DE102017214777A1 - Buffering polymers and polymer networks for dental applications - Google Patents

Abstract

A radically polymerizable composition for use in the treatment and prevention of dental indications associated with a pH change comprising (1) 10-90% by weight of solvent, (2) 5-50% by weight of at least a radical-polymerizable monomer having buffer groups, (3) 0-50% by weight of at least one monofunctional free-radically polymerizable monomer, (4) 0-20% by weight of at least one crosslinking radically polymerizable monomer, and (5) 0.01-5% by weight .-% contains at least one initiator for the radical polymerization, each based on the total mass of the composition.

Description

The present invention relates to free-radically polymerizable compositions which are particularly suitable for the treatment of initial carious lesions of fissures, smooth surfaces, interdental surfaces and tooth necks, for caries protection at selected tooth areas, for obtaining a local buffering effect in the mouth of a patient and remineralization of teeth.

Background of the invention

Tooth decay begins when acids deplete minerals from the hydroxyapatite portion of the hard tooth substance. This reduces the density of the mineral and thus increases its porosity. This makes the hard tooth substance more permeable to liquids and ions. The acid can reach your teeth directly through food, especially acidic drinks. However, of greater importance are carbohydrates, especially sucrose, which are fermented by biofilms on the teeth to organic acids, especially lactic acid. The pH value in the biofilm can drop to 4 - 5 in just a few minutes ( Lingstrom et al., 1993, J Dent Res. 72: 865-870 ).

Good oral hygiene and the topical application of fluoride to the teeth have proven to be particularly effective in the prevention of tooth decay. Fluoride reduces the solubility of hydroxyapatite. In recent decades, fluoride has led to an impressive decline in caries disease in children ( Marthaler and Petersen, 2005, Int Dent J, 55: 351-358 ). Unfortunately, while the caries-reducing effect of fluorides in permanent teeth of children has been clinically proven, this success is unfortunately accompanied by frequent findings of fluorosis ( Ismail and Hasson, 2008, J Am Dent Assoc, 139: 1457-1468 ). These findings indicate that alternatives to fluorides have to be found in caries prevention.

The US 2016/256362 A1 describes a process for the preparation of stabilized calcium phosphate. Here, a solution or dispersion of calcium salts is reacted with an organic phosphate having a polymerizable methacrylate or vinyl group. The stabilized calcium phosphate is said to be suitable for the production of dental materials which allow the regeneration of dentin by the release of calcium and phosphate ions.

The US 2015/0335790 A1 describes cross-linked zwitterionic hydrogels that can be mineralized and that are to be used, inter alia, for the production of dental implants.

The US 8,779,024 B2 describes acid-neutralizing resins for dental applications. The neutralization of acids is intended to prevent inactivation of amine co-initiators in the dental materials.

The US 8,686,063 B2 describes the infiltration of enamel for the prevention and treatment of caries lesions. The molten area to be treated is etched with hydrochloric acid, then the infiltrant is applied and then polymerized. The infiltrants contain radically polymerizable monomers and solvents and have a penetration coefficient of> 100 cm / s.

The US 9,211,236 B2 describes infiltrants for dental applications containing crosslinking and acid group-containing monomers. The infiltrants have a dynamic viscosity at 23 ° C of less than 50 mPa · s.

US 8,686,063 B2 and US 9,211,236 B2 describe the infiltration of tooth hard tissue with infiltrants, which form a dense plastic during the polymerization, which is hardly permeable to liquids and ions. This is equivalent to a seal with plastic, which no longer allows a later natural remineralization of the carious lesions.

The EP 1 222 910 B2 describes dental materials based on multifunctional acrylamides, which are characterized by a very good resistance to hydrolysis under acidic conditions. The claimed compositions contain an acidic polymerizable monomer and a polymerization initiator, and optionally, solvents and fillers.

The EP 0 909 761 B1 discloses polymerizable phosphonic acids with good hydrolytic stability under acidic conditions and their use in adhesives, cements or composites and Dental materials containing at least one free-radical initiator and optionally comonomers, solvents or fillers.

Brief description of the invention

The invention has for its object to provide materials that are suitable for the treatment of initial caries lesions of fissures, smooth surfaces, interdental surfaces and tooth necks, for caries protection in selected areas of teeth and remineralization of teeth and for the prevention and treatment of tooth erosion.

1. (1) 10 - 90% Gew.-% Lösungsmittel,
2. (2) 5 - 50 Gew.-% mindestens eines radikalisch polymerisierbaren Monomers mit Puffergruppen,
3. (3) 0 - 50 Gew.-% mindestens eines monofunktionellen radikalisch polymerisierbaren Monomers,
4. (4) 0 - 20 Gew.-% mindestens eines vernetzenden radikalisch polymerisierbaren Monomers und
5. (5) 0,01 - 5 Gew.-% mindestens eines Initiators für die radikalische Polymerisation enthalten, jeweils bezogen auf die Gesamtmasse der Zusammensetzung.

This object is achieved by free-radically polymerizable compositions which

1. (1) 10 - 90% by weight of solvent,
2. (2) 5 to 50% by weight of at least one radical-polymerizable monomer having buffer groups,
3. (3) 0-50% by weight of at least one monofunctional free-radically polymerizable monomer,
4. (4) 0-20% by weight of at least one crosslinking radically polymerizable monomer and
5. (5) 0.01 to 5 wt .-% of at least one initiator for the radical polymerization, each based on the total mass of the composition.

1. (1) 20 - 80 Gew.-%, bevorzugt 50 - 80 Gew.-% Lösungsmittel,
2. (2) 5 - 30 Gew.-%, bevorzugt 10 - 20 Gew.-% mindestens eines radikalisch polymerisierbaren Monomers mit Puffergruppen,
3. (3) 0 - 30 Gew.-%, bevorzugt 10 - 20 Gew.-% mindestens eines monofunktionellen radikalisch polymerisierbaren Monomers,
4. (4) 0 - 10 Gew.-%, bevorzugt 0,5 - 10 Gew.-% mindestens eines vernetzenden radikalisch polymerisierbaren Monomers und
5. (5) 0,1 - 3 Gew.-%, bevorzugt 0,1 - 1 Gew.-% mindestens eines Initiators für die radikalische Polymerisation enthalten.

According to the invention, free-radically polymerizable compositions are preferred

1. (1) 20-80% by weight, preferably 50-80% by weight of solvent,
2. (2) 5 to 30% by weight, preferably 10 to 20% by weight, of at least one free-radically polymerizable monomer having buffer groups,
3. (3) 0-30% by weight, preferably 10-20% by weight of at least one monofunctional free-radically polymerizable monomer,
4. (4) 0-10 wt.%, Preferably 0.5-10 wt.%, Of at least one crosslinking radically polymerizable monomer and
5. (5) 0.1 to 3 wt .-%, preferably 0.1 to 1 wt .-% of at least one initiator for the radical polymerization.

