Primer and kit consisting of primer and dental material

Abstract

To provide primers onto which polymerizable dental materials can be applied directly; and to provide kits of primers and polymerizable dental materials that are precisely matched to each other, thus simultaneously ensuring simplified processing and excellent adhesion conditions.SOLUTION: Provided is a liquid dental primer composition comprising: a polymerizable (meth)acrylate or (meth)acrylamide monomer having (i) at least one acidic group and (ii) at least one hydrophilic group; or two (meth)acrylate or (meth)acrylamide monomers, one of the (meth)acrylate or (meth)acrylamide monomers (i) having at least one acidic group and the other (ii) having at least one hydrophilic group. The liquid dental primer composition is characterized by the absence of a photoinitiator, a polymerization catalyst, and an organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a primer for bonding dental restorations to dentin and / or dental enamel, comprising a polymerizable (meth)acrylate or (meth)acrylamide monomer (i) with at least one acidic group, e.g., a phosphate group, and at least one hydrophilic group, e.g., a terminal hydroxy group, or two polymerizable (meth)acrylate or (meth)acrylamide monomers (ii). one of which (i) contains at least one acidic group and one of which (ii) contains at least one hydrophilic group, and the polymerizable (meth)acrylate or (meth)acrylamide monomer (i) and / or (ii) or further polymerizable (meth)acrylate or (meth)acrylamide monomer (iii) contains 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-polyfunctional groups, in particular in the form of terminal (meth)acrylate, (meth)acrylamide and / or aryl groups, in particular in the form of organometallic vanadium compounds, such as vanadyl(V) derivatives, or aromatic amines or organic solvents, without containing a photoinitiator or vanadium compound as a polymerization catalyst. [Background technology]

[0002] Polymerizable dental materials are often used in treatment procedures to restore destroyed natural tooth structure. The quality of the restored tooth's results is determined by the satisfaction of aesthetic and functional requirements. Therefore, from an aesthetic point of view, these dental materials must be visually distinguishable from the substance of natural teeth. However, in addition, they must also be sufficiently hard, and the build-up materials used must be fixed to the natural tooth so that the applied dental materials can withstand the high forces exposed during chewing.

[0003] Polymerizable dental materials used to build missing tooth structure are commonly referred to as core building materials. Preferably, hydrophobic methacrylic acid monomers are used in these materials. In practice in dental surgery, it has been shown that it is preferable if these core building materials are available in paste form so that dentists can build them in the patient's mouth and make models. Such models are usually applied in several layers, and after application, each layer is cured and thus polymerized. However, this procedure is very time-consuming due to the multiple curing steps.

[0004] In addition to constructing missing tooth structure, polymerizable dental materials are also used in so-called polymerizable composite cements. These cements are used for the anchoring of crowns and other dental replacement materials.

[0005] Finally, polymerizable dental materials are also used as so-called bulk filling composites, where the tooth cavity created after caries removal is filled with material.

[0006] As mentioned above, one of the requirements for polymerizable dental materials is to establish a strong bond between the applied material and the natural tooth structure, ensuring long-term stability under considerable mechanical demands. This adhesion can be achieved through the use of adhesives (dental bonding agents), which provide better wetting of the tooth substance and therefore better adhesion of the applied material. Typically, three different mechanisms of action are required for this purpose. Thus, in the first generation, such adhesives contained three components, which initiated different mechanisms of action in three stages, one after the other chronologically.

[0007] In the first step, the first component etches the natural tooth material, particularly the tooth enamel, to roughen its surface. For the inner tooth material, particularly dentin, the etching dissolves minerals from the collagen complex of the natural tooth material, leaving essentially only collagen fibers on the tooth surface. In the first step, typically, 35% by weight phosphoric acid is used, which is applied to the natural tooth material. The acid must then be removed by rinsing with water and then drying in air.

[0008] In the second step, adhesion between the applied dental material and the natural tooth tissue must be ensured. To this end, the etched tooth surface is coated with a so-called primer. This usually contains a hydrophilic monomer that can penetrate into the exposed collagen-fiber complex. The primer must then be cured.

