Biocompatible enamel-dentin single-component adhesives

Abstract

To provide biocompatible enamel-dentin single-component adhesives.SOLUTION: A dental material comprises at least one copolymer obtained by: (I) copolymerization of one or more monomers MG with a polymerizable (meth)acrylate group, one or more OH group-containing (meth)acrylates MF, one or more strongly acidic adhesive monomers MH, and optionally one or more polymerizable carboxylic acid monomers MCS; (II) reacting the obtained copolymer A0 in a polymer-analogous reaction with a functionalized, radically polymerizable monomer MP, which reacts with the OH groups of the monomer MF in the polymer chain of A0 to form a copolymer AP having pendant polymerizable groups, and (III) neutralizing the copolymer Ap with a base. The material is particularly suitable as a dental adhesive.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to dental materials based on copolymers having adhesive properties, which are particularly suitable as adhesives for direct or indirect dental restorations. [Background technology]

[0002] In dentistry, enamel-dentin adhesives are primarily used to create strong and durable bonds between direct or indirect restorative materials and dental tissues (enamel and dentin). These enamel-dentin adhesives usually contain a mixture of various radically polymerizable methacrylate monomers, polymers, initiator systems, solvents (e.g., aqueous ethanol or acetone), and other additives (e.g., stabilizers and rheological additives). This monomer mixture, in turn, usually contains strong acid adhesive monomers, such as methacrylic group-containing dihydrogen phosphate esters with self-etching properties that ensure strong bonding to dental tissues, dimethacrylates, such as bis-GMA and triethylene glycol dimethacrylate (TEGDMA), that promote rapid formation of a stable adhesive layer, and hydrophilic monomers, such as 2-hydroxyethyl methacrylate (HEMA), to promote penetration capabilities. Polymers such as methacrylated polyacrylic acid or itaconic acid copolymers are said to improve the film formation of the adhesive and make it less susceptible to technology levels. Mixtures of camphorquinone (CQ) and tertiary amines, such as 4-dimethylaminobenzoic acid ethyl ester (EMBO), are primarily used as polymerization initiators for visible light curing, and these mixtures are combined with redox initiator systems in dual cure systems.

[0003] US Patent No. 5,700,875 discloses dental adhesives containing 60-98 wt% of a polymerizable monomer mixture, 2-40 wt% of a polymer, and 0.01-35 wt% of a polymerization initiator. The monomer mixture contains 2-25 wt% of an acidic monomer having a sulfate group, a carboxylic acid group, a carboxylic anhydride group, or a phosphoric acid group. The polymer is a copolymer based on alkyl (meth)acrylate, styrene monomer, hydroxyalkyl (meth)acrylate, butadiene, polyalkyl methacrylate, and / or polyvinyl acetate, and is dissolved or dispersed in the monomer mixture. These adhesives are described as easy to handle and having excellent adhesive properties.

[0004] RR Moraes, JW Garcia, ND Wilson, SH Lewis, MD Barros, B. Yang, CS Feifer, JW Stansbury, J. Dent. Res. 91 (2012): 179-184 investigate the effect of adding nanogel particles to dental adhesives. For this purpose, isobornyl methacrylate and methacrylate-functionalized nanogels of UDMA or ethoxylated bis-GMA, with particle sizes of 10-100 nm, were dispersed in bis-GMA-HEMA-ethanol mixtures at concentrations of 17 wt% and 23 wt%, respectively, and mechanical properties and dentin adhesion were determined in turn. Improved mechanical properties and dentin adhesion values ​​were measured.

[0005] US Patent Application Publication No. 2013 / 0224692 discloses a dental adhesive containing up to 15% by weight of a photocurable ionomer, radiopaque metal oxide nanoparticles, phosphorus-containing acidic monomers, other monomers, water, a polar solvent and an initiator. Ionomers are defined as polymers having ionic, radically polymerizable groups, such as polyalkene carboxylic acids obtained by homo- or copolymerization of unsaturated mono-, di- or tricarboxylic acids and modified with monomers containing isocyanate groups.

[0006] EP 3 120 827 A1 discloses radically polymerizable dental materials suitable for use as dental adhesives, coating materials, filling composites and cements. These materials contain at least one radically polymerizable (meth)acrylate copolymer having a strongly acidic phosphoric acid group and a number-average molecular weight of 1,000 to 200,000 g / mol, radically polymerizable monomers with and without acid groups, and an initiator for the radical polymerization. The combination of the acidic polymer and the acidic monomer optimizes adhesion to enamel and dentin.

[0007] One drawback of known dental adhesives is that they usually have a rather large residual monomer content after hardening. Although the monomers used are not systemically toxic, these monomers exhibit undesirable effects and lead to contact allergic reactions.

[0008] To improve biocompatibility, various concepts have been proposed in the state of the art, notably shell adhesives and bioadhesives brought about by so-called ormocer-containing adhesives. ORMOCER (ORganically MOdified CERamics) are co-condensates (heteropolysiloxanes) of di- or trialkoxysilanes containing organic groups and possibly Ti or Zr alkoxides.

[0009] DE 196 43 007 A1 discloses adhesion promoters and adhesives based on reaction products of peptides or proteins derived from byssus filaments of mussels with radically polymerizable monomers, which are stated to be suitable for dental purposes.

[0010] WO 2006 / 045034 relates to a dental primer containing 0.1-50% by weight of DOPA (3,4-dihydroxyphenyl-L-alanine) in combination with a dilute mineral acid. DOPA is intended to allow simultaneous priming and etching of the tooth prior to application of a restorative material.

[0011] US 2011 / 0288252 discloses heteropolysiloxanes (ormocers) based on silanes containing dialkoxy and dihydroxyphenyl groups and modified with DOPA groups for the preparation of adhesives. These heteropolysiloxanes can be cured by hydrolytic condensation with water or by radical polymerization of the polymerizable groups that may be present.

[0012] The drawback of such bioadhesives is their relatively low adhesive effectiveness and the long times, often hours or days, required to achieve full adhesive effectiveness, and therefore these bioadhesives have not found practical application as enamel-dentin adhesives.

[0013] Biocompatibility generally refers to the degree of tissue compatibility of a material used in the body or in contact with a body surface. Biocompatible materials should behave neutrally towards the body and should not produce any negative effects. In particular, biocompatible materials should not have any toxicological, allergenic, mutagenic, teratogenic or carcinogenic effects. Dental materials should not irritate oral tissues and other body tissues.

[0014] DE 10 2018 204 655 A1 discloses a glass ionomer cement containing an acid-reactive powder, a multiprotonic acid, water, and dispersed polymer particles. The preferred polymer particles are polyurethane particles. Preferably, the particles have an average particle size of less than 1 μm. Preferably, the particles are prepared as a primary or secondary dispersion. The polymer particles should be toxicologically safe and improve the crack and fracture strength of the cement. The materials preferably do not contain polymerizable compounds such as (meth)acrylates.

[0015] By primary dispersion, the skilled person understands a polymer dispersion obtained by first emulsifying the monomers in water and then polymerizing them in the dispersed phase. An emulsifier or protective colloid is required for the production of the primary dispersion. To prepare the secondary dispersion, the polymer is prepared by solution polymerization in a volatile organic solvent. The resulting polymer solution is then dispersed in an aqueous phase and the solvent is then removed. The acidic or basic groups of the polymer are neutralized before dispersion. The salt groups formed during neutralization stabilize the polymer particles in the dispersion. Depending on the charge of these polymer particles, a distinction is made between anionic and cationic stabilized secondary dispersions. For the production of anionic secondary dispersions, for example, copolymers with acidic groups, e.g. carboxyl groups, are used, which are neutralized by the addition of a base. In this case, the stabilization of the secondary polymer dispersion is achieved by carboxylate groups on the surface of the polymer particles. If copolymers containing basic groups, such as tertiary amino groups, are used, cationic subdispersions are obtained, in which case neutralization is effected by addition of an acid.

[0016] The side dispersions are characterized by the fact that they do not require emulsifiers or protective colloids. Emulsifiers increase the water vapor permeability and water sorption of the polymer coating. Y. Liu, W.-J. Soer, J. Scheerder, G. Satgurunathan, J.-L. Keddie, ACS Applied Materials & Interfaces 7 (2015) 12147-12157 show that emulsifier-free side dispersions of 2-ethylhexyl acrylate, acrylic acid, and n-butyl methacrylate show lower water sorption and lower water diffusion coefficients compared to similar coatings with comparable emulsion polymers, and therefore better barrier properties.

[0017] EP 0 305 850 A1 discloses aqueous sub-dispersions based on copolymers containing phosphate groups, which are obtained by polymerizing a mixture of 25-98% by weight of (meth)acrylic esters, 1-10% by weight of (meth)acrylic acid, 1-8% by weight of phosphoric ester phosphates having radically polymerizable groups, and, if necessary, further olefinically unsaturated compounds. These dispersions are stated to be suitable for the preparation of coatings filled with active pigments for corrosion protection.

