KR810001123B1 - High fluoride compatibility dentifrice abrasives and compositions - Google Patents

Abstract

An Abrasive compn. conyains an amorphous silica, pptd. by acidulation of a soln. of an alkaline earth metal silicate in soft water, which is intimately reacted with an alkaline earth, pref Ca, Sr or Mg, partic, Ca, salt to give 10-300, pref. 10-100, ppm. alkaline earth ions. The amorphous silica has a radioactive abrasion value > 40, a compressed mass of 0.24-0.55 g/ml an oil absorption of 70-95 cm3/100g, a BET specific surface of 100-250 m2/g, and a heat loss of 4-6 %. This silica is used in dentifrice pastes.

Description

Toothpaste composition with compatible high fluoride

FIELD OF THE INVENTION The present invention relates to an improved toothpaste polishing agent, particularly to a precipitated silica polishing agent treated with a novel alkaline earth metal suitable for a dentifrice composition having a therapeutic effect, which comprises a soluble fluoride salt as an enamel dissolving agent and a soluble phosphate as a penetrating agent. It is about. The present invention also relates to a method for preparing the improved precipitated silica abrasive and to an improved abrasive-containing toothpaste comprising an enamel dissolving agent (i.e. fluoride) and a tooth permeation agent.

The toothpaste composition exhibits high fluoride compatibility and high washing action.

The abrasive material for the oral cavity serves to remove various deposits including the dental film from the tooth surface. The periosteum is tightly bonded and often brown or yellowish in ugly shape. A good toothpaste material is one that does not excessively polish the dental tissue and removes the gingiva maximally. Therefore, researchers in the field have made an unremitting effort to develop toothpaste abrasives that do not overly polish oral tissue and have satisfactory cleaning power.

Toothpastes that have a therapeutic effect in addition to an abrasive typically contain a fluoride ion source. It is known that the incidence of chia caries occurring on the tooth enamel surface with fluoride ions is reduced. In particular, it is known that fluoride ions interact with enamel to reduce the acid solubility of the enamel, especially when the pH of the solution is about 4-8. Enamel treated with fluoride makes the formation of chia caries more difficult. Therefore, the toothpaste composition having a therapeutic effect provides useful fluoride ions in the brush solution formed in the oral cavity during use.

It has been hypothesized that the efficacy of fluoride treatments showing enamel solubility / anticaries induction depends on the amount of fluoride ions that can be absorbed into the treated enamel. Of course, it is desirable to formulate a toothpaste composition that provides the largest fluoride ions in the formed brush solution. However, the ionic fluoride anti-carriage agent is intended to be used in toothpaste suitable for home use, but the ionic fluoride tends to be inactivated, thereby making it impossible to absorb enamel and thus could not theoretically provide the maximum soluble fluoride.

In other words, toothpaste loses its ability to provide a theoretical maximum of soluble fluoride even in storage rooms (at increasing temperatures). The content of “soluble fluoride” in any given toothpaste composition relates to the ppm concentration of fluoride ions found in the supernatant centrifuged with a 1: 3 (1: 3 toothpaste: water) slurry ratio of water to toothpaste.

Fluoride ion sources tend to interact with toothpaste impurities and toothpaste components such as abrasives, butters and the like. This interaction reduces the ability to provide soluble fluorides when using fluoride sources. The nature of maintaining the level of soluble fluoride in the toothpaste composition after storage is referred to as "toothpaste fluoride compatibility". Thus, toothpaste fluoride compatibility of certain toothpaste compositions is the theoretical maximum percentage of fluoride source measured in actual soluble fluoride after storage at a certain time and temperature (eg, for 1 week at 49 ° C). Similarly, the ability to interact with fluoride sources in order to reduce the level of soluble fluorides measured in theoretical maximum amounts of such dentifrice components, such as abrasives, in the presence of a fluoride source (especially in the presence of a pelvic penetrant) will be described herein. It is called ＂. The experimental procedure for determining the dentifrice fluoride compatibility value and the abrasive fluoride compatibility value will be described in detail later.

One of the particularly troublesome toothpaste formulations in formulating fluoride toothpastes is precipitated silica abrasives. Precipitated silica abrasives can be preferably used in toothpaste because they preferably exhibit low dentin polishing values. Certain precipitated silica abrasives of the prior art are usually compatible with soluble fluoride sources, but are highly abrasive and insufficient for effective cleaning. Some other precipitated silica abrasives of the prior art show acceptable washing behavior but have been shown to have low abrasive fluoride compatibility as measured by the method described below. It is evident that none of the prior art precipitated silica abrasives exhibited both "high abrasive fluoride compatibility" and acceptable cleaning behavior (indicated by standard radioactive dentin polishing values). Therefore, there is a clear need to formulate precipitated silica abrasives that exhibit both high “polishing agent fluoride compatibility” and acceptable cleaning action. It is therefore an object of the present invention to provide a precipitated silica abrasive which exhibits a high “polishing agent fluoride compatibility” and an acceptable cleaning action.

Toothpaste components that are particularly susceptible to destruction of soluble fluoride components in certain toothpaste compositions are soluble phosphates. Soluble phosphate for toothpaste enhances the ability of fluoride ions to penetrate the pubic membrane. For this reason, it is preferable to include soluble phosphate in the fluoride toothpaste composition. However, toothpastes exhibit low toothpaste fluoride compatibility values, especially when soluble phosphate penetrant penetrants tend to increase the loss of soluble fluoride in toothpastes containing this material, especially when combined with silica tooth polishing agents. There is an obvious need to formulate precipitated silica abrasives that exhibit high toothpaste fluoride compatibility when soluble phosphate is used in the toothpaste fluoride as a permeate penetrant.

There is a need to provide fluoride dentifrices that may include precipitated silica abrasives in combination with soluble phosphates, thus providing fluoride dentifrice compositions containing soluble phosphates and precipitated silica abrasives and exhibiting relatively high values of soluble fluorides after storage. It is an object of the present invention.

It has surprisingly been found that the above objects are achieved by the present invention which provides a novel precipitated silica abrasive treated with an alkali metal material, in particular calcium. The present tooth polishing agents can be used to make fluoride toothpastes—particularly soluble phosphates—have high toothpaste fluoride compatibility and good cleaning response.

Of course, it is known that toothpaste compositions which have a therapeutic effect include calcium phosphate as an abrasive, but these calcium substances are usually present in large quantities, for example, US Patent Nos. 3,624,199 and 1975 by Noflet and his joint research on December 30, 1971. US Patent No. 3,864,471 to Mars and his collaborators, dated February 7, 1986. Toothpaste components containing small amounts of alkaline earth metals, such as calcium ions, are known in the art and compositions of this type are described in the United States, in particular US Pat. No. 3,991,177, of November 9, 1976, by Vidra. The patent has developed a toothpaste composition comprising from 0.001 to 0.3% by weight of a stabilizer-active agent such as calcium chloride and a stabilizer-active agent of dextrase enzyme. The composition may include a fluoride having a therapeutic effect and includes calcium carbonate as an abrasive.