• (6) 1 - 3000 ppm, bevorzugt 1 - 1000 ppm, besonders bevorzugt 1 - 300 ppm Stabilisator, bezogen auf die Gesamtmasse der Zusammensetzung.

According to a further preferred embodiment, the radically polymerizable compositions additionally contain

• (6) 1 - 3000 ppm, preferably 1 - 1000 ppm, particularly preferably 1 - 300 ppm stabilizer, based on the total mass of the composition.

For the monomers ( 2 ) 3 ) and ( 4 ) are different substances.

These compositions can be applied intraorally to the tooth where, after free radical polymerization, they form an elastic temporary protective film, e.g. around orthodontic ligaments and braces around. It is also possible that they are applied to demineralized dental areas, where they then penetrate into the porous structure and then, e.g. be polymerized with light. This forms a protective buffering polymer in the demineralized zones beneath the tooth surface. However, the compositions according to the invention can also be polymerized extraorally to form parts, which are then used intraorally as a component.

The object of this invention is the generation of buffering polymers and polymer networks that can be applied in the mouth. These prevent the pH of the acid from dropping at the point of application. In this way, demineralization of the teeth is prevented and remineralizing conditions are maintained over an extended period of time. If the acid attack is over, for example, when the acidic beverage has been swallowed, the buffering polymer or polymer network can return the absorbed protons by contact with the neutral saliva and is thus converted back into the basic form. The polymers are obtained by free-radical polymerization of the compositions according to the invention. These contain at least one monomer with functional groups that have buffering properties. The polymers or polymer networks formed have a remineralisationsfördernde effect and prevent in demineralized teeth progression of tooth decay. They promote the Addition of calcium and calcium phosphate minerals from the saliva and thus favor the remineralization of the teeth.

Detailed description of the invention

The compositions according to the invention contain as radically polymerizable monomers with buffer groups (buffering monomers) preferably free-radically polymerizable phosphonic acids and / or dihydrogen phosphates. Preferred phosphonic acid monomers are vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamido-4-methylpentylphosphonic acid, 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid (DHPBAA), 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl ester (DHPOBAE) and 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid-2,4 , 6-trimethylphenylester. Preferred polymerizable phosphoric acid esters are 2-methacryloyloxypropyl dihydrogenphosphate, 1,3-bis (methacrylamido) propan-2-yl dihydrogenphosphate (DMAAPDHP), 2- (phosphonooxy) propane-1,3-diylbis (2-methylacrylate) (POPBMA), 2- Methacryloyloxyethyl dihydrogen phosphate, 2-methacryloyloxyethylphenyl hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, mono- (1-acryloylpiperidin-4-yl) phosphoric acid, 6- (methacrylamido) hexyl dihydrogen phosphate and 1,3-bis (N-acryloyl-N-propylamino) -propan-2-yl yl dihydrogen phosphate.

The buffering monomers can be used in the acid form or in the form of their salts. Preferred salts are the sodium, potassium and ammonium salts as well as salts with quaternary cationic ammonium ions starting from amines such as e.g. Ethylenediamine, triethanolamine, cocoalkyl (dihydroxyethyl) amine, tetra (2-hydroxypropyl) ethylenediamine and tris (hydroxymethyl) aminomethane (Tris).

The salts of the buffering monomers can be obtained by dissolving the monomer or monomers in the acid form in the solvent and then neutralizing it by adding a base. Preferred bases are ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide and ethylenediamine, triethanolamine, cocoalkyl (dihydroxyethyl) amine, tetra (2-hydroxypropyl) ethylenediamine and tris (hydroxymethyl) aminomethane (Tris). This procedure is particularly advantageous for the calcium salts because they are often poorly soluble.

As monofunctional radically polymerizable monomers, hydrophilic monomers are preferred, i. Monomers having one or more hydrophilic groups. Monofunctional free-radically polymerizable monomers are understood to mean monomers having a free-radically polymerizable group, polyfunctional radically polymerizable monomers being monomers having 2 or more radically polymerizable groups. Preferred monofunctional monomers are HEMA, 1-hydroxymethylacrylic acid methyl ester or ethylester, 1-hydroxymethylacrylic acid 2-hydroxyethyl ester, 2,3-dihydroxypropyl, methacrylate, 5,6-dihydroxyhexyl methacrylate, 2-hydroxy-3-methoxypropyl methacrylate , 2-hydroxy-3-ethoxypropyl methacrylate, N, N-dimethylacrylamide, N- (hydroxymethyl) acrylamide, N- (hydroxymethyl) methacrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide, N- (5-hydroxypenthyl ) acrylamide, N- (5-hydroxypentyl) methacrylamide, N-vinylpyrrolidone and N-methyl-N- (3-hydroxypropyl) acrylamide.

Hydrophilic monomers are preferably used as crosslinking free-radically polymerizable monomers. Crosslinking monomers are multifunctional monomers, i. Monomers having 2 or more, preferably 2 to 4 radically polymerizable groups. Preferred crosslinking monomers are bisacrylamides, such as methylene or ethylenebisacrylamide, N, N'-diethyl-1,3-bis (acrylamido) -propane (NDEBAAP), 1,3-bis (methacrylamido) -propane, 1,4-bis ( acrylamido) butane or 1,4-bis (acryloyl) piperazine. Bisacrylamides can e.g. be synthesized from the corresponding diamines by reaction with (meth) acrylic acid chloride. Further preferred hydrophilic crosslinker monomers are glycerol dimethacrylate, PEG-200 and PEG-400 dimethacrylate.

The compositions of the invention also contain at least one initiator for the radical polymerization. For the initiation of the radical photopolymerization benzophenone, benzoin and their derivatives or β-diketones or their derivatives, such as 9,10-phenanthrenequinone, 1-phenylpropane-1,2-dione, diacetyl or 4,4-dichlorobenzil are preferably used. Particularly preferred camphorquinone and 2,2-dimethoxy-2-phenyl-acetophenone and particularly and most preferably β-diketones are used in combination with amines as a reducing agent. Preferred amines are 4- (dimethylamino) benzoic acid esters, N, N-dimethylaminoethyl methacrylate, N, N-dimethyl-sym-xylidine and triethanolamine. Also particularly suitable are Norrish type I photoinitiators, especially acylphosphine oxides (eg 2,4,6-trimethylbenzoyl-diphenylphosphine oxide), TPO) or bisacylphosphine oxides (eg bis (2,4,6-trimethylbenzoyl) phenylphosphine; Irgacure 819) and monoacyl trialkyl or Diacyldialkylgermanium compounds, such as Benzoyltrimethylgermanium, Dibenzoyldiethylgermanium or bis (4-methoxybenzoyl) diethylgermanium. It is also possible to use mixtures of the various photoinitiators, for example dibenzoyldiethylgermanium in combination with camphorquinone and ethyl 4-dimethylaminobenzoate.

