EP3937880A1 - Primer and kit consisting of the primer and dental material - Google Patents

Abstract

The invention relates to an aqueous dental one-component primer composition and to a kit including said primer composition and a composite. The primer composition according to the invention is a self-etching and self-priming composition. The composition comprises a polymerizable (meth)acrylate- or (meth) acrylamide monomer with (i) at least one acidic group such as a phosphoric acid group and (ii) at least one hydrophilic group such as a terminal hydroxy group or two polymerizable (meth)acrylate- or (meth)acrylamide monomers one of which (i) has at least one acidic group and the other (ii) has at least one hydrophilic group. Furthermore, at least one of the polymerizable (meth)acrylate- or (meth)acrylamide monomers has (i) a polyfunctionality of 3, 4, 5, 6, 7, 8, 9 or 10 and/or (ii) a further polymerizable (meth)acrylate- or (meth)acrylamide monomer (iii) with a polyfunctionality of 3, 4, 5, 6, 7, 8, 9 or 10 is contained in the composition. This polyfunctionality relates to the polymerizability of the entity. In particular, there are at least three, preferably terminal, (meth)acrylate, (meth)acrylamide and/or allyl groups. The primer composition is furthermore characterized by the absence of a photoinitiator, a polymerization catalyst and an organic solvent.

Description

Primer and kit consisting of primer and dental material

The present invention relates to a primer for binding dental restoratives to dentine and / or tooth enamel, which contains a polymerizable (meth) acrylate or (meth) acrylamide monomer (i) at least one acidic group such as a phosphoric acid group and with (ii) at least a hydrophilic group such as a terminal hydroxy group or two polymerizable (meth) acrylate or (meth) acrylamide monomers of which one (i) has at least one acidic group and one (ii) has at least one hydrophilic group, one of which is polymerizable (meth) acrylate - or (meth) acrylamide monomers (i) and / or (ii) or another polymerizable (meth) acrylate or (meth) acrylamide monomer (iii) a 3,4,5,6,7,8, 9, 10-polyfunctionality, in particular in the form of preferably terminal, (meth) acrylate, (meth) acrylamide and / or allyl groups, and which, however, neither a photoinitiator nor a vanadium compound as a polymerization catalyst, in particular in the form of an organometallic vanadium compound, e.g. Contains vanadyl (V) derivatives or aromatic amines or an organic solvent.

In the therapeutic treatment for the restoration of destroyed natural tooth substance, polymerizable dental materials are often used. It is crucial for the quality of the result of the restored tooth that the aesthetic and functional requirements are met. From an aesthetic point of view, these dental materials must therefore not be visually distinguishable from natural tooth substance. In addition, however, they must also be sufficiently hard and the construction materials used must be attached to the natural tooth parts in such a way that the applied dental materials withstand the high forces they are exposed to when chewing. The polymerizable dental materials used to build up missing tooth substance are usually referred to as core build-up materials. Preferably used in this hydrophobic methacrylate monomers. In practical use in the dental practice, it has proven to be beneficial if these stump building materials are present in paste form so that the dentist can build and model them in the patient's mouth. Such a model is usually applied in several layers and, after application, hardened, i.e. polymerized, layer by layer. However, this procedure is very time-consuming due to the multiple curing steps.

In addition to building up missing tooth structures, polymerizable dental materials are also used in what are known as polymerizable composite cements. These cements are used to fix dental crowns and other dental prosthesis materials.

Finally, polymerizable dental materials are also used as so-called bulk-fill composites. Here, tooth cavities, i.e. the spaces created by fleas after the removal of caries, are filled with the material.

As already described, one of the many requirements placed on the polymerizable dental material is that a firm connection between the applied material and the natural tooth substance must be established, which ensures years of stability under the considerable mechanical requirements. Such a fluffing can be achieved by using adhesives (dental bonding agents), the adhesives on the tooth substance leading to better wetting and thus also to better flapping of the applied material. Usually three different mechanisms of action are required for this. In the first generation, such adhesives therefore had three components, which initiated different mechanisms of action one after the other in three steps. In a first step, the natural tooth substance is etched by means of the first component, whereby the surface of the natural tooth substance, in particular also the tooth enamel, is roughened. For the internal tooth substance, in particular the dentine, this means that the etching removes minerals from the collagen composite of the natural tooth substance, so that the collagen fibers essentially remain on the tooth surface. For the first step, 35% by weight of phosphoric acid was usually used, which is applied to the natural tooth substance. The acid must then be removed by rinsing with water and then drying with air.

In a second step, the adhesion between the applied dental material and the natural tooth substance must be ensured. For this purpose, the etched tooth surface is coated with a so-called primer. This usually contains hydrophilic monomers, which can penetrate the exposed collagen-fiber composite. Usually the primer has to be cured.

In a third step, it must then be ensured that there is sufficient adhesion between the primer and the polymerizable dental material. This is problematic because, as described, the primer has hydrophilic monomers, but the dental material has hydrophobic monomers. Therefore, a further coating, a so-called bonding, must first be applied in order to achieve sufficient adhesion between the polymerizable dental material and the natural tooth substance.

A particular disadvantage of the method described is the long treatment time due to the three separate steps. In addition, the different substances must be stored in different packaging and the risk of contamination and mix-up is increased. Products have already been developed in the past which combine one or more of the above-mentioned steps in one substance or a substance mixture, so that at least one step is omitted. In a typical variant, the etching is carried out first and then a product is applied which comprises both hydrophilic and hydrophobic monomers and therefore combines the function of primer and bonding in itself.

In another variant, the etching can be combined with the primer, which is usually done in such a way that the hydrophilic monomers of the primer have phosphoric acid groups which etch the natural tooth substance. The substance required for bonding is then applied separately.

A further development of the adhesives described above are the so-called all-in-one adhesives, also called "one-step adhesives" or one-step adhesion promoters. These include all three steps described above in a single step, so that a single substance performs the functions of etchant, primer and bonding combined in one. This leads to considerable time savings for the treating dentist and the patient. This advantage comes at the price of the disadvantage that the monomers containing phosphoric acid groups not only etch the natural tooth substance, but also react with the polymerizable dental material to be applied, so that the hardening of core build-up material, cement or bulk-fill composite can be disturbed. Here amine co-initiators are protonated and thereby inactivated.

This is particularly important because the curing of the polymerizable dental materials is a complex process in itself: On the one hand, the polymerizable dental materials to be applied must be able to cure at moderate temperatures, since they are used in the patient's mouth. As a rule, redox initiators are therefore used, which accelerate the curing process at temperatures of around 37 ° C. Typically a redox initiator system is used which comprises a per-compound together with a co-initiator. The per compound is presented as a so-called catalyst paste in a first paste and the co-initiator in the so-called base paste in a second paste. When used, the dental compound and co-initiator are brought together by mixing the pastes, so that a redox reaction takes place, which supplies the radicals required for polymerizing the organic monomers contained in the dental material. Usually the pastes are stored separately from one another in order to ensure high storage stability.

An example of such dental materials with an initiator system made of inorganic peroxides, for example sodium or potassium peroxide sulfate in combination with an alkali or alkaline earth metal toluenesulfinate or an alkali or alkaline earth metal sulfite can be found in WO 2014/033280 A1.

Alternatively, light-curing dental materials can also be used which have a photoinitiator. The disadvantage here is that the treating dentist has to apply these materials in thin layers, since the irradiated light cannot penetrate into deeper layers of the dental material. In the individual layers are modeled and cured with light in the meantime, the treatment time is significantly extended.

If all-in-one adhesives and the described polymerizable Dentalma materials with redox initiator are used for the treatment, there is in regular cases insufficient polymerization at the interface between adhesives and dental material. This is due in particular to the effect already described, according to which the phosphoric acid groups contained in the AII-in-one adhesive protonate the amines used as co-initiators, whereby these are converted into an ammonium compound. As a result, the actually desired redox reaction of the original amines with the per compounds becomes The initiation of the polymerization reaction is prevented and insufficient curing occurs at the interface between adhesive and polymerizable dental material. In summary, all-in-one adhesives therefore usually lead to reduced adhesion of the dental material to the adhesive.

In order to improve the adhesive effect between tooth substance and polymerizable dental material with redox initiator through an all-in-one adhesive, EP 2 409 997 A1 describes a composition which penetrates the tooth substance and uses the moisture contained in the tooth substance to accelerate it To achieve curing of the dental material. The composition described comprises a monomer mixture, an inorganic peroxide, a reducing agent and other polymerization accelerators. The polymerization accelerator is dissolved by the moisture on the surface of the tooth substance, whereby the polymerization hardening at the adhesive interface and within the hardenable composition is improved. Examples of such a Be accelerator are sulfites but also ammonium salts such as the tetramethylammonium salt and the tetraethylammonium salt of benzenesulfonic acid. The polymerization accelerator is usually present in the base paste.

EP 1 780 223 B1 describes an adhesive for the dental sector, a polymerization accelerator, namely a water-soluble sulfite, being added as an additional co-initiator. The sulfite is dispersed in the polymerizable monomer and dissolved at the interface with the natural tooth substance by moisture in the tooth. Due to the additional reducing effect of the sulfite, there is accelerated hardening of the polymerizable dental material at the interface between adhesive and polymerizable dental material.

EP 2 554 154 A1 describes an adhesive and a curable composition in the form of a core build-up material with a high level of adhesion and durability. The adhesive includes a monomer mixture, water and a amine-based, sulfur-free reducing agent. The core build-up material also comprises a monomer mixture, a water-soluble, sulfur-containing reducing agent, an organic peroxide and an amine-based, sulfur-free reducing agent.

Finally, DE 10 2015 103 427 describes a composition that is intended to ensure that there is sufficient curing both within the polymerizable dental material and at the interface with adhesives, in particular all-in-one adhesives.