Other conventional methods for developing toothpaste compositions containing alkaline earth metal compounds or ions include Moth, US Pat. No. 3,995,356, issued June 25, 1963; Rosenthal 3,122,483, Feb. 25, 1964; Hess 3,669,221 dated June 13, 1972; Walter, 3,782,446, January 1, 1974; 3,842,168, October 15, 1974; 3,689,537 dated September 5, 1972 to Cooder. However, none of these prior art patents mentions a therapeutic toothpaste composition containing low structure precipitated silicon dioxide as an abrasive containing about 10 to 300 ppm of alkaline earth metals described in this chapter.

The present invention relates to the preparation of a new precipitated silicon dioxide toothpaste abrasive, a method for preparing the same, and a composition having the excellent toothpaste fluoride compatibility value and the excellent abrasiveness value by incorporating the same into a toothpaste. The main components of toothpaste are water-soluble fluoride ion sources, binders, certain amounts of curb and water.

The present invention relates to a low structure precipitated silicon dioxide material suitable for use as a toothpaste abrasive. The abrasive is ultimately associated with an alkaline earth metal, preferably calcium, of about 10 to 300 ppm, preferably 10 to 100 ppm, relative to the amount of dry matter recoverable. The tooth abrasive material has an abrasive fluoride compatibility in the range of at least 90% and at least 40 preferably RDA of about 70 to 120, fuel loss of about 4 to 6% (hereinafter referred to as LOI) of about 0.24 to 0.55 g / ml. Pavement density, retention absorption in the range of 75 to 95 cc / 100 g and average particle size of about 100 to 250 microns have a BEF surface area of about 100 to 250 m ² / g. When incorporated into toothpaste, dentifrices exhibit a high degree of incompatibility and excellent washing. The definition of low structure silicon dioxide material is described in the aforementioned US Pat. No. 3,893,840.

The tooth polishing material of the present invention is a general method, for example, in U.S. Patent No. 3,893,840 of July 8, 1975, Wisson 3,988,162 of October 26, 1976, and Application No. 703,496, which are simultaneously pending July 8, 1976. Precipitated silicon dioxide produced by the described method. Each of these patents and applications is incorporated herein by reference. The abrasive prepared by the above method was continuously treated with alkaline earth metal ions of the method described in this chapter. In general, a method for producing silicon dioxide is a method of acidifying an inorganic acid and a water-soluble alkali metal silicate solution in order to precipitate silicon dioxide.

The acid pH is maintained by the addition of acid, and the precipitated silicon dioxide produced is filtered and washed, and by-products such as alkali metal sulfate are removed to produce a wet residue. The resulting wet residue was reslurried with saturated or added water and treated with the required amount of alkaline earth metal ions in the form of soluble salts to produce the abrasive material of the present invention.

The abrasive products of the present application are alkaline earth metal ions and treated precipitated silicon oxides developed in U.S. Application No. 723,345, filed September 15, 1976 and Partial Serial Application No. 826,901, filed August 24, 1977. Separated from the composition. Silicon dioxide treated with alkaline earth metals developed in co-pending application No. 826,901 is an abrasive that is useful for incorporation into toothpaste compositions to prevent uneven aluminum toothpaste tubes. The anti-decay precipitated silicon dioxide described in Application No. 826,901 is silicon dioxide produced by the so-called sulfate solution method. In this method, an electrolyte such as an alkali metal sulfate was mixed with an alkali metal silicate solution during the acidification reaction with an acid described in US Pat. Nos. 3,960,586 and 3,928,541.

Whereas the product of Application No. 826,901 refers to precipitated silicon dioxide in which the product is directly mixed in the amount of alkaline earth metals falling within the scope of the present invention, the abrasive product of the present invention differs from silicon dioxide extracted by the sulfate-solution method. This is different. When the silicate solution silica material is used in a specific fluoride containing a toothpaste composition, it does not exhibit the excellent fluoride compatibility value of the present invention. The toothpaste polishing agent of the present invention exhibits excellent fluoride compatibility values only by silicon dioxide produced by the so-called purified water alkali metal silicate method.

The silicon dioxide abrasive of the present invention is an alkaline earth metal-treated precipitated silicon dioxide prepared with a purified water silicate solution. Further, alkali metal ions directly bonded to silicon dioxide produced in the product of the present invention must be present within a specific narrow range to provide fluoride compatibility for use in the present invention. Therefore, the abrasive product of the present invention has been measured by the toothpaste fluoride compatibility described in the present application in the prior application No. 826,901 usually shows a value of 89% or less while the fluoride compatibility value of at least 90%.

The improved fluoride compatibility of the toothpaste polishing agent was theorized based on how the siltanol group was attached to the surface of the silicon dioxide product. Therefore, the siltanol group on the surface of the material of the purified silicate derived from the silicon dioxide of the present invention is higher than the sulfate solution silicate derived from silicon dioxide developed in US application No. 826,901 filed on August 24, 1977. It is believed to be more useful. Furthermore, since the surface acidity of the purified water silicon dioxide is siltanol, the acidity higher than that of silicon dioxide derived from the sulfate solution method is higher. Since the siltanol groups differ from each other in the two materials, the intrinsic epidermal acidity is not well damped in the calcium treatment for / fluoride compatibility in the sulphate solution product. The product of Application No. 826,901 has a higher abrasive value than the silicon dioxide of this application. The abrasive is therefore distinguished from silicon dioxide treated with alkaline earth metals described in co-pending application number 826,901.

The precipitated silicon dioxide abrasive can be prepared well by loading it in a reactor for acidifying an alkali metal phosphate solution, preferably an aqueous solution of sodium silicate solution. The water-soluble sodium silicate solution has a concentration of sodium silicate, preferably from 12.5 to 15.5% by weight, more preferably from about 10 to 17% by weight, and the best result is a purified aqueous solution with sodium silicate composition of Na ₂ O, 26 SiO ₂ . . The temperature of the water-soluble sodium silicate solution is added at about 50 to 95 ° C., and the solution is acidified by continuously adding an aqueous solution of about 10 to 20% by weight of an acid-free acid so that the pH is in the range of 8.5 to 10.5. Sulfuric acid is preferable as the inorganic acid because sulfuric acid shows the best result. However, as known in the art (see US Pat. Nos. 3,988,162, 3,893,840, and Application No. 703,496, filed Jul. 8, 1976), other acidifying agents may use nitric acid, phosphoric acid, hydrochloric acid, carbonic acid, and the like. have. What was developed in the above-mentioned prior art patent and application number 703,496 was indeed inserted into this chapter to develop a method for producing silicon dioxide of the type considered in this chapter.

In the most preferred embodiment, only a portion of the alkali metal silicate solution was loaded into the reactor, stirred and the remainder of the sulfuric acid and alkali metal silicate solution was simultaneously added to the initial silicate solution at the reaction temperature.

Preferably about 8-12 wt% metal silicate is initially loaded into the reactor. The time for which the alkali metal silicate and sulfuric acid are added to the alkali metal silicate in the reactor can be predetermined and generally depends on the volume of the reactor and the difficulty of controlling the temperature and agitation. After the addition of the alkali metal silicate solution, the acidifying agent is continuously added until the pH of the reaction slurry is about 60. or less, preferably 4.6 to 5.0. The resulting slurry is precipitated silicon dioxide contained in the reaction medium.