[0018] EP 0 841 352 relates to a process for the preparation of poly(meth)acrylate sub-dispersions, which are described as having high storage stability. These dispersions are obtained by copolymerization in an organic solvent of monoethylenically unsaturated monomers such as alkyl esters of acrylic or methacrylic acid, ethylenically unsaturated monomers carrying alcoholic hydroxyl groups, carboxyl-containing unsaturated monomers such as acrylic or methacrylic acid, and optionally regulators. After completion of the copolymerization, the amount of water-soluble residual monomers in the polymerization mixture is described as being less than 0.1 wt%. These dispersions are described as being suitable as binders in water-dilutable coating compositions, for example primers, topcoats or clear varnishes, for coating wood, metal or plastics.

[0019] EP 1 270 619 discloses aqueous vinyl polymer sub-dispersions containing at least one amphiphilic polymer consisting of hydrophobic and hydrophilic segments. The amphiphilic polymer is intended to give these dispersions sufficient thermal stability. These dispersions are prepared by polymerizing a mixture of ethylenically unsaturated monomers in a water-solvent mixture in the presence of an initiator, with the addition of at least one amphiphilic polymer. The monomer mixture contains monoethylenically unsaturated monomers such as alkyl esters of acrylic or methacrylic acid, ethylenically unsaturated monomers carrying alcoholic hydroxyl groups, and carboxyl-containing unsaturated monomers such as acrylic or methacrylic acid. The monomer mixture may also contain monomers with sulfonic acid groups. These dispersions are described as suitable as binders or binder components in water-dilutable coating compositions, for example for primers, fillers, topcoats, clear varnishes, high gloss paints and one-coat paints, for example for industrial coatings, automotive OEM and refinish coatings.

[0020] B. Schlarb, MG Rau, S. Haremza, Prog. Org. Coat. 26 (1995) 207-215 show that by mixing two copolymers with different salt group contents, sub-dispersions can be prepared that allow the production of hydrophobic coatings. The authors combined a hydrophilic copolymer with salt groups with a hydrophobic copolymer without salt groups. The hydrophilic copolymer consists of 10 wt% acrylic acid, 53 wt% butyl acrylate and 37 wt% styrene, while the hydrophobic copolymer consists of 49 wt% n-butyl acrylate, 37 wt% styrene and 16 wt% methyl methacrylate. These coatings are characterized by low water absorption and are described as being particularly suitable for the production of anticorrosive paints and road marking paints. In a later publication, B. Schlarb, S. Haremza, W. Heckmann, B. Morrison, R. Muller-Mall, MGRau MG, Prog. Org. Coat. 29 (1996) 201-208, the authors show that by varying the copolymer ratio and composition, polymer latex particles with a core-shell structure can be prepared. O. Kutlug, S. Reck, A. Hartwig, Int. J. Adhes. Adhes., 91 (2019) 36-42, describe crosslinkable pressure-sensitive adhesives based on a sub-dispersion containing two different copolymers. The dispersion contains a carboxy copolymer of 10 wt% acrylic acid and 90 wt% 2-ethylhexyl acrylate, and an epoxy copolymer of 15 wt% glycidyl methacrylate, 20 wt% hydroxyethyl methacrylate, and 65 wt% 2-ethylhexyl methacrylate. These adhesives are described as exhibiting improved crosslinking and, as a result, better shear strength. [Prior art documents] [Patent documents]

[0021] [Patent Document 1] U.S. Patent No. 5,700,875 [Patent Document 2] US Patent Application Publication No. 2013 / 0224692 [Patent Document 3] European Patent Application Publication No. 3 120 827 [Patent Document 4] DE 196 43 007 A1 [Patent Document 5] International Publication No. 2006 / 045034 [Patent Document 6] US Patent Application Publication No. 2011 / 0288252 [Patent Document 7] DE 10 2018 204 655 A1 [Patent Document 8] European Patent Application Publication No. 0 305 850 [Patent Document 9] European Patent Application Publication No. 0 841 352 [Patent Document 10] European Patent Application Publication No. 1 270 619 [Non-patent literature]

[0022] [Non-Patent Document 1] RRMoraes, JWGarcia, NDWilson, SHLewis, MDBarros, B. Yang, CSPfeifer, JWStansbury, J.Dent.Res.91(2012):179-184 [Non-Patent Document 2] B.Schlarb,MGRau,S.Haremza,Prog.Org.Coat.26(1995)207-215 [Non-Patent Document 3] B. Schlarb, S. Haremza, W. Heckmann, B. Morrison, R. Muller-Mall, MGRau MG, Prog.Org..Coat.29(1996)201-208 [Non-Patent Document 4] O. Kutlug, S. Reck, A. Hartwig, Int. J. Adhes. Adhes., 91 (2019) 36-42 Summary of the Invention [Means for solving the problem]

[0023] The object of the present invention is to provide biocompatible dental materials which are suitable in particular as adhesives for dental applications, in particular as adhesives for bonding direct and indirect dental restorations to tooth tissue, i.e. enamel and dentin. These dental materials should ensure good adhesion to tooth tissue, in particular under oral cavity conditions. The present application provides, for example, the following: (Item 1) A dental material containing at least one copolymer, said copolymer comprising: (I) (a) one or more monomers M having a polymerizable (meth)acrylate group G , (b) one or more OH-containing (meth)acrylates M F , (c) one or more strongly acidic adhesive monomers M H , and (d) optionally, one or more polymerizable carboxylic acid monomers M CS Copolymerization of (II) The copolymer A0 obtained in step (I) is treated with a monomer M F At least one functionalized radically polymerizable monomer M which reacts with the OH group of P and reacting in a polymer-analogous reaction to form copolymer A bearing polymerizable side groups. P and forming (III) The copolymer A p Neutralize with a base A dental material obtained by the process. (Item 2) Said copolymer A0 has the following composition: (a) 20 to 80% by weight, preferably 40 to 70% by weight, of monomer M G , (b) 1 to 70% by weight, preferably 5 to 40% by weight, of monomer M F , (c) 1 to 40% by weight, preferably 5 to 30% by weight, of monomer M H , and (d) 0 to 30% by weight, preferably 5 to 20% by weight, of monomer M CS 8. The dental material according to any one of the preceding items, wherein all percentages are relative to the weight of copolymer A0. (Item 3) Copolymer A p The monomer M G , MF , M H , and M if necessary CS to copolymer A0 in an organic solvent, and the copolymer A0 with monomer M p (step (II)) and subsequent neutralization (step (III)), (IV) optionally adding water to the copolymer solution obtained in step (III) and stirring the solution; and (V) then, if necessary, removing the organic solvent by distillation; 2. The dental material according to any one of the preceding items, which is obtainable by performing (Item 4) Copolymer A P In addition to the second copolymer B P and the second copolymer B P The composition of copolymer A P 5. The dental material according to any one of the preceding items, which has a composition different from that of (Item 5) The above copolymer B P but, (I) (a) one or more monomers M having a polymerizable (meth)acrylate group G , (b) one or more OH-containing (meth)acrylates M F , (c) optionally, one or more polymerizable carboxylic acid monomers M CS Copolymerization of (II) The resulting copolymer B0 is treated with a monomer M F At least one functionalized radically polymerizable monomer M which reacts with the OH group of P and reacting in a polymer-analogous reaction to give copolymer B bearing polymerizable side groups. P and forming (III) The copolymer B p Neutralize with a base 2. The dental material of any one of the preceding items, which is available by (Item 6) Said copolymer B0 has the following composition: (a) 30 to 85% by weight, preferably 40 to 80% by weight, of monomer M G , (b) 5 to 55% by weight, preferably 10 to 50% by weight, of monomer M F , and (c) 1 to 40% by weight, preferably 5 to 30% by weight, of monomer M CS 8. The dental material according to any one of the preceding items, wherein all percentages are based on the weight of copolymer B0. (Item 7) Copolymer A P and copolymer B P A mixture of - copolymer A0 with the monomer M G , M F , M H , and, if desired, M CS and said copolymer A0 is prepared by copolymerization in an organic solvent of at least one monomer M p Copolymer A is produced by polymer-analogous reaction with P To convert to - copolymer B0 with said monomer M G , M F , and, if desired, M CS and the copolymer B0 is prepared by copolymerization in an organic solvent of at least one monomer M p By polymer-analogous reaction with P To convert to - the copolymer A P and the copolymer B P mixing the solution of - neutralizing the mixture by addition of a base; - adding water to the neutralized mixture, if necessary; and - then optionally removing the organic solvent. 2. The dental material of any one of the preceding items, which is available from (Item 8) The above monomer M P The amount of Copolymer A P Monomer building block M in F Of the OH groups in P reacts with, and If necessary, the above copolymer B P Monomer building block M F Of the OH groups in P react with 13. The dental material according to any one of the preceding items, in such an amount that (Item 9) The above monomer M G is selected from n-propyl methacrylate, neopentyl methacrylate, n-butyl methacrylate, phenylethyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, tetradecyl methacrylate and hexadecyl methacrylate, and the corresponding acrylic esters and mixtures thereof; and / or The above monomer M F is selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and mixtures thereof; and / or The above monomer M Pis selected from 2-isocyanatoethyl (meth)acrylate, addition products of 1 mole of 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate with 1 mole of each of the diisocyanates hexamethylene-1,6-diisocyanate (HMDI), 2,2,4-trimethyhexamethylene-1,6-diisocyanate (TMDI), isophorone diisocyanate (IPDI), 2-isocyanatoethyl methacrylate (IEMA), and mixtures thereof; and / or The above monomer M H is selected from 2-(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate and 10-(meth)acryloyloxydecyl dihydrogen phosphate, vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-(meth)acryloyloxyethylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid ethyl ester, and mixtures thereof; and / or The above monomer M CS is selected from (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid and their half esters, 2-(hydroxymethyl)acrylic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 10-(meth)acryloyloxydecylmalonic acid, 2-(meth)acryloyloxymethylsuccinic acid, 4-vinylbenzoic acid, and mixtures thereof; 10. A dental material according to any one of the preceding items. (Item 10) Copolymer A P Or B P , or A above P and B P5. The dental material according to any one of the preceding items, wherein the base for neutralizing the mixture with is selected from LiOH, KOH, NaOH, NH4OH, an organic amine, preferably ethylamine, n-butylamine, dibutylamine, trimethylamine, tributylamine (TBA), triethylamine (TEA), N-methylmorpholine, or dimethylcyclohexylamine, an amino acid derivative, preferably lysine methyl ester dihydrochloride, arginine hydrochloride, or glycine ethyl ester, an OH-functionalized amine, preferably methyldiethanolamine, diethylethanolamine, dimethylethanolamine, tris(hydroxymethyl)aminomethane, ethanolamine, diethanolamine, triethanolamine (TEOA), butanolamine, dibutanolamine, 3-dimethylamino-2-propanol (DMAP) or 1,3-diamino-2-propanol (DAP), a high molecular weight ether group-containing amine, preferably amino-terminated oligomeric ethylene oxide or propylene oxide oligomers, and mixtures thereof. (Item 11) The base or mixture of bases is added to the strongly acidic adhesive monomer M H 8. The dental material according to claim 7, wherein said hydroxypropyl ether is added in an amount of from 20 to 90 mol %, preferably from 25 to 80 mol %, and more preferably from 30 to 75 mol %, based on the content of hydroxypropyl ether. (Item 12) Copolymer A P and / or B. P 13. The dental material according to any one of the preceding items, wherein the number average molecular weight, as measured by gel permeation chromatography, is from 5,000 to 60,000 g / mol, preferably from 10,000 to 50,000 g / mol, and more preferably from 15,000 to 40,000 g / mol. (Item 13) - 10 to 50% by weight, preferably 15 to 45% by weight and more preferably 20 to 35% by weight of at least one copolymer A P and B as required P , - 50-90% by weight, preferably 55-85% by weight, and more preferably 65-80% by weight of a dispersion medium, and - optionally 10 to 70% by weight, preferably 15 to 60% by weight, and more preferably 20 to 55% by weight of water 13. The dental material according to claim 12, wherein the water content is included in the amount of the dispersion medium, if present, in each case based on the total mass of the dental material. (Item 14) 10. A dental material according to any one of the preceding items for use in the oral cavity in the restoration of damaged teeth, preferably as a dental adhesive or enamel-dentin adhesive. (Item 15) 13. Non-therapeutic use of a dental material according to any one of the preceding items as an adhesive in the manufacture or repair of dental restorations. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] overview The present invention relates to a process for the preparation of a polymerizable (meth)acrylate-containing monomer, G , one or more OH-containing (meth)acrylates M F , one or more strongly acidic adhesive monomers M H and optionally one or more polymerizable carboxylic acid monomers M CS (II) copolymerizing the resulting copolymer A0 with the monomer M F Functionalized radical polymerizable monomer M that reacts with the OH group of P and reacting in a polymer-analogous reaction to produce a copolymer A having pendant polymerizable groups. P and (III) forming copolymer A. p with a base. This material is particularly suitable as a dental adhesive. According to the invention, the object is to (I) (a) one or more monomers M containing one radically polymerizable (meth)acrylate group G , (b) one or more OH-containing (meth)acrylates M F , (c) one or more strongly acidic adhesive monomers M H , and (d) optionally one or more polymerizable carboxylic acid monomers M containing a radically polymerizable group; CS Copolymerization of (II) The copolymer A0 obtained in step (I) is treated with a monomer M F At least one functionalized radically polymerizable monomer M which reacts with the OH group of P in a polymer-analogous reaction to produce copolymer A bearing pendant polymerizable groups. P and forming (III) Copolymer A p Neutralize with a base At least one copolymer A available from P This is achieved by the dental material containing