Nevertheless, with all these uses of an adhesive, including an all-in-one adhesive and the polymerizable dental material, the problem remains that after the adhesive has been applied, it has to be cured. This means a relatively long treatment time not only for the patient, but also a complex preparative procedure for the dentist who uses it.

It is therefore the object of the present invention to provide a primer to which the polymerizable dental material can be applied directly. In particular, the task is to provide a kit made of primer and polymerizable dental material, which is exactly matched to one another and thus ensures simplified processing with very good adhesion conditions at the same time.

This problem is solved by a primer with the features of claim 1 ge.

Such an aqueous primer composition is self-etching and self-priming. It has a polymerizable (meth) acrylate or (meth) acrylamide monomer with (i) at least one acidic group such as a phosphoric acid group and with (ii) at least one hydrophilic group such as a terminal hydroxyl group or two polymerizable (meth) acrylate or (meth) acrylamide monomers of which one (i) at least one acidic group and one (ii) at least one hydrophilic group on. In addition, at least one of the polymerizable (meth) acrylate or methylacrylamide monomers (i) has a polyfunctionality, preferably at least three times the polyfunctionality, particularly preferably a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-fold polyfunctionality and / or (ii) it is a further polymerisable (meth) acrylate or methyl acrylamide monomer (iii) with a polyfunctionality. This polyfunctionality is preferably an at least three-fold polyfunctionality, particularly preferably a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-fold polyfunctionality. This polyfunctionality lies in the ability to polymerize. In particular, there are at least three, preferably terminal, (meth) acrylate, (meth) acrylamide and / or allyl groups. This primer composition is also characterized by the absence of the following substances: photoinitiators, vanadium compounds as polymerization catalysts, in particular in the form of organometallic vanadium compounds, e.g. vanadyl (V) derivatives, aromatic amines, and sulfinates and sulfonates, especially aromatic sulfonates such as sodium 4-toluenesulfonate. In addition, the primer composition according to the invention is characterized by the absence of an organic solvent.

The term polyfunctionality in the context of the invention relates to the ability to polymerize and thus to crosslink density. For example, a 3-polyfunctional monomer has three polymerizable groups.

This composite composition has the ability to act as a reducing agent (sodium sulfite), which can start a polymerization reaction by diffusing into the claimed primer composition after it has been applied. The polymerization is therefore no longer started by a catalyst and / or an initiator which is contained in the composition itself, but rather is rather based on mass transport, in particular based on diffusion. It is consequently possible for the dentist, even without the risk of premature hardening, to prepare the tooth for the application of the dental material, then to apply the dental material and to achieve hardening of the entire system in a single step.

In addition, the addition of a polymerization catalyst (copper and / or iron compound) in the primer composition and / or an organic, water-soluble oxidizing agent (e.g. sodium persulfate) in the composite composition accelerates the curing process and the adhesive bond at the interface between Primer and composite as well as primer and tooth substance are improved.

It has also proven beneficial to add iron and / or copper compounds. Iron is preferably in the +11 or +111 oxidation state and copper in the +1 or +11 oxidation state.

The iron compounds can be inorganic iron compounds such as in particular iron halides, iron sulfates, iron nitrates, iron perchlorates, iron phosphates, iron pyrophosphates, iron tetrafluoroborates and / or iron thiocyanates. Organometallic iron compounds such as in particular iron acetylacetonates, iron carboxylates such as e.g. Iron-2-ethylhexanoate, iron acetate, iron oxalate, iron ethylenediamine tetraacetate, iron citrate, iron phthalcyanine, iron gluconate, iron ascorbate, iron lactate, iron fumarate, egg sentartrate, iron methacrylate and / or iron alkoxide are possible.

In the same way, inorganic copper compounds such as in particular copper halides, copper sulfates, copper nitrates, copper perchlorates, copper phosphates, copper pyrophosphates, copper tetrafluoroborates and / or copper thiocyanates can be used. This also applies to organometallic copper compounds such as, in particular, copper acetylacetonates, copper carboxylates such as Copper-2-ethylhexanoates, copper acetates, copper oxalates, copper ethylenediamine tetraacetates, copper citrates, copper phthalcyanines, copper gluconates, copper ascorbates, copper lactates, copper fumarates, copper tartrates, copper methacrylates and / or copper alkoxides.

Surprisingly, it is also found that very good adhesion values can be achieved for the claimed systems, which are still in place even after aging processes shown artificially. In particular, the adhesion values even after thermocycling, in particular after thermocycling described in more detail with reference to the exemplary embodiments, are still above a value of> 10 MPa with a variance of 4 MPa. Such a system particularly preferably has an adhesion value of> 12 MPa with a variance of 4 MPa. A system in which the adhesion value does not deviate by more than a variance of 4 MPa is very preferred.

The term (meth) acrylamide group and the term (meth) acrylate group are to be understood in the sense of the invention in such a way that both methacrylamide groups and acrylamide groups or methacrylate groups and acrylate groups are to be understood.

With regard to the monomers used, it is possible on the one hand to use a single monomer which has both a polyfunctionality, in particular 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-fold polymerizable (meth) acrylate - Or (meth) acrylamide groups as well as an acidic, possibly also an additional hydrophilic group. A distinction must be made here in particular that an acidic group can always be understood as a hydrophilic group at the same time. The preferred example is:

Dipentaerythritol penta (meth) acrylate phosphate (PENTA)

In this case, the acidic group is also to be understood as a hydrophilic group.

Examples of monomers that also have an additional hydrophilic group are 1 -mono (methacrylate) -1-phosphoric acid-1-hydroxytrimethylolethane or propane or sorbitol tri (meth) acrylate monophosphoric acid monohydroxide.

[2- (hydroxymethyl) -2- (phosphonooxymethyl) butyl] 2-methylprop-2-enoate

[1 - (hydroxymethyl) -2,3,4-tris (2-methylprop-2-enoyloxy) -5-phosphonooxy-pentyl]

2-methylprop-2-enoate It is also possible for two monomers to be present, the monomer which has the polyfunctionality also having an acidic or a hydrophilic group, whereas the second monomer then has at least one functionality in each case acidic or a hydrophilic group.

Finally, it is also possible to use three different monomers, namely one with the decisive polyfunctionality, one with an acidic group and one with a hydrophilic group. The basic structure of all monomers used is based on the idea that a basic structure, the so-called spacer group, is provided. The respective groups are located there. The following table shows the preferred framework structures and, through X, the respective positions of the functional groups. X can stand for the same radical, but also for different radicals from Ri to R _n . Furthermore, cyclic aromatic hydrocarbons, cycloalkanes, aliphatic polyethers, PEG, PPG, PTMEG, paraformaldehyde and alkanes can function as spacers. The connection between the framework, the so-called spacer, and functional groups is typically made via a connecting group, the so-called linking element. This can in particular be a carboxylic acid ester, urethane and / or amide group. A polyfunctional monomer with, for example, a tri-functionality and an additional hydrophilic group therefore has the following structure:

Element C-end link

Functional groups in the sense of polyfunctionality are in particular to be understood as meaning styrene, methacrylic, acrylic, allyl, methacrylamide and / or acrylamide groups in any combination. These groups are radically polymerizable.

Acid groups in the context of the invention are in particular to be understood as meaning carbonate, sulfate, sulfonate, sulfinate, phosphate, phosphonate, phosphinate groups or that a monomer is selected as containing at least one monomer from a group

MDP (10-methacryloyloxydecyl dihydrogen phosphate), or MAC (carboxylic acid-substituted MDP),

PENTA (dipentaerythritol penta (meth) acrylate phosphate),

GDMAP (1,3-glycerol dimethacrylate phosphate),

4-META (4- (2-methacryloxyethoxycarbonyl) phthalic anhydride),

10-methacrylamidodecyl dihydrogen phosphate (A-MDP) and

PMGDM (pyromellitic acid-bis-glycerol dimethacrylate) is. These ensure that the tooth substance is adequately etched.

A hydrophilic group in the context of the invention is to be understood as meaning at least one hydroxyl, one amino, one amine, one thiol, one hydrochloride or one polyether group. With regard to the hydrophilic groups, it has been found to be particularly favorable if the hydrophilic group is an n-position hydroxyl or an n-position amine or a chain polyether group, since this increases their functionality.

It is particularly preferably used

2-hydroxyethyl methacrylate (HEMA). The claimed primer composition is preferably a one-component composition in order to keep handling as simple as possible for the dentist. Furthermore, in a preferred embodiment of the invention, the pH of the monomer mixture is <3.5, preferably <2.5 and particularly preferably between 1.5 and 2.5. In any case, the lower limit is favorably but not necessarily> 1.5. In one embodiment according to the invention, the proportion of a polyfunctional monomer is between 0.1 and 10% by weight, preferably between 1 and 5% by weight, which ensures particularly good polymerization.

In a preferred embodiment, a composition according to the invention has a proportion of 15 to 35 wt.%, Preferably 20 to 30 wt.% MDP (GDMAP, 4-META, A-MDP, PMGDM), a proportion of 0.05 up to 5% by weight, preferably 0.05 to 2% by weight BHT, a proportion of 0.05 to 0.5% by weight, preferably 0.1 to 5% by weight 2- (dimethylaminoethyl methacrylate ( DMAEMA), hydroquinone monomethylether (MEHQ), catechol derivatives and / or HALS (sterically hindered amines))) and a proportion of 25 to 35% by weight, preferably 27 to 33% by weight of water (preferably deionized). In addition, a proportion of 0.05 to 10% by weight, preferably 1 to 5% by weight of the polyfunctional monomer is added, which is particularly advantageously trimethylpropane trimethacrylate (glycerol propoxytriacrylate), pentaerythritol trimethacrylate, sorbitol pentamethacrylate GENOMER * ® 4691, N, N diallyl methacrylamide, N, N-iso-valerylidene bis-methacrylamide. The proportion of HEMA (N-2-hydroxyethyl methacrylamide), N- (2-hydroxypropyl) methacrylamide corresponds to the difference to 100% by weight. It is particularly important in this context that the polyfunctional monomer used is soluble in the mixture contained. In particular, it is soluble in a mixture of water with the monomer having an acidic group and / or the monomer having the hydrophilic group. It is very particularly preferably soluble in a mixture of water, MDP or one of its derivatives and HEMA or one of its derivatives, very particularly preferably in the proportions given above.