As initiators for a polymerization conducted at room temperature or under oral conditions (37 ° C), preferably redox initiator combinations, e.g. Combinations of benzoyl peroxide with N, N-dimethyl-sym-xylidine or N, N-dimethyl-p-toluidine. Combinations of one or more inorganic peroxides, especially potassium and ammonium peroxodisulfate, with one or more reducing agents, such as sulfite, hydrogen sulfite, thiosulfate, sulfinic acids, amines, endiols or Fe (II) salts, are particularly suitable for aqueous compositions. In addition, redox systems consisting of organic peroxides or hydroperoxides and reducing agents, e.g. Ascorbic acid, barbiturates, thioureas or sulfinic acids, particularly suitable. Furthermore, as transition metal redox catalysts, it is possible to use compounds of transition metals which have at least two stable valence states. These are, in particular, compounds of the elements copper, iron, vanadium, nickel or cobalt, particular preference being given to copper compounds and these being preferred as organosoluble compounds, such as, for example, be used as acetylacetonate, naphthenate or 2-ethylhexanoate. Mixtures of photo and redox initiators can also be used.

Initiators distinguish between mono- and bimolecular initiators. TPO and bis (4-methoxybenzoyl) diethylgermanium are examples of monomolecular photoinitiators. Camphorquinone and amine or peroxide and amine are examples of bimolecular initiators. All amounts relating to initiators indicate the total amount of initiator components, e.g. the total amount of camphorquinone and amine or the total amount of peroxide and amine unless otherwise specified.

As solvents, the compositions of the invention preferably contain water (H ₂ O) and / or a polar organic solvent. Water-miscible organic solvents are preferred as polar organic solvents, in particular ethanol (EtOH), acetone, isopropanol (iPr), propylene glycol (PPG), glycerol, ethylene glycol, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, methanol, dimethylformamide (DMF). , Propanol, butanol. Dioxane, methyl ethyl ketone, monopropylene glycol monomethyl ether. Ethanol, isopropanol, propylene glycol, DMSO, mixtures thereof and their mixtures with water are particularly preferred. In addition to the pure solvents and solvent mixtures can be used.

Particularly suitable stabilizers are aerobic inhibitors such as substituted phenols, for example 2,6-di-tert-butyl-4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ) or anaerobic inhibitors such as phenothiazine and phenylenediamine or stable radicals such as 2,2,6 , 6-tetramethyl-piperidine-N-oxyl (TEMPO) or galvinoxyl (2,6-di-tert-butyl-α- (3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1 -ylidene) - _p -tolyloxy). The stabilizers are said to prevent premature or uncontrolled free-radical polymerization of the compositions.

In addition, the compositions of the invention may advantageously contain further additives, e.g. microbicidal agents, fluoride ion-releasing additives or UV absorbers, especially neutralizers and / or soluble buffers.

As neutralizers or soluble buffers are particularly suitable bases which are soluble in the compositions of the invention. Preferred examples are ammonia, sodium hydroxide, potassium hydroxide, ethylenediamine, triethanolamine, cocoalkyl (dihydroxyethyl) amine, tetra (2-hydroxypropyl) ethylenediamine and tris (hydroxymethyl) aminomethane (Tris). Neutralizers serve to neutralize the pH of the composition, which is acidic due to the buffering or acidic monomers used.

In addition, the compositions of the invention may advantageously contain inorganic or organic salts. Preferred are metal salts, e.g. Calcium, potassium, ammonium salts. Particularly suitable are calcium salts which are readily soluble in polar organic solvents. These are especially calcium chloride and calcium nitrate and other calcium salts of comparable solubility, e.g. Calcium acetate and calcium lactate. Inorganic salts such as e.g. Calcium salts can aid remineralization.

Preference is given to compositions which contain 0-55% by weight and preferably 0-30% by weight of at least one dissolved calcium salt, preferably calcium chloride and / or calcium nitrate. Calcium salts, which are completely soluble in the amount used in the solvent used and the amount of solvent used at room temperature, are referred to herein as soluble salts.

Particular preference is given to compositions which consist of the stated components. Furthermore, preference is given to those compositions in which the individual components are each selected from the abovementioned preferred and particularly preferred substances. The compositions according to the invention are preferably in the form of solutions and accordingly preferably contain no undissolved constituents, in particular no fillers.

To prepare the compositions of the invention, the ingredients of the composition are dissolved in the solvent. The solvent serves primarily to dissolve the other components of the composition. On the other hand, it also ensures that no dense plastic is obtained in the polymerization but a polymer or polymer network that is permeable to ions that are needed for the remineralization of the teeth, such as calcium and phosphate ions.

The buffering monomers or their salts serve to impart buffering properties to the polymer or polymer network. The buffering polymers and polymer networks are designed to be substantially deprotonated at neutral pHs. An acid attack, e.g. by acidic beverages or food or by the degradation of sugars to organic acids by microorganisms, then the polymer is able to absorb protons and thus reduce a pH reduction. The pKa of the buffering polymers and networks is preferably in the range of from 5.5 to 7.5, more preferably from 6.0 to 7.5, and most preferably from 6.5 to 7.0. Thus, the polymer or polymer network is capable of starting from a natural neutral pH in the mouth in an acid attack, e.g. by acidic foods, stomach acid or acidic fermentation products of microorganisms, at the place of application to reduce the drop in pH. At pHs below 6.5 to 7.0, the polymers pick up protons and release them at pH values greater than 6.5 to 7.0 so they can buffer again at the next acid attack. This minimizes the mineral loss of the tooth hard substance (enamel, dentin). The pK value of the buffering polymer and polymer networks can be adjusted by the choice of monomers, their proportion in the composition and the crosslinker content. Due to the pKa values of the buffering polymers and / or networks mentioned, demineralization of hydroxyapatite is effectively prevented on the one hand, and on the other hand the remineralization of the teeth is promoted by the saliva, thus achieving an optimal protective function overall.

The compositions preferably also contain crosslinking monomers and / or comonomers. These optional comonomers serve to adjust the solubility of the buffering polymers or polymer networks in the solvent and / or water used. Crosslinking monomers ensure that after the polymerization, the buffering polymers or polymer networks are not removed from the demineralized areas.

In addition, the compositions of the invention contain at least one initiator for the radical polymerization. If photoinitiators are used, they can be dissolved in the overall composition. When using redox initiators, the composition is divided into two portions. Then an initiator component, e.g. the peroxide, a part and the second initiator component, e.g. the reducing agent (activator) added to the other part. For polymerization, the two parts are then mixed together.

Other ingredients, such as stabilizers, neutralizers or additives, may also be added to the composition.

The compositions of the invention are applied to the surface to be treated and then polymerized, for example by photopolymerization. Unlike conventional adhesives, the compositions of the invention are not dried before polymerization. This avoids that the solvent evaporates. This forms a polymer or polymer network according to the invention, which is permeable to ions. In this way elastic temporary protective films can be produced, e.g. around orthodontic ligaments and braces around. It is also possible to apply the compositions to demineralized tooth areas where they then penetrate into the porous structure and e.g. can be polymerized with light. This forms a protective buffering polymer in the demineralized zones beneath the tooth surface. Prior to applying the composition, the enamel may optionally be surface etched with acid to facilitate penetration of the composition. Phosphoric acid is preferably used for this purpose. Thereafter, the formulation is applied and polymerized in the defect.