[0009] Next, in the third step, sufficient adhesion must be ensured between the primer and the polymerizable dental material. This poses a problem if the primer contains hydrophilic monomers as described, but the dental material contains hydrophobic monomers. Therefore, an additional coating, known as a bonding agent, must first be applied to achieve sufficient adhesion between the polymerizable dental material and the natural tooth structure.

[0010] A particular drawback of the described method is the long processing time due to the three separate steps. Furthermore, the different substances have to be stored in different packaging, which increases the risk of contamination and mix-up.

[0011] In the past, products have been developed that combine one or more of the above steps in one substance or mixture of substances, thereby omitting at least one step. In a typical variant, etching is carried out first, and then a product is applied that contains both hydrophilic and hydrophobic monomers, thus combining the functions of primer and binder.

[0012] In another variant, etching can be combined with a primer, usually in which the hydrophilic monomers have phosphate groups that (slightly) etch natural tooth material, after which the material required for bonding is applied separately.

[0013] A further development of the adhesives mentioned above are so-called all-in-one adhesives, also known as "one-step adhesives" or one-step adhesion promoters. These incorporate all three of the above steps in one single step, thus combining the functions of etchant, primer, and bond in a single substance. This results in considerable time savings for the treating dentist and the patient. However, this advantage comes at the expense of the drawback that phosphate-containing monomers not only (slightly) etch natural tooth tissue but also subsequently react with applied polymerizable dental materials, thereby potentially interfering with the hardening of core building materials, cements, or bulk filling composites. Here, the amine co-initiator is protonated and therefore inactivated.

[0014] This is especially important because the hardening of polymerizable dental materials is itself a complex process: on the one hand, the applied polymerizable dental materials must be hardenable at moderate temperatures, since they are used in the patient's mouth. Therefore, redox initiators are usually used, which accelerate the hardening process at temperatures of about 37°C. Typically, redox initiator systems containing a percompound together with a coinitiator are used. Here, the percompound is present in the first paste as a so-called catalyst paste and in the second paste as a co-initiator in the so-called base paste. In use, the dental compound and the co-initiator are combined by mixing the pastes so that a redox reaction occurs that provides the radicals necessary for the polymerization of the organic monomers contained in the dental material. The pastes are usually stored separately from each other to ensure high storage stability.

[0015] For example, such dental materials having an inorganic peroxide initiator system, such as sodium peroxide or potassium peroxide in combination with an alkali or alkaline earth toluene sulfinate or alkali or alkaline earth sulfite, can be found in US Pat. No. 5,629,999.

[0016] Alternatively, light-curing dental materials containing photoinitiators can be used. The drawback is that the irradiated light cannot penetrate deeper layers of the dental material, so the treating dentist must apply these materials in thin layers. By modeling single individual layers and curing them multiple times with light, the processing time is significantly extended.

[0017] When the all-in-one adhesive and the polymerizable dental material described above with a redox initiator are used for treatment, insufficient polymerization usually occurs at the interface between the adhesive and the dental material. This is due, in particular, to the effect already described, whereby the phosphate group contained in the all-in-one adhesive protonates the amine used as a co-initiator, thereby converting it into an ammonium compound. As a result, the desired redox reaction between the original amine and the percompounds to initiate the polymerization reaction is prevented, resulting in insufficient curing at the interface between the adhesive and the polymerizable dental material. Therefore, in summary, the all-in-one adhesive usually reduces the adhesive strength of the dental material on the adhesive.

[0018] In order to improve the adhesive action between tooth structure and polymerizable tooth material with a redox initiator by means of an all-in-one adhesive, Patent Document 2 describes a composition that penetrates the lower stance of the tooth and uses the moisture contained in the tooth structure to promote the hardening of the tooth material. The described compositions contain a monomer mixture, inorganic peroxides, reducing agents, and other polymerization accelerators. The polymerization accelerators are dissolved by moisture on the tooth surface and improve polymerization cure at the adhesive interface and within the hardenable composition. Examples of such accelerators are sulfites, but also ammonium salts such as tetramethylammonium and tetraethylammonium salts of benzenesulfonic acid. Typically, the polymerization accelerator is present in the base paste.