In addition, at least one inorganic or organic peroxide compound can be included. The per-oxygen compound is preferably a peroxide, a peroxide ester, a diacyl peroxide, a dialkyl peroxide, a peroxyketal, a peroxyketone, a hydroperoxide or hydrogen peroxide.

In a preferred embodiment, the organic per-oxygen compound is a diacyl peroxide, in particular a benzoyl peroxide, preferably dibenzoyl peroxide. Further examples of suitable peroxides include m-toluoyl peroxide, 2,5-dimethyl-2,5-bis (benzoyl peroxide) hexane, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxyisopropyl carbonate. Examples of suitable peroxide esters include tert-butyl peroxybenzoate and bis-tert-butyl peroxy isophthalate. Examples of suitable dialkyl peroxides include dicumyl peroxide, di-tert-butyl peroxide and lauroyl peroxide. Examples of suitable peroxyketals include 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane and 1,1-bis (tert-hexylperoxy) cyclohexane. Examples of suitable peroxy ketones include methyl ethyl ketone peroxide, cyclohexanone peroxide and methyl acetoacetate peroxide. Examples of suitable hydroperoxides include tert-butyl hydroperoxide, cumene hydroperoxide and p-diisopropylbenzene peroxide.

The primer according to the invention preferably contains one or more additives, preferably buffer salts, metal scavengers, surfactants, active ingredients, flavorings and / or odorants, fluoridizing agents, bleaching substances, desensitizers, bonding agents, dyes, color pigments, indicators, others Initiators or initiator components, stabilizers, polymerization inhibitors, thixotropic auxiliaries and antibacterial substances or combinations of two or more thereof.

The invention is also based on the object of also providing a kit in which a primer according to the invention is used together with a pasty two-component composite and thereby optimal adhesion results can be achieved.

In addition to the primer described, such a kit has a polymerizable dental material. The polymerizable dental material contains at least one catalyst paste (A) and at least one base paste (B). The catalyst paste comprises at least one organic peroxygen compound and at least one filler. The base paste contains at least one radically polymerizable organic (meth) acrylic monomer, at least one filler, a co-initiator of the free radical polymerization and at least one salt-like, water-soluble and powdery reducing agent (hereinafter also: reducing agent) dispersed in the base paste (B) . Furthermore, at least one phase transfer catalyst is provided in the at least one catalyst paste and / or the at least one base paste, which is an ammonium, a phosphonium and / or a sulfonium salt which contains an inorganic or organic anion, preferably with the exception of anions Sulfinic acids or sulfonic acids.

The use of a phase transfer catalyst according to the invention improves the adhesion to the tooth substance. This can be explained by the fact that the salt-like, water-soluble and powdery reducing agent is dissolved at the interface with the primer and can then diffuse through the phase transfer catalyst at the interface between the composite and the primer in order to accelerate the polymerization through reaction with the Achieve per-oxygen connection. Due to the division of the polymerizable dental material into at least one catalyst paste and at least one base paste, high storage stability is achieved. By mixing these individual components, the polymerizable dental material is produced, which quickly hardens under oral conditions (appropriate temperature and humidity).

The proportion of the phase transfer catalyst in the catalyst paste and / or the base paste, based on the total mass of the catalyst paste and / or the base paste, is preferably 0.01 to 5% by weight, preferably 0.01 to 2% by weight, particularly preferred 0.05 to 1% by weight and very particularly preferably 0.05 to 0.5% by weight. The mentioned weight fraction of the phase transfer catalyst in the catalyst paste and / or the base paste based on the total mass of the catalyst paste and / or the base paste must be chosen so low that the curing of the polymerizable dental material does not proceed so quickly that processing of the dental material is difficult or even prevented. At the same time, the weight percentage mentioned must be selected to be so high that the polymerization of the dental material is accelerated as intended within the dental material mass.

According to a preferred embodiment of the invention, the phase transfer catalyst is contained in the catalyst paste. This has been found to be particularly favorable in terms of storage stability, since potential activation of the reducing agent present in the base paste with the phase transfer catalyst and subsequent reaction of the reducing agent with air oxygen can be prevented as described above.

Drying agents can be added for further stabilization. Examples include: silica gel, zeolites, aluminum oxide, calcium oxide, calcium sulfate, potassium carbonate, potassium hydroxide, copper sulfate and / or sodium hydroxide. Examples of bases include: sodium hydroxide, calcium hydroxide, calcium oxide. According to the invention, a reducing agent is understood to be a substance which, in combination with the peroxygen compound, forms a redox system which is suitable for initiating a free-radical polymerization of the polymerizable (meth) acrylic monomer. Furthermore, the reducing agent reduces a reaction of a free-radical, growing polymer chain with the diradical oxygen, which can lead to the termination of the polymerization reaction in that the reducing agent reacts with the oxygen after it has dissolved.

As water-soluble in the context of the present invention, a substance is understood which has a solubility of at least 10 g / L, preferably at least 15 g / L, particularly preferably at least 30 g / L, and very particularly preferably at least 50 g / L in having distilled water at a temperature of 25 ° C.

The reducing agent is preferably selected from the group of sulfites, in particular from the group of alkali metal sulfites, alkaline earth metal sulfites, (NH ₄ ) ₂ SO 3, hydrogen sulfites, disulfites, thiosulfites, thionates and dithionites. Sodium sulfite is particularly preferably used as the reducing agent. The reducing agents mentioned have been found to be particularly suitable for the present invention, since they have low solubility in the organic monomer and are dispersed in the base paste, but can be introduced into the organic monomer particularly well by the phase transfer catalyst used according to the invention.

The weight proportion of the reducing agent, based on the total mass of the at least one base paste, is preferably less than 10% by weight, particularly preferably less than 5% by weight, particularly preferably less than 3% by weight and very particularly preferably (2nd ± 1) wt%. A co-initiator is provided in the at least one base paste, which is suitable for initiating a polymerization reaction of the organic (meth) acrylic monomer with the per-oxygen compound, regardless of the reducing agent.

The co-initiator is preferably selected from the group of primary, secondary and / or tertiary amines, in particular secondary amines and / or tertiary amines. Examples of suitable secondary amines and / or suitable tertiary amines include o-tolyldiethanolamine, m-tolyldiethanolamine, p-tolyldiethanolamine, N-methylaniline, N, 2-dimethylaniline, N, 3-dimethylaniline, N, 4-dimethylaniline, Ethyl 2-methylaminobenzoate, ethyl 3-methylaminobenzoate, ethyl 4-methylaminobenzoate, ethyl 2-dimethylaminobenzoate, ethyl 3-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, methyl 2-anisidine, methyl 3-anisidine, methyl-4-anisidine, N, N, -dimethyl-o-toluidine, N, N, -dimethyl-m-toluidine and / or N, N, -dimethyl-p-toluidine.

The weight fraction of the co-initiator used, based on the total mass of the at least one base paste, is preferably less than 5% by weight, particularly preferably less than 2% by weight, particularly preferably less than 1.5% by weight , but in any case also more than (0.1 ± 0.05) wt .-%, given before (0.8 ± 0.05) wt .-%.

The per-oxygen compound is preferably a peroxide, a peroxide ester, a diacyl peroxide, a dialkyl peroxide, a peroxyketal, a peroxyketone or a hydroperoxide. It is crucial for the per-oxygen compound used that the per-oxygen compound, in combination with the reducing agent and the co-initiator, forms a redox system which is suitable for initiating a radical polymerization of the organic (meth) acrylic monomer. In other words, the redox potentials of the per-oxygen compound and the reducing agent or the co-initiator must be coordinated with one another in such a way that that there is a redox reaction between the two and that radicals are formed which start polymerization of the (meth) acrylic monomer.

In a preferred embodiment, the organic per-oxygen compound is a diacyl peroxide, in particular a benzoyl peroxide, preferably dibenzoyl peroxide.

Further examples of suitable peroxides include m-toluoyl peroxide, 2,5-dimethyl-2,5-bis (benzoyl peroxide) hexane, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxyisopropyl carbonate. Examples of suitable peroxide esters include tert-butyl peroxybenzoate and bis-tert-butyl peroxy isophthalate. Examples of suitable dialkyl peroxides include dicumyl peroxide, di-tert-butyl peroxide and lauroyl peroxide. Examples of suitable peroxyketals include 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane and 1,1-bis (tert-hexylperoxy) cyclohexane. Examples of suitable peroxy ketones include methyl ethyl ketone peroxide, cyclohexanone peroxide and methyl acetoacetate peroxide. Examples of suitable hydroperoxides include tert-butyl hydroperoxide, cumene hydroperoxide, and p-diisopropylbenzene peroxide.

The weight fraction of the per-oxygen compound, based on the total mass of the at least one catalyst paste, is preferably less than 5% by weight, particularly preferably less than 2% by weight, particularly preferably less than 1% by weight and very particularly preferably (1.0 ± 0.2)% by weight.

The redox initiator systems mentioned can also be supplemented with at least one other initiator system. For example, at least one photoinitiator or at least one thermally activatable radical initiator, for example azo compounds, can be provided in the polymerizable dental material. These additional initiator systems can be provided in the at least one catalyst paste and / or the at least one base paste. Such initiator classes are known to those skilled in the art.

A photoinitiator, which is preferably provided, enables the practitioner to cure prematurely with a polymerization lamp at any time. Photoinitiator systems made from camphorquinone and an aromatic amine are usually used to light-cure dental materials. When irradiated with blue light with a wavelength in the range of 470 nm, such a mixture generates radicals which completely cure the material in less than a minute. The photoinitiator can be present in the catalyst paste and / or the base paste.