After the pH was about 6.0 or less, the slurry was added during the digestion period at a temperature of 10 ° to 30 ° above the reaction temperature, and the reaction pH was adjusted again as necessary. The resulting slurry is then filtered and washed with added water to remove other reaction byproducts such as sodium sulfate that may be included in the silicon dioxide product. The humidity of the resulting filtrate residue is about 60-66 and is a low structure material. The reaction described above is usually the same as the reaction developed in Applicant's Patent Nos. 3,893,840, 3,988,162 and Application No. 703,496 on the preparation of silicon dioxide prepared from purified water alkali metal silicates.

In the process of the present invention, upon filtering and washing the silicon dioxide wet residue, the material was treated with alkaline earth metal ions to produce the novel abrasive product of the present invention. According to the method of the present invention, the wet-cleaned filtration residue is made to be reslurried with its own water or agitated by adding purified water at ambient temperature to make it reslurried. While stirring, the slurry is treated with sufficient alkaline earth metal ions, preferably calcium ions, in the form of soluble salts to give alkaline earth metal of about 10 to 300 ppm or 0.001 to 0.03 wt% (depending on the weight of dry recoverable silicon dioxide). It binds the ions closely with silicon dioxide.

Alkaline earth metal ions added in the present state are easily used, and calcium ions which are inexpensive and easily incorporated into silicon dioxide are preferable. Calcium ions can be incorporated into silicon dioxide at this stage in water-soluble form, ie, at least 0.07 g / 100 cc H ₂ O at 20 °, such as calcium nitrate, calcium oxide, calcium hydroxide or a solution of calcium chloride. Marble or calcium hydroxide is preferred. Organic salt solutions such as calcium acetate, calcium formate and the like may also be used. Strokedium and magnesium salts of alkaline earth metals can also be used. Edible salts can also be used.

After treatment with alkaline earth metal ions, the residue slurry was stirred vigorously for 10-20 minutes, preferably 15 minutes, to produce an effective level of alkaline earth metal for treating the surface of the silicon dioxide abrasive. The product was then dried. Preferably the drying is carried out in a spray dryer having a temperature of 483 ° C. and an outlet temperature of 122 ° C. known in the art.

[Toothpaste]

The present invention provides a toothpaste having a therapeutic effect containing the novel precipitated silica polishing system. In addition to the abrasive, the toothpaste composition of the present invention comprises a specific amount of water soluble fluoride ion source, binder, curb and water. These additional toothpaste components and optional toothpaste components are described in detail below.

[Polishing agent]

As noted above, the present precipitated silica abrasives are particularly suitable for incorporation in dentifrice compositions that exhibit a therapeutic effect containing fluoride. Toothpaste having a therapeutic effect using the above abrasives satisfactorily cleans teeth and exhibits excellent abrasive fluoride compatibility. The toothpaste composition essentially contains about 6 to 35% by weight, preferably about 10 to 20% by weight of the precipitated silica abrasive.

[Fluoride Ion Source]

The toothpaste composition having the present therapeutic effect also includes a water-soluble fluorine-containing substance which provides fluoride ion in an aqueous solution of about 0.01 to 3% by weight, preferably about 0.1 to 1.0% by weight. The fluoride ion combines with tooth enamel to reduce enamel solubility to acid. Application of fluoride ions to tooth enamel prevents the tooth from corroding.

Various fluoride ion-producing materials can be used as the source of soluble fluoride in the composition. Examples of suitable fluoride ion-producing materials are described in US Patent No. 3,535,421 to October 20, 1970 of Brini's many researchers and US Patent No. 3,678,154 of July 18, 1972 to many researchers of Wider, both of which are incorporated herein by reference. Inserted for reference. The excellent sources of fluoride ion used here are sodium fluoride (NaF), tin fluoride (SnF ₂ ), potassium fluoride (KF), potassium fluoride stannous (SnF ₂ -KF), indium fluoride (InF ₃ ), tin fluoride ( Sn F ₂ ), ammonium fluoride (NH ₄ F) and chlorine tin fluoride (SnClF). Sodium fluoride and stannous fluoride and mixtures thereof are particularly good.

When brushing teeth using the toothpaste of the present invention, the fluoride ion in the aqueous solution in contact with the tooth surface is preferably included in the toothpaste composition in an amount of about 50 to 500 ppm, preferably 100 to 400 ppm. In more detail, the solution may be prepared as a toothpaste slurry (weight) of 3: 1 water / toothpaste composition, and the slurry is continuously centrifuged to obtain an aqueous supernatant. The fluoride ion concentration in the supernatant can be measured with a "soluble fluoride" provided by a given fluoride toothpaste composition.

[Binder]

The binder is essentially used to prevent separation of the liquid and solid phase in the toothpaste composition. Such binder materials are known in the field of dentifrice manufacture. The most known ones used as binders are seaweed boneoids such as caracanine (Island archa biscarinine) and cellulose derivatives such as sodium carboxymethylcellulose and hydroxyethylcellulose. Another form of binder suitable for the present invention is a resin such as 1) vegetable resins such as guar resins and 2) fermentation products such as xanthan resins. The binder component is usually included in the toothpaste composition of 0.1 to 5% by weight, preferably 0.2 to 2% by weight. Natural and synthetic water dissipation of water binders are easily corroded by microorganisms and molds, so this toothpaste is preferably added with a relatively small amount of preservative. Examples of commonly used preservatives are esters of parahydroxybenzoate.

Toothpaste binders are described in more detail in U.S. Patent Nos. 2,839,448, issued June 17, 1958, and 3,862,307, issued in January 21, 1975 by Di Gulio. These patents are incorporated herein by reference.

[Stone curb]

Another essential ingredient in this toothpaste composition is curb. Suitable curb agents are also known in the toothpaste art. Curb retains moisture and prevents the toothpaste composition from curing when exposed to air. Some curbs add flavor and aroma to toothpaste compositions. Curbstone is usually included in the toothpaste composition in an amount of about 5 to 55% by weight, preferably about 20 to 36% by weight.

Suitable diluents for the present invention are edible polyalcohols such as glycerin, sorbitol, cleitol and propylene glycol. Sorbitol is often used in a 70% aqueous solution known as sorbo. A mixture of glycerin and sorbitol is particularly good as a curb ingredient in toothpaste compositions.

[water]

Water is another essential ingredient of the toothpaste of the present invention. The water used in the manufacture of commercial toothpaste should be non-ionized and free of organic impurities. Water in the toothpaste composition is about 15 to 80% by weight, preferably about 15 to 40% by weight.

[Optional Ingredients]

In addition to the essential ingredients mentioned above, the toothpaste of the present invention may contain various known optional toothpaste components. The optional ingredients are (1) foaming agents, (2) periodontal penetrants, (3) flavoring and flavoring agents, (4) anti-calcite anti-spotting agents, and (5) pigments and coloring agents.

1) Foam

An excellent optional ingredient is a foaming agent. Suitable foaming agents are those that are stable and foam well through a wide range of non-soap anions, nonions, cations, zwitterions and amphoteric organic purifiers. This type of foam is described in U.S. Patent No. 3,959,458 to Agri-Cola et al., May 25, 1976, and United States Patent No. 3,937,807 to Heplel, February 10, 1976. All of these patents are incorporated herein by reference.

