell the anionic polyelectrolyte.
Surfactants and fragrances may then be added. Alternatively, the premix contains water and a humectant,
The anionic polymer electrolyte may be added in this order. The invention is illustrated by the following examples, but it will be understood that the invention is not limited thereto. Each composition is manufactured as directed;
All amounts of various ingredients are by weight unless otherwise specified. Example Toothpastes A, B, and C below were manufactured by the method described below.

[Table] This toothpaste is manufactured by adding an anionic polyelectrolyte to the water/glycerin phase and hydrating it, then adding ingredients other than sodium lauryl sulfate and fragrance, and mixing the system under vacuum with a planetary mixer. Finally, sodium lauryl sulfate and fragrance were added.

[Table] The viscosity deviation was still at a high level, which is characteristic of a toothpaste with a desirable creamy consistency. The total soluble fluorine content (unit: ppm) remaining in this toothpaste is as follows.

[Table] Desired level of total soluble fluorine content remains.
Very desirable viscosity, good rheology and high soluble fluorine retention are also obtained using Permasorb 10 (200 mesh passes). This Permasorb material may be substituted for other surface treated polyelectrolytes mentioned above. It is clear that the above embodiments are merely illustrative of the present invention, and that various modifications are possible.

Claims (1)

[Scope of Claims] 1. As a gelling agent that further imparts moisturizing properties to a dentifrice, at least about 90% of the particles have a particle size of less than 500μ, and about 99% of the particles have a particle size of greater than 2μ, and at least Contains approximately 0.5-20% by weight of a water-absorbing anionic polyelectrolyte polymer surface-treated with one type of polyvalent cation;
Usually water-insoluble and dentally acceptable abrasive 20−
The toothpaste containing 75% by weight. 2 The anionic polymer electrolyte is about 0.5 to 3% by weight
A dentifrice according to claim 1, wherein the dentifrice is present in an amount of . 3. The toothpaste according to claim 1, wherein the anionic polymer electrolyte is polyacrylate and the polyvalent cation is aluminum. 4 The anionic polyelectrolyte has a particle size of about 0.0716
About 0.329% by weight is greater than 74μ; About 1.25% by weight is greater than 44μ; About 98.35% by weight is greater than 44μ
4. The dentifrice of claim 3, having a particle size distribution of less than 44μ and an average particle size of about 30μ. 5. The dentifrice of claim 3, wherein in addition to the anionic polyelectrolyte, about 2 to 10% by weight of a humectant is present. 6. The toothpaste according to claim 5, wherein the humectant is glycerin. 7. A dentifrice containing a fluorine-containing compound in an amount to provide about 0.01 to 1% fluorine by weight, and wherein the anionic polyelectrolyte is present in an amount of about 0.5 to 2% by weight. The toothpaste according to item 4. 8. The toothpaste according to claim 7, wherein the fluorine-containing compound is sodium monofluorophosphate.