[0019] Patent Document 3 describes adhesives for dental applications in which a polymerization accelerator, i.e., a water-soluble sulfite, is added as an additional co-initiator. The sulfite is dispersed in the polymerizable monomer and dissolved by the moisture in the tooth at the interface with natural tooth tissue. The additional reducing effect of the sulfite accelerates the hardening of the polymerizable dental material at the interface between the adhesive and the polymerizable dental material.

[0020] Patent Document 4 describes an adhesive and curable composition in the form of a core build-up material having high adhesion and resistance. The adhesive contains a monomer mixture, water, and an amine-based free sulfur reducing agent. The core build-up material also contains a monomer mixture, a water-soluble sulfur-containing reducing agent, an organic peroxide, and an amine-based sulfur-free reducing agent.

[0021] Finally, US Pat. No. 5,629,999 describes compositions which should ensure that sufficient hardening occurs both within the polymerizable dental material and at the interface with the adhesive, especially the all-in-one adhesive.

[0022] Nevertheless, the use of all these adhesives, all-in-one adhesives, and polymerizable dental materials remains problematic in that the adhesive must be cured after its application, which not only results in relatively long treatment times but also in time-consuming preparation procedures for the dentist to use. [Prior art documents] [Patent documents]

[0023] [Patent Document 1] International Publication No. 2014 / 033280 [Patent Document 2] European Patent Application Publication No. 2409997 [Patent Document 3] European Patent No. 1780223 [Patent Document 4] European Patent Application Publication No. 2554154 [Patent Document 5] German Patent Application Publication No. 102015103427 Summary of the Invention [Problem to be solved by the invention]

[0024] It is therefore an object of the present invention to provide a primer onto which a polymerizable dental material can be applied directly. In particular, it is an object of the present invention to provide a kit of primer and polymerizable dental material that are precisely matched to each other and therefore simultaneously ensure simplified processing and very good bonding conditions. [Means for solving the problem]

[0025] This object is solved by a primer having the features of claim 1.

[0026] Such aqueous primer compositions are self-etching and self-undercoating.

[0027] It comprises a polymerizable (meth)acrylate or (meth)acrylamide monomer having (i) at least one acidic group, e.g., a phosphate group, and (ii) at least one hydrophilic group, e.g., a terminal hydroxy group, or two polymerizable (meth)acrylate or (meth)acrylamide monomers, one of which (i) comprises at least one acidic group and one of which (ii) comprises at least one hydrophilic group. Furthermore, at least one of the polymerizable (meth)acrylate or methylacrylamide monomers comprises (i) a polyfunctionality, preferably at least 3 times polyfunctionality, particularly preferably 3, 4, 5, 6, 7, 8, 9 or 10 times polyfunctionality, and / or (ii) a further polymerizable (meth)acrylate or methylacrylamide monomer (iii) having multifunctionality. Preferably, the multifunctional group is at least 3-fold multifunctional, particularly preferably 3-fold, 4-fold, 5-fold, 6-fold, 7-fold, 8-fold, 9-fold or 10-fold multifunctional. This multifunctionality is inherent in the ability to polymerize. In particular, there are at least three, preferably terminal, (meth)acrylate, (meth)acrylamide and / or aryl groups.

[0028] Furthermore, this primer composition is characterized by the absence of the following substances: photoinitiators, vanadium compounds as polymerization catalysts, in particular organometallic vanadium compounds such as vanadyl(V) derivatives, aromatic amines, and sulfinates and sulfonates, in particular aromatic sulfonates, such as sodium-4-toluenesulfonate. The primer composition according to the present invention is also characterized by the absence of organic solvents.

[0029] In the sense of the present invention, the term "multifunctional" relates to the ability to polymerize and therefore the crosslink density. For example, a monomer with trifunctionality contains three polymerizable groups.