Suitable photoinitiators are, for example, alpha-diketones such as camphorchinone, especially D, L-camphorquinone, in conjunction with secondary and tertiary amines and, if necessary, mono- and bisacylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2 , 6-dichlorobenzoyl) -4-n-propylphenylphosphine oxide and benzaldehydes, Ivocerin, BAPO, TPO etc.

The weight fraction of the photoinitiator preferably used based on the total mass of the at least one base paste and / or the at least one catalyst paste is preferably less than 1% by weight, particularly preferably less than 0.5% by weight, particularly preferably less than 0 , 2% by weight and very particularly preferably (0.09 ± 0.04)% by weight.

In particular for the use of the polymerizable dental material as a core build-up material and as a polymerizable composite cement, it is preferred if both a redox initiator system and a photoinitiator are provided. Such polymerizable dental materials are also referred to as dual-curing. In a preferred embodiment of the invention, the (meth) acrylic monomer is selected from the group of the acrylamides and / or the acrylates or methacrylates (collectively called (meth) acrylates). Both bifunctional or higher functional acrylic acid and methacrylic acid esters or monofunctional (meth) acrylic acid esters can be provided.

The free-radically polymerizable organic (meth) acrylic monomers used with preference include acrylates or methacrylates containing aromatic groups, acrylates or methacrylates containing aliphatic groups, acrylates or methacrylates containing polyether groups, acrylates or methacrylates containing polyester groups, acrylates or methacrylates containing polyurethane groups or combinations of two or more several of these monomers.

Examples of suitable (meth) acrylates include bisphenol A di (meth) acrylate, bis GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxylated bisphenol A di (meth) acrylate, UDMA (a mixture of isomers of di - 2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate and di-2- (meth) -acryloxyethyl-2,3,3-trimethylhexamethylene dicarbamate), trimethylolpropane trimethacrylate (TMPTMA), isobornyl methacrylate (IBMA), 2- Hydroxyethyl methacrylate (HEMA) and / or glycerol-1,3-dimethacrylate (GDMA), as well as ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tetrahydrofurfuryl ( meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2- ethoxyethyl (meth) acrylate, 2-methoxy-ethyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate, 2- Hydroxy-1,3-di (meth) acryloxy-propane, neopentylglycol-di (meth) acrylate, 1,3-butanediol-di (meth) acrylate, 1,4-butanediol-di (meth) acrylate, 1, 6- Hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1, 10-De candiol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, 1, 14-tetra-decanediol di (meth) acrylate, 1, 16-hexa-decanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol methane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene glycol di (meth) acrylate, mono- or polyethylene glycol di (meth) acrylate, e.g. ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate, mono- or polypropylene glycol di (meth) acrylate, and mono- or polybutylene glycol di (meth) acrylate, in particular mono- or polytetramethylene glycol di (meth) acrylate, where the polyalkylene glycol derivatives include both those with branched and linear structures.

In addition, (meth) acrylics with urethane bond (s) are included as examples of mixture components for the (meth) acrylics mentioned. Suitable examples include di-2- (meth) acryloxyethyl-2,2 ^' , 4-trimethylhexa-methylenedi-carbamate, di-2- (meth) acryl-oxyethyl-2,4,4 ^' -trimethylhexamethylene dicarbamate and 1, 3,5-tris [1,3-bis {(meth) -acryloyloxy} -2-propoxycarbonylamino-hexane] -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione. In addition, a (meth) acrylate of a urethane oligomer is mentioned as an example, which is derived from 2,2'-di (4-hydroxy-cyclohexyl) propane, 2-oxepanone, hexamethylene diisocyanate and 2-hydroxy-ethyl (meth) acrylate, and a ( Meth) acrylate of a urethane oligomer, which is derived from 1,3-butanediol, hexa methylene diisocyanate and 2-hydroxy-ethyl (meth) acrylate. These (meth) acrylates can be used alone or as a mixture of two or more in combination in the polymerizable dental material.

The phase transfer catalyst is selected from the group of ammonium salts, phosphonium salts and / or sulfonium salts with inorganic or organic anions, anions of sulfinic acids and anions of sulfonic acids being excluded. The salts can be used either in water or in water-free form.

Suitable examples of heterocyclic ammonium salts include N- (allyloxycarbonyloxy) succinime, 3-benzyl-5- (2-hydroxyethyl) -4-methyl-thiazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-butyl -2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1.3-Didecyl-2-methylimidazolium chloride, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, 3-ethyl 5- (2-hydroxyethyl) -4-methylthiazolium bromide, hexacylpyridinium bromide, hexadecylpyridinium chloride, 5- (2-Hydroxyethyl) -3,4-dimethylthiazolium iodide, 1-methylimidazolium hydrogen sulfate, methyl viologen dichloride and

1.2.3-Trimethylimidazolium salts.

Commercially available phase transfer catalysts can also be used with the present invention. Suitable examples include Aliquat® 336, a quaternary ammonium salt, where Ri is methyl and R2, R3 and R4 are octyl and / or decyl, mainly octyl, or Arquad® 2HT-75.

Examples of preferred anions are anions selected from the group of halides, hydroxides, anions of inorganic acids, anions of organic acids, with the exception of anions of sulfinic acids and anions of sulfonic acids, pseudohalogen anions or halogen complexes of aluminate, silicate, phosphate or arsenate.

Particularly preferred anions are fluoride, chloride, bromide, iodide, hydroxide, sulfate, hydrogen sulfate, dihydrogen phosphate, phosphate, phosphonate, borate, chlorate, perchlorate, nitrite, nitrate, hydrogen carbonate, carbonate, tetrafluoroborate, tetrachloroaluminate, hexafluorophosphate, hexafluorophosphate, Acetate, butyrate, fumarate, maleate, glutarate, lactate, malate, malonate, oxalate, pyruvate or tartrate.

The following anions have been found to be particularly favorable: hydrogen sulfate, sulfate, dihydrogen phosphate, chloride and tetrafluoroborate.

Inorganic or organic materials can be used as fillers for the catalyst paste and the base paste. The fillers can be reinforcing fillers or non-reinforcing fillers or mixtures thereof. Highly disperse, active fillers with a BET surface area of at least 50 m ² / g are particularly suitable as reinforcing fillers. Particularly suitable are those with an individual particle size in the nanometer range, which can be present as aggregates and / or agglomerates. Preferred reinforcing fillers are substances selected from the group consisting of aluminum hydroxide, zinc oxide, titanium dioxide, zirconium oxide, silicon dioxide and precipitated and / or pyrogenic silica. Of course, the compounds mentioned above can be used individually or in any combination with one another, both in hydrophilic and in hydrophobized form.

Furthermore, the at least one reinforcing filler is preferably in the form of nanoparticles, as a fibrous or lamellar filler, for example as a mineral, fibrous filler, or as a synthetic, fibrous filler.

The proportion of reinforcing filler in the dental material according to the invention is usually 0.1 to 80% by weight, preferably 0.5 to 50% by weight and particularly preferably 1 to 40% by weight, based on the total dental material.

In principle, the same substances are suitable as non-reinforcing fillers as for the reinforcing fillers, but the non-reinforcing fillers necessarily have a BET surface area of less than 50 m ² / g (series Pigments Degussa Kiesel acids, number 12, page 5 and number 13, page 3) exhibit. Preferred non-reinforcing fillers are substances which are selected from the group consisting of alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal fluorides, alkaline earth metal carbonates, calcium apatite (Cas [(F, CI, OH, V CO) | (P0 ₄ ) 3], in particular calcium hydroxylapatite (Cas [ (OFI) | (P0 ₄ ) 3], titanium dioxide, zirconium oxide, aluminum hydroxide, silicon dioxide, precipitated silica, calcium carbonate and dental glasses (barium, strontium, aluminum, fluoride). In the case of bisphenol A-free and aromatic-free monomer compositions in the composite, non-reinforcing fillers with a refractive index less than 1.55 are often preferred.

In the case of bulk-fill composites in particular, grain sizes smaller than or equal to 1.5 μm are preferred.

Of course, the compounds mentioned above can be used individually or in any combination with one another, both in hydrophilic and in hydrophobicized form.

The non-reinforcing fillers used preferably have an average grain size greater than 0.1 μm (Ullmann Encyclopadie der Technischen Chemie, Volume 21, page 523).

The proportion of non-reinforcing filler in the dental material according to the invention is usually 0.1 to 80% by weight, preferably 0.5 to 50% by weight and particularly preferably 1 to 40% by weight, based on the total dental material.

The total proportion of reinforcing and non-reinforcing fillers in the dental material according to the invention is usually 0.1 to 80% by weight, preferably 0.5 to 80% by weight, particularly preferably 1 to 75% by weight, and very particularly preferably 5 to 70% by weight, based on the total dental material.

Furthermore, larger amounts of selected radiopaque fillers can also be present in the at least one base paste and / or the at least one catalyst paste. These are preferably irregularly shaped or spherical YbF3 or YF3 powder with an average grain size of the primary particles of 40 nm to 1.5 μm and particularly preferably core-shell combination products made from YF3 or YbF3 core and SiC -Bowl, the Si0 ₂ shell surface being very particularly preferably silanized. In particular, such a core-shell combination product has a refractive index of 1.48 to 1.54, a mean grain size of the agglomerated particles between 0.5 and 5 pm measured with a laser diffraction particle size measuring device SALD-2001 (Schimadzu) and a specific one BET surface area, measured with a Tristar 3000 device from Micromeritics, from 2 m ² / g to 5 m ² / g. The refractive index of the core-shell combination product made of YbF3 core and SiC shell is between 1.52 and 1.54.