Useful anionic foaming agents are water soluble salts of alkylsulfates of alkyl groups having 8 to 18 carbon atoms and water soluble salts of sulfonated monoglycerides of fatty acids having 10 to 18 carbon atoms. Sodium laurylsulfate and sodium coconet monoglyceride sulfonate are examples of anionic surfactants of this type.

Nonionic foams that can be used in the toothpaste of the present invention can be broadly defined as a compound prepared by concentrating an alkylene oxide group (hydrophilic in nature) and an organic hydrophobic compound which may be aliphatic or alkyl-aromatic in nature. have. Examples of suitable nonionic foaming agents are pluronics, condensation products of alkylphenols for polyethylene oxides, condensation products of ethylene oxide and flopylene oxide and ethylenediamine, ethylene oxide condensers of aliphatic alcohols, long-chain tertiary amine oxides, Long-chain tertiary phosphine oxides, long-chain dialkylsulfoxides and mixtures of these materials.

Zwitterionic synthetic foams usable in the toothpaste of the present invention may be broadly described as derivatives of aliphatic tetramethylammonium phosphonium in which aliphatic groups may be branched, wherein one of the aliphatic substituents comprises 8 to 18 carbon atoms and Another includes anionic water soluble groups such as carboxy, sulfonate, sulfate, phosphate or phosphonate.

The weakly ionic product which can be used in the toothpaste of the present invention is a quaternary ammonium compound having one long alkyl chain having about 8 to 18 carbon atoms such as lauryltrimethylammonium chloride, cetylpyridinium chloride, cetyltrimethyl It can be broadly defined as ammonium bromide, di-isobutyl-phenoxyethoxyethyl-dimethylbenzyl ammonium chloride, coconetalkyltrimethylammonium nitrile, cetyl pyridinium fluoride, and the like. Particularly excellent is the four-membered ammonium fluoride described in U.S. Patent No. 3,535,421 to Brinner et al., October 20, 1970, the fourth ammonium having a detergency. Cationic foams can act as fungicides in certain toothpastes.

Cationic foams usable in the present invention may be broadly described as derivatives of aliphatic binary and tertiary amines in which aliphatic groups may be straight or branched chain, wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and One contains an anionic water soluble group such as carboxylate, sulfonate, sulfate, phosphate or phosphonate.

The amount of the foaming agent included in the toothpaste composition of the present invention is 0.1 to 6% by weight of the total composition.

2) phosphate toothpaste

The toothpaste composition of the present invention is a very preferred optional ingredient and contains about 5 to 12, preferably 7 to 11% by weight of a water-soluble phosphate quench membrane penetrant. The soluble phosphate makes it easy for fluoride ions to penetrate into the dentate membrane which is naturally produced on the surface of the tooth. Fluoride-containing toothpastes using the phosphate grades described in this chapter have been found to enhance fluoride plaque diffusion and improve tooth enamel fluoride absorption compared to fluoride toothpastes that do not contain the phosphate penetrant.

While a relatively high level of soluble phosphate exhibits the permeate penetrating effect of fluoride in fluoride toothpaste, the salts present also simultaneously reduce the soluble fluoride stability of the toothpaste upon storage. Surprisingly, however, it has been found that the soluble phosphate is included in silica-containing fluoride toothpastes and exhibits particularly good fluoride compatibility when a precipitated silica abrasive treated with certain alkaline earth metals is used.

Phosphates optionally included in the toothpaste composition are water-soluble. For the purposes of the present invention, “water soluble” phosphate is a salt that exhibits a solubility of at least about 3.0 g / 100 cc H ₂ O at 20 ° C.

Phosphate is an anion phosphorus compound surrounded by four oxygen atoms in which each atom of phosphorus is arranged at each corner of the tetrahedron. The tetrahedron, chain, ring, and oxygen atom can be divided to form a correlated tetrahedron polymer.

Simple phosphates are ortho phosphates. Polymeric phosphates include polyphosphates such as pyrophosphate and trilipphosphate. Cyclic phosphates are metaphosphates.

Suitable examples of water soluble polyphosphates that can be used in the present invention are tetrapotium pyrophosphate, tetrasodium pyrophosphate, disodium pyrophosphate, sodium tripolyphosphate and potassium tripolyphosphate. Examples of suitable water soluble metaphosphates are monophosphate, sodium trimetaphosphate, sodium hexametaphosphate and sodium heptamethaphosphate. Most of the above water-soluble polyphosphates and metaphosphates are used in hydrated salt form.

The best phosphate useful in the present invention is a simple orthophosphate salt. Orthophosphate salts are derived from the tribasic orthophosphoric acid of the structural formula. Water soluble sodium, potassium and ammonium salts can also be used.

There are about ten different crystalline sodium orthophosphate salts containing various hydrates. For example, they are NaH ₂ PO ₄ , NaH ₂ PO ₄ ㆍ H ₂ O, NaH ₂ PO ₄ ㆍ 2H ₂ O, Oa ₂ HPO ₄ , NaHPO ₄ , 2H ₂ O, NaH ₂ PO ₄ ㆍ 7H ₂ O, NaH ₂ PO ₄ 12H ₂ O, NaH ₂ PO ₄ 6H ₂ O, NaH ₃ PO ₄ 8H ₂ O and mixtures thereof. Good sodium orthophosphates are NaH ₂ PO ₄ H ₂ O, NaH ₂ PO ₄ 2H ₂ O and mixtures thereof. Especially good is a mixture of NaH ₂ PO ₄ .H ₂ O and Na ₂ HPO ₄ .2H ₂ O mixed with a weight ratio of monodium to disodium salt within about 1: 3 to 1: 5.

Potassium and ammonium orthophosphate can also be used as periosteum penetrants. Examples of the potassium and ammonium salts are KH ₂ PO ₄ , K ₁ HPO ₄ , K ₂ HPO ₄ ㆍ 2H ₄ O, K ₂ HPO ₄ ㆍ 6H ₂ O, K ₂ PO ₄ ㆍ 3H ₂ O, K ₃ PO ₄ ㆍ 7H ₂ O, K ₃ PO ₄ .9H ₂ O, (NH ₄ ) H ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ , (NH ₄ ) ₃ PO ₄ and mixtures of these salts.

Particularly useful phosphate mixtures for the toothpaste are mixtures of NaH ₂ PO ₄ H ₂ O and K ₂ HPO ₄ 2H ₂ O with a weight ratio of sodium depotium salt mixed in about 1: 3 to 1: 5.

Soluble phosphate of the present invention is a commercially useful material. Such phosphate salts useful in the present invention are described in detail in Kirk and Odmer's Encyclopedia of Chemical Technology, 2nd Edition, Vol. 15, published by Intercontinents, 1968, pages 232-276.

The toothpaste composition preferably contains about 0.5 mol / 1000 g water to 2.0 mol / 1000 g water phosphate in an aqueous solution in contact with the tooth surface when brushing teeth using the toothpaste of the present invention. Again, the supernatant in water and toothpaste slurry of 3: 1 was used to simulate the solution.

Additional dental permeation agents may optionally be added to the fluoride-containing toothpaste of the present invention. The optional ingredient further enhances the fluoride plaque penetration effect exhibited by phosphate. For example, the penetrant is hydroxyl acid and salts thereof, such as citric acid, trisodium citrate, maleic acid and tatar acid. When using the additional periodontal penetrant includes 0.2 to 5.0% by weight of the toothpaste composition.

