DE102008014225A1 - Remineralizing dentifrices and process for their preparation - Google Patents

Abstract

A method of making a remineralizing dentifrice comprising the steps of: a) completely dissolving at least one organic calcium salt selected from the group of physiologically acceptable organic acids in warm water at 35-80 ° C; b) concentrating the solution under reduced pressure at a heating bath temperature of 50-150 ° C; c) depressurization to atmospheric pressure and subsequent addition of at least one organic acid at a constant temperature; d) concentrating the solution under reduced pressure at a heating bath temperature of 50-150 ° C; e) relaxing the hot, flowable calcium salt hydrate melt to normal pressure; aa) providing a dentifrice base composition comprising: 25-45% by weight of water; 25-45% by weight of humectant; 0.5-3% by weight of binder and thickener; bb) producing a mixture of the toothpaste base composition while heating to a temperature range of 40 to 70 ° C; cc) adding the calcium salt hydrate melt to the tempered at 40 to 70 ° C base composition with subsequent stirring until a homogeneous dentifrice mixture is formed, wherein the proportion of calcium salt hydrate melt, based on the total weight of the dentifrice mixture, between 7 and 49.5 wt .-% and the sum of the quantities of the constituents from step aa) add up to 100%; dd) cooling the dentifrice mixture.

Description

The The present invention relates to a process for the preparation of Dentifrices containing a remineralizing amorphous salt hydrate melt a calcium salt, as well as the dentifrice and its use.

The use of remineralising salt hydrate melts as an additive in the manufacture of dentifrices is disclosed in U.S. Pat WO 2007/022765 A1 described.

Problematic is in combination with dentifrices with swelling and binding agents the uniform release as well as distribution remineralizing agents in the mouth.

Especially Dentifrices that are sold as a pasty mix in the trade come, even when using electric toothbrushes slow and incomplete. This has the consequence that a even distribution in the oral cavity at average Care duration is often not guaranteed.

Especially problematic are toothpastes, where due to the locally high concentration on ingredients user-side an unfamiliar and common as unpleasant described "Mouthfeeling" caused becomes. This causes the dental care often prematurely aborted and insufficiently performed becomes.

adversely is also that many known in the art amorphous salt hydrate melts an unattractive and / or bitter taste have, which are covered by the addition of flavors got to. Furthermore, the uniform setting a pH value for the effectiveness of the salt melts the remineralization required, with a particular on the tongue margins perceived bitter taste in the application in addition to shorten the nursing time leads and so on appropriate pH value can not adjust.

task The present invention is a process for the preparation to offer a dentifrice with which a dentifrice can be provided that overcomes the aforementioned disadvantages and has a good remineralizing effect.

One Another aspect of the present invention is the provision a dentifrice that has an improved mouthfeeling and thus provides increased compliance of the user.

About that In addition, another aspect of the present invention is the provision a stable composition of a Salzhydratschmelze having Dentifrice with good remineralization effect.

The The above objects are according to the features solved the independent claims.

at The attempts to remineralizing effect was surprisingly found that a dentifrice after adding a acidic, freshly prepared, dehydrated under reduced pressure Calcium salt hydrate melt with a residual water content in the range from 5% by weight to 25% by weight, preferably from 10% by weight to 20% Wt .-%, an increased reminalization of the teeth with constant consistency of the dentifrice and good portionability provides.

The Preparation of the salt hydrate melt was carried out on the basis of Calcium salts of physiologically acceptable, organic acids, although mixtures of different acids are used could.

Prefers the melt was made with at least one organic Acid selected from the group consisting of Lactic acid, citric acid and gluconic acid, this composition being an improved distribution and Wetting of all teeth in the oral cavity provides. in this connection has surprisingly been found that the Use of citric acid the effectiveness of the compositions regarding the remineralization of enamel despite the known calcium-complexing properties are not impaired.

Especially preferred is a salt hydrate melt containing a combination made from lactic acid and citric acid.

at These compositions will have a rapid viscosity decrease when used in combination with an improved mouthfeel and Taste provided.

