RU2800094C2 - Remineralizing dental material - Google Patents

Abstract

FIELD: teeth remineralization.

SUBSTANCE: group of inventions relates to the field of materials for teeth remineralization and their use. A remineralizing dental material that contains at least one cation and at least one anion, which act as interacting ions for the formation of a remineralizing substance, and at least one of the interacting ions is multiply charged and is present as an oppositely charged ion with a polyelectrolyte in a coacervate; as well as the use of the above dental material as a sealing material, covering material, corrective material and/or filling material are proposed. A kit for the manufacture of the above remineralization material, which contains: a. a first component with at least one coacervate with one of the interacting ions being an oppositely charged coacervate ion; b. a second component with water; wherein the second of the interacting ions is present as a free ion in aqueous solution in component b and/or as an oppositely charged ion of the second coacervate in one of the two components is proposed. Options for using the above kit include the following steps: i. applying component b to dentin and/or tooth enamel, ii. applying component a to dentin with component b and/or tooth enamel with component b, or: i. mixing component a and component b, ii. applying the mixture to dentin and/or tooth enamel.

EFFECT: use of the group of inventions ensures effective remineralization.

34 cl, 7 dwg, 7 tbl, 13 ex

Description

The present invention relates to a remineralizing dental material containing at least one cation and at least one anion that act as interacting ions to form a remineralizing substance. The following objects of the present invention are the use of this dental material, the method of its use and kit for its manufacture.

There are known dental materials for all types of conservative treatment of defects in the hard substance of the teeth. Since such materials exhibit a mineralizing effect, the aim is to stabilize the natural hard substance of the teeth that remains after an invasive treatment, for example, to prevent subsequent decay, which can be caused, for example, by bacteria. In this case, mineralization can be induced by releasing certain ions from the material, such as Ca ²⁺ or F ^- , with the introduction of suitable oppositely charged ions from saliva on the surface or in the bulk of the hard tissue of the teeth. After that, a new inorganic hard material is formed, having low solubility, which makes up for the loss of mineral material (performs mineralization) in the hard substance of the teeth. Other approaches focus on the formation of mineral solids, which are mainly hydroxyapatite or other apatites, without the need to introduce Ca ²⁺ ions or phosphate ions from saliva. In this case, according to the prior art, the main application is the so-called bioactive glasses.

The mineralization potential of prior art materials is generally limited. The reasons for this are, on the one hand, the limited number of available, i.e. partially soluble suitable ions that the materials in question contain (e.g. ionomer glass cements), and, on the other hand, the fact that in the materials of the classes in question, due to the nature of these materials, it is possible to use only limited amounts of ion sources (e.g. composite materials with bioactive glasses) taking into account acceptable physical properties. For such materials, the amount of released ions and/or formed mineral substituent is limited, and therefore may not be sufficient to reliably stabilize the hard matter of the teeth.

Document WO2017/161179A1 discloses a remineralization composition which contains a mixture of 45S5 bioglass and polyaspartic acid in a ratio of 60:40. This mixture provides only a low concentration of released ions. In addition, there are limitations regarding the choice and combination of released ions, and hence the nature of the remineralization.

US2010/0272764A1 discloses a polymerizable dental resin composite having remineralization capabilities. This composite material contains microcapsules, each of which contains a solution of calcium nitrate, a solution of potassium hydrogen phosphate and a solution of sodium fluoride. Ions are released through the semi-permeable membrane of the capsules under the action of a concentration gradient. It is indicated that these microcapsules can be obtained as a result of complex coacervation of oppositely charged polyelectrolytes. Here, the disadvantage is the low concentration of released ions.

The main problem to be solved by the present invention is to create a dental material of this type, which provides effective remineralization.

To solve this problem, according to the present invention, it is proposed that at least one of the interacting ions is multiply charged and is present as an oppositely charged ion in the coacervate.

First of all, an explanation of some of the terms used in the context of the present invention will be presented.

The present invention relates to a remineralizing dental material.

Remineralization and demineralization are biological processes that occur alternately at the interface between the tooth and the oral cavity, and in which inorganic ions are dissolved or reintroduced by saliva. Demineralization generally means an acid-induced (originating, for example, caries-causing plaque) loss of the mineral content of the tooth during the dissolution of the inorganic, mainly hydroxyapatite-containing constituent components of the tooth, which is the primary process of caries formation (article by P. Shellis in the book Caries, ed. H. Meyer-Lückel, S. Paris, K.R. Ekstrand, G. Thieme, 2012, p. 23).

Remineralization in a narrower sense is the replenishment of depleted mineral material, which is based on apatite, in the area of the tooth surface (article by P. Shellis in the book cited above, p. 23, 26; article by S. Twetmann, K. R. Ekstrand in the book cited above, p. 210). In the case of previous damage to the dental substance as a result of demineralization, this type of remineralization process leads to a certain elimination of defects. Restorative material may build up on existing apatite crystals within the tooth, resulting in crystal growth, although new apatite crystals may also form. Taking into account the current state of research, the authors suggest that the natural process of remineralization is accelerated in the presence of fluoride, even at low concentrations.

Remineralization in the sense of the present invention means any process in which inorganic material accumulates during deposition on the existing hard matter of teeth potentially damaged by demineralization. This precipitation may allow the growth of existing apatite crystals in the dental substance or, alternatively, may lead to the formation of new inorganic material in the area of remineralization. Suitable inorganic materials may be materials derived from apatite, or alternatively they may be other biocompatible compounds having low solubility. Within the scope of the present invention, they are referred to by the term "remineralizing agent".

Dental substance means any mineralized dental substance, in particular tooth enamel, dentin and dental cementum.

Interacting ions are cations and anions that are able to jointly form a remineralizing substance.

The term "coacervation" means the separation of two liquid phases. An ionic polymer or macroion (eg, ionic polyphosphate) together with a multiply charged, oppositely charged ion (eg, calcium ion) forms a coacervate, which is a relatively polymer-rich phase within a polymer solution.

Coacervates are polyelectrolytes crosslinked by multiply charged oppositely charged ions. In an aqueous environment, coacervates are present in the form of a phase having a higher viscosity. Depending on the molecular weight of the initial polyelectrolytes, coacervates are present in the form of liquid viscous or viscoplastic substances that form a separate phase in an aqueous medium. Coacervates exist only within a certain range of the ratio of the amount of substance of polyelectrolytes and multiply charged oppositely charged ions, and also only above a certain minimum concentration of polyelectrolyte. If the content of opposite charged ions is excessively low, or if the concentration of coacervate-forming substances (multiply charged oppositely charged ions and polyelectrolytes) is excessively low, no phase separation occurs in the aqueous medium.

Suitable coacervates form anionic or cationic polyelectrolytes and multiply charged cations or multiply charged anions. Suitable coacervates contain an ionic polyelectrolyte and multiply charged oppositely charged ions that crosslink this polyelectrolyte.

Coacervates are preferably prepared by mixing aqueous solutions containing anionic or cationic polyelectrolytes and multiply charged cations or anions. In this context, anionic polyelectrolytes and multiply charged cations are mixed, and cationic polyelectrolytes and multiply charged anions are also mixed.