[0030] This composite composition possesses the ability to initiate a polymerization reaction by diffusing a reducing agent (sodium sulfite) into the claimed primer composition after its application. Thus, polymerization is no longer initiated by a catalyst and / or initiator contained in the composition itself, but rather is based on a diffusion-based material transport. Therefore, dentists can prepare the tooth for application of the dental material, subsequently apply the dental material, and achieve hardening of the entire system in a single step, without the risk of premature hardening.

[0031] Additionally, the addition of polymerization catalysts (copper and / or iron compounds) in the primer composition and / or inorganic, water-soluble oxidizing agents (e.g., sodium persulfate) in the composite composition can accelerate curing and improve adhesive bonds at the interfaces between the primer and the composite, as well as between the primer and the dentin.

[0032] Furthermore, it has been shown to be preferable if iron and / or copper compounds are added. Preferably, the iron here is in the oxidation state +II or +III and the copper is in the oxidation state +I or +II.

[0033] The iron compound may be an inorganic iron compound such as, in particular, iron halide, iron sulfate, iron nitrate, iron perchlorate, iron phosphate, iron pyrophosphate, iron tetrafluoroborate and / or iron thiocyanate. Also possible are organometallic iron compounds, such as, in particular, iron acetylacetonate, iron carboxylates, for example iron 2-ethylhexanoate, iron acetate, iron oxalate, iron ethylenediaminetetraacetate, iron citrate, iron phthalocyanine, iron gluconate, iron ascorbate, iron lactate, iron fumarate, iron tartrate, iron methacrylate and / or iron alkoxides.

[0034] Likewise, inorganic copper compounds such as copper halides, copper sulfate, copper nitrate, copper perchlorate, copper phosphate, copper pyrophosphate, copper tetrafluoroborate and / or copper thiocyanate, among others, can be used. This is especially true for organometallic copper compounds such as copper acetylacetonate, copper carboxylates, e.g. copper 2-ethylhexanoate, copper acetate, copper oxalate, copper ethylenediaminetetraacetate, copper citrate, copper phthalocyanine, copper gluconate, copper ascorbate, copper lactate, copper fumarate, copper tartrate, copper methacrylate and / or copper alkoxides.

[0035] Surprisingly, it has now also been found possible to achieve very good adhesion values ​​for the claimed systems, which still stand even after an artificially simulated ageing process.

[0036] In particular, after thermocycling, especially after the thermocycling described in detail with respect to the embodiments, the adhesion values ​​still exceed values ​​of >10 MPa with a variance of 4 MPa. Particularly preferred, such systems have adhesion values ​​of >12 MPa with a variance of 4 MPa. Particularly preferred are systems in which the adhesion values ​​do not deviate by more than a variance of 4 MPa.

[0037] In the sense of the present invention, the terms (meth)acrylamide group and (meth)acrylate group should be understood to mean both methacrylamide and acrylamide groups, as well as methacrylate and acrylate groups.

[0038] Regarding the monomers used, it is possible to use a single monomer that contains both a multifunctional group, in particular a (meth)acrylate or (meth)acrylamide group that can be polymerized 3, 4, 5, 6, 7, 8, 9 or 10 times, and an acidic, optionally additional hydrophilic group.Here, it should be noted that the acidic group can also always be understood as a hydrophilic group.Preferred examples for this are:

[0039] [ka]

[0040] In this case, acidic groups must be understood as the same hydrophilic groups.

[0041] Examples of monomers further comprising additional hydrophilic groups are 1-mono(methacrylate)-1-phosphate-1-hydroxytrimethylethane or -propane, or sorbitol tri(meth)acrylate monophosphate monohydroxide.

[0042] [ka]

[0043] [ka]

[0044] Furthermore, there can be two monomers, where the monomer containing additional multifunctionality contains an acidic or hydrophilic group, while the second monomer contains at least one functionality in the form of an acidic or hydrophilic group, respectively.

[0045] Finally, it is still possible to use three different monomers, namely a monomer with a crucial multifunctional group, a monomer with an acidic group and a monomer with a hydrophilic group. Here, the main structure of all the monomers used is the result of considering that a main chain, a so-called spacer group, is provided. Each group is present on this spacer group. The following table shows preferred skeleton structures, and X indicates the position of each functional group. Here, X can represent the same group, or different groups R1 to Rn.