Prefers As calcium salt, calcium lactate, calcium citrate and calcium gluconate are used used. As further acid are preferred lactic acid or citric acid and gluconic acid, wherein particularly preferably the acid added to the Säureanion corresponding acid.

The inventors assume that dimers and oligomers (anhydrides) of the added acids are also proportionally formed by the representation of the melt at reduced pressure in the freshly prepared calcium salt melt, wherein also ge mixed anhydrides may be present.

With the simultaneously occurring during mixing rehydration reaction can also take advantage of the surprising benefits fresh melt illustrated dentifrice explained become, so z. B. the homogeneous distribution of the ingredients in the paste, the low segregation tendency, the higher effectiveness and the consistent doughy consistency.

Further Advantages will be apparent from the following explanation and the embodiments.

According to the invention the calcium salt hydrate melts fresh from an aqueous mixture at least one organic calcium salt and one or more Organic acids by dehydration under reduced Pressure and elevated temperature and subsequent Cooling won. The molten salt is falling as a ductile, macroscopically homogeneous mass. Here, the Melt in domains on a Nahordnung. The domains are in turn arranged chaotically distributed, so that in the X-ray diffractogram only uncharacteristic, extremely broad and diffuse diffraction signals become visible. This proves a X-ray amorphous, Non-crystalline arrangement of the above-described Nahorder having Domains in the solid.

• a) vollständiges Lösen von mindestens einem organischen Calciumsalz in warmen Wasser (T = 35–80°C);
• b) Einengen der Lösung unter vermindertem Druck und erhöhter Temperatur (Heizbad 50–150°C);
• c) Entspannen auf Normaldruck und anschließende Zugabe der mindestens einen organischen Säure bei konstanter Temperatur;
• d) Einengen der Lösung unter vermindertem Druck und erhöhter Temperatur (Heizbad 50–150°C);
• e) Entspannen auf Normaldruck der heißen, fließfähigen Schmelze.

The preparation of such a melt on a laboratory scale comprises the steps:

• a) complete dissolution of at least one organic calcium salt in warm water (T = 35-80 ° C);
• b) concentration of the solution under reduced pressure and elevated temperature (heating bath 50-150 ° C);
• c) depressurization to normal pressure and subsequent addition of the at least one organic acid at a constant temperature;
• d) concentration of the solution under reduced pressure and elevated temperature (heating bath 50-150 ° C);
• e) depressurization to normal pressure of the hot, flowable melt.

The Flowability offers the advantage that the melt directly in the further production process of the dentifrice can be processed by stirring into the matrix or can be poured into thin slices, which after Solidified granulated or ground so that a high surface-to-volume ratio of the particles what is the further processing, especially the renewed Loosen, relieved.

advantageously, are the first concentration in step b) 10-88%, preferably 25-85%, more preferably 45-80% and most preferably removes 80% of the amount of water introduced.

advantageously, is the organic acid before step c) up to 25 wt .-%. preferably 2-20% by weight, more preferably 3-10 Wt .-% and most preferably 4.6 wt .-% water based on the submitted total mass of the calcium salts added.

Especially preferably, the acid is added to the temperature before addition heated the submitted salt solution.

advantageously, when narrowing down in step d), a further 5-12% of the in Step a introduced amount of water, preferably 7-10%, especially preferably 8.5%, removed.

advantageously, the melt contains a calcium content of 1.5-3 Mol to 1 kg of melt based on elemental calcium, giving a Proportion of 6 wt .-% to 12 wt .-% corresponds.

Embodiment 1

In In a 1 liter beaker, 0.5 l of water is heated to 60 ° and with stirring and further heating gradually 172.28 g (0.559 mol) of calcium lactate pentahydrate and 43.58 g at the same time (0.097 mol) calcium gluconate added and stirred until a clear solution has emerged. The clear solution is transferred to the distillation flask and 0.40 l of water at a heating bath temperature of 130 ° C under reduced Distilled off pressure. After transition of the defined amount of water the heating is interrupted and the system is decompressed to normal pressure.