Coacervates form a separate liquid phase of increased viscosity in the mixture. The coacervates are preferably isolated. This is carried out in each case using suitable known methods such as decanting or centrifugation. The isolated coacervates are preferably purified. This is preferably carried out by simple washing with a solvent, preferably water.

The present invention has demonstrated that remineralizing material interacting ions having a high mineralization potential for tooth solids can be made available in dental material if at least one of said interacting ions is present as an oppositely charged ion in the coacervate. Since such materials exhibit a mineralizing effect, the aim is to stabilize the natural hard substance of the teeth that remains after an invasive treatment, for example, to prevent subsequent decay, which can be caused, for example, by bacteria. In this case, mineralization can be induced by releasing certain ions from the material, such as Ca ²⁺ or F ^- , with the introduction of suitable oppositely charged ions from saliva on the surface or in the bulk of the hard tissue of the teeth. After that, a new inorganic hard material is formed, having low solubility, which makes up for the loss of mineral material (performs mineralization) in the hard substance of the teeth.

On the other hand, the mineralization potential of known dental materials is limited. One of the reasons for this is that known components producing a mineralization effect can only be incorporated into the dental material in limited amounts so that other physical properties of said material are not impaired. Another reason is to limit the rate and amount of possible introduction of ions into the respective dental material and/or their release from the dental material, for example in the case of known ionomer glass cements.

For use according to the present invention, the dental materials producing the mineralizing effect are preferably present in liquid or paste form, but at least in a suitable form, and are applied in this form to the solid matter of the teeth to be treated. At the same time, they are manually applied to the surface and, possibly, give them the appropriate shape. Since remineralization processes are generally very slow, the material must remain in the area of application for at least a certain time after curing. In an application that is particularly suitable for a successful long-term treatment outcome, the material hardens after a certain time has elapsed, and the duration of the hardening should be sufficient for manual handling of this material. In this case, the material in hardened form also serves to protect the area of remineralization from mechanical and/or chemical degradation. Before and, if provided, after curing, the materials must retain the ability to release ions to mineralize the hard matter of the teeth by replenishing the mineral matter.

According to one preferred use, dental materials having a mineralization potential are intended to be used in an appropriate manner for the purpose of stabilizing tooth enamel. It can be tooth enamel partially destroyed by caries, tooth enamel in an area open for invasive dentistry, or in areas that are undermineralized as a result of improper formation of tooth enamel, for example, in molar-incisor hypomineralization (MIH). The desired dental material provides for the mineralization of undermineralized dental hard matter in contact with it and covers such areas for at least the period required to mineralize areas of tooth enamel. In addition, permanent exposure can be envisaged in the case of a filling material. Its application leads to stabilization of the tooth substance, which provides remineralization and physical protection during the period required for remineralization. In the case of such an application, the material in question also provides a perfect grip in the area to be treated.

The next desired specific application of mineralizing dental materials is for the purpose of stabilizing existing or remaining dentine. Such applications are directed, for example, to exposed dentin in the region of the open neck of the tooth. This clinical condition is known to be the most difficult to treat because long-term and impermeable sealing in this area is very difficult. This is particularly relevant in the treatment of cervical caries, the clinical treatment of which is difficult. In such an application, the material also produces both a physical protection effect and a mineralization effect and thus provides stabilization by its action. In this case also, for clinical reasons, the material must be capable of adhesive self-curing at the stage of its application to the dentin surface.

A further preferred use of such materials is related to their suitability as a corrective material, particularly when deep cavities are present and in some circumstances demineralized dentin remains in the cavity. In this case, too, the target is the effects of stabilization and continued protection. In the case of materials of the prior art, the problem is that correction materials based on inorganic compounds do not always have sufficient chemical resistance and/or do not provide or provide only insufficient adhesion to the substrate.

A preferred requirement for the formation of the replenishing mineral material is that it should be chemically at least as stable in an acidic aqueous environment as tooth hardness (hydroxyapatite), and preferably more stable. Stability in an acidic aquatic environment means resistance to dissolution in such an environment. The formation of such a chemically stable mineral substitute prevents dissolution of the material on the surface, for example, under conditions of microbiological attack and acid formation.

According to the present invention, it is preferred that one of the interacting ions is multiply charged and is present as an oppositely charged ion in the coacervate, and the second interacting ion is present in the aqueous solution.

According to this embodiment, the additional presence of a second polyelectrolyte having a different charge than the coacervate polyelectrolyte may be preferred. If in this case the coacervate polyelectrolyte is a cationic field and an electrolyte, this second polyelectrolyte is an anionic polyelectrolyte, and vice versa. It has been found that the introduction of such a second polyelectrolyte means providing additional depth of mineralization in the tooth substance (more specifically, in the dentin). This is an advantage, in particular in the case of demineralized dentin, in that the mineralization potential can be improved by the depth of penetration of the interacting ion that is contained in the coacervate, which provides improved remineralization into the depth of the dentin.

According to the present invention, both interacting ions can be multiply charged and are present as oppositely charged ions of the corresponding coacervate. More preferably, one of the interacting ions is doubly charged, i. the charge is 2. Preferred charge values are +3, +2, -2 and -3.

In addition to multiply charged cations/anions, coacervates can also contain singly charged cations/anions. It may be preferred that some of the multiply charged or singly charged cations have antimicrobial properties. Suitable cations having these properties are, for example, silver ions or copper ions. It may be preferred that some of the multiply charged or singly charged anions produce biological effects or, alternatively, remineralization-promoting effects. It appears to be particularly preferred when the fluoride is present as a singly charged anion.

The anionic polyelectrolytes for forming coacervates with multiply charged cations may preferably be selected from the group of organic polyelectrolytes, which is preferably comprised of:

polymers and copolymers which contain carboxylic acid groups, phosphoric acid groups, phosphonic acid groups and/or sulfonic acid groups, as well as the corresponding salts and corresponding partial esters; preferably polycarboxylic acids, polyalkylenephosphoric acids, polyalkylenephosphonic acids, for example polyvinylphosphonic acid, and polysulfonic acids, as well as the corresponding salts and the corresponding partial esters; more preferably poly(meth)acrylic acid, polyaspartic acid, polyitaconic acid, and polyglutamic acid, and the corresponding salts;

acidic proteins, derivatives of acidic proteins and the corresponding salts, which preferably form lysozyme or gelatin (type B);

acid polysaccharides and the corresponding salts, which preferably form carrageenan, pectin, alginic acid and hyaluronic acid.

The anionic polyelectrolytes for forming coacervates with multiply charged cations preferably have average molecular weights (weight average Mw) ranging from 3 kDa to 1500 kDa, more preferably from 5 to 500 kDa, more preferably from 8 kDa to 200 kDa, even more preferably from 8 to 50 kDa.

The multiply charged cations are preferably selected from the group consisting of mineral-forming cations; preferably metal cations; preferably metals of groups 2A, 3B, and 3A of the Periodic Table of the Elements, as well as lanthanides; more preferably Ba ²⁺ , Ca ²⁺ , Sr ²⁺ , Tb ³⁺ and Yb ³⁺ ; more preferably Ca ²⁺ and/or mixtures of metal cations containing Ca ²⁺ .