[0046] [Table 1]

[0047] Additionally, cyclic aromatic hydrocarbons, cycloalkanes, aliphatic polyethers, PEG, PPG, PTMEG, paraformaldehyde and alkanes can be used as spacers.

[0048] Typically, the link between the backbone, the so-called spacer, and the functional group can be realized by a linking group, the so-called linking element, which can be, in particular, (a) a carboxylic acid ester, urethane and / or amide group.

[0049] Thus, a multifunctional monomer having, for example, trifunctionality as well as additional hydrophilic groups would have the following structure:

[0050] [ka]

[0051] By functional groups in the sense of polyfunctionality, in particular styrene, methacryl, acrylic, aryl, methacrylamide and / or acrylamide groups in any combination are to be understood, which groups are capable of radical polymerization.

[0052] As acidic groups in the sense of the present invention, in particular carbonate, sulfate, sulfonate, sulfinate, phosphate, phosphonate, phosphinate groups are to be understood, or the monomer is selected as at least one monomer from the group comprising:

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] These ensure sufficient (slight) etching of tooth substance.

[0060] Hydrophilic groups in the sense of the present invention are to be understood as at least hydroxyl, amino, amine, thiol, hydrochloride or polyether groups. With regard to the hydrophilic groups, it is indicated that it is particularly preferred if the hydrophilic groups are n-bonded hydroxyl or n-bonded amine or main chain-bound polyether groups (polyhydroxyl groups, polyamine groups and main chain-bound polyether groups) due to their increased functionality.

[0061] Here, particularly preferably, [ka] is used.

[0062] Preferably, the claimed primer composition is a single component composition, as this keeps handling as simple as possible for the dentist.

[0063] Furthermore, in a preferred embodiment of the present invention, the pH value of the monomer mixture is ≦3.5, preferably ≦2.5, particularly preferably 1.5 to 2.5, but in any case, the lower limit does not necessarily have to be 1.5 or more.

[0064] In an embodiment according to the invention, the portion of polyfunctional monomers is between 0.1 and 10% by weight, preferably between 1 and 5% by weight, which ensures particularly good polymerization.

[0065] In a preferred embodiment, the composition according to the invention comprises 15 to 35% by weight, preferably 20 to 30% by weight, of MDP (GDMAP, 4-META, A-MDP, PMGDM) moieties, 0.05 to 5% by weight, preferably 0.05 to 2% by weight, of BHT moieties, 0.05 to 0.5% by weight, preferably 0.1 to 5% by weight, of 2-dimethylaminoethyl methacrylate (DMAEMA), hydroquinone monomethyl ether (MEHQ), pyrocatechol derivatives and / or HALS (sterically hindered amines), and 25 to 35% by weight, preferably 27 to 33% by weight, of water (preferably deionized).

[0066] Furthermore, particularly advantageously, portions of 0.05 to 10% by weight, preferably 1 to 5% by weight, of polyfunctional monomers are added, such as trimethylpropane trimethacrylate (glycerol propoxy triacrylate), pentaerythritol trimethacrylate, sorbitol pentamethacrylate GE-NOMER*® 4691, N,N-diarylmethacrylamide, N,N-isovalerylidenebismethacrylamide. The portion of HEMA (N-2-hydroxyethyl methacrylamide), N-(2-hydroxypropyl) methacrylamide corresponds to a difference of 100% by weight.

[0067] In this context, it is particularly important that the polyfunctional monomers used are soluble in the mixtures containing them, in particular in mixtures of water with monomers containing acidic groups and / or monomers containing hydrophilic groups. Particularly preferably, it is soluble in water, in a mixture of MDP or one of its derivatives and HEMA or one of its derivatives, particularly preferably in the abovementioned quantitative ratios.