In meanwhile, 21.89 g (0.194 mol) of lactic acid (80%) in a second cup with 10 ml of water to about 60 ° C. heated and stirred with 18.68 g (0.0972 mol) Citric acid is added, giving a clear solution arises. This solution is added to the distillation batch and the distillation continued under reduced pressure (0.4 bar) until another 0.1 l of water are transferred.

in the Distillation flask remains an only slightly colored mass of syrupy consistency, which cools down to approx. 80 ° remains liquid and pourable and can be further processed directly.

• aa) Vorlegen einer Zahnpastagrundzusammensetzung umfassend:
• – 25–45 Gew.-% Wasser;
• – 25–45 Gew.-% Feuchthaltemittel;
• – 0,5–3 Gew.-% Binde- und Verdickungsmittel;
• bb) Erwärmen der Grundzusammensetzung unter Rühren auf einen Temperaturbereich von 40–70°C bis eine homogene Mischung entsteht;
• cc) Zugeben der Calciumsalzhydratschmelze zur auf 40–70°C temperierten Grundzusammensetzung mit anschließendem Rühren bis eine homogene Zahnpflegemittelmischung entstanden ist, wobei der Anteil der Calciumsalzhydratschmelze an der Gesamtmischung zwischen 7 und 49,5 Gew.-% beträgt und und die Summe der Mengenangaben der Bestandteile ab Schritt aa) sich zu 100% addiert.
• dd) Abkühlen der Zahnpflegemittelmischung.

According to the invention, the addition of the inventive salt hydrate melt is carried out by the steps:

• aa) presenting a toothpaste base composition comprising:
• - 25-45% by weight of water;
• 25-45% by weight of humectant;
• - 0.5-3 wt .-% binding and thickening agents;
• bb) heating the base composition with stirring to a temperature range of 40-70 ° C until a homogeneous mixture is formed;
• cc) adding the calcium salt hydrate melt to the tempered to 40-70 ° C base composition with subsequent stirring until a homogeneous dentifrice mixture is formed, wherein the proportion of the calcium salt hydrate melt to the total mixture between 7 and 49.5 wt .-% is and the sum of the quantities Ingredients from step aa) added to 100%.
• dd) cooling the dentifrice mixture.

Subsequently The finished dentifrice mixture can be made up.

In an alternative display method according to the above proportions the melt in water with heating dissolved at 40-70 ° C, humectant, preferably xylitol, added, with the solution cools. Subsequently, binder is preferred Hydroxyethylcellulose, stirred into the solution and rest for 12 hours.

Preferably The toothpaste base composition further contains foaming agents (Surfactants), preservatives, dyes and / or color pigments and / or flavorings.

When Binders and thickeners are preferably hydroxyethyl cellulose (HEC), carboxymethylcellulose (CEC) and fumed silica as well used hydrated silicas.

Prefers contains the toothpaste base composition in addition Grinding and polishing agents with Mohs hardness between 2 and 3, more preferably dicalcium phosphate (DCP), dicalcium phosphate dihydrate (DCPD), sodium metaphosphate, silica gels and alumina hydrates.

Surprisingly has been shown that the addition of sodium fluoride in the base composition before the addition of the calcium salt hydrate melt the remineralization effect of the composition thus prepared contrary to expectations does not inhibit, but a significant improvement causes.

Of the maximum proportion of fluoride in the total composition is 1500 ppm (1.5 g / kg), preferably the proportion of fluoride 1500 to 1000 ppm, more preferably 1400 ppm.

Embodiment 2:

19.5 g of the melt according to the invention from Example 1 are dissolved with heating in 35.3 g of water and 43.8 g of xylitol, the solution being strong cools. Subsequently, 1.4 g of hydroxyethyl cellulose added and stirred. After 12 h, it has a clear gel educated.

In an alternative embodiment, the water before Heating 300 mg of NaF added.

The thus prepared compositions of the invention have a good resistance to segregation, a homogeneous, fine distribution of ingredients and especially in disposable tubes a consistent composition until the end of consumption on.

By the high level of available calcium ions in the compositions may be due to the use of fluorine compounds for remineralization be completely omitted, so that, for example Fluorosis or fluoride-induced discoloration the teeth are prevented.