The compositions according to the invention do not form a dense polymer during the polymerization. Rather, after polymerization and exchange of the solvent with water from the saliva, an ion-permeable polymer or polymer network is formed which allows remineralization of the tooth. Accordingly, the removal of excess material on the tooth surface is easily possible. Initial defects can be protected and remineralized in this way by a single treatment before further demineralization.

Alternatively, the compositions can be extraorally polymerized into a molded part which is then used intraorally as a component. Molded parts can be easily removed e.g. by crosslinking photopolymerization of mixtures of buffering monomers with one or more crosslinkers and other hydrophilic comonomers in solution in the presence of photo and / or redox initiators.

The compositions, buffering polymers and polymer networks of the present invention, collectively referred to as materials of the present invention, allow control of pH at the sites of a patient where they have been applied. They are therefore particularly suitable for the treatment and prevention of dental indications, which are associated with a change in the pH and in particular with a lowering of the pH. In particular, the materials of the present invention allow for local pH control or local buffering in the patient's mouth, e.g. a reduction in the pH of the acid after acidification in fissures, the porosities of hard tooth substance and around orthodontic braces and appliances. By "local" is meant a pH control or buffering in a limited area of the mouth where the buffering polymers or polymer networks were applied.

The compositions, buffer polymers and polymer networks of the present invention are particularly useful for preventing demineralization of teeth and dental hard tissue, especially after acid exposure, for remineralization of teeth and hard tooth substance, for treating or preventing caries or initial caries lesions, for caries protection at selected tooth areas, e.g. of fissures, smooth surfaces of teeth, interdental surfaces and tooth necks, for the prevention of the progression of caries and for the treatment and prevention of tooth erosion, in particular for the prevention and treatment of caries. The compositions according to the invention are suitable for promoting the new deposition of calcium and / or calcium phosphate minerals from the saliva and thus for the prevention and treatment of all indications which are associated with a corresponding demineralization of hard tooth substance.

As mentioned earlier, the acid can come from external sources, especially from food, or arise through internal processes, e.g. through fermentation processes in the mouth. However, it may also be stomach acid, e.g. in heartburn (reflux esophagitis) or frequent vomiting, e.g. in anorexia nervosa or bulimia, enters the oral cavity. The materials according to the invention are also suitable for the prevention and treatment of reflux-induced dental erosion or dental erosion caused by anorexia nervosa or bulimia.

In addition, the materials according to the invention are suitable for the prevention and treatment of pregnancy-related dental caries and erosion. The pH in the mouth of non-pregnant women is in the range of 6.6 - 7.6, with the 95% confidence interval even being relatively narrow between 7.3 - 7.6. In pregnant women, significantly lower pH values are found between 5.9 and 7.6, with a 95% confidence interval of 6.5 - 6.9. The solubility of enamel is highly pH dependent and is about 3 mg of hydroxyapatite / liter at pH 5, about 90 mg / I at pH 4 and about 1100 mg / I at pH 3. But even at higher pH values can Enamel already lose minerals. Even at pH 6.5, significantly higher calcium concentrations are found in water than at neutral pH. Pregnant women are thus exposed to an increased risk of caries and erosion defects due to demineralization of the teeth. This can be effectively prevented by using the compositions of the invention.

• 1 zeigt die Titrationskurven von DHPOBAE und Poly(DHPOBAE) aus Beispiel 1 in Wasser, titriert mit NaOH-Lösung (0,1 mol/l, 0,1 ml je 130 s).
• 2 zeigt die Titrationskurven für die Mehrfachtitration des in Wasser gequollenen Netzwerkes aus Beispiel 2, titriert mit Ca(OH)₂-Lösung (0,02 mol/l, 0,1 ml je 260 s) und rücktitriert mit HCI (0,04 mol/l, 0,1 ml je 260 s). Das Polymernetzwerk wurde dreimal nacheinander von sauer nach alkalisch und zurück titriert.
• 3 zeigt REM-Aufnahmen von Querschnitten der in Wasser bzw. SLS gelagerten Netzwerke aus Beispiel 2 nach Gefriertrocknung. Das in SLS gelagerte Netzwerk zeigt eine deutliche Verdichtung der Morphologie im Vergleich zu dem in Wasser gelagerten Netzwerk.
• 4 zeigt die EDX-Spektren von Querschnitten der gefriergetrockneten Netzwerke aus Beispiel 2. Das in SLS gelagerte Netzwerk zeigt im Gegensatz zur in Wasser gelagerten Probe ein deutliches Signal bei 3,7 keV, was der Röntgenemission von Calcium entspricht.
• 5 zeigt die Titrationskurven des in Wasser gequollenen Netzwerkes aus Beispiel 3, titriert mit Ca(OH)₂ Lösung (0,02 mol/l, 0,1 ml je 260 s) und rücktitriert mit HCl (0,04 mol/l, 0,1 ml je 260 s). Das gequollene Netzwerk wirkt in einem pH-Wert-Bereich von 6,5 bis 7,5 puffernd (markierter Bereich).
• 6 zeigt REM-Aufnahmen von Querschnitten der in Wasser (links) bzw. SLS (rechts) gelagerten und anschließend gefriergetrockneten Netzwerke aus Beispiel 3.
• 7 zeigt die EDX-Spektren von Querschnitten der gefriergetrockneten Netzwerke aus Beispiel 3. Das in SLS gelagerte Netzwerk zeigt im Gegensatz zur in Wasser gelagerten Probe ein deutliches Signal bei 3,7 keV, was der Röntgenemission von Calcium entspricht.
• 8 zeigt die Titrationskurven der Mehrfachtitration des in Wasser gequollenen Netzwerkes aus Beispiel 4, titriert mit Ca(OH)₂ Lösung (0,02 mol/l, 0,1 ml je 260 s) und rücktitriert mit HCI (0,04 mol/l, 0,1 ml je 260 s).
• 9 zeigt REM-Aufnahmen von Querschnitten der in Wasser (links) bzw. SLS (rechts) gelagerten und anschließend gefriergetrockneten Netzwerke aus Beispiel 4.
• 10 zeigt die EDX-Spektren von Querschnitten der gefriergetrockneten Netzwerke aus Beispiel 4. Das in SLS gelagerte Netzwerk zeigt im Gegensatz zur in Wasser gelagerten Probe ein deutliches Signal bei 3,7 keV, was der Röntgenemission von Calcium entspricht.
• 11 zeigt die Titrationskurven des in Wasser gequollenen Netzwerkes aus Beispiel 5, titriert mit Ca(OH)₂ Lösung (0,02 mol/l, 0,1 ml je 260 s) und rücktitriert mit HCI (0,04 mol/l, 0,1 ml je 260 s).
• 12 zeigt die EDX-Spektren von Querschnitten der gefriergetrockneten Netzwerke aus Beispiel 5. Das in SLS gelagerte Netzwerk zeigt im Gegensatz zur in Wasser gelagerten Probe ein deutliches Signal bei 3,7 keV, was der Röntgenemission von Calcium entspricht.
• 13 zeigt die Ergebnisse von Versuch A in Tabelle 2 aus Beispiel 7. Das Härteprofil auf der behandelten und isolierten Seite verläuft fast Deckungsleich. Die Lagerung der Dentin-Prüfkörper in der demineralisierenden Lösung bei pH 5,5 hat also zu keiner weiteren Abnahme der Härte geführt.
• 14 zeigt die Ergebnisse von Versuch B in Tabelle 2 aus Beispiel 7. Das Härteprofil auf der behandelten und isolierten Seite verläuft fast Deckungsleich. Die Lagerung der Dentin-Prüfkörper in der demineralisierenden Lösung bei pH 5,5 hat also zu keiner weiteren Abnahme der Härte geführt.
• 15 zeigt die Ergebnisse von Versuch C in Tabelle 2 aus Beispiel 7. Das Härteprofil der unbehandelten Negativkontrolle verläuft deutlich tiefer als auf der isolierten Seite. Die Lagerung der unbehandelten Dentin-Prüfkörper in der demineralisierenden Lösung bei pH 5,5 hat also zu weiteren deutlichen Abnahme der Härte geführt]