[0068] The composition may also contain at least one inorganic or organic peroxide compound, 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 peroxide compound is a diacyl peroxide, particularly benzoyl peroxide, preferably dibenzoyl peroxide. Further examples of suitable peroxides include m-toluoyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxide)hexane, tert-butylperoxy-2-ethylhexanoate, and tert-butylperoxyisopropyl carbonate. Examples of suitable peroxide esters include tert-butyl peroxybenzoate and bis-tert-butylperoxyisophthalate. 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 peroxyketones 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.

[0069] Preferably, the primer according to the present invention contains one or more additives, preferably buffer salts, metal scavengers, surfactants, active ingredients, flavoring and / or odorizing agents, fluorinating agents, bleaching substances, desensitizing agents, adhesive bond promoters, dyes, color pigments, indicators, further initiators or initiator components, stabilizers, polymerization inhibitors, thixotropic aids, and antimicrobial substances or a combination of two or more thereof.

[0070] Furthermore, it is an object of the present invention to provide a kit in which the primer according to the invention can be used together with a two-component paste complex, thus achieving optimum adhesive results.

[0071] Such kits include the described primer as well as 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, one coinitiator for radical polymerization, and at least one salt-like, water-soluble, and powder-like reducing agent dispersed in the base paste (B) (hereinafter also: reducing agent). Furthermore, at least one phase transfer catalyst is provided in the at least one catalyst paste and / or at least one base paste, which is preferably an ammonium, phosphonium and / or sulfonium salt containing an inorganic or organic anion, with the exception of anions of sulfinic or sulfonic acids.

[0072] The use of the phase transfer catalyst according to the present invention improves adhesion to tooth structure, which can be explained by the fact that the salt-like, water-soluble powder reducing agent is dissolved at the interface with the primer, and then diffuses through the phase transfer catalyst at the interface between the composite and the primer, achieving accelerated polymerization by reaction with the peroxygen compound. By dividing the polymerizable dental material into at least one catalyst paste and at least one base paste, high storage stability is achieved. Mixing these individual components produces a polymerizable dental material that hardens rapidly under the conditions present in the mouth (corresponding temperature and humidity).

[0073] Preferably, the portion of the phase transfer catalyst in the catalyst paste and / or base paste is 0.01 to 5% by weight, preferably 0.01 to 2% by weight, particularly preferably 0.05 to 1% by weight, and particularly preferably 0.05 to 0.5% by weight, based on the total mass of the catalyst paste and / or base paste. The stated weight portion of the phase transfer catalyst in the catalyst paste and / or base paste, based on the total mass of the catalyst paste and / or base paste, must be selected low so that the hardening of the polymerizable dental material is not so rapid that processing of the dental material is complicated or even hindered. At the same time, the mentioned weight fraction must be selected to be high so that polymerization of the dental material within the dental material bulk is promoted as intended.

[0074] According to a preferred embodiment of the present invention, the phase transfer catalyst is contained in a catalyst paste. With regard to storage stability, this has proven to be particularly advantageous, since potential activation of the reducing agent present in the base paste with the phase transfer catalyst and the subsequent reaction of the reducing agent with oxygen from the air can be prevented, as described above.

[0075] For further stabilization, a desiccant can be added. Examples of desiccants for this purpose include silica gel, zeolites, alumina, calcium oxide, calcium sulfate, potassium carbonate, potassium hydroxide, copper sulfate and / or sodium hydroxide. Examples of bases include sodium hydroxide, calcium hydroxide, and calcium oxide.

[0076] According to the present invention, the reducing agent is a substance which, when combined with a peroxygen compound, forms a redox system suitable for initiating the radical polymerization of polymerizable (meth)acrylic monomers. Furthermore, reducing agents impair the reaction of radicals and growing polymer chains with diradical oxygen, which can lead to termination of the polymerization reaction by reaction of the reducing agent after dissolution with oxygen.

[0077] In the sense of the present invention, a water-soluble substance means that the substance has a solubility in distilled water at a temperature of 25° C. of at least 10 g / L, preferably at least 15 g / L, particularly preferably at least 30 g / L, and particularly preferably at least 50 g / L.