Coacervates containing mixtures of cations are possible, for example by partial replacement of Ca ²⁺ ions, in particular Sr ²⁺ ions, in calcium-containing coacervates.

In one preferred embodiment, in the case of a Ca2 ⁺ polyacrylic acid coacervate, a pH value of at least 5 and a polyacrylic acid concentration of at least 1 mg/mL, more preferably at least 10 mg/mL, are used to form the desired releasable coacervate.

Cationic polyelectrolytes for the formation of coacervates with multiply charged anions are preferably selected from organic polyelectrolytes, preferably from the group consisting of polymers and copolymers that contain primary, secondary and/or tertiary amino groups, as well as the corresponding salts; preferably polyamines; more preferably polyallylamine, linear or branched polyethyleneimine, chitosan, polybetaine and polyarginine, and the corresponding salts; more preferably polyallylamine hydrochloride (PAH).

In one embodiment, the cationic polyelectrolyte coacervates may be a combination of polyallylamine hydrochloride (PAH) with a phosphate or hydrogen phosphate, which is an oppositely charged ion. According to this embodiment, it must be ensured that, for the purpose of making the coacervate, the polyallylamine is present in the highest possible protonated form and the phosphate ion is present in the highest possible deprotonated form.

The cationic polyelectrolytes for forming coacervates with multiply charged anions preferably have average molecular weights (weight average Mw) ranging from 3 kDa to 1500 kDa, preferably from 5 to 500 kDa, more preferably from 8 kDa to 200 kDa, even more preferably from 8 to 50 kDa.

The multiply charged anions are preferably selected from the group consisting of mineral-forming anions, preferably orthophosphate ions, diphosphate ions, metaphosphate ions, silicate ions, more specifically inorganic silicate ions, preferably orthosilicate, inosilicate and bandgap silicate ions, and partially organically modified silicate ions, more specifically alkyloxy silicate ions, sulfate ions, tungstate ions, vanadate ions, molybdate ions, and carbonate ions, more preferably orthophosphate ions, diphosphate ions, metaphosphate ions, sulfate ions, tungstate ions, vanadate ions, molybdate ions, more preferably orthophosphate ions and/or mixtures of orthophosphate ions with mineral-forming anions.

According to one embodiment of the present invention, the dental material is preferably a liquid and/or emulsion and/or suspension, preferably having a dynamic viscosity of greater than 50 mPa.s, preferably greater than 100 mPa.s.

According to a further embodiment of the present invention, the dental material is preferably a solid, preferably a powder.

According to a further embodiment of the present invention, the dental material is preferably a gel or paste.

Dental material may contain from 1 to 100 wt. % interacting ions and coacervate; while the preferred lower limits and upper limits are 5, 10, 15, 25 and so on up to 95 wt. %. The indicated intervals, constituting 5 wt. %, in each case can be combined arbitrarily according to the present invention with the formation of the ranges of the lower limits and upper limits.

The dental material according to the present invention preferably contains water, which is preferably from 5 to 95 wt. %; while the preferred lower limits and upper limits are 5, 10, 15, 25 and so on up to 95 wt. %. The indicated intervals, constituting 5 wt. %, in each case can be combined arbitrarily according to the present invention with the formation of the ranges of the lower limits and upper limits.

According to one embodiment of the present invention, the coacervate according to may have a water content of from 0.1 to 90 wt. %, preferably from 1 to 75 wt. %, preferably from 5 to 60 wt. %.

According to a preferred embodiment, after drying, for example, the coacervate may have a water content of 0.1 to 50 wt. %, preferably from 1 to 25 wt. %, preferably from 5 to 25 wt. %.

According to the present invention, it is preferred that the concentration of the polyelectrolyte that forms coacervates and the corresponding oppositely charged ions in the coacervate is from 10 to 100 wt. %; while the lower limits are preferably 25 or 40, preferably 45 wt. %; the upper limits are preferably 55 or 75, more preferably 85, 90 and 95 wt. %.

According to the present invention, it is preferred that fluoride ions are present as interacting ions.

According to the present invention, it is preferred that the interacting ions in the dental material are present mainly in soluble form (in particular before the formation of the remineralizing substance).

The dental material of the present invention may be present in a self-curing configuration.

According to the present invention, it is preferred that the dental material has a duration of action and/or a setting time of 1 to 5 minutes according to ISO 9917:2007.

According to the present invention, it is preferred that the cured dental material is self-adhesive and preferably has a shear bond strength of at least 3.5 MPa on tooth enamel and/or dentin.

The cured dental material preferably has a compressive strength greater than 50, preferably greater than 100, more preferably greater than 200 MPa, and a flexural strength greater than 20, preferably greater than 25 MPa according to ISO 9917:2007.

The dental material of the present invention has a high mineralization potential with respect to dental solids and, in particular, in its preferred form forms a mineral replacement material which has an acid solubility at pH 4.2 which is lower than that of hydroxyapatite.

According to the present invention, the dental material may contain additives such as pigments, dyes, antioxidants, preservatives, fillers, or other consistency restorers, which may be added, for example, to control rheological properties. To improve the mechanical properties, it is possible to introduce inert inorganic or organic fillers into the dental material, such as silicates, glasses, ZrO ₂ , BaSO ₄ , SiO ₂ , as well as prepolymers. In addition, fillers capable of actively influencing the mineralization process can be used. As illustrative examples, ion releasing glasses such as ionomer glasses and bioactive glasses, hydroxylapatite particles, amorphous calcium phosphate (ACP) or tetracalcium phosphate (TCP) can be cited here. Particularly preferred is hydroxyapatite, more specifically in the form of nanoparticles, in which the average particle diameter is from 5 to 100 nm. In addition, by adding water-soluble particles releasing interacting ions according to the present invention, in particular salts containing calcium ions, phosphate and fluoride ions, more specifically CaCl ₂ particles and (NH ₄ ) ₂ HPO ₄ particles, it is possible to achieve a further increase in the content of minerals and ion sources in these particles. Water-soluble citrates are another preferred additive. For coloring purposes, it is possible to add inorganic or organic colored pigments. Said pigments may serve to match the color of the material with the color of the hard substance of the teeth, or alternatively provide a contrast between the material and the tooth.

As further possible additives, it is possible to introduce into the system monomers, which are, for example, (meth)acrylates or polyelectrolytes containing double bonds. Through the additional possibility of curing the polyelectrolyte system according to the second curing mechanism, it is possible to further influence the properties of the described dental material. Depending on the architecture, polymerizable monomeric units can be cross-linked with polyelectrolytes. In addition, it is possible to partially functionalize the used coacervates.

According to the present invention, the term "aqueous solution" also extends to such solutions that contain water in a homogeneous system, for example, together with organic solvents. Such solutions preferably contain more than 10 wt. % water, preferably more than 50 wt. % water, and particularly preferably water is the only solvent.

Polyelectrolytes can be considered in particular as polymers which contain charged groups attached directly or via intermediate groups to the polymer chain. Said charged groups may be negatively charged groups or positively charged groups. It turns out to be preferable that charges of only one sign are present in each polymer chain. In this case, the number of charged groups in the polymer chain can vary within a wide range. For example, the polymer chain of a suitable polyelectrolyte may contain not only monomer units in which charge carriers are present, but also monomer units in which charge carriers are absent. A suitable polyelectrolyte preferably has a solubility of greater than 1 mg/ml.