The invention is explained in more detail below with reference to figures and examples.

• 1 shows the titration curves of DHPOBAE and poly (DHPOBAE) from Example 1 in water, titrated with NaOH solution (0.1 mol / l, 0.1 ml per 130 s).
• 2 shows the titration curves for the multiple titration of the water-swollen network of Example 2, titrated with Ca (OH) ₂ solution (0.02 mol / l, 0.1 ml per 260 s) and back-titrated with HCl (0.04 mol / 1, 0.1 ml per 260 s). The polymer network was titrated three times in succession from acid to alkaline and back.
• 3 shows SEM images of cross sections of the stored in water or SLS networks of Example 2 after freeze-drying. The network stored in SLS shows a significant densification of the morphology compared to the network stored in water.
• 4 Figure 3 shows the EDX spectra of cross-sections of the freeze-dried networks of Example 2. The SLS-supported network, unlike the sample stored in water, shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium.
• 5 shows the titration curves of the water-swollen network of Example 3, titrated with Ca (OH) ₂ solution (0.02 mol / l, 0.1 ml per 260 s) and back-titrated with HCl (0.04 mol / l, 0 1 ml each for 260 s). The swollen network acts in a pH range of 6.5 to 7.5 buffering (labeled area).
• 6 shows SEM images of cross sections of the stored in water (left) or SLS (right) and then freeze-dried networks from Example 3.
• 7 Figure 3 shows the EDX spectra of cross-sections of the freeze-dried networks of Example 3. The SLS-stored network, unlike the sample stored in water, shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium.
• 8th shows the titration curves of the multiple titration of the water-swollen network of Example 4, titrated with Ca (OH) ₂ solution (0.02 mol / l, 0.1 ml per 260 s) and back-titrated with HCl (0.04 mol / l, 0.1 ml per 260 s).
• 9 shows SEM images of cross sections of the stored in water (left) or SLS (right) and then freeze-dried networks of Example 4.
• 10 Figure 3 shows the EDX spectra of cross-sections of the freeze-dried networks of Example 4. The SLS-stored network, unlike the sample stored in water, shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium.
• 11 shows the titration curves of the water-swollen network of Example 5, titrated with Ca (OH) ₂ solution (0.02 mol / l, 0.1 ml per 260 s) and back-titrated with HCl (0.04 mol / l, 0 1 ml each for 260 s).
• 12 Figure 3 shows the EDX spectra of cross-sections of the freeze-dried networks of Example 5. The SLS-supported network, unlike the sample stored in water, shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium.
• 13 shows the results of experiment A in Table 2 of Example 7. The hardness profile on the treated and insulated side is almost coincident. The storage of the dentin specimens in the demineralizing solution at pH 5.5 has thus led to no further decrease in hardness.
• 14 shows the results of experiment B in Table 2 of Example 7. The hardness profile on the treated and insulated side is almost coincident. The storage of the dentin specimens in the demineralizing solution at pH 5.5 has thus led to no further decrease in hardness.
• 15 shows the results of experiment C in Table 2 of Example 7. The hardness profile of the untreated negative control is significantly lower than on the isolated side. The storage of the untreated dentin specimens in the demineralizing solution at pH 5.5 has thus led to a further significant decrease in the hardness]

embodiments

Example 1:

Investigation of the Buffering Effect of Poly (LDHPOBAE)

For the monomer solution, a solution was prepared consisting of 0.4 g of DHPOBAE, 0.002 g of TPO and 1.598 g of ethanol. This solution was injected between two glass slides separated by a 2 mm rubber ring and then exposed for four minutes to an LED light (Bluephase C8 G2 , "High", Ivoclar Viva-dent, Schaan, Liechtenstein) photopolymerized. During photopolymerization, precipitation of the poly (DHPOBAE) occurred. The resulting suspension was then dialyzed in water (double distilled) for at least five days, which was changed at least twice a day, and then dialyzed for one day in ethanol (dialysis membrane consisting of regenerated cellulose, MWCO 1000 Da). The product thus obtained was concentrated to dryness and finally dried in a vacuum oven at room temperature for twelve hours. The preserved in this way Poly (DHPOBAE) was analyzed by acid-base titration and the results compared with those of the monomer DHPOBAE.

The titration was carried out with a "Mettler Toledo T70" titrator, using a "Mettler Toledo DG111-SC" as the pH electrode. The titration agent used was NaOH solution with a concentration of 0.1 mol / l. The addition of the titrant (each 0.1 ml) was carried out at a distance of 130 s.

1 shows the titration curves (pH over titrant consumption) of the sample of Example 1. This is an example of a non-crosslinked buffering polymer. It becomes clear that the total titration curve of the poly (DHPOBAE) is shifted to higher pH values compared to the monomer. In addition, in the titration of the poly (DHPOBAE) there is no second transition point in the pH range between 8 and 11. With the polymer, the pK values blur and shift to higher values. The polymer releases the protons only at a higher pH than the monomer.