The at least one basic component and / or the at least one catalyst component preferably contains one or more additives, preferably buffer salts, water scavengers, metal scavengers, metal complexing agents, other paste formers, surfactants, active ingredients, substances that enable optical scanning, flavorings and / or odors, diagnostics enabling substances, tooth substance corrosive and / or adhesive substances such as MDP or A-MDP, fluoridizing agents, bleaching substances, desensitizing agents, adhesion promoters, dyes, colored pigments, indicators, further initiators or initiator components, stabilizers, polymerization inhibitors, thixotropic auxiliaries and antibacterial substances or combinations of two or more thereof.

The weight fraction of the additives based on the total mass of the at least one base component and / or the at least one catalyst component is generally 0 to 20% by weight, based on the total mass of the respective component, preferably 0.0001 to 15% by weight and particularly preferably from 0.001 to 10% by weight.

An advantageous use of the polymerizable dental material according to the invention is the production of a core build-up material, a polymerizable composite cement and / or a bulk-fill composite. The kit described expressly also includes kits which, in addition to the components described, also contain dental adhesion promoter compositions, in particular one-component compositions, for pretreating the restoration surface (for example glass ceramic, oxide ceramic, metal). These further primers preferably consist of (i) one or more alkoxysilane monomers (e.g. MPS) and / or (ii) one or more acidic monomers (e.g. phosphoric acid ester or carboxylic acid ester monomer (e.g. MDP and 4-META)) and / or (iii) one or more sulfur-containing monomers (e.g. 6- (4-vinylbenzyl-n-propyl) am ino-1, 3,5-triazine-2,4-dithiol ( VBATDT for short)) and / or one or more stabilizers such as BHT, and / or MEHQ and (v) an organic solvent.

It is therefore also possible to use compositions as dental adhesive material, as dental composite resin, as dental cement or the like, which contain a radical polymerizable monomer without an acidic group, an organic hydroperoxide compound, preferably with 5 or more carbon atoms with at least one hydroperoxide group bonded to a tertiary carbon , a thiourea system and fillers. In addition, an acidic component is included, which is added approximately in a weight proportion which corresponds to the sum of the masses of the monomer, the hydroperoxide and the thiourea system. The catalyst paste A comprises the organic hydroperoxide and the free-radically polymerizable monomer, which is preferably methacrylate, as well as fillers. The base paste B comprises the thiourea and also the itself or another radically polymerizable monomer, which is preferably methacrylate, as well as fillers.

Examples of the radical polymerizable monomer having no acidic group are an aromatic radical polymerizable monomer (having no acidic group and an aliphatic radical polymerizable monomer having no acidic group. A free-radically polymerizable monomer without an acidic group can be monofunctional, bifunctional or trifunctional or higher. Examples of the monofunctional, aromatic, radically polymerizable monomer without an acidic group are benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypro - pyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentylglycol- (meth) acrylic acid-benzoic acid Examples are esters. The bifunctional, aromatic, radical polymerizable monomer, which does not have an acidic group, has a hydroxyl group in the molecule) and a hydroxyl group in the molecule.

The preferred amount of the monomer, especially a hydrophilic monomer, in the catalyst and base paste is between 0.1 and 20% by weight, preferably 5 to 15% by weight.

The hydroperoxide compound having preferably 5 or more carbon atoms and at least one hydroperoxide group bonded to the tertiary carbon is a component which serves as an oxidizing agent for the redox polymerization initiator.

Examples of the hydroperoxide compound used in this invention having 5 or more carbon atoms and having at least one hydroperoxide group bonded to a tertiary carbon are cumene hydroperoxide, t-amyl hydroperoxide,

1 .1 .3.3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di- (hydroperoxy) hexane, p-diisopropylbenzene monohydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide. These can be used alone or in combination of two or more. Among them, it is preferable to use cumene hydroperoxide, and / or cumene hydroperoxide

1 .1 .3.3-Tetramethylbutyl hydroperoxide should be used.

The blending amount of the hydroperoxide compound is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight of the total mass. Pyridylthiourea or its derivative is a component that is preferably used as the thiourea that serves as a reducing agent for the redox polymerization initiator. The pyridylthiourea or its derivative is not particularly limited as long as the thiourea has a pyridyl group as a substituent and a compound of the following formula is used. (2-pyridyl) thiourea is particularly preferred.

The amount of pyridylthiourea or its derivative in the total mass is preferably 0.003 to 5% by weight, more preferably 0.008 to 1% by weight, based on the total mass.

The fillers already described are also used here as fillers.

It is also conceivable to add an acidic compound that activates the hydroperoxide compound. However, if the flydro peroxide compound is activated too strongly, the storage stability and the service life of the adhesive kit are impaired. Therefore, in the present invention, the mixing amount is limited. Examples of the acidic compound are phosphoric acid group, phosphoric acid mono ester group, pyrophosphoric acid group, thiophosphoric acid group, phosphonic acid group, phosphonic acid monoester group, carboxylic acid group, acid anhydride group, sulfonic acid group, sulfur. Examples are organic compounds with an acid group, e.g. an acid group, and inorganic acids such as e.g. Hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.

It is also possible to add vanadium and / or copper compounds here. These polymerization catalysts are preferably present in base paste B. Examples of the vanadium compound are vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadium oxalate, bis (maltolate) oxovanadium (IV), oxobis (1-phenyl-1), 3-butanedionate), Vanadium (V) oxytriisopropoxide, ammonium metavanadate (V), sodium ummetavanadate (V), vanadium pentoxide (V), ditetraoxide examples of these are vanadium (IV) and vanadyl sulfate (IV). Solubility of the concrete connection is a prerequisite. It is possible to combine the various vanadium compounds with one another.

The copper compound is preferably a compound which is soluble in a radical polymerizable monomer. Specific examples are copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, methacrylate acid copper, 4-cyclohexylbutyrate copper; ß-diketone copper: acetylacetone copper, trifluoroacetylacetone copper, hexafluoroacetylacetone copper, 2,2,6,6-tetramethyl-3,5-heptanedionate copper, benzoylacetone copper; ß-ketoester copper as copper acetoacetate; Copper alkoxide as copper methoxide, copper ethoxide, copper isopropoxide, copper 2- (2-butoxyethoxy) ethoxide, copper 2- (2-methoxyethoxyethoxy) ethoxide; Dithiocarbamic acid as copper, copper dimethyldithiocarbamate; Salts of copper and inorganic acids.

In addition, the use of phase transfer catalysts, as already described, is possible.

In both kit systems described, the use of an additional oxidizing agent has also proven to be beneficial. Persulfates such as alkali persulfates, for example sodium persulfate, potassium persulfate or alkaline earth sulfates, such as calcium persulfate and ammonium persulfate are particularly preferred. Also preferred are percarbonates such as alkali percarbonate, e.g. B. sodium percarbonate, potassium percarbonate, or alkaline earth metal percarbonate or ammonium percarbonate. Per borates such as alkali metal perborates such. B. sodium perborate, alkaline earth perborates or ammonium perborate or metal peroxides such as alkali peroxides, for example lithium peroxide, Nat rium peroxide, potassium peroxide or alkaline earth peroxides. The invention therefore also relates to a modular system (kit-of-parts) comprising the above-described components primer (one-component primer) and dental material (one-component or two-component composite) and possibly further primers.

With each of the modular systems, or kits for short, long-chain monomers to reduce stress and shrinkage can be used for the other component, the bulk-fill composite, regardless of the monomers used in the primer. These can be composed of a longer-chain spacer group (e.g. alkyl, cycloalkyl and / or aryl ether group, polybutadiene, polyethylene glycol, polypropylene glycol, polytetrahydrofuran), which are linked laterally or terminally to at least one polymerizable group, e.g. (Meth) acrylate, (meth) acrylamide, allyl, styrene. In addition, further linking groups such as urethane, amide, carbonic acid ester or carboxylic acid ester groups can be contained between the spacer group and the polymerizable group (s). Furthermore, the functionality can be increased further by incorporating one or more framework structures (the tabular listing of possible framework structures) at any point between spacer, linking group and / or polymerizable group.

Alpha-diketones and their derivatives, such as 9, 10-phenanthrenequinone, especially D, L-camphorquinone, in conjunction with secondary and tertiary amines and / or mono- and bisacylphosphine oxides, such as diphenyl ( 2,4,6-trimethylbenzoyl) phosphine oxide (TPO) and phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO) and bis- (2,6-dichlorobenzoyl) -4-n-propylphenylphosphine oxide. Organometallic photoinitiators are also suitable, for example benzoylgermanium derivatives such as bis (4-methoxybenzoyl) diethylgermanium and titanocenes such as bis [2,6-difluoro-3- (1-hydropyrrol-1-yl) phenyl] titanocene. The invention also relates to a hardened dental material which is obtained by mixing the catalyst paste (A) according to the invention and base paste (B) preferably in a ratio of 1:20 to 1: 1 and by polymerizing the polymerizable dental material.

The invention also relates to the use of a polymerizable dental material containing at least one catalyst paste (A) described above and at least one base paste (B) described above for the production of a core build-up material, a polymerizable composite cement and / or a bulk-fill composite for the production of core build-ups , Fixings and / or dental fillings.

The invention also relates to hardened denatal material, in which only one-component systems for both primers and composites are used to produce a core build-up material, a polymerizable composite cement and / or a bulk-fill composite for the manufacture of core build-ups, fastenings and / or dental fillings.

Developments, advantages and possible applications of the invention can also be found in the following description of the drawing and the exemplary embodiments. All of the features described and / or illustrated form the subject matter of the invention individually or in any combination, regardless of how they are summarized in the claims or their reference.

Creation of the primer compositions

The raw materials used BHT, DMAEMA (DMAPMA), acidic adhesive monomer (MDP, GDMAP, etc.), monofunctional monomer (HEMA, A-HEMA) and, depending on the respective recipe, no or a multifunctional monomer was used. weighed into a mixing can according to the recipes in the respective examples (PP 30 beaker, transparent, Hauschild, Germany) and homogeneously mixed for 1 min at 3500 rpm (Speedmixer DAC 150 FVZ, Hauschild, Germany). The amount of deionized water specified in each case was then added and the mixture was homogenized again for 1 min at 3500 rpm in the speed mixer.