Coacervates are obtained, as a rule, through the exchange of oppositely charged ions of dissolved polyions, which form coacervates with polyions. A preparation step of this type is carried out by simply mixing the polyions in aqueous solution with the corresponding coacervate-forming oppositely charged ions in aqueous solution. The resulting coacervates are then freed from excess residual ions by simple washing operations and can then be isolated as materials ranging from syrupy to highly viscous or viscoelastic. As a simple example, the sodium salt of polyacrylic acid is mixed with CaCl ₂ . Above a certain concentration of Ca ²⁺ ions in solution and an appropriate ratio of Ca ²⁺ ions and carboxylate ions, phase separation occurs and a liquid aqueous coacervate can be isolated. Coacervates can be used in liquid form in the continuous/macroscopic phase. The characteristic of coacervates according to the present invention is a variable water content. From the coacervate phase separated from the solution, water can be removed, for example, until a solid is obtained. This removal of water is reversible. Thereafter, the coacervates can be used, preferably in powder form. Powders are preferably obtained by drying and then grinding the dried coacervates. Drying takes place at temperatures below 250°C, preferably below 100°C, for example at 60°C and standard pressure, at 40°C and standard pressure, or preferably by lyophilization. Grinding can be carried out using a variety of technologies described in the documents of the prior art, in a dry or wet state, in a suitable liquid medium. A further possibility is the use in the form of suspensions or emulsions. Further powders, suspensions or emulsions in the aggregate may be referred to using the term "fine forms".

Hereinafter, for the purposes of simplicity, the coacervate based on anionic polyelectrolytes is referred to as the term "coacervate (a)", and the coacervate based on anionic polyelectrolytes is referred to as the term "coacervate (b)".

When the coacervate comes into contact with an aqueous solution containing an ion (interacting ion) capable of forming a compound having low solubility in water with a crosslinking oppositely charged ion of the coacervate, the compound having a low solubility is slowly deposited at the interface with the coacervate.

According to one embodiment, the aqueous coacervate contains polyacrylic acid and Ca ²⁺ ions as a base. According to this embodiment, phosphate can be used as the interacting ion. For purposes of mineralization in this form, it has been shown that a solution containing (NH ₄ ) ₂ HPO ₄ at a concentration of 10 mM to 250 mM, preferably 130 mM, is advantageous. Similarly, according to this embodiment, the pH value has a decisive influence on the formation of the mineral substituent. During mineralization, the pH value decreases without the use of additional buffer solutions. The use of a buffer solution, such as TRIS, for example, may be beneficial to the properties of the dental material.

According to a further embodiment, the aqueous coacervate contains polyallylamine phosphate ions as a base. In this case, Ca ²⁺ ions can be used as interacting ions. For mineralization purposes, solutions containing CaCl ₂ at a concentration of 10 mM to 250 mM, preferably 130 mM, have proven advantage. In addition, according to this embodiment, the pH value also has a decisive influence on the formation of the mineral substituent.

According to one embodiment, for a certain period of time, the surface of the tooth is in contact with a solution containing an interacting ion. Then, a coacervate is applied to this surface, which spreads over its area (for example, in the form of a film) and remains on it until sufficient mineralization of the tooth substance is carried out. An optional possibility is to apply another type of coacervate to this treated surface.

In the case of application in this way, the coacervate can be applied, on the one hand, in the form of a viscous liquid. On the side away from the tooth, the surface can then be protected for the desired period so that premature loss of the coacervate layer does not occur. If used in another way, the coacervate can be applied in a finely divided form to the surface of a tooth treated with an interacting ion. In this case, the use of coacervate in the form of a powder is also possible, since a sufficient amount of water is always present in the oral environment, which is necessary for mineralization processes.

According to a further embodiment, the coacervate is mixed in finely divided form with a solution of the interacting ion applied in this form to the surface of the tooth to be treated. In this case, the mineral substitute is also formed, starting from the interfaces of the coacervate particles, which are also able to act on the substance of the tooth.

The combination of coacervates based on oppositely charged polyelectrolytes leads, firstly, to the formation of highly cross-linked and solid interpolymer complexes of said polyelectrolytes, said complexes being insoluble in water. Secondly, in the case of a suitable choice of oppositely charged ions, a mineral substituent is formed. That is, the material undergoes solidification to form inorganic solids, the precursors of which form part of the original components in the form of coacervates.

In principle, the components containing coacervates (a) and (b) can be mixed with each other in the form of liquid components and isolated in the composition of the substance, which then very quickly turns into a solid. It may be more preferable to use finely divided coacervates which are mixed in the presence of water during use. The duration of action and the duration of hardening of such combinations of coacervates can in each case be controlled by the choice of particles or the distribution of particles by size. Another possibility is to layer the coacervates one after the other.

According to one preferred embodiment, the finely divided components containing coacervates (a) and (b) are mixed in the presence of aqueous solutions and applied to the substance of the tooth to be treated. They undergo hardening mainly as a result of the formation of insoluble interpolymer complexes. As the reaction progresses, the mineral substituent-forming ions are released from the coacervates, and the mineral substituent is formed in the area open to the coacervate mixtures, as well as in the area of the hard matter of the teeth.

According to one method of application, in which the dried ground components containing coacervates (a) and (b) are mixed with each other, it is necessary to add water or aqueous solutions to the mixture before applying to the substance of the tooth in order to allow the reaction to proceed. This addition to the mixture of water or aqueous solutions takes place preferably before application to the tooth substance, for example by manual agitation or by automatic means such as capsule agitation.

The powder and water or aqueous solution are preferably mixed in a weight ratio of 5:1 to 1:50, preferably 2:1 to 1:10, and more preferably 2:1 to 1:2. According to one preferred embodiment, the coacervates (a) and (b) are mixed in the form of powders in a weight ratio (the sum of the amounts of (a) and (b) and the amount of water or aqueous solution) ranging from 2:1 to 1:10, preferably from 2:1 to 1:1 and more preferably 3:2.

In addition, it is possible to apply individual powders or a mixture of powders to the wet surface of the tooth, where the reactions mentioned above take place.

In one preferred aspect, said mixed ground coacervates are a mixture of calcium polyacrylate-containing coacervate and polyallylamine phosphate-containing coacervate. In the case of this mixed coacervate, a weight ratio of 1:1 is advantageous. Furthermore, weight ratios ranging from 5:3 up to 3:5 are possible. The amount of water optionally added to the mixture is determined by the target consistency of the mixture, which is required for a particular application.

According to a further embodiment, the non-aqueous dispersion of the dried powder mixture of the coacervate components (a) and (b), which contains a fully water-miscible solvent (eg, glycerol), is mixed with an additional aqueous component prior to use. This mixture is then applied to the substance of the tooth to be treated, where hardening and mineralization processes take place.

It may be preferable to mix with each other before using aqueous emulsions of the components containing coacervates (a) and (b) in each case and optionally contain additionally soluble mineral substituent-forming salts in the aqueous phase. This mixture is applied to the substance of the tooth to be treated, where, in this case, the processes of hardening and mineralization take place.