[0025] In all cases, only monofunctional monomers, i.e. monomers having one radically polymerizable group, are used to prepare the copolymers A0. Multifunctional monomers, i.e. monomers having two or more radically polymerizable groups, cause crosslinking during polymerization and thus the formation of insoluble copolymers.

[0026] The copolymer A0 preferably has the following composition: (a) 20 to 80% by weight, more preferably 40 to 70% by weight, of monomer M G , (b) 1 to 70% by weight, more preferably 5 to 40% by weight, of monomer M F , (c) 1 to 40% by weight, more preferably 5 to 30% by weight, of monomer M H , and (d) 0 to 30% by weight, more preferably 5 to 20% by weight, of monomer M CS , and all percentages are based on the weight of copolymer A0. Particularly preferred are copolymers in which the sum of (a), (b), (c) and (d) is 100%.

[0027] The dental material according to the invention is particularly suitable as a dental restorative material, especially as a dental adhesive and more particularly as an enamel-dentin adhesive, and will therefore, for the sake of simplicity, also be referred to as an adhesive in the following.

[0028] According to a preferred embodiment of the present invention, copolymer A p is prepared in the form of a sub-dispersion. For this purpose, the monomer M G , M F , M H , and M if necessary CS The copolymerization of copolymer A0 with monomer M is carried out in an organic solvent. p (step (II)) and subsequent neutralization (step (III)), (IV) The copolymer solution obtained in step (III) is mixed with water, if necessary, and stirred; and (V) The organic solvent is then optionally evaporated off.

[0029] The addition of water in step (IV) may be omitted if an aqueous solution of base containing a sufficient amount of water to disperse the polymer solution is used for neutralization. The stirring in step (IV) is performed so that the copolymer solution from step (III) is dispersed in the aqueous phase.

[0030] Preferably, the (meth)acrylate is the monomer M G When homopolymerized, it has a glass transition temperature T below 40 °C. G In polymer analysis, the glass transition temperature T GCommonly used methods for determining the glass transition temperature T include differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). G is determined by the DMA in accordance with ISO-6721-11:2019.

[0031] Particularly preferred monomers M G are alkyl(meth)acrylates and cycloalkyl(meth)acrylates, in particular linear or branched C1-C 25 -Alkyl (meth)acrylate and C4-C 14 -cycloalkyl(meth)acrylate, more preferably linear C2-C 16 Alkyl methacrylate and C6-C 10 -cycloalkyl methacrylates, and even more preferably linear C2-C 10 -alkyl methacrylate, specifically n-propyl methacrylate (T G =35°C), neopentyl methacrylate, n-butyl methacrylate (T G =20℃), phenylethyl methacrylate (T G =26°C), n-pentyl methacrylate, n-hexyl methacrylate (T G =-5℃), cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate (T G =-20℃), n-dodecyl methacrylate (T G =-65℃), tetradecyl methacrylate (T G =-9°C) and hexadecyl methacrylate (T G =16°C), as well as the corresponding acrylates and mixtures thereof, with the methacrylates being preferred over the acrylates in all cases. Most preferred are n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, and mixtures thereof.

[0032] Preferred OH-containing (meth)acrylates M Fare monofunctional radically polymerizable monomers, and particularly preferred are monofunctional monomers having one OH group. More preferred are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and mixtures thereof. Even more preferred are 2- and 3-hydroxypropyl methacrylate (HPMA), especially 2-hydroxyethyl methacrylate (HEMA), and mixtures thereof.

[0033] Monomer M F The hydroxyl group of the copolymer A0 is the polymerizable monomer M P This monomer M P carries one functional group capable of reacting with the hydroxyl group to form a chemical bond, and at least one radically polymerizable group. A preferred functional group is an isocyanate group, and a preferred radically polymerizable group is a (meth)acrylate group, in particular a methacrylate group.

[0034] Preferred monomers M P are addition products of 2-isocyanatoethyl (meth)acrylate, 1 mole of 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate with 1 mole of a diisocyanate, preferably hexamethylene-1,6-diisocyanate (HMDI), 2,2,4-trimethylhexamethylene-1,6-diisocyanate (TMDI) or isophorone diisocyanate (IPDI), and mixtures thereof. Particularly preferred monomers M P is 2-isocyanatoethyl methacrylate (IEMA).

[0035] Copolymer A P The content of polymerizable groups in the copolymer A0 and therefore the degree of crosslinking is determined by the content of the monomer building blocks M F and the content of monomer M P The degree of reactivity of the monomer MP is the amount of monomer building block M F of OH groups are monomers M P is selected to react with

[0036] Strongly acidic adhesive monomer M H is a radically polymerizable monomer carrying at least one strongly acidic group and one radically polymerizable group. H has a pK of 0.5 to 4.0, preferably 1.0 to 3.5, and more preferably 1.5 to 2.5. a Preferred strongly acidic groups are phosphoric acid groups and phosphonic acid groups, and preferred radically polymerizable groups are (meth)acrylate groups, in particular methacrylate groups. Particularly preferred adhesive monomers M H are radically polymerizable phosphate esters, such as 2-(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 10-acryloyloxydecyl dihydrogen phosphate (ADP) and 10-methacryloyloxydecyl dihydrogen phosphate (MDP), and polymerizable phosphonic acids, such as vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-(meth)acryloyloxyethylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid ethyl ester (DHPBAE), and mixtures thereof. MDP, vinylphosphonic acid, DHPBAE and mixtures thereof are very particularly preferred.