3) flavoring agent

A fragrance may also be added to the composition. Suitable flavoring agents are winter green oil, peppermint oil, spearmint oil, sasafrase oil and cloves oil. Flavors that may be added are saccharin, dextrose labrobose, aspartame, D-tripropane, acetosulfame, dihydrochalcons and sodium cyclamate. The flavoring agent is usually used in 0.01 to 2% by weight and the flavoring agent is used in the 0.05 to 3% by weight.

4) anti-spot / anti-stone

Phosphorus containing stones and bis-biguanide antispots may optionally be added to the toothpaste of the present invention. Phosphorus-containing anti-stones and related substances, such as disodiumethane-1-hydroxy-1,1-diphosphate, are described in detail in Macon's researcher, Jan. 6, 1970, US Pat. No. 3,488,419. Bigguanide anti-branching agents such as chlorhexidine (1,6-bis (N ⁵ -P-chlorophenyl-M ¹ -biguanido) hexane, soluble and insoluble salts thereof and 1,2-bis (N ^5- Related substances, such as P-trifluorotomethyl-N ¹ -biguanido) ethane, are described in Heppen, U.S. Patent No. 3,934,002, January 20, 1976, Heppel, U.S. Patent No. 3,937,807, February 10,1976 Belgian Patent No. 843,244 of Gamble, December 22, 1976, and Procter and Belgian Patent 844,764 of Gamble, January 31, 1977. These patents are incorporated herein by reference.

When using selective anti-fastening and anti-burning agents, usually 0.01 to 2.5% by weight of the toothpaste composition is included.

5) Coloring and coloring agents, other

Several other optional ingredients known in the art may be added to the toothpaste composition to improve the conventional taste. These are pigments, dyes, stains, and the like. When using these optional ingredients, usually 0.001 to 2% by weight of the toothpaste is included.

The toothpaste composition of the present invention is prepared by only mixing the essential and optional ingredients in any known manner. Once prepared, the composition exhibits a pH value of about 4.0 to 8.0, preferably 6.5 to 7.5 when slurried with the composition at a weight ratio of 3: 1 to water. Fluoride toothpaste in the pH range of 4.0 to 8.0 exhibits particularly excellent tooth enamel dissolution resistance compared to toothpastes having a pH in the above range. At pH ranges of fraud, toothpaste scents relatively easily.

The toothpaste composition of this invention is used by a conventional method. Brush the tooth surface with the toothpaste composition or its slurry and immediately brush and clean it.

When the toothpaste is used in a conventional manner, the toothpaste ointment or slurry is usually in contact with the toothpaste surface for at least about 30 seconds. More preferably, the toothpaste ointment or slurry is in contact with the tooth surface for at least about 60 seconds.

The following examples illustrate the invention and do not limit the scope thereof. In the following examples, unless otherwise indicated, parts means parts by weight.

Example 1

A 30,000-liter impregnated net reactor jacketed for steam heating with a specific gravity of 1.121 and aqueous sodium silicate solution of 42 grams of sodium oxide (3.78% sodium oxide (Na ₂ O), 9.53 silicon dioxide) Add 1.794 liters (SiO ₂ ) The reaction medium is stirred (or stirred) and heated to 88 ° C. At this time, 10% sulfuric acid (concentration 1.066) and an aqueous sodium silicate solution are added to the reaction medium at the same time. Add 151.4 meters of sulfuric acid per minute and 351 liters of sodium silicate solution per minute, keeping the reaction temperature at 88 ° C ± 1 ° C, and add two aqueous solutions to the reaction medium for a predetermined time. The sulfuric acid is continuously added until the slurry pH is between 4.8 and 5.0, and the final silica slurry is filtered and washed to remove the by-product (sodium sulfate) generated during the reaction and to dry the filtrate. Afterwards the powder is powdered to the desired degree The dried silica can easily respond to various biochemical tests and the analysis will be consumed below (see Table 1).

This example uses a formulation of a control (control) product without addition of alkaline earth metals.

Example 2

A 10,000-liter bulmang reactor with a jacketed steam-heated specific gravity of 1.121 and 1.794 liters of aqueous sodium silicate solution (3.78% Na ₂ O, 9.53% SiO ₂ ) containing 42 grams of sodium oxide per liter Put it.

The reaction medium is heated to 88 ° C. with continuous stirring (or stirring). At this time, sulfuric acid having a concentration of 10% (specific gravity 1.066) and an aqueous sodium silicate solution are simultaneously added to the reaction medium.

Add 151.4 liters of sulfuric acid per minute and 351 liters of sodium silicate solution per minute while maintaining the reaction temperature at 88 ° C ± 1 ° C. Both solutions are placed in the reaction medium for a predetermined time. Sodium silicate is no longer added after 47 minutes and sulfuric acid is added until the slurry pH is 4.8-5.0.

The reaction slush boils at 100 ° C. for 20 minutes and the reaction pH is adjusted again between 4.8-5.0.

The final silica gel is filtered and washed to remove byproducts (sodium sulfate) produced during the reaction.

The washed filter cake is added to the slurry and stirred under ambient temperature (or environmental temperature) without adding water.

During stirring, the slurry was treated with 102 g of hydrated sashimi (calcium hydroxide) based on advanced standards (US Fine Food Evaluation Standard) and 25 ppm of calcium ions based on the total weight of the silicon tetraoxide abrasive, which can be re-dried in the slurry form. Do the processing.

After the calcium ion treatment, the slurry body is vigorously stirred for 15 minutes so that calcium ion can effectively act on the surface of the silicon dioxide abrasive. The final product was spray dried at the inlet temperature of 483 ° C. and the outlet temperature of 122 ° C., and then made into powder to characterize the abrasive and physical properties as in Example 1.

Example 3

The method of this example is the same as in Example 2 except that sulfuric acid is added at a rate of 162.7 liters per minute and 204 grams of calcium hydroxide to reach 50 ppm of calcium ions.

This characterizes Example 3.

Example 4

This embodiment is similar to Example 2 except that 166.5 liters of sulfuric acid is added per minute, and 408 grams of calcium hydroxide is added so that the calcium ion in silicon dioxide reaches 100 ppm.

This characterizes Example 4.

Example 5

In this example, when preparing a silica abrasive for toothpaste, an aqueous sodium silicate solution (4.09% NaO, 10.31% SiO ₂ ) containing 1,420 liters of specific gravity of 1.131 and 4.6.3 grams per liter was added to the reactor as a reaction medium. .

The reactor is heated to 91 ° C. with continued stirring of the reaction medium. At this time, while maintaining the reaction temperature at 91 ± 1 ℃ 12% sulfuric acid (specific gravity 1.08) and sodium silicate aqueous solution, sulfuric acid 162.7 liters per minute, sodium silicate 315.7 liters per minute.

Sodium silicate is no longer added after 47 minutes and sulfuric acid is added until the slurry pH is 4.6-4.8. The reaction slurry is heated to 100 ° C. for 20 minutes and the reaction pH is adjusted again between 4.6-4.8.

The final silica slurry is filtered and washed to remove sodium sulfate, which is a byproduct of the reaction. The washed filtration is stirred at ambient temperature without addition of water and brought back to slurry.