An aqueous emulsion of a coacervate or a plurality of coacervates as a dental material contains at least 1 percent by weight, preferably at least 2 percent by weight, more preferably at least 5 percent by weight of coacervate.

Mixing can be carried out in each case manually or using automatic mixing methods such as, for example, transferring the two-component material from dual cartridges and mixing with a static or dynamic mixer.

According to one preferred application, in order to obtain an accelerated bond between the tooth surface and the dental material, before applying the coacervate components (a) and (b) mixed with each other, the hard substance of the teeth to be treated is treated with an aqueous solution containing a polyacid or polybase, or the corresponding salts. It appears particularly advantageous to apply the polyacid and then the mixture of (a) and (b) to the surface of the substance of the tooth to be treated. According to the following application, the aqueous solution of the polyacid is first applied to the tooth substance, and then the aqueous solution of the polybase is applied, before finally the mixture of (a) and (b) is applied. According to the present invention, the use of a polyacid or polybase as described herein prior to use of a dental material is to be distinguished from the similar inventive addition of such a polyacid or polybase to said dental material of the present invention.

Due to its properties of mineral substituent formation and mineralization over time, the dental material of the present invention exhibits a more intense interaction with the hard matter of the teeth and thus counteracts the effect of destabilizing adhesion due to the environment. Such interaction may include, for example, building bridges of mineral substitute between the dental material and the hard substance of the teeth.

Because the amounts of mobile ions in coacervates are comparatively large, the mineralization potential of coacervates for dental hard matter is correspondingly high. By choosing a combination of oppositely charged ions in the coacervate, it is also possible to influence the nature of the mineral substituent and thus its chemical stability.

The next object of the present invention is a set for the manufacture of remineralization dental material according to the present invention, which contains the following components:

a first component that contains at least one coacervate with one of the interacting ions as the oppositely charged coacervate ion;

a second component that contains water;

wherein the second of the interacting ions is present as a free ion in aqueous solution in the second component and/or as an oppositely charged ion of the second coacervate in one of the two components.

Preferably at least one of the components is a solid, preferably a powder.

According to a further preferred embodiment, at least one of the components is a liquid, preferably having a dynamic viscosity at 23°C of greater than 10 mPa.s, more preferably greater than 50 mPa.s, even more preferably greater than 100 mPa.s.

According to a further preferred embodiment, at least two of the components are pastes.

According to a further preferred embodiment, at least two of the components are gels.

According to the present invention, it is preferred that at least one of the components, preferably at least two of the components, have a pH value of 7 to 9 at 23°C.

The kit preferably contains an additional component c, which preferably has a pH value of less than 7, and contains an adhesion promoter. The adhesion promoter is preferably a polyacid or polyamine which is protonated, preferably to an extent of at least 10%. The use of a polyacid or polyamine described herein prior to application of the dental material of the present invention is to be distinguished from the similar addition of said materials to said dental material of the present invention as provided by the present invention. Similarly, according to the present invention, it is possible that such a component has a dual function as an adhesion promoter, on the one hand, and as a constituent component of said dental material, on the other hand.

Preferably, components a and b are contained in a device suitable for mixing, preferably in a mixing capsule containing preferably a powder and/or liquid, and/or in a multi-chamber cartridge as part of a cartridge system for extruding the components through a mixing needle containing preferably two pastes or two gels.

According to one preferred embodiment, one of the interacting ions is multiply charged and is present as an oppositely charged ion in the coacervate; the second interacting ion is present in the aqueous solution. At least one of the components further comprises a second polyelectrolyte which has a different charge than the coacervate polyelectrolyte.

According to the present invention, it is preferred that component a contains at least one coacervate (a) or (b) and contains at least one polyelectrolyte and an electrolyte which has a different charge than the coacervate polyelectrolyte and is not present in the coacervate form.

According to the present invention, it is preferred that component a contains at least one coacervate powder containing multiply charged anions as oppositely charged ions and at least one anionic polyelectrolyte powder.

According to the present invention, it is preferred that component a contains at least one coacervate powder containing multiply charged cations as oppositely charged ions and at least one cationic polyelectrolyte powder.

According to the present invention, it is preferred that component a contains at least one first coacervate powder containing alkaline earth metal ions, preferably calcium ions, as oppositely charged ions, and at least one second coacervate powder containing multiply charged anions as interacting ions.

The next object of the present invention is a method of using the kit according to the present invention, comprising the following steps:

i. application of component b to dentin and/or tooth enamel, preferably in the form of a liquid

ii. applying component a to dentin with component b and/or tooth enamel with component b, preferably in the form of a powder, paste, gel or viscous liquid.

Similarly, the object of the present invention is a method of using the kit according to the present invention, comprising the following steps:

i. mixing component a and component b,

ii. applying the mixture to the dentin and/or tooth enamel, preferably in the form of a paste or gel.

A further object of the present invention is the use of the dental material according to the present invention as a sealing material, a covering material, a corrective material and/or a filling material, as a temporary filling cement, for pulp capping, as a bone cement, as a dental varnish, as a crack-sealing material, as a desensitizing agent, as a remineralizing agent in the prevention or treatment of carious lesions; or for the purpose of manufacturing said materials.

Working examples of the present invention are shown below.

Methods

Loss on drying

In each case, immediately after synthesis, the coacervates were weighed and then kept in a Heraeus VT6025 vacuum oven from Thermo Scientific at 40° C. and 50 mbar for at least 24 hours. The weight loss on drying was calculated as the difference between the initial weight and the final weight.

Thermogravimetric analysis (TGA)

Thermogravimetric analysis (TGA) was performed in air at a temperature of 25°C to 1000°C and a heating rate of 10 K/min using a Netzsch STA 449FS Jupiter instrument.

The parameter to be evaluated was the weight loss up to 250° C., which corresponded to the residual water content, in the preparation of lyophilized powders.

Energy dispersive X-ray spectroscopy (EDX)

The content of elements was determined using the following instruments: a desktop scanning electron microscope (SEM)/EDLS TM 3000 M from Hitachi and a Quantax EDLS detector from Bruker. Lyophilized powders were used.

Compressive strength

The test specimens were made using a two-component mold, which was made of stainless steel and contained six cylindrical holes having a height of 4±0.02 mm and a diameter of 2±0.01 mm. The mold was placed on a glass plate and the dental material was introduced into the holes. When the holes were filled with material, the edges of the holes were aligned. The samples were kept in the form at a temperature of 37°C and almost 100% relative humidity for one hour. After that, the samples, together with the mold, were removed from the wet chamber. The mold was opened, samples having a height of approximately 4 mm and a diameter of approximately 2 mm were removed, and the compressive strength was measured using a universal testing machine model Z 010/TN2A from Zwick, determining the compressive strength after 1 hour. To determine the compressive strength after 4 days, the demoulded test samples were again kept in a humid chamber at a temperature of 37°C and 100% relative humidity for 4 days. After that, the samples were removed from the chamber, and the compressive strength using the specified universal testing machine from Zwick under the following conditions:

constant movement speed: 1.0 mm/min;

calculation of compressive strength (CS) according to the following formula: CS [MPa]=F/(p⋅r ² ), where:

F is the maximum force (in newtons) applied to the specimen;

r is the radius (in millimeters) of the sample.