[0037] Radical polymerizable carboxylic acid monomer M CSis a monomer containing at least one carboxylic acid group, preferably one to two carboxylic acid groups, and one radically polymerizable group. Preferred radically polymerizable groups are vinyl groups, acrylic groups, and vicinal or geminal substituted ethylene groups, and in particular methacrylic groups. The ethylene group can be vicinal or geminal substituted, for example, by -CH3 and -COOH, -COOH and -CH2-COOH, or by two COOH groups. Preferred monomers M CS are (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid and their half esters, 2-(hydroxymethyl)acrylic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 10-(meth)acryloyloxydecylmalonic acid, 2-(meth)acryloyloxymethyl succinic acid, 4-vinylbenzoic acid, and mixtures thereof. Acrylic acid, and especially methacrylic acid (MAA), are particularly preferred.

[0038] Preferred according to the invention is copolymer A P In addition, the composition is copolymer A P At least one second copolymer B having a composition different from that of P and preferably, (I) (a) one or more monomers M having one polymerizable (meth)acrylate group G , (b) one or more OH-containing (meth)acrylates M F , and (c) optionally, one or more polymerizable carboxylic acid monomers M CS Copolymerization of (II) The resulting copolymer B0 is treated with the monomer M F At least one functionalized radically polymerizable monomer M which reacts with the OH group of P and reacting in a polymer-analogous reaction to give copolymer B having pendant polymerizable groups. P and forming (III) Copolymer Bp Neutralize with a base at least one second copolymer B available from P The adhesive comprises:

[0039] The copolymer B0 preferably has the following composition: (a) 30 to 85% by weight, more preferably 40 to 80% by weight, of monomer M G , (b) 5 to 55% by weight, more preferably 10 to 50% by weight, of monomer M F , and (c) 1 to 40% by weight, more preferably 5 to 30% by weight, of monomer M CS and all percentages are based on the weight of copolymer B0. Particularly preferred are copolymers in which the sum of (a), (b) and (c) is 100%.

[0040] Copolymer B p is also preferably prepared in the form of a sub-dispersion. The sub-dispersion of copolymer B0 is prepared in the same manner as copolymer A0 by reacting monomers M G , M F , and, if desired, M CS The copolymer B0 is then prepared by copolymerization (step (I)) of the monomers M p and reacted in a polymer-like reaction to produce copolymer B. P (Step (II)) to give the monomer M P is preferably the amount of monomer building block M F of OH groups are monomers M P Then, copolymer B can be neutralized by adding a base (step (III)), and if necessary, water can be added to the resulting copolymer solution (step (IV)), and then, if necessary, the organic solvent can be distilled off (step (V)). Copolymer B can then be neutralized by adding a base (step (III)), and optionally, water can be added to the resulting copolymer solution (step (IV)), and then, if necessary, the organic solvent can be distilled off (step (V)). P The resulting sub-dispersion of copolymer A PA sub-dispersion containing two or more different copolymers is referred to herein as a sub-co-dispersion. Preferably, the monomer M G , M F , M P , and M if necessary CS But copolymer B P and A P The same or different monomers used to prepare B P Copolymer B can be used to prepare P Any strongly acidic monomer M H In all cases, only monofunctional monomers, i.e., monomers having one radically polymerizable group, are included in the copolymer B. P is used to prepare

[0041] According to a preferred embodiment of the present invention, the secondary codispersion is copolymer A P and copolymer B P and 2 are prepared separately and mixed together before neutralization, and only afterwards are they neutralized by adding a base. Water is then added, if necessary, to the neutralized copolymer dispersion, and then, if necessary, the organic solvent is distilled off.

[0042] Copolymer A p Or B P , or A P and B PPreferred bases for neutralizing the acidic monomer building blocks in admixture with LiOH, KOH, NaOH, NH4OH and organic amines, preferably ethylamine, n-butylamine, dibutylamine, trimethylamine, tributylamine (TBA), triethylamine (TEA), N-methylmorpholine or dimethylcyclohexylamine, amino acid derivatives, preferably lysine methyl ester dihydrochloride, arginine hydrochloride or glycine ethyl ester, OH-functionalized amines, preferably methyldiethanolamine, diethylethanolamine, dimethylethanolamine, tris(hydroxymethyl)aminomethane, ethanolamine, diethanolamine, triethanolamine (TEOA), butanolamine, dibutanolamine, 3-dimethylamino-2-propanol (DMAP) or 1,3-diamino-2-propanol (DAP), high molecular weight ether group-containing amines, and mixtures thereof. Preferred high molecular weight ether group-containing amines are oligomeric ethylene oxide or propylene oxide oligomers with amino group terminals. Such polyetheramines are commercially available, for example, under the name JEFFAMINE®. The bases mentioned are preferably used in the form of aqueous solutions. Particularly preferred are aqueous solutions of DMAP, TBA, TEA, DAP and mixtures thereof.

[0043] Copolymer A P and B. P The acid groups of the strongly acidic adhesive monomer M can be completely or preferably partially neutralized. Preferably, a base or a mixture of bases is added to the strongly acidic adhesive monomer M H Based on the content of A, it is added in an amount of from 20 to 90 mol%, more preferably from 25 to 80 mol%, and even more preferably from 30 to 75 mol%. P and B P When using mixtures with, neutralization is preferably carried out after mixing the copolymers.

[0044] The particle size of the copolymer particles in the formed sub-dispersion can be clearly adjusted by the type of base used and the degree of neutralization. According to the invention, particles having an average particle size of 1 to 700 nm, in particular 5 to 500 nm and especially 20 to 300 nm are preferred.

[0045] Unless otherwise stated, all particle sizes herein are volume average particle sizes (D50 values), i.e., 50% of the total volume of all particles is comprised of particles having a diameter smaller than the stated value. Thus, the D10 value is the volume diameter at which 10% of the total filler volume is smaller than the specified value.

[0046] Particle size determination in the range of 0.1 μm to 1000 μm is preferably carried out by static light scattering (SLS), for example using an LA-960 static laser scattering particle size analyzer (Horiba, Japan) or a Microtrac S100 particle size analyzer (Microtrac, USA). Here, a laser diode with a wavelength of 655 nm and an LED with a wavelength of 405 nm are used as light sources. The use of two light sources with different wavelengths allows the measurement of the entire particle size distribution of a sample in only one measurement run. This measurement is carried out as a wet measurement. For this purpose, an aqueous dispersion of the filler is prepared and the light scattered thereby is measured in a flow cell. The scattered light analysis for calculating the particle size and particle size distribution is carried out according to Mie theory and in accordance with DIN / ISO 13320. Measurement of particle sizes in the range from 1 nm to 0.1 μm is preferably carried out by dynamic light scattering (DLS) of aqueous particle dispersions, preferably using a He-Ne laser with a wavelength of 633 nm at a scattering angle of 90° and 25° C., e.g. using a Malvern Zetasizer Nano ZS (Malvern Instruments, Malvern UK).

[0047] In the case of aggregated and agglomerated particles, the primary particle size can be determined from TEM images. Transmission electron microscopy (TEM) is preferably carried out using a Philips CM30 TEM at an accelerating voltage of 300 kV. For sample preparation, a droplet of the particle dispersion is applied to a carbon-coated 50 Å thick copper grid (mesh size 300 mesh), and then the solvent is evaporated. The particles are counted and the arithmetic mean is calculated.

[0048] The adhesive according to the invention preferably comprises copolymer A P (multiple options possible) and B as appropriate P In addition to the above, it contains at least one dispersion medium, particularly preferably ethanol, isopropanol, tert-butyl alcohol, water or a mixture thereof, most preferably ethanol, water or a mixture thereof. Most preferably, it is water.

[0049] Furthermore, these adhesives may contain one or more initiators for radical polymerization, preferably photoinitiators, in particular camphorquinone in combination with 4-dimethylaminobenzoic acid ethyl ester. However, the polymerization of the adhesive may also occur together with the polymerization of, for example, a radically curable restorative material applied to the adhesive. In this case, it is assumed that initiator components and / or radicals diffuse from the restorative material into the adhesive layer and induce the curing of the adhesive. The addition of initiators is therefore optional, and adhesives that do not contain initiators for radical polymerization are particularly preferred.

[0050] Additionally, these adhesives may contain one or more fillers and / or one or more additives.

[0051] Preferably, the adhesive according to the invention has the following composition: - 10 to 50% by weight, preferably 15 to 45% by weight and more preferably 20 to 35% by weight of at least one copolymer A P and optionally at least one copolymer BP , and - 50-90% by weight, preferably 55-85% by weight, and more preferably 65-80% by weight of a dispersion medium has.

[0052] These adhesives are preferably - 10 to 70% by weight, preferably 15 to 60% by weight, and more preferably 20 to 55% by weight of water Contains:

[0053] These adhesives also - 0.001 to 10% by weight, preferably 0.01 to 8% by weight, and more preferably 0.1 to 5% by weight of an initiator for free radical polymerization may contain

[0054] More preferably, - 0-10% by weight, preferably 0-5% by weight and more preferably 0-3% by weight of a filler, and / or - 0-5% by weight, preferably 0-3% by weight, and more preferably 0-2% by weight of one or more additives It is an adhesive containing.