The polyfunctional monomer was used in the same molar ratio, in other words in the same amount of substance.

Sample preparation

To test the bond strength, broken permanent molars of humans were used, so that near-surface dentin, i.e. H. Dentine as close as possible to the enamel is used so that the fluctuations are kept as low as possible. The teeth were stored in a 0.5% aqueous chloramine-T solution in the refrigerator at 2 to 8 ° C and thoroughly rinsed with running water before preparing the tooth surface.

To prepare the sample, the teeth are embedded in a suitable material (VariKwick liquid (LOT: 2013004123)) and the surface preparation is carried out by grinding in an automatic grinding machine with rotating grinding wheels and automatic water supply. In accordance with ISO 6344-1, P400 silicon carbide sandpaper is used to prepare a sufficiently large bond area. After grinding whoever rinsed the embedded teeth thoroughly with water to remove all foreign substances such. B. to remove remaining abrasive grains. The prepared surfaces must then be used for the test within 4 hours.

For the test, the tooth is rinsed under running water for 10 seconds. Then water is applied with filter paper or by a light / briefly A jet of oil- and water-free compressed air removed immediately before the adhesive was applied. The adhesive is applied evenly to the entire prepared tooth surface and massaged in for 20 s. The tooth is then inserted into a compound screw clamp, which contains a white plug-in form for the composite cylinder with a hole diameter of (2.38 ± 0.03) mm. The filling trough of the mold is arranged centrally over a point on the tooth that is suitable for the bond, whereby it is ensured that the bond point consists only of the dentine seen before. The mold is then lowered down to the tooth surface.

In all cases, a composite produced according to Example 3 of DE 10 2015 103 427 A1 (composition 2 in each case) is used as the composite.

Its base paste has the following composition:

Table 1: Base paste composition

The catalyst paste of this composite has the following composition:

Table 1: Catalyst paste composition

It is inserted into the mold and applied to the composite surface and cured in a drying cabinet at 37 ° C for 6 - 7 minutes. A light curing with a targeted use of an external light source is not carried out.

The composite test specimens are stored for 24 (± 2) hours in water at 37 (± 2) ° C. The bond strength of the test specimens is tested immediately after they have been removed from the water.

For each of the examples, 10 teeth are prepared in the manner described.

Thermocycling

Five of the ten teeth were then subjected to a thermal cycling stress test. For this purpose, these five test specimens were placed in a thermocycling device (Thermocycler THE 1200, from SD Mechatronik GmbH, Feldkirchen-Westerham, Germany) for 5000 cycles in an alternating bath between 5 (± 1) ° C cold and 55 (± 1) ° C warm water thermomechanically loaded. The test specimens remained in each of the two baths for 30 seconds, with a draining time of 5 seconds in between.

Adhesion determination

The determined adhesion values were determined by means of a shear test method with which the shear bond strength between the dental material and the tooth structure can be determined. This procedure is described for dental adhesives in the DIN EN ISO 29022 standard. A “shearing device with a recessed blade” (Zwick Universalprüfmachsine, Zwick, Ulm, Germany) served as the testing device. Immediately after removal from the water, the composite specimen is clamped in the metal specimen holder. The test specimen is loaded at a crosshead speed of 1.0 mm / min until it breaks and the maximum force (F) before the bond breaks is recorded. The shear bond strength (shear stress) is calculated using the following equation: s = F ² A- ¹ with c: shear stress in MPa (megapascals)

F: measured maximum force in N

A: bond area, given in mm ²

Due to the specified diameter of the composite cylinder of 2.38 mm, the bonded area is 4.45 mm ² in all measurements carried out.

The measurement was made for the five of the 10 teeth immediately after the described storage to determine an initial adhesion value. The five teeth that had previously been thermocycling were then measured in the same way. The individual shear bond strength values as well as the mean value and standard deviation of all five measurements were determined and documented. The measurement accuracy fluctuates by around 4 MPa. The following values in the examples each represent the mean values over the five test specimens concerned.

example 1

No polyfunctional compound is used. Example 1 therefore does not fall under the inventive idea. Be in the manner described

20 wt .-% MDP with the following structure o

49.7 wt .- / HEMA with the following structure o

0.1 wt .-% butylhydoxytoluene (BHT) with the following structure and

0.2% by weight of 2- (dimethylamino) ethyl methyl acrylate with the following structure

first alone and then mixed together with 30% by weight of water. The average adhesive value initially averaged 18.0 MPa, but fell to 8.0 MPa after the thermocycling described. This falling value shows that the adhesive bond is not suitable for long-term use in the patient's mouth, since an adequate adhesive effect is not ensured. Example 2

Glycerol propoxylate triacrylate with the following structural formula is used as a polyfunctional compound:

In the manner described, 20 wt .-% MDP, 47.2 wt .-% HEMA, 0.1 wt .-% BHT and 0.2 wt .-% 2- (dimethylamino) ethyl methyl acrylate and 2.5 wt .-% % Glycerylpropoxytriacrylate as triacrylate first alone and then mixed together with 30 wt .-% water.

The average adhesive value initially averaged 10.4 MPa, but rose to a value of 12.2 MPa after the thermocycling described. Here, the bond is not only ensured in the long term, but also improves over the simulated aging cycle.

Example 3 The polyfunctional compound used is pentaerythritol dimethyl acrylate in a mixture of approx. 25% by weight of mono-, 50% by weight, di- and 25% by weight of tri-methacrylate with the following structural formula:

Mono-, di-, trimethacrylate In the manner described, 20 wt .-% MDP, 48.1 wt .-% HEMA, 0.1 wt .-% BHT and 0.2 wt .-% 2- (dimethylamino) ethyl methyl acrylate and 1.6 wt .-% % Pentaerythritol dimethacrylate as dimethacrylate first alone and then mixed together with 30% by weight of water.

The average adhesive value was initially 12.8 MPa, but rose to 14.4 MPa after the thermocycling described. Here, too, the adhesive bond is not only ensured in the long term, but also improves over the simulated aging cycle.

Example 4

Trimethylpropane trimethacrylate with the following structural formula is used as a polyfunctional compound:

In the manner described, 20% by weight of MDP, 47.7% by weight of HEMA, 0.1% by weight of BHT and 0.2% by weight of 2- (dimethylamino) ethyl methyl acrylate and 2% by weight of trimethylpropane trimethacrylate are used as trimethacrylate first alone and then mixed together with 30% by weight of water.

The average adhesive value initially averaged 20.1 MPa and then fell slightly to a value of 17.1 MPa after the thermocycling described. These adhesive values are significantly better than the limit value of 10 MPa that is usually used, so that these values also ensure a very good adhesive bond between tooth and polymerizable dental material in the long term. Example 5

Trimethylolpropane trimethacrylate with the following structural formula is used as a polyfunctional compound:

Notwithstanding Example 4, MDP is replaced by GDMAP, so that in the manner described, 19.1% by weight of GDMAP, 48.6% by weight of HEMA, 0.1% by weight of BHT and 0.2% by weight % 2- (dimethylamino) ethyl methacrylate and 2% trimethylpropane trimethacrylate as trimethacrylate are mixed first alone and then together with 30% by weight of water.

The average adhesive value initially averaged 12.7 MPa and rose to a value of 15.7 MPa after thermocycling.

Example 6

Pentaerythritol trimethacrylate with the following structural formula is used as a polyfunctional monomer:

In the manner described, 20% by weight of MDP, 47.7% by weight of HEMA, 0.1% by weight of BHT and 0.2% by weight of 2- (dimethylamino) ethyl methacrylate and 2% by weight of pentaerythritol trimethacrylate are used as trimethacrylate first alone and then mixed together with 30% by weight of water.

The average adhesive value initially averaged 22.3 MPa and then fell to a value of 16.9 MPa after the thermocycling described. These adhesion values are significantly better than the limit value of 10 MPa that is usually used, so that these values also ensure a very good adhesive bond between the tooth and the polymerizable dental material in the long term.

Example 7 The polyfunctional compound used is sorbitol pentamethacrylate with the following structural formula:

In the manner described, 20 wt .-% MDP, 46.6 wt .-% HEMA, 0.1 wt .-% BHT and 0.2 wt .-% 2- (dimethylamino) ethyl methyl acrylate and 3.1 wt. % Sorbitol pentamethacrylate as pentamethacrylate first alone and then mixed together with 30% by weight of water. The average adhesive value initially averaged 16.9 MPa and then rose to a value of 17.3 MPa after the thermocycling described. These adhesion values are both well above the limit value of 10 MPa, so that this system also ensures a very good adhesion effect.

Example 8

Aliphatic urethane hexaacrylate (GENOMER * 4691® Rahn AG) with the following assumed structural formula is used as a polyfunctional compound:

In the manner described, 20% by weight MDP, 45.9% by weight / HEMA, 0.1% by weight BHT and 0.2% by weight 2- (dimethylamino) ethyl methyl acrylate and 3.8% by weight % aliphatic urethane hexaacrylate as hexaacrylate first alone and then mixed together with 30% by weight of water.

The average adhesion value was initially 14.9 MPa and after the described thermocycling 18.3 MPa. Once again, very good permanent adhesion is ensured here.

Table 3 shows an overview of the different adhesion values for different polyfunctional compounds:

* with GDMAP instead of MDP

Example 9 A tetrafunctional alkoxylated pentaerythritol tetramethacrylate with the following assumed structural formula is used as the polyfunctional compound: In the manner described, 20% by weight MDP, 46.1% by weight / HEMA, 0.1% by weight BHT and 0.2% by weight 2- (dimethylamino) ethyl methyl acrylate and 3.6% by weight % tetrafunctional alkoxylated pentaerythritol tetramethacrylate as tetra methacrylate, first alone and then mixed together with 30% by weight of water.