The measurement was carried out in each case for six samples, and the average value was determined from the six measured values.

Shear bond strength

To determine shear bond strength (SBS), pulp-free bovine cutters were immersed in Viscovoss GTS cold curing resin with methyl ethyl ketone peroxide (MEKP) MEN hardener from Voss Chemie. Immediately prior to testing, the used teeth were wet abraded on tooth enamel or dentin using P120 sandpaper and then wet reworked using P500 fine sandpaper. Before testing, the teeth were kept in demineralized water. To measure the teeth were removed from demineralized water. Then, a two-component Teflon mold with a hole diameter of 3.0 mm according to ISO/TS 11405:2003 was installed and fixed with a metal brace, and the cavity was filled with dental material. After filling the cavity, the Hostaphan film was placed and the glass plate was positioned and fixed with another metal brace. The filled molds were kept in a humid chamber at a temperature of 37°C for 4 days, and then the contents of the molds were removed. The test samples were then subjected to measurement using a shear device according to ISO10477:2004 and a force-distance diagram device model Z010/TN2A from Zwick GmbH & Co. (Ulm, Germany) at a travel speed of 0.5 mm/min. In each case, the study was carried out for three samples.

Dynamic viscosity

Viscosity was measured at a temperature of 23°C using a dynamic viscometer with two plates (dynamic shear rheometer from Rheometric Scientific Inc.). The measurement was carried out in the steady-state voltage sweep mode with gap sizes from 0.1 to 0.5 mm at a shear stress in the range from 0 to 50 Pa.

Mineralization/X-Ray Diffractometry (XRD)

The dental material obtained in Example 6 was cured in the form of a thin layer. The material was then kept in a humid chamber at 37° C. for 5 days. The dried material was ground in a mortar and analyzed in that state using a Bruker D8 Discover X-ray diffractometer.

Coacervates (a) and interacting ions in aqueous solution were used (examples 9 and 10).

After the end of the mineralization time, the mixture was centrifuged, decanted and washed three times with ultrapure water 1.75. The washed centrifuged residues were then dried at 37°C.

In each case, the dried products in the form of powders were examined by X-ray diffractometry (XRD) to determine the respective mineral phases.

In Examples 11 and 12, mineralized material was removed from the interior of the gel product and analyzed as such using a Bruker D8 Discover X-ray diffractometer.

Particle Sizing

To determine the particle size distribution, 250 mg of lyophilized and crushed coacervates were dispersed in 20 ml of ethanol for 5 minutes in an ultrasonic bath. Thereafter, the particle size was measured using a Fraunhofer diffraction particle size analyzer (laser diffraction particle size analyzer LS 13 320 with universal fluid module from Beckmann Coulter) in denatured ethanol.

Used chemicals

- Polyacrylic acid sodium salt solution (NaPAA15, Mw=15 kDa, 35 wt% solution from Sigma Aldrich)

- Polyacrylic acid (PAA100, Mw=100 kDa, 35 wt% solution from Sigma Aldrich)

- Polyallylamine hydrochloride (PAH15, Mw=15 kDa, solution 15 wt. % from Polyscience

- Polyallylamine hydrochloride powder (Mw=17.5 kDa from Sigma)

- Trisodium citrate tetrahydrate (Sigma Aldrich)

- Calcium chloride dihydrate (Roth)

- Diammonium hydrogen phosphate (Sigma Aldrich)

- Strontium chloride (Roth)

- Sodium hydroxide (Merck)

- Hydrochloric acid (Merck)

- Ultrapure water (MilliQ, Merck Millipore)

- Gelatin (300 blum, type A)

Synthesis of coacervates based on salts of polyacrylic acid (examples 1-4)

An aqueous solution of calcium chloride or an aqueous solution of strontium chloride was slowly added to an aqueous solution of the sodium salt of polyacrylic acid with vigorous stirring. Phase separation was observed during the addition. After completion of the addition, stirring was continued for five minutes, and then the mixture was kept at rest for 10 minutes for further separation. The resulting upper solution was decanted and the remaining phase was washed three times using 400 ml of ultrapure water each time. A viscous liquid was obtained.

The pH values in each case were adjusted using solutions of hydrochloric acid and/or sodium hydroxide. The quantities, concentrations and pH values of the solutions used are presented in Table 1.

Synthesis of coacervate based on polyallylamine hydrochloride (example 5)

An aqueous solution of (NH ₄ ) ₂ HPO ₄ was slowly added to an aqueous solution of polyallylamine hydrochloride with vigorous stirring. Phase separation was observed during the addition. After completion of the addition, stirring was continued for five minutes, and then centrifugation was carried out at an acceleration of 7700 g for 3 minutes for further separation. The resulting upper solution was decanted and the remaining phase was washed three times using 10 ml of ultrapure water each time. A viscous liquid was obtained.

The pH values in each case were adjusted using solutions of hydrochloric acid and/or sodium hydroxide. The quantities, concentrations and pH values of the solutions used are presented in Table 2.

Water content/mass loss on drying of the viscous liquids obtained in examples 1, 4 and 5

The water content in viscous liquids was determined from the weight loss on drying. The weight loss on drying is presented as water content in Table 3a.

The content of ions in freeze-dried samples of viscous liquids obtained in examples 1, 4 and 5

The content of ions was determined as the content of elements by the method of energy dispersive X-ray spectroscopy (EDX). The residual water content in the lyophilized viscous gels was determined by thermogravimetry (TGA). The residual water content and elemental content are presented in Table 3b.

Preparation of coacervate powders

Coacervate powder (P1)

Water was removed from the viscous liquid obtained in Example 1 by lyophilization. The resulting material was ground in a vibrating mill (Pulverisette 0 from Fritsch) for 7 hours, then in a crushing mill (Pulverisette 2 from Fritsch) for 6 hours and finally in a ball mill (ball distribution: 55x16 mm, 14x25 mm, 4x40 mm) for 18 hours.

The residual water content in the resulting white powder was determined by TGA. The residual water content was 8% by weight. Particle size distribution: D ₁₀ =1.0 µm and D ₅₀ =4.4 µm.

Coacervate Powder (P2)

Water was removed from the viscous liquid obtained in Example 5 by lyophilization. The resulting material was ground in a vibrating mill (Pulverisette 0 from Fritsch) for 7 hours, then in a capsule mixer (1 ml; ball diameter: 3.15 mm; Silamat from Ivoclar Vivadent) for 60 seconds, and finally in a capsule mixer (1 ml; ball diameter: 0.1 mm; Silamat from Ivoclar-Vivadent) for 60 seconds.

The residual water content in the resulting white powder was determined by TGA. The residual water content was 8% by weight. Particle size distribution: D ₁₀ =2.4 µm and D ₅₀ =24.6 µm

Polyallylamine hydrochloride powder (P3)

This powder is a second cationic polyelectrolyte which, according to the present invention, can be used together with an anionic polyelectrolyte containing coacervate and which provides depth of mineralization in the manner already described above and illustrated in the examples.

Example 6. Obtaining a self-adhesive self-curing dental material from coacervate powders P1 and P2

To obtain a dental material, 150 mg of powder P1 was mixed with 150 mg of powder P2. This mixture of powders, as well as 0.2 ml of water, was added separately from one mixing capsule to another Applicap mixing capsule from DMG (Hamburg).