[0078] Preferably, the reducing agent is selected from the group of sulfites, in particular from the group of alkali metal sulfites, alkaline earth metal sulfites, (NH4)2SO3, hydrogen sulfites, disulfites, thiosulfites, thionates and dithionites. Particularly preferably, sodium sulfite is used as reducing agent.

[0079] The reducing agents mentioned have been shown to be particularly suitable for the present invention since they have low solubility in the organic monomers and are present in the base paste in dispersed form, but can be particularly well introduced into the organic monomers by the phase transfer catalysts used according to the present invention.

[0080] The weight portion of the reducing agent, based on the total weight 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 particularly preferably (2±1)% by weight. In at least one base paste, a coinitiator suitable for initiating the polymerization reaction of the organic (meth)acrylic monomer and the peroxygen compound, independent of the reducing agent, is provided.

[0081] Preferably, the coinitiator is selected from the group of primary, secondary and / or tertiary amines, in particular secondary and / or tertiary amines. Examples of suitable secondary amines and / or suitable tertiary amines are 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.

[0082] The proportion by weight of coinitiator used is preferably less than 5% by weight, particularly preferably less than 2% by weight, particularly preferably less than 1.5% by weight, based on the total mass of the at least one base paste, but in any case more than (0.1±0.05)% by weight, preferably more than (0.8±0.05)% by weight.

[0083] Preferably, the peroxygen compound is a peroxide, peroxide ester, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyketone, or hydroperoxide.

[0084] The peroxygen compound used must be determined so that the peroxygen compound combined with the reducing agent and coinitiator forms a redox system suitable for initiating the radical polymerization of the organic (meth)acrylic monomer. In other words, the redox potentials of the peroxygen compound and the reducing agent and / or coinitiator must be adjusted to each other so that a redox reaction occurs between them, forming radicals that initiate the polymerization of the (meth)acrylic monomer.

[0085] In a preferred embodiment, the organic peroxide compound is a diacyl peroxide, particularly benzoyl peroxide, preferably dibenzoyl peroxide. Further examples of suitable peroxides include m-toluoyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxide)hexane, tert-butylperoxy-2-ethylhexanoate, and tert-butylperoxyisopropyl carbonate. Examples of suitable peroxide esters include tert-butylperoxybenzoate and bis-tert-butylperoxyisophthalate. 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 peroxyketones include ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide. Examples of suitable hydroperoxides include tert-butyl hydroperoxide, cumene hydroperoxide, and p-diisopropylbenzene peroxide.

[0086] The weight portion of the peroxide compound is preferably less than 5% by weight, particularly preferably less than 2% by weight, particularly preferably less than 1% by weight, particularly preferably (1.0±0.2)% by weight, based on the total mass of the at least one catalyst paste.

[0087] The above-mentioned redox initiator system can also be supplemented with at least one additional initiator system.Therefore, for example, at least one photoinitiator or at least one heat-activatable radical initiator, such as an azo compound, can be provided in the polymerizable dental material.These additional initiator systems can be provided in at least one catalyst paste and / or at least one base paste.Those skilled in the art are familiar with such initiator classes.

[0088] The photoinitiator preferably provided allows the practitioner to quickly cure with a polymerization lamp at any time. Typically, camphorquinone and aromatic amine photoinitiator systems are used for light curing of dental materials. When irradiated with blue light having a wavelength in the range of 470 nm, such a mixture generates radicals that completely cure the material in less than one minute. Photoinitiators may be present in the catalyst paste and / or the base paste.

[0089] Suitable photoinitiators are, for example, secondary and tertiary amines, and optionally mono- and bisacylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis-(2,6-dichlorobenzoyl)-4-n-propylphenylphosphine oxide, and diketones, such as camphorquinone, in particular D,L-camphorquinone, associated with benzaldehyde, Ivocerin, BAPO, TPO, etc.

[0090] The weight portion 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, particularly preferably (0.09±0.04)% by weight.

[0091] In particular for the use of polymerizable dental materials as core build-up materials and as polymerizable composite cements, it is preferred if both a redox initiator system and a photoinitiator are provided. Such polymerizable dental materials are also called dual-curing materials.