[0055] All amounts given relate in each case to the total mass of the adhesive, the content of water, if present, being included in the amount of the dispersion medium. The adhesive according to the invention is preferably present in the form of a single component.

[0056] The amount of carrier fluid is metered so that the adhesive has the desired viscosity, ie, so that it can be easily applied and spread well onto the substrate to be bonded, such as teeth.

[0057] Preferred initiators for the preparation of adhesives are photoinitiators such as benzophenone, as well as benzoin and its derivatives, and α-diketones and their derivatives, such as 9,10-phenanthrenequinone, 1-phenylpropane-1,2-dione, diacetyl or 4,4'-dichlorobenzil. Preferred photoinitiators are camphorquinone and 2,2-dimethoxy-2-phenyl-acetophenone, and especially α-diketones in combination with amines as reducing agents, such as 4-(dimethylamino)-benzoic acid esters, N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym-xylidine or triethanolamine. Also preferred are Norrish type I photoinitiators, in particular bisacylphosphine oxides, acyl of monoacyltrialkyl and diacyldialkylgermanium compounds, such as benzoyltrimethylgermanium, dibenzoyldiethylgermanium and bis-(4-methoxybenzoyl)diethylgermanium. Further preferred are mixtures of different photoinitiators, for example dibenzoyldiethylgermanium in combination with camphorquinone and 4-dimethylaminobenzoic acid ethyl ester, most preferred is camphorquinone in combination with 4-dimethylaminobenzoic acid ethyl ester.

[0058] Preferred fillers are organic or inorganic filler particles. Preferred inorganic particle fillers are amorphous spherical materials based on oxides such as SiO2 or ZrO2 or mixed oxides of SiO2 and ZrO2. Nanoparticle fillers, for example pyrogenic or precipitated silicas with an average primary particle size of 5 to 200 nm, and preferably 10 to 50 nm, are particularly preferred. The fillers serve to improve the mechanical properties and / or to adjust the viscosity and are preferably added before the dispersion is formed. The adhesive may contain one or more fillers.

[0059] Other suitable additives include stabilizers, microbicides and fluoride ion releasing additives.

[0060] Surprisingly, it has been found that the adhesive according to the invention exhibits high adhesion to natural tooth tissue and thus allows for firm attachment of direct and indirect restorations to the tooth. However, the adhesive according to the invention is also suitable for bonding restorations together and for repairing dental restorations. Copolymer A P and B. P carries radically polymerizable groups which allow crosslinking and hardening of the adhesive and ensure good mechanical properties. Furthermore, these groups can react with radically polymerizable groups of, for example, a dental filling material and thus improve the adhesion of this dental filling material.

[0061] It should be noted that these adhesives exhibit high and durable adhesion even under oral conditions. This is surprising because copolymer A P and copolymer B P Both copolymers A and B are composed of hydrophilic monomers to a significant extent, so that adhesive layers formed therefrom should be hydrophilic and therefore sensitive to moisture. P and B. P It has been found that by carefully selecting the type and amount of monomers used to prepare the copolymer, as well as by selectively incorporating polymerizable side groups into the copolymer chain, it is possible to obtain adhesives which ensure stable adhesion even under humid conditions and are therefore eminently suitable for dental applications, and in particular for use in the oral cavity.

[0062] A particular advantage of the adhesives according to the invention is that they do not contain monomers, in particular radically polymerizable monomers, which is advantageous from a toxicological point of view.They are therefore characterized by high biocompatibility.Furthermore, they also preferably do not contain emulsifiers and surfactants.

[0063] Biocompatibility was investigated using water extracts of the cured adhesive by standardized test methods. These extracts showed no cytotoxicity and no genotoxicity towards mouse fibroblast cells.

[0064] A preferred method for preparing the copolymers of the present invention is described below.

[0065] Copolymer A P and copolymer B P , monomer M G , M F , and, where appropriate, M H and M. CS The poly(meth)acrylates were synthesized by radical polymerization, preferably by solution polymerization in a water-miscible organic solvent that dissolves the poly(meth)acrylates well and is easily volatile. Preferred solvents are acetone (boiling point: 56° C.), methyl ethyl ketone (80° C.), diethyl ketone (102° C.), methyl isobutyl ketone (116° C.), tetrahydrofuran (66° C.) and acetonitrile (82° C.), and mixtures thereof. Acetone and methyl ethyl ketone are particularly preferred. These monomers are preferably used in a total monomer concentration of 10-60% by weight, preferably 15-50% by weight, and more preferably 20-40% by weight, based on the mass of the reaction mixture.

[0066] Polymerization is preferably carried out in the presence of an initiator for radical polymerization.Preferred polymerization initiators for preparing copolymers are thermal initiators, for example azo compounds such as 2,2'-azobis(isobutyronitrile) (AIBN), 2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobisbutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile) or 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), peroxides such as dilauryl peroxide, tert-butylperoxy-2-ethyl hexanoate, tert-butyl peroxybenzoate or di-tert-butylperoxide, dicumyl peroxide, peroxydicarbonates such as dicyclohexyl peroxydicarbonate or bis-(4-tert-butylcyclohexyl peroxydicarbonate). Particularly preferred are AIBN, tert-butylperoxy-2-ethylhexanoate, tert-butyl peroxybenzoate or di-tert-butylperoxide. It is preferred to post-add the initiator during the course of the polymerization in order to achieve complete monomer conversion. If necessary, the post-polymerization can be carried out at elevated temperatures. The total initiator concentration used is preferably in the range of 0.1 to 5.0% by weight, particularly preferably 0.5 to 4.0% by weight, and most preferably 0.7 to 2.5% by weight, based on the mass of the reaction batch. Any residual monomers present are preferably removed by dialysis or reprecipitation of the copolymer.

[0067] The number average molecular weight M of the polymer formed nincreases with increasing monomer concentration and decreasing initiator concentration. Chain length regulators can be added to selectively adjust the molar mass even at high monomer concentrations. Preferred chain length regulators are thiols, such as mercaptoethanol, tert-dodecyl mercaptan or lauryl mercaptan, disulfides, such as diisopropyl xanthogen disulfide. Particularly preferred chain length regulators are amino acid derivatives containing thiol groups, such as N-acetyl-(L)-cysteine ​​(AC), N-acetyl-L-cysteine ​​methyl ester, N-acetyl-L-cysteine ​​ethyl ester, most preferred being AC. Amino acid derivatives containing thiol groups give polymers with particularly good biocompatibility. Chain length regulators are preferably used in concentrations of 0.1 to 5.0% by weight, more preferably 0.5 to 4.0% by weight, and even more preferably 0.7 to 3.0% by weight, based on the mass of the reaction mixture.

[0068] Initiators and chain regulators are incorporated into the polymer as end groups during polymerization. As is usual in polymer chemistry, they are not taken into account when specifying the composition of the polymer.

[0069] Number-average molar mass M of copolymers A0 and B0 n is preferably in the range of from 5,000 to 60,000 g / mol, more preferably from 10,000 to 50,000 g / mol, and most preferably from 15,000 to 40,000 g / mol, and the number average molar mass M n is determined by gel permeation chromatography (GPC).

[0070] Gel Permeation Chromatography (GPC) is a relative quantitative method in which molecules are separated based on their size, or more precisely, their hydrodynamic volume. Absolute molecular masses are determined by calibration with known standards. Preferably, narrowly distributed polystyrene standards are used as calibration standards. These are commercially available. A styrene-divinylbenzene column is used as the separation material and tetrahydrofuran (THF) is used as the eluent. The styrene-divinylbenzene column is appropriate for synthetic polymers that are soluble in organic solvents. Measurements are carried out using dilute solutions (0.05-0.2% by weight) of the polymer to be investigated.

[0071] Alternatively, the number-average molar mass can be determined by well-known methods from freezing point depression (freezing point depression), boiling point elevation (boiling point elevation) or vapor pressure depression (vapor pressure osmometry). These are absolute quantitative methods that do not require calibration standards. A four to six concentration series of dilute polymer solutions with concentrations from 0.005 to 0.10 mol / kg is tested and the measured values ​​are then extrapolated to a concentration of 0 mol / kg.

[0072] The copolymer is then reacted with the monomer M P , preferably with 2-isocyanatoethyl methacrylate (IEMA) in a polymer-analogous reaction. This reaction is preferably carried out in the copolymer solution from the first step. For this purpose, the monomer M pFor example, IEMA is dissolved in an organic solvent, preferably acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, tetrahydrofuran or acetonitrile, particularly preferably acetone, and added dropwise to the polymer solution at a temperature of 20 to 60° C., preferably 40 to 55° C. To accelerate these reactions, catalysts such as tin(II) oxalate or octanoate, dibutyltin dilaurate, tri-o-tolyl bismuth, triphenyl bismuth, tris-(2-methylphenyl) bismuth, tris-(2-methoxyphenyl) bismuth or bismuth(III) neodecanoate can be added. Particularly preferred are bismuth catalysts, such as tri-o-tolyl bismuth or bismuth(III) neodecanoate, which are characterized by a high biocompatibility. According to a particularly preferred embodiment, the monomer M P The reaction is carried out without a catalyst.