Example 2:

Investigation of buffer effect and calcium uptake of a polymer network of DHPOBAE and NDEBAAP

For the monomer mixture, a solution was prepared consisting of 0.39 g of DHPOBAE, 0.01 g of NDEBAAP, 0.002 g of TPO and 1.598 g of isopropanol. This solution was injected between two glass slides separated by a 2 mm rubber ring and then exposed for four minutes to an LED light (Bluephase C8 G2 , Level "high", Ivoclar Vivadent, Schaan, Liechtenstein) photocrosslinked. The resulting, easily removable gel film was then stored for at least five days in water (double distilled), which was changed at least twice a day. The swollen network treated in this way was examined proportionally by means of acid-base titration with calcium hydroxide solution / hydrochloric acid solution or with artificial saliva (SLS, saliva-like solution, 0.72 mmol / l KH ₂ PO ₄ , 30 mmol / l KCl, 50 mmol / l 2- (4- (2-hydroxyethyl) piperazin-1-yl) ethane-1-sulfonic acid (HEPES), 1.2 mmol / l CaCl ₂ , pH 7 (adjusted with 2 mol / l KOH solution)) longer time ( 14 Days) with daily SLS changes. After treatment with SLS, freeze-drying followed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX).

The titration was carried out with a "Mettler Toledo T70" titrator, using a "Mettler Toledo DG111-SC" as the pH electrode. The titrant used was Ca (OH) ₂ solution having a concentration of 0.02 mol / l or HCI solution with a concentration of 0.04 mol / l. The addition of the titrant (in each case 0.1 ml) took place at intervals of 260 s.

2 shows the titration curves (pH over titrant consumption) of the sample from Example 2. It is clear that the swollen network in a pH range of 6.5 to 7.5 acts buffering (marked area). The same sample was titrated three times from acid to alkaline and then back titrated from alkaline to acid. This simulates a repeated acid attack. 2 shows that the buffering network is repeatedly able to buffer acid, as in the case of back titrations, and then releases its protons again at pH values above about 6.5, thus again being able to buffer acids.

3 shows SEM images of cross-sections of the stored in water or SLS networks (storage for 13 days, with daily change of the solution) after freeze-drying. The network stored in SLS shows a significant densification of the morphology compared to the network stored in water.

The elemental composition of cross-sections of the freeze-dried networks was examined by EDX and evaluated for calcium content. In contrast to the sample stored in water, the SLS-stored network shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium (see 4 ; Storage time 13 days each; 4 shows the EDX spectra normalized to the intensity at 3 keV).

Example 3:

Investigation of buffer effect and calcium uptake of a polymer network of DHPOBAA and NDEBAAP

For the monomer mixture, a solution was prepared consisting of 0.34 g DHPOBAA, 0.06 g NDEBAAP, 0.002 g TPO and 1.598 g ethanol / water ( 50 / 50 , V / V). This solution was injected between two glass slides separated by a 2 mm rubber ring and then exposed for four minutes to an LED light (Bluephase C8 G2 , Level "high", Ivoclar Vivadent, Schaan, Liechtenstein) photocrosslinked. The resulting, easily removable gel film was then stored for at least five days in water (double distilled), which was changed at least twice a day. The swollen network treated in this way was investigated proportionately by means of acid-base titration with calcium hydroxide solution / hydrochloric acid solution or with artificial saliva (SLS, saliva-like solution, 0.72 mmol / l KH 2 PO 4, 30 mmol / l KCl). 50 mmol / l 2- (4- (2-hydroxyethyl) piperazin-1-yl) ethane-1-sulfonic acid (HEPES), 1.2 mmol / l CaCl 2, pH 7, adjusted with 2 mol / l KOH Solution) for a longer time ( 14 Days), with daily change of SLS, treated. After treatment with SLS, freeze-drying followed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX).

The titration was carried out with a "Mettler Toledo T70" titrator, using a "Mettler Toledo DG111-SC" as the pH electrode. The titrant used was Ca (OH) ₂ solution having a concentration of 0.02 mol / l or HCI solution with a concentration of 0.04 mol / l. The addition of the titrant (in each case 0.1 ml) took place at intervals of 260 s.

5 shows the titration curves (pH over titrant consumption) of the sample from Example 3. It is clear that the swollen network in a pH range of 6.5 to 7.5 acts buffering (marked area).

6 shows SEM images of cross-sections of the stored in water or SLS networks (storage for 13 days, with daily change of the solution) after freeze-drying. The network stored in SLS shows a significant densification of the morphology compared to the network stored in water.

The elemental composition of cross-sections of the freeze-dried networks was examined by EDX and evaluated for calcium content. In contrast to the sample stored in water, the SLS-stored network shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium (see 7 ; Storage time 13 days each; 7 shows the EDX spectra normalized to the intensity at 3 keV).

Example 4:

Investigation of the buffering and calcium uptake of a polymer network of DHPOBAE, DHPOBAA and DEBAAP

For the monomer mixture, a solution was prepared consisting of 0.17 g DHPOBAE, 0.17 g DHPOBAA, 0.06 g NDEBAAP, 0.002 g TPO and 1.598 g ethanol / water (50/50, v / v). This solution was injected between two glass slides separated by a 2 mm rubber ring and then exposed for four minutes to an LED light (Bluephase C8 G2 , Level "high", Ivoclar Vivadent, Schaan, Liechtenstein) photocrosslinked. The resulting, easily removable gel film was then stored for at least five days in water (double distilled), which was changed at least twice a day. The swollen network thus treated was examined by acid-base titration with calcium hydroxide solution / hydrochloric acid solution.

The titration was carried out with a "Mettler Toledo T70" titrator, using a "Mettler Toledo DG111-SC" as the pH electrode. The titrant used was Ca (OH) ₂ solution having a concentration of 0.02 mol / l or HCI solution with a concentration of 0.04 mol / l. The addition of the titrant (in each case 0.1 ml) took place at intervals of 260 s.

8th shows the titration curves (pH over titrant consumption) of the sample from Example 4. It is clear that the swollen network in a pH range of 6.5 to 7.5 acts buffering (marked area). Here, the buffering monomers were used in the acid form. Therefore, the titration starts at pH 4. After the addition of calcium hydroxide as a titrant, the pH initially dropped a bit because of the attachment of the calcium to the phosphonic acid monomer protons were released. Thereafter, the pH increased (1st titration). Subsequently, the polymer network was back titrated back into the acid with hydrochloric acid, here is a pronounced buffer effect in the pH range of 7.5 to 6.5 can be seen. Then a second titration with calcium hydroxide.

9 shows SEM images of cross-sections of the stored in water or SLS networks (storage for 13 days, with daily change of the solution) after freeze-drying. The network stored in SLS shows a densification of the morphology compared to the network stored in water.

The elemental composition of cross-sections of the freeze-dried networks was examined by EDX and evaluated for calcium content. In contrast to the sample stored in water, the SLS-stored network shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium (see 10 ; Storage time 13 days each; 10 shows the EDX spectra normalized to the intensity at 3 keV).