In a preferred embodiment is the dentifrice as a two-component preparation, wherein the first component a fluoride for the addition of fluoride, for example as amine fluoride on teeth and the second component is a calcium salt in a high concentration in the form of the invention Salt hydrate melt has, so that the remineralization complementary to conventional dentifrices forced and calcium is stored in the enamel.

In a particularly preferred embodiment is at least the calcium salt component in microencapsulated or nanoencapsulated form which delays the release of salt during oral hygiene, so that first a fluoride layer on the tooth is raised before the calcium is released. In this way Prevents premature precipitation of fluorspar its calcium content due to the poor solubility of the compound no longer available for remineralization stands and reaches a maximum accelerated remineralization.

In Another embodiment is the fluoride component encapsulated, so that initially a remineralization through the calcium and a long-term remineralization by the subsequently released and on the teeth adhering fluoride enters in conjunction with the saliva.

Another preferred embodiment provides for encapsulation of fluoride and calcium components so that they are alternately released in at least three sequential steps to ensure optimal remineralization Afford.

A another embodiment comprises a microencapsulated Acid or an acid anhydride, which is time-delayed be released so that over a longer Period of low required for remineralization pH in the oral cavity is maintained. Preferably, the microcapsules For this mucoadhesive properties, so that too even after completion of the dental care an optimal pH range is held.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - WO 2007/022765 A1 [0002]

Claims (23)