While stirring, 510 g of hydrated lime (calcium hydroxide) of the Pharmacopoeia Standard (US Fine Food Standards) were treated, based on the total weight of the silicon dioxide abrasive, which can be made into dry powder in the form of slurry, and 125 ppm calcium ion treatment. do.

After the calcium ion treatment, the slurry body is stirred vigorously so that the calcium ion effectively works on the silicon dioxide abrasive.

The final product is spray dried at the inlet temperature of 483 ° C and the outlet temperature of 122 ° C, and then made into a rubber to characterize its properties.

Example 6

This is the same as in Example 5 except that first 1608 liters of sodium silicate solution is added to the reactor as the reaction medium and 170.3 liters of sulfuric acid per minute and 315.7 liters of sodium silicate solution per minute.

The washed filter medium added 816 gr of calcium hydroxide to the surface of the silica abrasive to reach 200 ppm of calcium ions.

This characterizes Example 6.

Example 7

This is the same as in Example 2 except that 2,040 grams of calcium hydroxide is added so that the calcium ion reaches 500 ppm.

This characterizes Example 7.

After the preparation of the final products from Examples 1 to 7, its physical characteristics and results are shown in Table 1 below.

TABLE 1

* Water loss when heating SiO ₂ abrasive to 105 ° C and 900 ° C.

** Determination of Oil Absorption, ASTM, D 281-31.

*** J. Am. Chem. Soc. 60, 309-319 (1938).

**** Measured with Coulter Counter Model TA II

Example 8

The composition of the toothpaste is as follows.

Component amount (wt%)

Precipitated Silica Abrasive (Example 2) 16.0

Sodium Fluoride (NaF) 0.28

Zolbirol Solution (70%) 32.0

Glycerin 13.0

Sodium Carrageenan 0.75

Monosodium Ototophosphate Monohydrate (NaH ₂ PO ₄ H ₂ O) 2.15

Disodium orthophosphate dihydrate (Na ₂ HPO ₄ 2H ₂ O) 8.34

Sodium Alkyl Sulfate Solution (28.8%) 6.0

Coconal Monoglycerides Sodium Sulfonate 0.9

Spices 1.22

Sodium Bucarin 0.3

Pigment (FD & G Blue # 1 Solution 1%) 0.35

Tiranium Dioxide (TiO ₂ ) 0.5

Trisodium citrate dihydrate (C ₆ H ₇ Na ₃ O ₇ 2H ₂ O) 0.25

Distillation qs

Total amount 100.0

The toothpaste composition is prepared by mixing the ingredients in a conventional toothpaste manufacturing method, first containing a water-soluble ingredient in a container and shaken appropriately, it is convenient to add a thin film penetrant, a perfume, a humectant, and then add other ingredients.

Clays prepared as above with water (water: component = 3: 1) have a pH of about 7.1.

Such a composition has a good effect on the treatment of fluoride in dental tissues due to its high toothpaste fluoride bootability, and also shows a good cleaning effect and an RDA of 100.

After prolonged storage at 80 ° F, the toothpaste has little loss of soluble fluoride.

Similar fluoride treatment effects and toothpaste fluoride compatibilities and cleaning effects were shown in place of sodium fluoride in Example 8, instead of the same amount of tartaric acid fluoride, sodium chlorofluoride, potassium fluoride, potassium tartrate fluoride, indium fluoride, zinc It can also be found in toothpastes using fluoride and ammonium fluoride.

Similar fluoride treatment effect and cleaning effect of NaH, instead of the same amount of phosphate in the mixture of Example _{8 2 PO4, NaH 2 PO 4} .2H 2 O, NaH 2 PO 4 and _{2H 2 O, Na 2 HPO 4} , Na 2 HPO 4 ㆍ 2H ₂ O, Na ₂ HPO ₄ ㆍ 7H ₂ O, Na ₃ PO ₄ ㆍ 6H ₂ O, Na ₃ PO ₄ ㆍ 8H ₂ O, KH ₂ PO ₄ , K ₂ HPO ₄ , K ₂ HPO ₄ ㆍ 2H ₂ O , K ₂ HPO ₄ ㆍ 6H ₂ O, K ₃ PO ₄ ㆍ 3H ₂ O, K ₃ PO ₄ ㆍ 7H ₂ O, K ₃ PO ₄ ㆍ 9H ₂ O, (NH ₄ ) H ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ , (NH ₄ ) ₃ PO ₄ and NaH ₂ PO ₄ ㆍ H ₂ O and Na ₂ HPO ₄ ㆍ 2H ₂ O A weight ratio of 1: 3 to 1: 5, NaH ₂ PO ₄ ㆍ H ₂ O And a mixture having a weight ratio of K ₂ HPO ₄ 2H ₂ O of 1: 3 to 1: 5, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, disodium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, monopotassium metaphosphate, Sodium trimetaphosphate, sodium hexametaphosphate and sodium heptamethaphosphate, (this composition has a pH of 4 to 8) can also be found in used toothpaste.

Example 9

Toothpaste with good abrasive composition is as follows.

Composition amount (wt%)

Precipitated Silica Abrasive (Example 3) 35.0

Sodium Fluoride (NaF) 0.22

Glycerin 5.0

Zolbirol Solution (70%) 20.0

Carboxymethyl Cellulose (0.7 D.S) 0.5

Magnesium Aluminum Silicate 0.3

Monosodium orthophosphate monohydrate (NaH ₂ PO ₄ ㆍ H ₂ O) 0.3

Disodium orthophosphate dihydrate (Na ₂ HPO ₄ 2H ₂ O) 0.3

Sodium Alkyl Sulfate Solution (28.8%) 2.3

Coconal Monoglycerides Sodiumsulfonate 0.7

Spices 0.9

Sodium Bucarin 0.2

Titanium dioxide 0.5

Speckle 0.5

Distillation qs

Total amount 100.0

Similar fluoride treatment effects, toothpaste fluoride compatibilities and cleaning effects were obtained in equivalent amounts of NaH ₂ PO ₄ , NaH ₂ PO ₄ ㆍ H ₂ O, NaH ₂ PO ₄ ; 2H ₂ O, Na ₂ instead of the phosphate mixture in Example 9. HPO ₄ , Na ₂ HPO ₄ 2H ₂ O, Na ₂ HPO ₄ ㆍ 7H ₂ O, Na ₃ PO ₄ ㆍ 6H ₂ O, Na ₃ PO ₄ ㆍ 8H ₂ O, KH ₂ PO ₄ , K ₂ HPO ₄ , K ₂ HPO ₄ 2H ₂ O, K ₂ HPO ₄ 6H ₂ O, K ₃ PO ₄ ㆍ 3H ₂ O, K ₃ PO ₄ ㆍ 7H ₂ O, K ₃ PO ₄ ㆍ 9H ₂ O, (NH ₄ ) H ₂ A mixture of PO ₄ , (NH ₄ ) ₂ HPO ₄ and NaH ₂ PO ₄ H ₂ O and Na ₂ HPO ₄ 2H ₂ O having a weight ratio of 1: 3 to 1: 5 Na ₂ HPO ₄ 2H ₂ O and K ₂ A mixture having a weight ratio of HPO ₄ 2H ₂ of 1: 3 to 5: 5, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, disodium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, monopotassium metaphosphate, sodium trimethaphosphate , Sodium hexametaphosphate, sodium heptamethaphosphate (composition pH is 4.0 to 8.0).