Example 5:

Investigation of the buffer effect, the calcium uptake and the caries protection effect of a polymer network of DHPOBAE and NDEBAAP

For the monomer mixture, a solution was prepared consisting of 0.34 g DHPOBAE, 0.06 g NDEBAAP, 0.002 g TPO and 1.598 g DMSO. This solution was injected between two glass slides separated by a 2 mm rubber ring and then exposed for four minutes to an LED light (Bluephase C8 G2 , Level "high", Ivoclar Vivadent, Schaan, Liechtenstein) photocrosslinked. The resulting, easily removable gel film was then stored for at least five days in water (double distilled), which was changed at least twice a day. The swollen network thus treated was examined by acid-base titration with calcium hydroxide solution / hydrochloric acid solution.

The titration was carried out with a "Mettler Toledo T70" titrator, using a "Mettler Toledo DG111-SC" as the pH electrode. The titrant used was Ca (OH) ₂ solution having a concentration of 0.02 mol / l or HCI solution with a concentration of 0.04 mol / l. The addition of the titrant (in each case 0.1 ml) took place at intervals of 260 s.

11 shows the titration curves (pH over titrant consumption) of the sample from Example 5. It is clear that the swollen network in a pH range of 6.5 to 7.5 acts buffering (marked area).

After storage of cross-sections of the networks in water or SLS (storage time 13 days, with daily change of the solution) and freeze-drying. SEM images were taken, the elemental composition of the cross-sections analyzed by means of EDX and evaluated for the calcium content. In contrast to the sample stored in water, the SLS-stored network shows a clear signal at 3.7 keV, which corresponds to the X-ray emission of calcium (see 12 ; 12 shows the EDX spectra normalized to the intensity at 3 keV).

Example 6:

Preparation of radically polymerizable compositions for the treatment of teeth

By mixing the components, the solutions described in Table 1 were prepared. Table 1: Compositions which form networks buffering by photopolymerization Solvent [% by weight] Monomer 1 [% by weight] Monomer 2 [% by weight] Crosslinker [% by weight] Initiator [% by weight] EtOH / H ₂ O / iPr (80/15/5, V / V / V) [84.95] DHPOBAE [10] - NDEBAAP [5] TPO [0.05] EtOH / H ₂ O / iPr (80/15/5, V / V / V) [79.95] DHPOBAE [10] - NDEBAAP [10] TPO [0.05] EtOH / H ₂ O / iPr (80/15/5, V / V / V) [79.95] DHPOBAE [15] - NDEBAAP [5] TPO [0.05] EtOH / H ₂ O (80/20, v / v) [79.9] DHPOBAE [10] - NDEBAAP [10] TPO [0,1] EtOH / H ₂ O (80/20, v / v) [79.9] DHPOBAE [15] - NDEBAAP [5] TPO [0,1] EtOH / H ₂ O (50/50, v / v) [79.9] DHPOBAE [8,5] DHPOBAA [8,5] NDEBAAP [3] TPO [0,1] DMSO [79.9] DHPOBAE [17] - NDEBAAP [3] TPO [0,1] EtOH / H ₂ O (50/50, v / v) [79.9] DHPOBAE [17] - NDEBAAP [3] TPO [0,1] iPr [79.9] DHPOBAE [17] - NDEBAAP [3] TPO [0,1] iPr [79.9] DHPOBAE [19.5] - NDEBAAP [0.5] TPO [0,1] PPG [79.9] DHPOBAE [17] - NDEBAAP [3] TPO [0,1] PPG [79.9] DHPOBAE [19.5] - NDEBAAP [0.5] TPO [0,1] EtOH / H ₂ O (50/50, v / v) [79.9] DHPOBAA [17] - NDEBAAP [3] TPO [0,1] DMSO [79.9] DHPOBAA [17] - NDEBAAP [3] TPO [0,1]

Example 7:

Investigation of the caries protective effect of polymer networks

The caries protection on the tooth was tested in a model with a chemically generated lesion in bovine dentine. Bovine teeth were embedded in resin to prepare the dentin specimens and the dentin was exposed with SiC abrasive paper with water cooling. By storage for 7 days at 37 ° C in a demineralizing solution, an artificial lesion was created in the dentin. The demineralizing solution contained 50.0 mmol / l acetic acid, 3.0 mmol / l KH ₂ PO ₄ , 3.0 mmol / l CaCl ₂ .2H ₂ O, 1.0 ppm methylene diphosphonic acid and as preservative still 100 ppm sodium azide. The pH was adjusted to pH 5.0 with KOH.

Half of the lesions in the dentin were isolated with nail polish so that an unchanged reference surface isolated from this point remained and the free test area was treated with compositions A and B according to the invention (see Table 2). For this purpose, the compositions were each applied with a brush on the test surface and left there for 2 minutes. The excess material was removed with a soft tissue tissue and the tooth was removed with a polymerization lamp (Bluephase G2 , Mode "high", Ivoclar Vivadent, Schaan, Liechtenstein) for 60s illuminated. Subsequently, the dentine specimen was stored at 37 ° C for 24 hours in artificial saliva and then for 7 days in the demineralizing solution, but this time adjusted to pH 5.5. For comparison, an untreated control was performed by also isolating dentin specimens with lesions in half with nail varnish and then storing them in the demineralizing solution at pH 5.5 for 7 days without treatment of the test area. Each treatment was performed on two teeth each.

After storage, the dentin specimens were rinsed briefly with water, blotted dry, and the nail polish of the isolated half (reference surface) was removed with ethanol. From both the isolated reference surface and the treated test area, the surface hardness on the dentine was measured with a nanoindenter. Thereafter, the surfaces of the dentin specimens were covered with resin so that a slice of the tooth cross-section could then be sawn out with a diamond saw. After polishing the cross-section of the treated side and the isolated reference side three hardness profiles were measured (each 30 impressions, each 20μm vertical distance to a depth of 600μm, Berkovich indenter, 100 mN load, loading with 600 mN / min., 2 s hold time at F _max ). The hardness profiles were calculated using the Vickers hardness values automatically calculated by the device.

The following 14 to 16 show the measured hardness profiles of the isolated reference halves or treated test halves after 7 days of storage in the demineralizing solution. In the untreated negative control, the curve of the test half is well below the curve of the isolated half. The storage of untreated dentin specimens in the demineralization solution of pH 5.5 has thus led to a further loss of hardness. However, the treatments with Compositions A and B of Table 2 have caused the demineralization solution of pH 5.5 to not further reduce hardness on the test half as compared to the isolated reference half. Thus, these compositions have provided protection against demineralization. Table 2: Treatments of Demineralized Dentin Specimens Zus. DMSO EtOH H ₂ O DHPOBAE NDEBAAP TPO Ca (NO ₃ ) ₂ .4H ₂ O A 79.9 - - 17.0 3.0 0.1 - B - 19.1 10.6 17.0 3.0 0.1 50.2 C Disordered negative control A: Monomer mixture from example 5 B: Solution of 0.34 g of DHPOBAE, 0.06 g of NDEBAAP, 0.002 g of TPO, 1.0042 g of Ca (NO ₃ ) ₂ .4H ₂ O, 0.3826 g of EtOH and 0.2112 g of H ₂ O. C: untreated negative control.