[0073] Then, copolymer A p and B. P The acidic groups of copolymer A are neutralized by adding a base. P and B. P are preferably mixed together prior to neutralization. Copolymer A is dissolved in an organic solvent that is at least partially miscible with water and has a boiling point lower than that of water, or an azeotrope whose boiling point is lower than that of water. p , or A P and B P To the mixture of is added one or more bases. Preferably, the bases are added stepwise in the form of an aqueous solution.

[0074] If the amount of water in the base solution is not sufficient to disperse the copolymer solution or if the base is not used in the form of an aqueous solution, water is added to the neutralized copolymer solution. The mixture is preferably vigorously stirred and then the organic solvent is preferably at least partially evaporated. Upon evaporation of the solvent, a viscous sub-dispersion or sub-codispersion is formed. The resulting sub-dispersion or sub-codispersion contains particles of the copolymer(s). This sub-dispersion or sub-codispersion can be used directly as an adhesive or can be used to prepare an adhesive.

[0075] The advantageous properties of the dental material according to the invention are due in large part to the free-radically polymerizable copolymer A P and B as required P These are present in the form of particles, which allows the preparation of stable dispersions. These copolymers carry acidic groups which, after neutralization, result in anionic stabilization of the dispersion. At the same time, the combination of a strong acid monomer with a carboxylic acid monomer results in high adhesion to dentin and enamel. After application of these adhesives to the tooth surface and subsequent drying, these copolymers form a well-adhered polymer film, which allows for the formation of a strong bond with dental restorative materials, such as restorative composites, by the monomer M. P Copolymer A enables strong bonding via the polymerizable group. P , and B, if present P allows the preparation of one-component, monomer-free adhesives that are highly biocompatible.

[0076] Suitable copolymers according to the invention can preferably be prepared by the methods described above. However, copolymer A P and B. Pcan also be synthesized by other known radical polymerization methods, such as by the methods of substance polymerization, precipitation polymerization, suspension or emulsion polymerization, and living free radical polymerization, which are known in the prior art. The copolymers obtained by these processes can be dissolved in organic solvents that are at least partially miscible with water and have a boiling temperature lower than that of water, and can be reacted with the polymerizable monomers M by a polymer-analogous reaction. P The polymer solution can then be dispersed in water with vigorous stirring, the acid groups fully or partially neutralized with a base before, after or during dispersion in water, and finally the organic solvent is substantially evaporated. These copolymers can then be dispersed in a suitable dispersion medium.

[0077] The materials according to the invention are particularly suitable as dental materials for use in the oral cavity for the restoration of damaged teeth by dentists (therapeutic applications), especially as dental adhesives and in particular as enamel-dentin adhesives.

[0078] The materials according to the invention can also be used as extra-oral materials (non-therapeutic), for example as adhesives in the manufacture or repair of dental restorations. These materials are also suitable as adhesives for the manufacture and repair of inlays, onlays, crowns or bridges.

[0079] For application, the adhesive according to the invention is preferably applied to the prepared enamel and / or dentin surface with a brush and possibly rubbed onto the surface. Film formation can be accelerated by evaporation of the liquid, for example by blowing air or by heating with an artificial heat source or radiation. In this process, an adherent polymer film is formed. The enamel and / or dentin surface can be preconditioned beforehand by conventional means, for example by etching with 37% phosphoric acid and / or drying with an air stream. However, this is not necessary and excellent adhesion is achieved even without pretreatment with acid. Then, for example, a light-curing restorative composite can be applied and cured by irradiation with light. If the adhesive contains a photoinitiator, the adhesive layer can be cured by irradiation before the restorative composite is applied.

[0080] With the adhesives according to the invention, shear bond strengths to dentin and enamel of 15 MPa or higher can be achieved, ensuring a very good and durable bond between the restorative material and the tooth tissue.

[0081] The invention will now be described in more detail in the following examples, which demonstrate that the enamel-dentin single-component adhesive according to the invention is biocompatible and provides good enamel-dentin bonding. EXAMPLES

[0082] Example 1: Copolymer A by controlled free radical copolymerization in solution and functionalization with 2-isocyanatoethyl methacrylate (IEMA) P Synthesis of a) Copolymerization in solution:

[0083] In a beaker, 55 g of n-butyl methacrylate (BuMA), 15 g of 2-hydroxyethyl methacrylate (HEMA), 20 g of MDP and 10 g of methacrylic acid (MAA) were dissolved in 100 g of acetone using an ultrasonic bath. In a second beaker, 1 g of AIBN and 1 g of N-acetylcysteine ​​were dissolved in 50 g of acetone with stirring. These two solutions were combined and transferred to the larger dropping funnel of an apparatus consisting of a 500 ml three-neck flask equipped with a reflux condenser, two dropping funnels (50 ml and 250 ml), a nitrogen feed (on the larger dropping funnel), a bubble counter (on the reflux condenser) and a large magnetic stirring bar. In the three-neck flask, 100 g of acetone was introduced. Then, about 25% by volume of the acrylate solution was placed in the three-neck flask. The entire apparatus was thoroughly purged with nitrogen for 15 minutes. The nitrogen flow was then controlled and reduced until one bubble per second was visible in the bubble counter. Under nitrogen flow, the solution was refluxed in the three-neck flask for 30 minutes (oil bath temperature of 80° C.), after which the solution remaining in the dropping funnel was added to the boiling polymerization solution within 90 minutes. After the addition, 1 g of AIBN dissolved in 50 g of acetone was again quickly added to the boiling solution via the smaller dropping funnel. After a total polymerization time of 7 hours, the solution polymerization was stopped by switching off the apparatus and cooling. A clear, slightly viscous solution of copolymer A0 was obtained. b) Copolymer A P To form the IEMA of A0 (=M P ) functionalization

[0084] The polymer solution of A0 obtained above was transferred to a 1 l three-neck flask equipped with a 100 ml dropping funnel and a reflux condenser. A solution of 17.84 g IEMA dissolved in 50 g acetone was prepared and transferred to the dropping funnel. At a temperature of 50° C., the IEMA solution was added to the polymer solution within 1 hour. The solution was then heated to 50° C. for another 3 hours. To complete the reaction, the resulting solution was then stirred at room temperature for another 14 hours. The complete conversion of isocyanate was monitored by FTIR spectroscopy (NCO band). The amount of IEMA used corresponded to the complete conversion of the HEMA building block in A0. After the reaction was completed, the solution was very viscous, so the copolymer A was added to the polymer solution within 1 hour. P The solution was diluted with 100 g of acetone. Example 2:

[0085] Copolymer B by controlled free radical copolymerization in solution and functionalization with IEMA P Synthesis of a) Copolymerization in solution:

[0086] In one beaker, 60 g BuMA, 30 g HEMA and 10 g MAA were dissolved in 100 g acetone using an ultrasonic bath. In a second beaker, 1 g AIBN and 1 g N-acetylcysteine ​​were dissolved in 50 g acetone with stirring. These two solutions were combined and transferred to the larger dropping funnel of an apparatus consisting of a 500 ml three-neck flask equipped with a reflux condenser, two dropping funnels (50 ml and 250 ml), a nitrogen feed (on the larger dropping funnel), a bubble counter (on the reflux condenser) and a large magnetic stirring bar. In this three-neck flask, 100 g acetone was introduced. Then, about 25% by volume of methacrylate solution was placed in the three-neck flask. The entire apparatus was thoroughly purged with nitrogen for 15 minutes. The nitrogen flow was then controlled and reduced until one bubble per second was visible in the bubble counter. The solution was refluxed in the three-neck flask for 30 min (oil bath temperature of 80° C.) under nitrogen flow, after which the solution remaining in the dropping funnel was added to the boiling polymerization solution within 90 min. After the addition, 1 g of AIBN dissolved in 50 g of acetone was quickly added again to the boiling solution via the smaller dropping funnel. After a total polymerization time of 7 h, the solution polymerization was stopped by switching off the equipment and cooling. A clear solution of copolymer B0 was obtained. b) Copolymer B P To form the IEMA of B0 (=M P ) functionalization

[0087] The polymer solution of B0 obtained above was transferred to a 1 l three-neck flask equipped with a 100 ml dropping funnel and a reflux condenser. A solution of 17.84 g IEMA dissolved in 50 g acetone was prepared and transferred to the dropping funnel. At a temperature of 50° C., the IEMA solution was added to the polymer solution within 1 hour. The solution was then heated to 50° C. for another 18 hours. The complete conversion of the isocyanate was monitored by FTIR spectroscopy (NCO band). The amount of IEMA used corresponded to the complete conversion of the HEMA building block in B0. After the completion of the reaction, copolymer B P A clear slightly yellowish solution was obtained. Example 3: A P and B. P Preparation of a co-dispersion based on (70% neutralization)

[0088] Copolymer A obtained in Example 1 P and about 1 / 8 of the solution of copolymer B obtained in Example 2 P Approximately 1 / 8 of each of the solutions was weighed separately into a beaker. These two solutions were mixed in a 250 ml round bottom flask under vigorous stirring. To the resulting cloudy solution, 560 mg of dimethylamino-1-propanol (DMAP) dissolved in 12.5 g of demineralized water was added quickly in small portions using a glass pipette. This amount of DMAP was determined by the amount of copolymer A. p This corresponds to the amount required to neutralize 70% of the phosphate groups in the acetone. After the addition was complete, a clear solution was present. Acetone was removed from the solution on a rotary evaporator at a pressure of about 250 mbar and a water bath temperature of about 40° C. After removal of the organic solvent, the secondary co-dispersion was obtained as a milky viscous liquid. Example 4: Preparation of adhesives based on the co-dispersions from Example 3 and measurement of shear bond strength to dental tissue

[0089] To 6 g of the secondary co-dispersion obtained in Example 3, the photoinitiator components camphorquinone (CQ: 45 mg) and ethyl 4-(dimethylamino)benzoate (EMBO: 16 mg), both dissolved in a total of 4 g of ethanol, were added, and the mixture was mixed by vigorous shaking to form a clear solution. The solid content of the mixture was 30 wt %. This mixture was used as the adhesive for shear adhesion measurements.