Process for producing a remineralizing Dentifrice comprising the steps of: a) complete Dissolving at least one organic calcium salt selected from the group of physiologically acceptable organic acids, in warm water at 35-80 ° C b) Concentrate the solution under reduced pressure at a bath temperature from 50-150 ° C; c) depressurize to normal pressure and then adding at least one organic acid at constant temperature; d) concentration of the solution under reduced pressure at a heating bath temperature of 50-150 ° C; e) Relax the hot, flowable calcium salt hydrate melt at normal pressure; aa) presentation of a toothpaste base composition full: 25-45% by weight of water; 25-45 % By weight of humectant; 0.5-3 wt .-% binding and Thickener; bb) preparing a mixture of the dentifrice base composition while heating to a temperature range of 40 to 70 ° C; cc) adding the calcium salt hydrate melt to at 40 to 70 ° C tempered base composition followed by Stir until a homogeneous dentifrice mixture emerged wherein the proportion of calcium salt hydrate melt based on the Total weight of the dentifrice mixture between 7 and 49.5% by weight is the sum of the quantities of the ingredients from step aa) adds up to 100%. dd) cooling the dentifrice mixture. Process for producing a remineralizing Dentifrice comprising the steps of: a) complete Dissolving at least one organic calcium salt selected from the group of physiologically acceptable organic acids, in warm water at 35-80 ° C b) Concentrate the solution under reduced pressure at a bath temperature from 50-150 ° C. c) depressurize to normal pressure and then adding at least one organic acid at constant temperature; d) concentration of the solution under reduced pressure at a heating bath temperature of 50-150 ° C. e) Relax the hot, flowable calcium salt hydrate at normal pressure; aa1) Preparation of 25-45 wt .-% water and dissolving the calcium salt hydrate melt at 40 to 70 ° C, wherein the proportion of calcium salt hydrate melt based on the total weight the dentifrice mixture is between 7 and 49.5% by weight and the sum of the quantities of the constituents from step aa1) add up to 100%. bb1) addition of 25-45% by weight Humectant, preferably xylitol, with cooling the solution; cc1) addition of 0.5-3% by weight Binders and thickeners and subsequent swelling over 12 h. Method according to one of the preceding claims, characterized in that the dentifrice base composition at least one other ingredient selected from Group consisting of foaming agents, surfactants, preservatives, Dyes, pigments and flavorings. Method according to one of the preceding claims, characterized in that the binding and thickening agent at least one component selected from the group consisting from hydroxyethylcelluloses, carboxymethylcelluloses, highly dispersed Silicas and hydrated silicas, contains. Method according to one of the preceding claims, characterized in that the dentifrice base composition additionally at least one grinding and polishing agent with Mohs hardness between 2 and 3, preferably selected from the group consisting of dicalcium phosphate (DCP), Dicalcium phosphate dihydrate (DCPD), sodium metaphosphate, silica gels and alumina hydrates. Method according to one of the preceding claims, characterized in that before adding the melt Fluoride, preferably sodium fluoride, is initially charged, wherein the fluoride concentration based on the total mass of the finished dentifrice mixture 1500 ppm does not exceed. Method according to one of the preceding claims, characterized in that the freshly prepared Cacliumsalzhydratschmelze a residual water content in the range of 5-25 wt .-%, preferably 10-20% by weight. Method according to one of the preceding claims, characterized in that the melt is produced selected with at least one organic acid from the group consisting of lactic acid, citric acid and gluconic acid, wherein a combination of lactic acid and citric acid is particularly preferred. Method according to one of the preceding claims, characterized in that the calcium salt is selected from the group consisting of calcium lactate, calcium citrate and calcium gluconate, particularly preferred that the calcium salt with the added Acid-corresponding acid anions selected is. Method according to one of the preceding claims, characterized in that the Melt contains a calcium content of 1.5-3 mol based on 1 kg of melt based on elemental calcium. Method according to one of the preceding claims, characterized in that the calcium salt hydrate melt introduced liquid by stirring in the process or that the solid calcium salt hydrate melt particulate with a defined surface-to-volume ratio the particle is introduced into the process. Process for producing a remineralizing Dentifrice comprising the steps of: a) It gets water heated to 60 ° and stirred and Further heating gradually calcium lactate pentahydrate and simultaneously Calcium gluconate was added and stirred, with the weight ratio of water: calcium lactate pentahydrate: calcium gluconate 500: 172: 44 is; b) the clear solution is in the Transferring the distillation flask and a volume fraction of water 4/5 based on the original amount of water at a heating bath temperature of 130 ° C under reduced Distilled off pressure; c) in a container become lactic acid (80%) with water heated to 60 ° C and stirring added with citric acid, wherein the weight ratio of Lactic Acid: Water: Citric Acid 22:10:19, and then added to the mixture obtained in b); d) the distillation is continued under reduced pressure at 0.4 bar, up to a total of all distillation steps, an amount of water equal the quantity of water submitted under (a) has been transferred; Method for granulating a calcium salt hydrate melt, characterized in that a liquid Salzhydratschmelze solidified by cooling and then to Particles with a defined surface-to-volume ratio is further processed. Dentifrice comprising: - 25 to 45% by weight of water; - 7 to 49.5 wt .-% calcium salt hydrate melt after one of the preceding method claims; - 25 up to 45% by weight of humectant, 0.5 to 3% by weight Binding and thickening agents, where sum of wt .-% - information add up to 100%. Dentifrice comprising: - 35.3 % By weight of water; - 19.5 wt .-% calcium salt hydrate melt according to one of the preceding method claims; - 43,8 % By weight of humectant, - 1.4 wt .-% binding and Thickeners, where the sum of the wt .-% - information adds up to 100%. Dentifrice according to one of the two preceding Claims, characterized in that additionally a fluoride-containing compound is contained, wherein the fluoride content based on the total mass of the dentifrice does not exceed 1500 ppm. Dental care product according to the preceding claim, characterized in that the dentifrice as a two-component preparation a first component containing a fluoride compound for attachment of fluoride on the hard tooth substance, and a second component, containing a calcium salt hydrate melt in a high concentration according to one of the preceding method claims, contains. Dental care product according to the preceding claim, characterized in that at least one of the two components at least partially in encapsulated form. Dentifrice after one of the six previous ones Claims, characterized in that the dentifrice an at least partially encapsulated acid and / or acid anhydride contains. Dental care product according to the preceding claim, characterized in that the encapsulation mucoadhesive is executed. Dental care product, producible according to one of the preceding Method claims. Use of a dentifrice according to one of previous claims for the cosmetic repair of Primary lesions of the incisors. Use of a dentifrice according to one of previous claims for preventive and therapeutic Treatment of demineralization damage of the hard tooth substance.