Example 10

The colorful toothpaste has the following composition.

Component amount (wt%)

Precipitated Silica Abrasive (Example 4) 20.0

Sodium Fluoride (NaF) 0.24

Zolbirol Solution (70%) 57.0

Glycerin 15.0

Sodium Carrageenan 0.5

Phosphoric Acid (85%) 0.10

Sodium Alkyl Sulfate Solution (28.8%) 4.0

Spices 1.0

Sodium Bucarin 0.2

Pigment ((FD & G Blue # 1 solution 1%) 0.05

Midstream q.s

Total amount 100.0

Example 11

The composition of toothpaste with low abrasive power is as follows.

Component amount (wt%)

Precipitated Silica Abrasive (Example 3) 6.0

Tartaric Acid Fluoride (SnF ₂ ) 0.40

Zolbirol Solution (70%) 51.0

Glycerin 25.6

Sodium Carboxymethyl Cellulose (0.7DS) 1.0

Zolbyran Monoisostearate 2.00

Sodium Alkyl Sulfate Solution (28.8%) 6.0

Spices 1.20

Sodium Bucarin 0.28

Pigment (FD & C Blue # 1 Solution 1%) 0.25

Pyrogenic Clositic Silica (Aerosol 200) 5.00

Distilled water q.s

Total amount 100.0

Test and Evaluation Analysis

The precipitated silica abrasive herein can be used as an excellent toothpaste component containing a soluble phosphate membrane permeant.

Toothpaste containing the above ingredients has a high compatibility between the abrasive and fluorine, and also has excellent tooth cleaning action.

In the following tests and evaluations, the precipitated silica abrasive containing the toothpaste component of the present invention can prove to find excellent compatibility.

Further, as in the present invention, the toothpaste of the present invention is demonstrated in the following tests and evaluations that the toothpaste of the present invention has better abrasive-fluorine compatibility than other toothpastes prepared similarly without containing alkaline earth metals.

Here, not only the high fluoride compatibility of the toothpaste component, but also excellent quenching action.

Thus, abrasives made from the sulfate acidification process proved to have no high fluorine compatibility in fresh water, even though they contained alkaline earth metals.

Abrasive, fluorine compatibility

The abrasive slurry test over 24 hours can be used to select (or find out) the relative compatibility with the fluoride with the precipitated silica abrasive.

The above test shows the usefulness of soluble fluorine in fluoride-containing toothpaste after 4 weeks at 80 ° F.

The abrasive slurry test over 24 hours is a method used to calculate the fluorine melting formula, which can be defined as the theoretical maximum useful fluorine percentage obtained by measuring the amount of soluble fluorine after 24 hours.

In this abrasive slurry test (orion special ion electrode method), a standard sodium fluoride solution containing 1624 ppm of fluorine contained 2.80 grams of sodium fluoride, 21.5 grams of NaHPO ₄ , and 83.4 grams of Na ₂ HPO ₄ ㆍ 3H ₂ O. It was dissolved in grams of ion-exchanged distilled water and stored in a polyethylene container.

Separate 30 grams of the above aqueous solution separately. 7 grams of the silica abrasive to be tested is dispersed in 30 grams of aqueous solution and left for 24 hours at 100 ° F (37.8 ° C). After 24 hours, the abrasive / fluorine solution is centrifuged at 15,000 rpm for 20 minutes or until the supernatant is clear.

Remove 10 ml from the supernatant and place in a plastr bottle. Then 10 ml of EDTA / THAM aqueous solution is put back into the plastic bottle.

EDTA / THAM aqueous solution is mixed with sodium hydroxide by mixing 0.2-regulator concentration of EDTA (ethylenediamine tetraacetic acid, disodium salt) and 0.2-purifier concentration of THAM (2-amino-2-hydroxymethyl-1,2-propanediol) pH 8.0 was adjusted.

Put the high bar into a plastic bottle and start the high bed quietly.

Fluoride ion concentration is determined by direct potential difference using an Orion fluoride electrode (Model 95-09).

(Electromotive force) shows the ppm concentration of fluorine in the supernatant by the algebraic equation.

The fluorine compatibility can be calculated by expressing the measured ppm concentration of fluorine as a percentage of theoretically effective soluble fluorine.

By using this method, the relative compatibility values of the abrasives and fluorine in the various kinds of abrasives prepared according to Examples 1 to 7 are determined. The results of the evaluation are shown in Table II below.

TABLE 2

Abrasive Fluoride Compatibility

From the results in Table 2, it can be seen that the abrasive containing the alkali nor metal has a higher abrasive fluorine compatibility than the alkali no metal.

Therefore, the silica abrasive prepared in Examples 2 to 6 proves to have high abrasive fluorine compatibility in the toothpaste component containing fluorine and a membrane permeant.

Toothpaste abrasive, fluoride compatibility

The silica abrasive and the membrane permeant contained in the toothpaste of the present invention are excellent in abrasive and fluorine compatibility.

The toothpaste formulated for evaluation has the composition of Example 8, which only differs in the abrasive component.

In order to determine the fluorine compatibility value, a soluble fluorine crystal method similar to the above-mentioned abrasive and fluorine compatibility value determination method is used.

In this method, the toothpaste is stored in a tube for a certain period of time. Then add 15 grams of ingredients to a 100 ml beaker and 45.0 grams of distilled water.

And the toothpaste is plated to be uniformly dispersed in distilled water to make a slurry state.

The slurry is centrifuged at 15,000 rpm for 20 minutes or until the supernatant is clear.

The supernatant is then treated as in the abrasive-fluorine compatibility determination method described above. The dissolved fluorine concentration of each toothpaste can be calculated similarly to the abrasive-fluorine soluble value.

The fluoride compatibility of each toothpaste was evaluated in Table 3. The abrasives evaluated were those prepared by Examples 1-7 and those characterized in Table 1 above.

TABLE 3

Fluoride Compatibility in Toothpaste

From the results in Table 3, it can be seen that the abrasive treated with alkaline earth metals had similar components but had better abrasive-fluorine compatibility than the toothpaste components as in Example 1 not treated with alkaline earth metals.

From the results in Table 3, it can be obtained that the toothpaste silica abrasive of the present invention does not severely reduce the soluble fluorine effectiveness of the fluorine ion object even when the toothpaste is stored.

Of course, the toothpaste component of the present invention also recognizes that the amount of effective soluble fluorine is reduced to some extent depending on the temperature during long-term storage and storage.

Therefore, the fluoride compatibility of toothpaste is generally lower than that shown in Table 3 above, depending on the long-term storage or severe temperature during storage.

Table 4 presents data on the changes in abrasive-fluorinated compatibility of various toothpastes at long-term storage and at elevated temperatures.

TABLE 4

Fluoride compatibility in toothpaste (high temperature / long term storage)

From the data in Table 4, it can be seen that the toothpaste of the present invention maintains a relatively high level of abrasive-fluorine compatibility even under long-term storage or at high temperatures.

Competition function

The tooth cleaning ability of the silica abrasive of the present invention was calculated by a radioactive hemorrhoidal polishing test (RDA). The RDA value can be used to calculate the relative competencies of different types of toothpaste abrasives.