[0090] For shear bond strength measurements to enamel and dentin, according to ISO 29022:2013 (Dental - Adhesion - Notched shear bond strength test), bovine teeth were embedded in silicone molds made of Dublisil 15 (addition cross-linked vinyl polysiloxane, Dreve Company) with embedding / casting resin (Visco-Voss GTS, Vosschemie Company, or Bosworth Fast Tray) such that the labial side of the bovine substrate was at the lower / bottom side of the silicone mold and the bovine substrate was covered with 2-5 mm of embedding / casting resin. The resin-covered teeth together with the mold were degassed in a vacuum oven at approximately 400 mbar for approximately 30 seconds. Curing was carried out overnight at room temperature and ambient pressure. The test specimens were removed from the silicone molds the next day. The tooth surfaces ground with abrasive paper (grit sizes 120 and 400) were rinsed with lukewarm water and pre-tempered to 37 °C. The dentin or enamel surfaces were wiped dry (Kimtech Wipes). All dentin and enamel shear bond strength values ​​were determined without prior etching of the teeth with H3PO4 in the so-called self-etching mode.

[0091] The adhesive was then applied directly to the tooth surface with an applicator (Microbrush applicator, Microbrush International, USA) without pretreatment with acid, agitated with gentle pressure for approximately 20 seconds, and then sprayed with an oil-free air stream to remove the solvent until a film was formed that did not move when exposed to the air stream. Thereafter, LED lamps (Blue Phase Style, 1200 mW / cm 2The specimens were exposed to light using a 10-second 5000 dl IR (560 nm, Ivoclar Vivadent AG). The test specimens prepared in this way were clamped in a clamping device with the prepared side facing up, according to EN ISO 29022:2013. Care was taken to ensure that the adhesive layer was not damaged during the insertion and positioning of the tooth, as well as during the placement of the upper part of the clamping device. Specimens in which the adhesive layer was damaged due to premature contact with the top of the clamping device were discarded. The tooth was fixed in the clamping device by slightly tightening the retaining screw. A dental filling composite (Tetric Evo-Ceram BulkFill, Ivoclar Vivadent AG) was then applied through the opening of the clamping device in a layer thickness of 2-4 mm. The applied adaptive pressure was selected in such a way that the composite was in contact with the adhesive without any air bubbles. Excessive pressure would result in leakage of the composite below the clamping device and the formation of composite beads around the composite cylinder. The test specimens with such circular composite beads were discarded.The composite was then polymerized according to the manufacturer's instructions (10 seconds, 560 nm, Blue Phase Style Polymerization Lamp, Ivoclar Vivadent AG).

[0092] To measure the shear bond strength, adhesively bonded composite cylinders were sheared from the teeth at 23°C using a Zwick-Roell Z010 testing machine (500N load cell, test speed 1mm / min) according to the Ultradent method (EN ISO 29022, 2013). The shear bond strength was determined to be 16.2MPa (dentin) and 19.5MPa (enamel). These are excellent bond strength values ​​for an enamel-dentin adhesive and ensure a durable bond between the filling composite and the tooth tissue. Example 5: Determination of the biocompatibility of the adhesive from Example 4

[0093] To measure the biocompatibility of the adhesive from Example 4, the adhesive was photocured into thin slices, and then the slices were dispersed in water. Cell viability was determined by WST-1 assay using mouse fibroblasts of cell line LS929. This assay uses the tetrazolium salt WST-1 (4-(3-(4-iodophenyl)-2-(4-nitrophenyl)-2H-5-tetrazolium)-1,3-benzene=disulfonate), which is enzymatically converted by viable metabolically active cells into a red formazan dye, the intensity of which is determined photometrically. This assay was designed according to the publication by YM Pupo et al. ("Cytotoxicity of Etch-and-Rinse, Self-Etch, and Universal Dental Adhesive Systems in Fibroblast Cell Line 3T3", Scanning Vol. 2017, Article ID 9650420). Monomeric HEMA was used as a positive control. No cytotoxicity was found against mouse fibroblasts.

[0094] Furthermore, genotoxicity was tested by comet assay according to DIN EN ISO 10993-3 (2018). The comet assay is based on the determination of damaged DNA strands by gel electrophoresis. Extracts of the cured adhesive did not show any DNA damaging effect in the comet assay and therefore no genotoxicity towards mouse fibroblast cells. Example 6: A P and B. P Preparation of co-dispersions based on (50% and 30% neutralization)

[0095] As in Example 3, copolymer A obtained in Example 1 was P and copolymer B obtained in Example 2. P1 / 8 of each of the solutions was weighed separately into a beaker. These two solutions were mixed in a 250 ml round bottom flask under vigorous stirring. To the resulting cloudy solution, 400 mg of DMAP dissolved in 12.5 g of demineralized water was added in small portions quickly using a glass pipette. In the second batch, 240 mg of DMAP dissolved in 12.5 g of demineralized water was added to the resulting cloudy solution. These amounts of DMAP were calculated based on the total amount of copolymer A. p This corresponds to a neutralization of 50% and 30%, respectively, of the phosphate groups in . Acetone was removed from the formed clear solutions on a rotary evaporator at a pressure of about 250 mbar and a water bath temperature of about 40° C. After removal of the organic solvent, the secondary co-dispersions were obtained in each case as milky viscous dispersions.

[0096] Similar to Example 4, adhesives with 30% solids were prepared with these dispersions by adding CQ, EMBO and ethanol, and the shear bond strength to dental tissues was investigated. Adhesion values ​​of 15.1 MPa (dentin) and 20.5 MPa (enamel) were measured for the 50% neutralized dispersions, and adhesion values ​​of 18.1 MPa (dentin) and 21.9 MPa (enamel) were measured for the 30% neutralized dispersions.

Claims

1. A dental material containing at least one copolymer, wherein the copolymer is (I) (a) Monomer M having one or more polymerizable (meth)acrylate groups Ｇ , (b) (meth)acrylate M containing one or more OH groups Ｆ , (c) One or more strongly acidic adhesive monomers M Ｈ , and (d) one or more polymerizable carboxylic acid monomers M, as needed. ＣＳ copolymerization, (II) The copolymer A obtained in step (I) ０ is reacted with at least one functionalized radically polymerizable monomer M ０ that reacts with the OH group of monomer M Ｆ in the polymer chain of A Ｐ by a polymer-analogous reaction to form a copolymer A Ｐ carrying a polymerizable side chain group, and (III) The copolymer A ｐ Neutralize with a base. A dental material characterized by being obtained by

2. The aforementioned copolymer A ０ However, the composition is as follows: (a) 20 to 80% by weight, preferably 40 to 70% by weight, monomer M Ｇ , (b) 1 to 70% by weight, preferably 5 to 40% by weight, monomer M Ｆ , (c) 1 to 40% by weight, preferably 5 to 30% by weight, monomer M Ｈ , and (d) 0 to 30% by weight, preferably 5 to 20% by weight, monomer M ＣＳ It has, where all percentages are copolymer A ０ The dental material according to claim 1, relating to the mass of the material.

3. The aforementioned copolymer A ｐ However, the monomer M produced by step (I) Ｇ M Ｆ M Ｈ , and M as needed ＣＳ Copolymer A ０ The copolymerization of the copolymer A in an organic solvent, and the copolymer A ０ and monomer M ｐ After the reaction with (step (II)) and subsequent neutralization (step (III)), (IV) If necessary, add water to the copolymer solution obtained in step (III), and stir the solution, (V) Next, remove the organic solvent by distillation, if necessary. The dental material according to claim 1 or 2, which can be obtained by performing the following.

4. The monomer M Ｇ (Multiple selections possible) are selected from n-propyl methacrylate, neopentyl methacrylate, n-butyl methacrylate, phenylethyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, tetradecyl methacrylate and hexadecyl methacrylate, as well as the corresponding acrylic acid esters and mixtures thereof; and / or The monomer M Ｆ (Multiple) are selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and mixtures thereof; and / or The monomer M Ｐ (Multiple) are selected from addition products of 2-isocyanatoethyl (meth)acrylate, 1 mole of 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate with 1 mole each of diisocyanate, hexamethylene-1,6-diisocyanate (HMDI), 2,2,4-trimethylhexamethylene-1,6-diisocyanate (TMDI), isophorone diisocyanate (IPDI), 2-isocyanatoethyl methacrylate (IEMA), and mixtures thereof; and / or The monomer M Ｈ (Multiple) are selected from 2-(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate and 10-(meth)acryloyloxydecyl dihydrogen phosphate, vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-(meth)acryloyloxyethylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-ethyl acrylate, and mixtures thereof; and / or The monomer M ＣＳ (Multiple) are selected from (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, and their semi-esters, 2-(hydroxymethyl)acrylic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 10-(meth)acryloyloxydecylmalonic acid, 2-(meth)acryloyloxymethylsuccinic acid, 4-vinylbenzoic acid, and mixtures thereof. The dental material according to claim 1 or 2.