The average adhesion value was initially 11.0 MPa and after the described thermocycling 12.3 MPa. Here, the adhesive bond is not only ensured in the long term, but also improves over the simulated aging cycle.

Example 10 Analogous to Example 4, trimethylolpropane tri-methacrylate with the following assumed structural formula is used as the polyfunctional compound:

This series of experiments is intended to show the influence of the proportion of phosphoric acid 10-methacryloyloxydecyl dihydrogen phosphate (MDP) or the accelerator 2- (dimethylamino) ethyl methacrylate (DMAEMA) on the adhesive effect of the resulting composite. The proportion of 2-hydroxyethyl methacrylate (HEMA) was adjusted accordingly to 100%. The results are summarized in Table 3 below.

Table 3: Overview of the adhesive effect with different amounts of MDP and HEMA

** Reference example

It turns out that the presence of 2- (dimethylamino) ethyl methacrylate has a positive effect on the adhesive effect both initially and after thermocycling. The best results are achieved with a 10-methacryloyloxydecyl dihydrogen phosphate of about 20-30%.

Example 11 As a polyfunctional compound, analogously to Example 4, trimethylolpropane trimethacrylate with the following assumed structural formula is used:

In the manner described, 20% by weight of MDP, 47.7% by weight of HEMA, 0.1% by weight of BHT and 0.2% by weight of 2- (dimethylamino) ethyl methyl acrylate and 2% by weight of trimethylpropane trimethacrylate are used as trimethacrylate first alone and then mixed together with 30% by weight of water.

The primer was then tested with the base / catalyst pastes 1-4 described above. The results are summarized in Table 4 below.

Table 4: Influence on different systems of base and catalyst pastes

** Reference example

It can be seen that the average initial adhesion value in the case of the strongly hydrophilic composites 3 and 4, in contrast to the relatively hydrophobic base / catalyst pastes 1, is significantly increased.

The average adhesive value was initially 14.9 MPa and after the thermocycling (TC) described, 18.3 MPa. So again here is a very good permanent adhesion ensured. The influence of the hydrophilicity is particularly evident after the thermocycling described.

Example 12

Analogous to Example 4, trimethylolpropane tri-methacrylate with the following assumed structural formula is used as the polyfunctional compound:

This series of experiments is intended to show the influence of the accelerators copper (II) acetylacetonate and iron (III) EDTA in the presence of sodium persulfate on the adhesive effect of the resulting composite. The proportion of 2-hydroxyethyl methacrylate (HEMA) was adjusted accordingly to 100%.

Copper-containing primer (Cu): In the manner described, 20% by weight MDP, 47.2% by weight HEMA, 0.1% by weight BHT, 0.2% by weight 2- (Dimethyla- mino) ethyl methyl acrylate and 2% by weight trimethylpropane trimethacrylate as trimethacrylate and 0.5% by weight copper (II) acetylacetonate first alone and then mixed together with 30% by weight water.

Iron-containing primer (Fe): In the manner described, 20 wt .-% MDP, 47.0 wt .-% HEMA, 0.1 wt .-% BHT, 0.2 wt .-% 2- (dimethylamino) ethyl methyl acrylate and 2% by weight of trimethylpropane trimethacrylate as trimethacrylate and 0.7% by weight of iron (III) EDTA, first alone and then mixed together with 30% by weight of water. The primers were then tested with the previously described base pastes 2B and 3B as well as the corresponding catalyst pastes 2 and 3. The results are summarized in Table 5 below.

Table 5: Influence on different systems of base and catalyst pastes

It turns out that the presence of copper (II) acetylacetonate and sodium persulfate leads to a lower average initial adhesion value for the relatively hydrophobic base / catalyst paste 2B / 2 compared to the reference base / catalyst paste 2/2.

A trend towards higher average initial adhesion values and improved adhesion values after thermocycling, however, can be observed when using the copper-containing or iron-containing primer in the presence of sodium persulfate with the significantly more hydrophilic base / catalyst pastes 3B / 3 compared to the reference values . In particular, the combination of Cu-Primer / 3B / 3 shows an increase in the average adhesion value from 24.1 MPa to 25.3 MPa after thermocycling and thus a high level of resistance even with simulated aging.

Claims

Claims

1. Aqueous dental primer composition comprising a polymerizable (meth) acrylate or (meth) acrylamide monomer with (i) at least one acidic group and with (ii) at least one hydrophilic group or two polymerizable (meth) acrylate or (meth) acrylamide monomers of which one (i) has at least one acidic group and one (ii) has at least one hydrophilic group, characterized in that one of the polymerizable (meth) acrylate or (meth) acrylamide monomers (i) and / or (ii) or a further contained polymerizable (meth) acrylate or (meth) acrylamide monomer (iii) has a 3,4, 5,6,7,8, 9, 10-polyfunctionality, and is characterized by the absence a photoinitiator, a polymerization catalyst and an organic solvent.

2. Composition according to claim 1, characterized in that it additionally contains a copper and / or iron compound.

3. Composition according to claim 1 or 2, characterized in that the at least one acidic group is a carbonate, sulfate, phosphate, phosphonate, phosphinate, or the monomer with the acidic group MDP, PENTA, GDMAP, MAC, 4- META, A-MDP, PMGDM or (poly) vinyl carboxylic acids, in particular acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, β-carboxyethyl acrylate and their copolymers and combinations thereof may be included.

4. Composition according to one of the preceding claims, characterized in that the hydrophilic group is a hydroxyl, an amine or a polyether group.

5. The composition according to claim 4, characterized in that the hydrophilic group is a terminal or pendant hydroxyl or a terminal or pendant amino group or a chain polyether group.

6. Composition according to one of the preceding claims, characterized in that the (meth) acrylate or (meth) acrylamide monomer (iii) with the 3, 4, 5, 6, 7, 8, 9, 10-polyfunctionality according to the respective gen multiples correspondingly many functional groups in the form of (meth) acrylate, (meth) acrylamide, styrene and / or allyl groups.

7. Composition according to one of the preceding claims, characterized in that the polyfunctional monomer has a basic structure with a structure selected from glycerol, trimethylolpropane, pentaerythriol, xylitol, triglycerol, dipentaerythritol, sorbitol, hydrocarbons, cycloalkanes, aliphatic polyethers, PEG , PPG, PTMEG, para formaldehyde and straight or branched hydrocarbons comprising group.

8. Composition according to one of the preceding claims, characterized by the absence of vanadium compounds, in particular special vanadium acetylacetonate and vanadyl acetylacetonate, aromatic amines, sulfonates and / or aromatic sulfonates, sulfinates and / or aromatic sulfinates.

9. Composition according to one of the preceding claims, characterized in that the dental primer composition is a one-component composition.

10. Composition according to any one of the preceding claims, characterized in that the pH of the composition has a value <3.5, preferably <2.5, particularly preferably between 1.5 and 2.5 and in any case> 1, Has 0.

11. Composition according to one of the preceding claims, characterized in that the proportion of the polyfunctional monomer is between 0.1 and 10% by weight.

12. Composition according to one of the preceding claims, characterized in that MDP in a proportion of 15 to 35 wt .-%, HEMA with a proportion of 35 to 60 wt .-% and water with a proportion of 20 to 50 wt. -% is included.

13. Composition according to claim 12, characterized in that the polyfunctional monomer is present in dissolved form in the composition.

14. Composition according to one of the preceding claims, characterized in that 0.005 to 1 wt .-% BHT and / or hydroquinone monomethyl ether (MEHQ), catechol derivatives and / or HALS (sterically hindered amines) and / or 0.05 to 5 % By weight of 2- (dimethylamino) ethyl methacrylate is / are contained.

15. Composition according to one of the preceding claims, characterized in that at least one inorganic or organic peroxide compound is also included.

16. Dental adhesive material kit, comprising a liquid dental primer composition according to any one of claims 1 to 15 and a pasty, polymerizable two-component dental material, containing a catalyst paste (A) and a base paste (B), the catalyst paste (A) at least one organic per-oxygen compound, at least one free-radically polymerizable organic (meth) acrylate monomer and at least one filler contains, and where the base paste (B) contains at least one radically polymerizable organic (meth) acrylate monomer, an amine as a co-initiator of the radical polymerization, at least one filler and at least one salt-like, water-soluble and powdery reducing agent dispersed therein.

17. Dental adhesive material kit, comprising a liquid dental primer composition according to one of claims 1 to 15 and a pasty, polymerizable two-component dental material containing a catalyst paste (A) and a base paste (B), wherein the Ka catalyst paste (A) contains at least one organic per-oxygen compound, at least one radically polymerizable organic (meth) acrylate monomer and at least one filler, and where the base paste (B) contains at least one radically polymerizable organic (meth) acrylate monomer, an amine as a co-initiator of radical polymerization, at least one filler and at least one salt-like, water-soluble and powdery reducing agent dispersed therein, the catalyst paste (A) and / or the base paste (B) containing at least one phase transfer catalyst selected from the group of ammonium, phosphonium and / o sulfonium salts, which are an inorganic od he contain organic anions, with the proviso that the phase transfer catalyst in the case of organic anions only has those with 1-4 carbon atoms and that anions of sulfinic acids and sulfonic acids are excluded.

18. Dental adhesive material kit according to one of claims 16 or 17, characterized in that the phase transfer catalyst is only present in the catalyst paste (A) and / or that the proportion of the at least one phase transfer catalyst, based on the total mass of the catalyst paste (A) and / or the base paste (B) is 0.01 to 5% by weight.

19. Dental adhesive material kit according to one of claims 16 to 18, characterized in that the at least one salt-like, water-soluble and powdery reducing agent is selected from the group of sulfites, in particular from the group of alkali metal sulfites and very particularly sodium sulfite and / or the salt-like, water-soluble and pulverulent oxidizing agent is preferably an alkali persulfate, particularly preferably sodium persulfate, an alkali percarbonate and / or an alkali perborate, and / or that the co-initiator of the radical polymerization is a primary, secondary or tertiary amine, preferably a secondary or tertiary amine and is particularly preferably a tertiary amine.