The powder and liquid were mixed using a vibratory mixer (Silamat from Ivoclar Vivadent AG) for 20 seconds and a ready-to-use dental material was obtained.

Immediately after mixing, the resulting dental material was removed from the mixing capsule using the mixing capsule needle and processed.

Example 7. Obtaining a self-adhesive self-curing dental material from coacervate powder P1

300 mg of powder P1 and 0.2 ml of solution (NH^HPCm (130 mM, pH 9) were mixed by hand with a spatula on a tray for approximately 30 seconds to obtain a ready-to-use dental material.

Example 8. Obtaining a self-adhesive self-curing dental material from coacervate powder P1

300 mg of ground powder P1 and 0.2 ml of a solution containing 130 mM (NH ₄ ) ₂ HPO ₄ and 100 mM sodium citrate and adjusted to pH 9 were manually mixed for approximately 30 seconds to obtain a ready-to-use dental material. Compared to example 7, this material hardens significantly faster.

Example 9

40 mg of crushed powder P1 and 1.75 ml of a solution of 130 mM (NH ₄ ) ₂ HPO ₄ adjusted to pH 9 were manually mixed with a spatula for approximately 30 seconds in a 2 ml reaction vessel (Eppendorf tube), shaken for a short time, and then kept in a horizontal position at room temperature for 5 minutes and 24 hours, respectively.

Example 10

40 mg of coacervate powder P1 was mixed with 1.75 ml of an aqueous solution containing 130 mM (NH ₄ ) ₂ HPO ₄ and 100 mM sodium citrate (similar to example 8) in a 2 ml reaction vessel (Eppendorf tube), shaken for a short time, and then kept in a horizontal position at room temperature for 5 minutes and 24 hours, respectively.

Study

The compressive strength was determined for the dental materials obtained in examples 6-8. Compressive strength values are presented in Table 4.

The compressive strength was highest for the material obtained in example 7. For all dental materials, the compressive strength values were higher after 4 days than after 1 hour after treatment.

Shear bond strength (SBS)

Shear bond strength was measured in Examples 6-8. The dental material is self-adhesive. Cracks or deformations were observed in the samples, which occurred before shear failure.

Mineralization

The mineralization of the mixtures obtained in examples 6, 9 and 10, was investigated by the XRD method. The discovered mineral phases are presented in Table 5.

Obtaining a Model Substance

For the application examples presented below, model substances for demineralized dentin were first prepared. Each model substance consists of a gel that is solid at room temperature.

At a temperature of 40°C was dissolved 10 g of gelatin (type A, 300 bloom) in 90 ml of an aqueous solution having a pH of 9 and containing 130 mm diammonium hydrogen phosphate and 100 mm tetrahydrate trisubstituted sodium citrate. The resulting gelatin solution was placed in standard 24-well titer plates and allowed to cool to room temperature. Immediately after reaching room temperature, solid gel samples were removed from the titration plate using a spatula and placed in an aqueous solution.

Application of dental materials to model substances

Dental materials were in each case applied to the surface of the model substance, i.e. on the upper surfaces of the disk-shaped gel samples, and then kept at room temperature in 10 ml of an aqueous solution having pH 9 and containing 130 mM diammonium hydrogen phosphate and 100 mM trisodium citrate tetrahydrate, so that the dental material and model substance were covered with the solution, or they were kept in a conditioning cabinet under conditions of 100% relative humidity and room temperature. After 2 days, 3 days, 4 days, 8 days or 12 days, gel samples were removed and washed with ultrapure water. Then, using a razor blade, cross-sections of disk-shaped gel samples were obtained. These cross sections were examined optically to determine whether mineralized material is present below the surface of the model material and how deeply this material penetrates into the model material.

Examples 11-13

Self-adhesive self-curing dental materials were obtained in the same way as in example 6. Powders/powder mixtures and liquids used in this case are presented below in table 6 below.

The liquid constituent used is an aqueous solution containing (NH ₄ ) ₂ HPO ₄ and sodium citrate, which was also already used in Example 8.

In Examples 12 and 13, the powder mixture contains P3 powder as the second cationic field and an electrolyte which is used together with an anionic polyelectrolyte containing coacervate (P1 powder) and which provides depth of mineralization in the manner already mentioned above.

To prepare the dental material, 150 mg of the respective powder/powder mixture as well as the liquid constituent were injected separately from one mixing capsule into another Applicap mixing capsule from DMG (Hamburg). The powder and liquid were mixed using a vibratory mixer (Silamat from Ivoclar Vivadent AG) for 20 seconds and a ready-to-use dental material was obtained.

Immediately after mixing, the resulting dental material was removed from the mixing capsule using the mixing capsule needle and processed.

The dental materials obtained in this way were applied to the model substance, and the mineralization was examined in accordance with the following application examples.

Example 11

The dental material obtained in Example 11 and listed above in Table 6 was applied to the model substance and kept in an aqueous solution as described above.

After 4 days, a small depth of mineralization was observed. After 12 days, the observed depth of mineralization remained small (Fig. 1). For mineral material produced in gelatin, calcium, carbon, phosphorus and oxygen were found throughout the depth (FIG. 2). The mineral material was identified as hydroxyapatite by XRD (FIG. 3).

Example 12

The dental material obtained in Example 12 and listed above in Table 6 was applied to the model substance and kept in an aqueous solution as described above.

Already after 3 days, a significant depth of mineralization was observed (Fig. 4). Dental material applied to the gelatinous surface provides adhesion to the surface, is stable and does not break down. The resulting mineral material can be identified as hydroxylapatite when measured by XRD (FIG. 5). For mineral material produced in gelatin, calcium, carbon, phosphorus and oxygen can be detected by EDRS analysis (FIG. 6).

Example 13

The dental material obtained in Example 13 and listed above in Table 6 was applied to the model substance and kept in the conditioning chamber as described above.

Already after 2 days, a significant depth of mineralization was observed (Fig. 7). Dental material applied to the gelatinous surface provides adhesion to the surface, is stable and does not break down. The resulting mineral material was identified as hydroxyapatite by XRD.