5. The base for neutralizing the copolymer AP is LiOH, KOH, NaOH, NH ４ The dental material according to claim 1 or 2, comprising an OH group, an organic amine, preferably ethylamine, n-butylamine, dibutylamine, trimethylamine, tributylamine (TBA), triethylamine (TEA), N-methylmorpholine, or dimethylcyclohexylamine, an amino acid derivative, preferably lysine methyl ester dihydrochloride, arginine hydrochloride, or glycine ethyl ester, an OH-functionalized amine, preferably methyldiethanolamine, diethylethanolamine, dimethylethanolamine, tris(hydroxymethyl)aminomethane, ethanolamine, diethanolamine, triethanolamine (TEOA), butanolamine, dibutanolamine, 3-dimethylamino-2-propanol (DMAP), or 1,3-diamino-2-propanol (DAP), a high molecular weight ether group-containing amine, preferably amino-terminated oligomeric ethylene oxide or propylene oxide oligomer, and mixtures thereof.

6. The base or mixture of bases is the strongly acidic adhesive monomer M Ｈ The dental material according to claim 1 or 2, which is added in an amount of 20 to 90 mol%, preferably 25 to 80 mol%, and more preferably 30 to 75 mol%, based on the content of the above.

7. The dental material according to claim 1 or 2, wherein the copolymer AP has a number average molecular weight of 5,000 to 60,000 g / mol, preferably 10,000 to 50,000 g / mol, and more preferably 15,000 to 40,000 g / mol, as measured by gel permeation chromatography.

8. - 10 to 50% by weight, preferably 15 to 45% by weight, and more preferably 20 to 35% by weight, at least one copolymer AP - A dispersion medium in an amount of 50 to 90% by weight, preferably 55 to 85% by weight, and more preferably 65 to 80% by weight, - If necessary, 10 to 70% by weight, preferably 15 to 60% by weight, and more preferably 20 to 55% by weight of water The dental material according to claim 1 or 2, wherein the water content, if present, is included in the amount of the dispersion medium, based on the total mass of the dental material in each case.

9. The monomer M Ｐ The amount The aforementioned copolymer A Ｐ Inside monomer construction block M Ｆ Of the OH groups, 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 40 to 100 mol%, are M Ｐ The dental material according to claim 1 or 2, in an amount that reacts with [the substance].

10. Copolymer A Ｐ In addition, the second copolymer B Ｐ The second copolymer B contains Ｐ The composition is copolymer A Ｐ A dental material according to claim 1 or 2, which has a different composition from that of the dental material according to claim 1 or 2.

11. The aforementioned copolymer B Ｐ but, (I) (a) Monomer M having one or more polymerizable (meth)acrylate groups Ｇ , (b) (meth)acrylate M containing one or more OH groups Ｆ , (c) If necessary, one or more polymerizable carboxylic acid monomers M ＣＳ copolymerization, (II) The obtained copolymer B ０ B ０ monomer M in the polymer chain Ｆ At least one functionalized radical polymerizable monomer M reacts with the OH group of the OH group. Ｐ Then, copolymer B, which is formed by reacting it with a polymer-like reaction to support polymerizable side chain groups. Ｐ To form, and (III) The copolymer B ｐ Neutralize with a base. The dental material according to claim 10, which is available by [company name].

12. The aforementioned copolymer B ０ However, the composition is as follows: (a) 30 to 85% by weight, preferably 40 to 80% by weight, monomer M Ｇ , (b) 5 to 55% by weight, preferably 10 to 50% by weight, monomer M Ｆ , and (c) 1 to 40% by weight, preferably 5 to 30% by weight, monomer M ＣＳ It has, where all percentages are copolymer B ０ The dental material according to claim 11, which is based on the mass of the dental material.

13. Copolymer A Ｐ and copolymer B Ｐ A mixture of the above - Copolymer A ０ The monomer M Ｇ M Ｆ M Ｈ , and M if desired ＣＳ The copolymer A is prepared by copolymerization in an organic solvent. ０ at least one monomer M ｐ Through a polymer-like reaction with copolymer A, Ｐ To convert to - Copolymer B ０ The monomer M Ｇ M Ｆ , and M if desired ＣＳ The copolymer B is prepared by copolymerization in an organic solvent. ０ at least one monomer M ｐ Through a polymer-like reaction with copolymer B, copolymer B Ｐ To convert to - Copolymer A Ｐ Solution of the copolymer B Ｐ Mixing with the solution, - Neutralize the mixture by adding a base. - Add water to the neutralized mixture as needed, and - Then, if necessary, remove the organic solvent. The dental material according to claim 10, which is available by [method].

14. The monomer M Ｐ The amount The aforementioned copolymer A Ｐ Inside monomer construction block M Ｆ Of the OH groups, 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 40 to 100 mol%, are M Ｐ It reacts to, and The aforementioned copolymer B Ｐ Monomer construction block M Ｆ Of the OH groups, 10 to 100 mol%, preferably 30 to 80 mol%, and more preferably 40 to 60 mol%, are M Ｐ And they react The dental material according to claim 11, in such an amount.

15. The monomer M Ｇ (Multiple selections possible) are selected from n-propyl methacrylate, neopentyl methacrylate, n-butyl methacrylate, phenylethyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, tetradecyl methacrylate and hexadecyl methacrylate, as well as the corresponding acrylic acid esters and mixtures thereof; and / or The monomer M Ｆ (Multiple) are selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and mixtures thereof; and / or The monomer M Ｐ (Multiple) are selected from addition products of 2-isocyanatoethyl (meth)acrylate, 1 mole of 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate with 1 mole each of diisocyanate, hexamethylene-1,6-diisocyanate (HMDI), 2,2,4-trimethylhexamethylene-1,6-diisocyanate (TMDI), isophorone diisocyanate (IPDI), 2-isocyanatoethyl methacrylate (IEMA), and mixtures thereof; and / or The monomer M Ｈ (Multiple) are selected from 2-(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate and 10-(meth)acryloyloxydecyl dihydrogen phosphate, vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-(meth)acryloyloxyethylphosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-ethyl acrylate, and mixtures thereof; and / or The monomer M ＣＳ (Multiple) are selected from (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, and their semi-esters, 2-(hydroxymethyl)acrylic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 10-(meth)acryloyloxydecylmalonic acid, 2-(meth)acryloyloxymethylsuccinic acid, 4-vinylbenzoic acid, and mixtures thereof. The dental material according to claim 11.

16. The copolymer A Ｐ or B Ｐ or the base for neutralizing the mixture of A Ｐ and B Ｐ is LiOH, KOH, NaOH, NH ４ OH, an organic amine, preferably ethylamine, n-butylamine, dibutylamine, trimethylamine, tributylamine (TBA), triethylamine (TEA), N-methylmorpholine, or dimethylcyclohexylamine, an amino acid derivative, preferably lysine methyl ester dihydrochloride, arginine hydrochloride, or glycine ethyl ester, an OH-functionalized amine, preferably methyldiethanolamine, diethylethanolamine, dimethylethanolamine, tris(hydroxymethyl)aminomethane, ethanolamine, diethanolamine, triethanolamine (TEOA), butanolamine, dibutanolamine, 3-dimethylamino-2-propanol (DMAP) or 1,3-diamino-2-propanol (DAP), a high molecular weight ether group-containing amine, preferably an amino group-terminated oligomeric ethylene oxide or propylene oxide oligomer, and a mixture thereof, and the dental material according to claim 11.

17. The base or mixture of bases is the strongly acidic adhesive monomer M Ｈ The dental material according to claim 11, which is added in an amount of 20 to 90 mol%, preferably 25 to 80 mol%, and more preferably 30 to 75 mol%, based on the content of the above.

18. The aforementioned copolymer A Ｐ and / or B Ｐ The dental material according to claim 11, wherein, when measured by gel permeation chromatography, it has a number average molecular weight of 5,000 to 60,000 g / mol, preferably 10,000 to 50,000 g / mol, and more preferably 15,000 to 40,000 g / mol.

19. - 10 to 50% by weight, preferably 15 to 45% by weight, and more preferably 20 to 35% by weight, of at least one copolymer A Ｐ and B Ｐ , - A dispersion medium in an amount of 50 to 90% by weight, preferably 55 to 85% by weight, and more preferably 65 to 80% by weight, - If necessary, 10 to 70% by weight, preferably 15 to 60% by weight, and more preferably 20 to 55% by weight of water The dental material according to claim 11, wherein the content of the water is included in the amount of the dispersion medium, if present, based on the total mass of the dental material in each case.

20. The dental material according to claim 1 or 2, preferably for intraoral use as a dental adhesive or enamel-dentin adhesive in the restoration of damaged teeth.

21. Non-therapeutic use of the dental material according to claim 1 or 2 as an adhesive in the manufacture or repair of dental restorations.