20. Dental adhesive material kit according to one of claims 16 to 19, characterized in that it is dual-curing, and that at least one photoinitiator is additionally provided in the catalyst paste (A) and / or in the base paste (B).

21. Dental adhesive material kit according to one of claims 16 to 20, characterized in that the (meth) acrylate monomer in the catalyst paste (A) and / or in the base paste (B) is between 10 and 80 Wt .-%, preferably 15 to 65 wt .-% is provided. In addition, preference is given to a proportion of hydrophilic (meth) acrylate monomers between 0.1 and 20% by weight, particularly preferably between 5 and 15% by weight.

22. Dental adhesive material kit according to your of claims 16 to 21, characterized in that the at least one radically polymerizable organic (meth) acrylate monomer is selected from the group of di- or higher acrylates, di- or higher acrylamides, di- or higher methacrylates and / or the di- or higher methacrylamides or that the at least one free-radically polymerizable organic (meth) acrylate monomer is selected from the group of acrylates or methacrylates containing aromatic groups, acrylates containing aliphatic groups or methacrylates, polyether groups Acrylates or methacrylates, aliphatic or aromatic (meth) acrylate monomers containing hydroxyl and / or amino groups, acrylates or methacrylates containing polyester groups, acrylates or methacrylates containing polyurethane groups or combinations of two or more of these monomers, which are preferably monomers, the mines have at least two acrylate and / or methacrylate groups or that the at least one free-radically polymerizable organic (meth) acrylate monomer is selected from the group of monomers bisphenol A diacrylate, bisphenol A di-methacrylate, bisphenol glycidyl acrylate, bisphenol glycidyl methacrylate ( Bis-GMA), ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 1,6-bis (acryloxy-2-ethoxycarbonylamino) -2,4,4-trimethyl-hexane, 1,6 Bis (methacryloxy-2-ethoxy-carbonylamino) -2,4,4-trimethyl-hexane (UDMA), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, glycerine 1, 3-acrylate, glycerine 1,3-dimethacrylate (GDMA), 1,2-ethanediylbis (oxy-2-hydroxy-3, 1-propanediyl) -bis (2-methyl acrylate), 1, 12-dodecanediol diacrylate, 1, 12-dodecanediol dimethacrylate , Triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene diacrylate, tetraethylene glycol dimethacrylate or combinations of two or more of these monomers or that the radically polymerizable organic (meth) acrylate monomers are free of structural units with aromatic radicals, in particular do not contain any structural units derived from bisphenol A.

23. Dental adhesive material kit according to one of claims 16 to 22, characterized in that the organic per-oxygen compound is selected from the group of organic peroxides and in particular is a diacyl peroxide or a halogenated derivative thereof.

24. Dental adhesive material kit according to one of claims 16 to 23, characterized in that the anion of the phase transfer catalyst is selected from the group of halides, hydroxides, anions of inorganic acids, pseudohalogen anions or the halogen complexes of aluminate , Silicate or phosphate, or the anions of organic acids with 1-4 carbon atoms, except anions of sulfinic acids and sulfonic acids.

25. Dental adhesive material kit, comprising a liquid dental primer composition according to one of claims 1 to 15 and a pasty, polymerizable two-component dental material containing a catalyst paste (A) and a base paste (B), wherein the Ka catalyst paste (A) at least one organic hydroperoxide and at least one free-radically polymerizable organic (meth) acrylate monomer and contains at least one filler, and wherein the base paste (B) contains at least one free-radically polymerizable organic (meth) acrylate monomer, a thiourea as co-initiator of the free-radical polymerization and at least one filler.

26. Dental adhesive material kit according to claim 25, characterized in that the organic flydroperoxide is cumene hydroperoxide and / or cumene hydroperoxide and / or the thiourea (2-pyridyl) thiourea and / or acetylthiourea.

27. Dental adhesive material kit according to one of claims 25 or 26, characterized in that the (meth) acrylate monomer in the catalyst paste (A) and / or in the base paste (B), between 10 and 80% by weight, preferably 15 to 65% by weight is provided. In addition, preference is given to a proportion of hydrophilic (meth) acrylate monomers between 0.1 and 20% by weight, particularly preferably between 5 and 15% by weight.

28. Dental adhesive material kit according to one of claims 25 to 27, characterized in that the at least one radically polymerizable organic (meth) acrylate monomer is selected from the group of di- or higher acrylates, di- or higher acrylamides, di- or higher methacrylates and / or the di- or higher methacrylamides or that the at least one free-radically polymerizable organic (meth) acrylate monomer is selected from the group of acrylates or methacrylates containing aromatic groups, acrylates containing aliphatic groups or methacrylates, polyether groups Acrylates or methacrylates, aliphatic or aromatic (meth) acrylate monomers containing hydroxyl and / or amino groups, acrylates or polyester groups Methacrylates, acrylates or methacrylates containing polyurethane groups or combinations of two or more of these monomers, which are preferably monomers that have at least two acrylate and / or methacrylate groups or that the at least one free-radically polymerizable organic (meth) acrylate monomer is selected from the group of monomers bisphenol A diacrylate, bisphenol A di methacrylate, bisphenol glycidyl acrylate, bisphenol glycidyl methacrylate (Bis-GMA), ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A di methacrylate , 1,6-bis (acryloxy-2-ethoxycarbonylamino) -2,4,4-trimethyl-hexane, 1,6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4,4-trimethyl-hexane (UDMA ), Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethyl acrylate, 3-hydroxy-proplacrylate, 2-hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, glycerol-1, 3-acrylate, glycerol-1, 3-dimethacrylate ( GDMA), 1,2-ethanediylbis (oxy-2-h Hydroxy-3, 1-propanediyl) bis (2-methyl acrylate), 1, 12-dodecanediol diacrylate, 1, 12-dodecanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene dimethacrylate, tetraethylene dimethacrylate, tetraethylene acrylate glycol of two or more of these mono or more of these mono-methylene acrylate glycols or that the radically polymerizable organic (meth) acrylate monomers are free from structural units with aromatic radicals, in particular do not contain any structural units derived from bisphenol A.

29. Dental adhesive material kit according to one of claims 25 to 28, characterized in that a vanadium and / or copper connection is provided.

30. Dental adhesive material kit according to one of claims 25 to 28, characterized in that the at least one salt-like, water-soluble and powdery reducing agent is selected from Group of sulfites, in particular from the group of alkali metal sulfites and especially sodium sulfite and / or the salt-like, water-soluble and powdered oxidizing agent is preferably an alkali persulfate, particularly preferably sodium persulfate, an alkali percarbonate and / or an alkali perborate,

31. Dental adhesive material kit according to one of claims 25 to 30, characterized in that the catalyst paste (A) and / or the base paste (B) contains at least one phase transfer catalyst which is selected from the group of ammonium, phosphonium and / o of the sulfonium salts which contain an inorganic or organic anion, with the proviso that the phase transfer catalyst in the case of organic anions only has those with 1-4 carbon atoms and that anions of sulfinic acids and sulfonic acids are excluded.

32. Dental adhesive material kit according to one of claims 25 to 31, characterized in that it is dual-curing and therefore at least one photoinitiator is additionally provided in the catalyst paste (A) and / or in the base paste (B).

33. Dental adhesive material kit comprising a one-component primer composition according to one of claims 1 to 15 and a pasty one-component composite composition containing at least one free-radically polymerizable organic (meth) acrylate monomer, at least one filler and at least one photoinitiator.

34. Dental adhesive material kit according to claim 33, characterized in that the at least one radically polymerizable organic (meth) acrylate monomer is selected from the group of di- or higher acrylates, di- or higher acrylamides, di- or higher methyacrylates and / or the di- or higher methacrylamides or that the at least one free-radically polymerizable organic (meth) acrylate monomer is selected from the group of acrylates or methacrylates containing aromatic groups, acrylates containing aliphatic groups or methacrylates, acrylates or methacrylates containing polyether groups, hydroxyl - and / or amino groups-containing aliphatic or aromatic (meth) acrylate monomers, polyester-containing acrylates or methacrylates, polyurethane-containing acrylates or methacrylates or combinations of two or more of these monomers, preferably monomers containing at least two acrylate - u nd / o of the methacrylate groups or that the at least one radically polymerizable organic (meth) acrylate monomer is selected from the group of the monomers bisphenol A diacrylate, bisphenol A di methacrylate, bisphenol glycidyl acrylate, bisphenol glycidyl methacrylate (Bis -GMA), ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, 1,6-bis (acryloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhexane, 1,6 -Bis (methacryloxy-2-ethoxy-carbonylamino) -2,4,4-trimethyl-hexane (UDMA), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethyl acrylate, 3-hydroxy-proplacrylate, 2-hydroxyethyl methacrylate ( HEMA), 3-hydroxypropyl methacrylate, glycerine-1,3-acrylate, glycerine-1,3-dimethacrylate (GDMA), 1,2-ethanediylbis (oxy-2-hydroxy-3, 1-propanediyl) -bis (2 methyl acrylate), 1, 12-dodecanediol diacrylate, 1, 12-dodecanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene diacrylate, tetraethylene glycol dimethacrylate or combinations of two or more of these monomers or that the free-radically polymerizable organic (meth) acrylate monomers are free of structural units with aromatic radicals, in particular do not contain any structural units derived from bisphenol A.

35. Dental adhesive material kit according to one of claims 33 or 34, characterized in that a phase transfer catalyst and a reducing agent selected from the group of sulfites, in particular from the group of alkali metal sulfites and most particularly sodium sulfite and / or an oxidizing agent, preferably sodium persulfate is.

36. Use of the kit according to one of claims 16 to 35 for the manufacture and bonding of a core build-up material, a polymerizable composite cement and / or a bulk-fill composite for the manufacture of core build-ups, attachments and / or tooth fillings on at least one tooth.