Claims (43)

1. A remineralization dental material containing at least one cation and at least one anion that act as interacting ions to form a remineralizing substance, wherein at least one of the interacting ions is multiply charged and is present as an oppositely charged ion with a polyelectrolyte in the coacervate. 2. Dental material according to claim 1, in which one of the interacting ions is multiply charged and is present as an oppositely charged ion in the coacervate, and the second interacting ion is present in an aqueous solution. 3. Dental material according to claim 1 or 2, in which there is additionally a second polyelectrolyte, which has a different charge than the coacervate polyelectrolyte. 4. Dental material according to claim 1, in which both interacting ions are multiply charged and are present as oppositely charged ions of the corresponding coacervate. 5. Dental material according to any one of paragraphs. 1-4, in which the anionic polyelectrolytes for the formation of coacervates with multiply charged cations are selected from the group of organic polyelectrolytes, which is preferably comprised of: a. polymers and copolymers which contain carboxylic acid groups, phosphoric acid groups, phosphonic acid groups and/or sulfonic acid groups, as well as the corresponding salts and corresponding partial esters; preferably polycarboxylic acids, polyalkylenephosphoric acids, polyalkylenephosphonic acids and polysulfonic acids, as well as the corresponding salts and corresponding partial esters; more preferably poly(meth)acrylic acid, polyaspartic acid, polyitaconic acid and polyglutamic acid, and the corresponding salts; b. acidic proteins, acidic protein derivatives and the corresponding salts, which are preferably formed by lysozyme or gelatin (type B); c. acid polysaccharides and the corresponding salts, which preferably form carrageenan, pectin, alginic acid and hyaluronic acid. 6. Dental material according to any one of paragraphs. 1-5, in which the anionic polyelectrolytes for the formation of coacervates with multiply charged cations have average molecular weights (mass average values Mw) ranging from 3 to 1500 kDa, preferably from 5 to 500 kDa, more preferably from 8 to 200 kDa, even more preferably from 8 to 50 kDa. 7. Dental material according to any one of paragraphs. 1-6, wherein the multiply charged cations are selected from the group consisting of mineral-forming cations; preferably metal cations; preferable to metals of groups 2A, 3B, and 3A of the Periodic Table of the Elements, as well as lanthanides; more preferably Ba ²⁺ , Ca ²⁺ , Sr ²⁺ , Tb ³⁺ and Yb ³⁺ ; more preferably Ca ²⁺ and/or mixtures of metal cations containing Ca ²⁺ . 8. Dental material according to any one of paragraphs. 1-7, in which the cationic polyelectrolytes for the formation of coacervates with multiply charged anions are selected from organic polyelectrolytes, preferably from the group consisting of polymers and copolymers that contain primary, secondary and/or tertiary amino groups, as well as the corresponding salts; preferably polyamines; more preferably polyallylamine, linear or branched polyethyleneimine, chitosan, polybetaine and polyarginine, and the corresponding salts; more preferably polyallylamine hydrochloride (PAH). 9. Dental material according to any one of paragraphs. 1-8, in which the cationic polyelectrolytes for the formation of coacervates with multiply charged anions have average molecular weights (weight average values Mw) ranging from 3 to 1500 kDa, preferably from 5 to 500 kDa, preferably from 8 to 200 kDa, even more preferably from 8 to 50 kDa. 10. Dental material according to any one of paragraphs. 1-9, in which the multiply charged anions are selected from the group consisting of mineral-forming anions, preferably orthophosphate ions, diphosphate ions, metaphosphate ions, silicate ions, more specifically, inorganic silicate ions, preferably orthosilicate, inosilicate and band gap silicate ions, and partially modified with organic groups silicate ions, more specifically alkyloxy silicate ions, sulf ions, tungstate ions, vanadate ions, molybdate ions, and carbonate ions, more preferably orthophosphate ions, diphosphate ions, metaphosphate ions, sulfate ions, tungstate ions, vanadate ions, molybdate ions, more preferably orthophosphate ions and/or mixtures of orthophosphate ions with mineral-forming anions. 11. Dental material according to any one of paragraphs. 1-10, in which the proportion of the coacervate component is more than 1 percent by weight, preferably more than 2 percent by weight, more preferably more than 5 percent by weight. 12. Dental material according to any one of paragraphs. 1-11, which is a liquid and/or emulsion and/or suspension. 13. Dental material according to any one of paragraphs. 1-11, which is a gel. 14. Dental material according to any one of paragraphs. 1-11 which is a paste. 15. Dental material according to any one of paragraphs. 1-14, which contains from 1 to 95 wt.% interacting ions and coacervate; while the preferred lower limits and/or upper limits are 5, 10, 15, 25 and so on up to 95 wt.%. 16. Dental material according to any one of paragraphs. 1-15, which contains water, preferably from 5 to 95 wt.%, while the preferred lower limits and/or upper limits are 5, 10, 15, 25, and so on up to 95 wt.%. 17. Dental material according to any one of paragraphs. 1-16, wherein the coacervate has a water content of 0.1 to 90% by weight, preferably 1 to 75% by weight, more preferably 5 to 60% by weight. 18. Dental material according to any one of paragraphs. 1-17, in which the concentration of the coacervate-forming polyelectrolyte and the corresponding oppositely charged ions in the coacervate is from 10 to 95 wt.%; while the preferred lower limits are 25 or 40, preferably 45 wt.%, the preferred upper limits are 55 or 75, preferably 85 and 90 wt.%. 19. Dental material according to any one of paragraphs. 1-18, in which fluoride ions are present as interacting ions. 20. Dental material according to any one of paragraphs. 1-19, and the interacting ions are present in the dental material, mainly in a soluble form. 21. Dental material according to any one of paragraphs. 1-20 which is self-curing. 22. Set for the manufacture of remineralization dental material according to any one of paragraphs. 1-21, which contains the following components: a. a first component that contains at least one coacervate with one of the interacting ions being an oppositely charged coacervate ion; b. a second component containing water; wherein the second of the interacting ions is present as a free ion in aqueous solution in component b and/or as an oppositely charged ion of the second coacervate in one of the two components. 23. A kit according to claim 22, wherein at least one of the components is a solid, preferably a powder. 24. The kit of claim 22, wherein at least one of the components is a liquid, preferably having a dynamic viscosity of greater than 10 mPa.s, preferably greater than 50 mPa.s, more preferably greater than 100 mPa.s. 25. The set according to claim 22, in which both components are pastes. 26. The kit according to claim 22, in which both components are gels. 27. Set according to any one of paragraphs. 22-26, in which at least one of the components, preferably at least two of the components has a pH value of from 7 to 10 at 23°C. 28. Set according to any one of paragraphs. 22-27, which contains an additional component c, which preferably contains an adhesion promoter. 29. Set according to any one of paragraphs. 22-28, in which components a and b are contained in a device suitable for mixing, preferably in a mixing capsule containing preferably a powder or liquid, and/or in a multi-chamber cartridge, which is part of a cartridge system for extruding the components through a mixing needle, containing preferably two pastes or two gels. 30. Set according to any one of paragraphs. 22-29, in which one of the interacting ions is multiply charged and is present as an oppositely charged ion with a polyelectrolyte in the coacervate, and the second interacting ion is present in an aqueous solution, and at least one of the components additionally contains a second polyelectrolyte, which has a different charge than the coacervate polyelectrolyte. 31. Set according to any one of paragraphs. 22-24, 27-29, in which component a contains at least one first coacervate powder containing alkaline earth metal ions, preferably calcium ions as oppositely charged ions, and at least one second coacervate powder containing multiply charged anions as interacting ions. 32. The method of using the set according to any one of paragraphs. 22-31, comprising the following steps: i. applying component b to dentin and/or tooth enamel, preferably in the form of a liquid, ii. applying component a to dentin with component b and/or tooth enamel with component b, preferably in the form of a powder, paste, gel or viscous liquid. 33. The method of using the kit according to any one of paragraphs. 22-31, comprising the following steps: i. mixing component a and component b, ii. applying the mixture to the dentin and/or tooth enamel, preferably in the form of a paste or gel. 34. The use of dental material according to any one of paragraphs. 1-21 as a sealing material, covering material, corrective material and/or filling material.