The RDA value (measured by the following method) of the precipitated silica abrasive has a value of at least 40, usually 70 to 120, which proves to be a good dental cleaner.

Previously precipitated silica abrasives had high fluorine compatibility but on the other hand had a poor rDA value.

However, the polishing agent treated with the alkali alkali metal has not only high fluorine compatibility but also excellent purifying action.

Several toothpastes with relatively high fluorine compatibility in the currently available (precipitated) silica abrasives were selected for evaluation analysis by RDA value. The test is carried out in a dentifrice substance having the dentifrice component of Example 8 which only differs slightly in abrasive components.

RDA values of the toothpastes shown in Table 5 were determined by the following method.

This test method is described in more detail in Journal of Dental Research, Julg-Aaguat 1976 by Hefferren, pp 563-573.

The method of calculating the RDA value is as follows.

A. Selection and manipulation of teeth

At the time of extraction, choose healthy short-term permanent teeth without dental caries.

Then scrub the teeth with a scalpel (or surgical scalpel).

The crown and root end of each tooth were cut using an abrasive disk to length 14 mm; Make a hemorrhoid sample at least 2 mm wide. Prepare a cut piece of root or one more tooth and use it as a modifier of radiation self-adsorption.

B. Investigation of hemorrhoids

The root and hemorrhoids prepared in step A are struck in a neutron stream of 2 × 10 ¹² neutrons / cm 2 for 3 hours.

C. Enclosure of Root

After irradiation, the irradiated roots are enclosed in a dental cold treatment methacrylate resin and then mounted in a higher toothbrushing machine. The toothbrushes used during the test run 50 brushes and use a moderately flat pepsondent toothbrush.

D. Preparation of Hemorrhoidal Surface

Before starting the test, the newly enclosed and irradiated roots are brushed approximately 6,000 times using a standard slurry (50 ml of 10 grams of calcium phosphate + 0.5% CMC-10% glycerin solution).

As you continue your test for a few days, brush your teeth 1,000 times before starting.

E. Testing

At the end of the preparation, brush the hemorrhoid specimens with standard slurries (slurry as in step D) at the end of the test run at about 1,500 times. The test involves brushing a sample of hemorrhoids 1,500 times with a slurry of test product (toothpaste). (25 grams of toothpaste + 40 ml of ion-tested distilled water)

F. Sample Preparation of Modified Factors

The fertilization element is dissolved in a solution of 250 ml of hemorrhoids or other teeth prepared in step B by mixing 5 ml of hydrochloric acid with distilled water.

1 ml of this aqueous solution is added to a test toothpaste and a standard slurry prepared in a similar manner to step E and neutralized by addition of 0.1NNaOH.

Radiation tracking measurement

The radioactivity of the slurry samples (1.0 ml) is determined by the Inter technique SL-30 liquid scintillation coefficient.

인치크기로 편평한 불수강용기에 넣고 뉴클리어시키고 가이거 계수측정방법(Nuclear chicago Ge-ger Counting Sys)을 사용한다.Another measuring method is a 3 ml aliquot of each slurry with a bottom of 1 inch ×

Place in an inch-sized flat steel container, nucleate, and use Nuclear chicago Ge-ger Counting Sys.

[Calculation]

The radioactive hemorrhoidal polishing (RDA) value of a toothpaste is multiplied by 100 by the mean fertilization coefficient of the toothpaste relative to the mean coefficient of the reference toothpaste. Hemorrhoid polishing finish of reference toothpaste shall be any hemorrhoidal polishing value of 100 units.

The results of the RDA value determination are shown in Table 5 below.

TABLE 5

Radioactive Hemorrhoids (RDA)

1. Precipitated Silica (N. Y. C) sold by Deju Inc.

2. Choseop Crossfield End Suns Limited (London, UK) sold by Dejusa Corporation.

3. Philadelphia-Quirz Campani (Bali Forge, Pa) sold by Dejus Inc ..

4. Chose Crossfield End Suns Limited (London, UK) sold by Dejusa Corporation.

It can be seen from Table 5 that the precipitated silica abrasive currently on sale has a high abrasive-fluorine compatibility but not enough abrasive to be used as a toothpaste abrasive.

It is surprisingly found that the precipitated silica abrasives of the present invention also have high abrasive-fluorine compatibility and, at the same time, excellent RDA polishing values.

The degree of tooth cleaning can be known from this RDA polishing degree.

Freshwater Abrasives and Sulfate Abrasives

The abrasive of the present invention has a similar relationship to the silica abrasive of Calcium Treated Application No. 826,901 but is very different in properties. To identify the difference, the following evaluation analysis is conducted.

The sulphate liquid silicon dioxide to be tested is made according to Application No. 826,901 and US Patent 3,960,586 issued in January 1976. The method is as follows.

Dry sodium sulfate was added to 10 gallons of water so that the concentration of sodium sulfate in the reaction medium was 10% and placed in a 200 gallon reactor.

Sodium silicate is added thereto to adjust the pH of the reaction medium to 9.0.

The reaction temperature is 65 ° C. (150 ° F.).

Aqueous sodium silicate has a nominal molar ratio of SiO ₂ / Na ₂ O of 2.5 and a concentration of 2.0 pounds per gallon.

Sodium silicate is added to the reaction medium for 4 minutes. Then, the addition of sodium silicate is stopped, and sulfuric acid having a concentration of 11.4% is added until the pH of the reaction medium reaches 9.0, and then an aqueous sodium silicate solution and an aqueous sulfuric acid solution are added simultaneously for 35 minutes.

At 35 minutes, the addition of sodium silicate is stopped and sulfuric acid is added until the pH of the slurry reaches 5.5.

Then decompose at 77 ° C. for 20 minutes. The wet material is treated in the same manner as in Example 2. In other words, it is divided into six parts and treated with 50, 100, 200, 400, and 800 ppm of calcium with an aqueous solution of calcium hydroxide.

The wet material is dried and treated as in Example 2.

Table 6 shows the characteristics of each, and the first abrasive was not treated with calcium at all.

Table 6 shows the results of the evaluation analysis.

TABLE 6

* Measured by the test described in Table 2.

From the results of Table 6, it can be seen that the calcium-treated "yellow dyeing" abrasive of Application No. 826,901 has a lower abrasive-fluorine compatibility value than the silica grinding agent of "fresh water" of the present invention (see Table 2).

The addition of alkaline earth metal to the abrasive produced by the sulphate solution method does not show a marked increase in the abrasive-fluorine compatibility.

However, when compared with Table 2, it can be seen that the addition of alkaline earth metal to the abrasive of the present invention made by the fresh water method greatly improves the abrasive-fluorine compatibility.

Claims (1)

Toothpaste with compatible high fluoride characterized by reacting silicon dioxide with alkaline earth metal salts such as calcium, strontium and magnesium in the range of 10 to 100 ppm and acidifying the reactant (alkali metal silicate) with an inorganic acid to precipitate amorphous silicon dioxide. Composition. (However, the amorphous silicon dioxide has a radioactive dentin polishing value of at least 40, the specific gravity of the pack is 0.24 to 0.55 / ml, the content is 70 to 95 ccs / 100g, the BET surface area is 100 to 250 m 2 / g, the combustion loss degree 4 to 6%.)