13 shows the results of composition A. The hardness profile on the treated and insulated side is almost coincident. The storage of the dentin specimens in the demineralizing solution at pH 5.5 has thus led to no further decrease in hardness.

14 shows the results of composition B. The hardness profile on the treated and insulated side is almost coincident. The storage of the dentin specimens in the demineralizing solution at pH 5.5 has thus led to no further decrease in hardness.

15 shows the results of composition C. The hardness profile of the untreated negative control is significantly lower than on the isolated side. The storage of the untreated dentin specimens in the demineralizing solution at pH 5.5 has thus led to a further significant decrease in hardness.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2016/256362 A1 [0004]
• US 2015/0335790 A1 [0005]
• US 8779024 B2 [0006]
• US 8686063 B2 [0007, 0009]
• US 9211236 B2 [0008, 0009]
• EP 1222910 B2 [0010]
• EP 0909761 B1 [0011]

Cited non-patent literature

• Lingstrom et al., 1993, J Dent Res. 72: 865-870 [0002]
• Marthaler and Petersen, 2005, Int Dent J, 55: 351-358 [0003]
• Ismail and Hasson, 2008, J Am Dent Assoc, 139: 1457-1468 [0003]

Claims (15)

A radically polymerizable composition for use in the treatment and prevention of dental indications associated with a pH change (1) 10 - 90% by weight of solvent, (2) 5 to 50% by weight of at least one radical-polymerizable monomer having buffer groups, (3) 0-50% by weight of at least one monofunctional free-radically polymerizable monomer, (4) 0-20% by weight of at least one crosslinking radically polymerizable monomer and (5) 0.01 to 5 wt .-% of at least one initiator for the radical polymerization, in each case based on the total mass of the composition. Radical polymerizable composition according to Claim 1 containing (1) 20-80% by weight, preferably 50-80% by weight of solvent, (2) 5-30% by weight, preferably 10-20% by weight of at least one free-radically polymerizable monomer having buffer groups, (3) 0-30% by weight, preferably 10-20% by weight of at least one monofunctional free-radically polymerizable monomer, (4) 0-10% by weight, preferably 0.5-10% by weight of at least one crosslinking agent radically polymerizable monomer and (5) 0.1 to 3 wt .-%, preferably 0.1 to 1 wt .-% of at least one initiator for the radical polymerization. Radical polymerizable composition according to Claim 1 or 2 which additionally contains (6) 1 - 3000 ppm, preferably 1 - 1000 ppm, particularly preferably 1 - 300 ppm stabilizer. Radically polymerizable composition according to any one of Claims 1 to 3 containing as monomer (2) at least one monomer selected from vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamido-4-methylpentylphosphonic acid, 2- [4- (4- Dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid (DHPBAA) or 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl] -acrylic acid ethyl ester (DHPOBAE) or 2- [4- (dihydroxyphosphoryl) -2-oxa-butyl ] -acrylic acid-2,4,6-trimethylphenyl ester, 2-methacryloyloxypropyl dihydrogen phosphate, 1,3-bis (methacrylamido) propan-2-yl dihydrogen phosphate (DMAAPDHP), 2- (phosphonooxy) propane-1,3-diylbis (2- methyl acrylate) (POPBMA), 2-methacryloyloxyethyl dihydrogenphosphate, 2-methacryloyloxyethylphenylhydrogenphosphate, 10-methacryloyloxydecyldihydrogenphosphate, mono- (1-acryloylpiperidin-4-yl) phosphoric acid, 6- (methacrylamido) hexyldihydrogenphosphate and 1,3-bis (N-acryloyl-N -propylamino) -propan-2-yl-dihydrogenphosphate is selected, and / or as monomer (3 ) contains at least one monomer consisting of HEMA, 1-hydroxymethylacrylic acid methyl or ethyl ester, 1-hydroxymethylacrylic acid 2-hydroxyethyl ester, 2,3-dihydroxypropyl methacrylate, 5,6-dihydroxyhexyl methacrylate, 2-hydroxy 3-methoxypropyl methacrylate 2-hydroxy-3-ethoxypropyl methacrylate, N, N-dimethylacrylamide, N- (hydroxymethyl) acrylamide, N- (hydroxymethyl) methacrylamide, N-methyl-N- (2-hydroxy-ethyl) -acrylamide, N - (5-hydroxypenthyl) acrylamide, N- (5-hydroxypentyl) methacrylamide, N-vinylpyrrolidone and N-methyl-N- (3-hydroxypropyl) acrylamide is selected and / or containing as monomer (4) at least one monomer which from methylene or ethylenebisacrylamide, N, N'-diethyl-1,3-bis (acrylamido) -propane (NDEBAAP), 1,3-bis (methacrylamido) -propane, 1,4-bis (acrylamido) -butane, 1 , 4-bis (acryloyl) piperazine, glycerol dimethacrylate, PEG-200 and PEG-400 dimethacrylate. Radically polymerizable composition according to any one of Claims 1 to 4 containing as solvent (1) water (H ₂ O), ethanol (EtOH), acetone, isopropanol (iPr), propylene glycol (PPG), glycerol, ethylene glycol, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, methanol, dimethylformamide (DMF), propanol, butanol. Dioxane, methyl ethyl ketone, monopropylene glycol monomethyl ether or a mixture thereof. Radically polymerizable composition according to any one of Claims 1 to 5 which additionally contains 0-55% by weight and preferably 0-30% by weight of dissolved calcium salt, preferably calcium chloride and / or calcium nitrate. Radically polymerizable composition according to any one of Claims 1 to 6 for use in the remineralization of teeth. Radically polymerizable composition according to any one of Claims 1 to 6 for use in reducing the drop in the pH of a patient's mouth after exposure to acid. Radically polymerizable composition according to any one of Claims 1 to 6 to provide a local buffering effect in the mouth of a patient. Radically polymerizable composition according to any one of Claims 1 to 6 for use in the treatment or prevention of caries, initial caries lesions or caries protection on selected dental areas. Radically polymerizable composition according to any one of Claims 1 to 10 wherein the composition is adapted for application to a tooth surface and subsequent polymerization without prior removal of the solvent. A polymer for use in reducing the demineralization of teeth, in the remineralization of teeth, in reducing the drop in pH in the mouth, a patient after acid exposure and / or for the treatment or prevention of caries caused by the radical polymerization of a composition according to one of the Claims 1 to 6 is available. Polymer after Claim 12 which has a pKa in the range from 5.5 to 7.5, more preferably from 6.0 to 7.5, and most preferably from 6.5 to 7.0. Use of a radically polymerizable composition according to any one of Claims 1 to 6 for the treatment of fissures, smooth surfaces, interdental surfaces and tooth necks. Use of a radically polymerizable composition according to any one of Claims 1 to 6 for the prevention or treatment of dental erosion, such as reflux-induced dental erosion, erosion caused by anorexia nervosa or bulimia, or dental caries due to pregnancy or tooth erosion.

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