[0092] In a preferred embodiment of the present invention, the (meth)acrylic monomer is selected from the group of acrylamides and / or acrylates and / or methacrylates (summarized as (meth)acrylates). Here, both difunctional or higher acrylic and methacrylic acid esters or monofunctional (meth)acrylic acid esters can be provided.

[0093] Preferred examples of radically polymerizable organic (meth)acrylic monomers include aromatic groups containing acrylate or methacrylate, aliphatic groups containing acrylate or methacrylate, polyether groups containing acrylate or methacrylate, polyester groups containing acrylate or methacrylate, polyurethane groups containing acrylate or methacrylate, and combinations of two or more of these monomers.

[0094] Examples of suitable (meth)acrylates are bisphenol A di(meth)acrylate, bis-GMA (addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxylated bisphenol A di(meth)acrylate, UDMA (an isomeric mixture 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 glycerin-1,3-dimethacrylate (GDMA), as well as ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, glycidyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxy-ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, neopentyl glycol 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-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,16-Hexadecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetraethylene glycol di(meth)acrylate, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate; mono- or polyethylene 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 derivative includes both branched and linear structures.

[0095] In addition, with regard to the (meth)acrylic compounds, (meth)acrylic compounds having a urethane bond are encapsulated as an example of a mixed component. Suitable examples include di-2-(meth)acryloxyethyl-2,2′,4-trimethylhexamethylene dicarbamate, di-2-(meth)acryloxyethyl-2,4,4′-trimethylhexamethylene dicarbamate, and 1,3,5-tris[1,3-bis{(meth)-acryloyloxy}-2-propoxycarbonylaminohexane]-1,3,5-(1H,3H,5H)triazine-2,4,6-trione. Further examples include (meth)acrylates of urethane oligomers derived from 2,2'-di(4-hydroxycyclohexyl)propane, 2-oxepanone, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, and (meth)acrylates of urethane oligomers derived from 1,3-butanediol, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate. These (meth)acrylates can be used alone or as a mixture of two or more in combination with a polymerizable dental material.

[0096] The phase transfer catalyst is selected from the group of ammonium, phosphonium and / or sulfonium salts with inorganic or organic anions, excluding anions of sulfinic and sulfonic acids. The salts used can be both water-containing and water-free salts.

[0097] Suitable examples of heterocyclic ammonium salts include N(aryloxycarbonyloxy)succinimide, 3-benzyl-5-(2-hydroxyethyl)-4-methyl-thiazolium chloride, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1,3-didecyl-2-methylimidazolium chloride, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide, hexacylpyridinium chloride, 5-(2-hydroxyethyl)-3,4-dimethylthiazolium iodide, 1-methylimidazolium hydrogen, viologen methyl dichloride, and 1,2,3-trimethylimidazolium salts.

[0098] Commercially available phase transfer catalysts can also be used in the present invention. Suitable examples include quaternary ammonium salts such as Aliquat® 336 (wherein R1 is methyl and R2, R3 and R4 are octyl and / or decyl, with octyl being particularly present), or Arquad® 2HT75.

[0099] Examples of preferred anions are anions selected from the group of halides, hydroxides, anions of inorganic acids, anions of organic acids (excluding anions of sulfinic acids and sulfonic acids), pseudohalogen anions or halogen complexes of aluminates, silicates, phosphates or arsenates.

[0100] Particularly preferred anions include fluoride, chloride, bromide, iodide, hydroxide, sulfate, sulfate tartrate, phosphate bitartrate, phosphate, phosphonate, borate, chlorate, perchlorate, chlorite, nitrate, carbonate tartrate, carbonate, tetrafluoroborate, tetrachloroaluminate, hexafluorosilicate, hexachloroarsenate, formate, acetate, butyrate, fumarate, maleate, glutarate, lactate, malate, malonate, oxalate, pyruvate or tartrate.

[0101] The following anions have been shown to be particularly preferred: hydrogen sulfate, sulfate, dihydrogen phosphate, chloride and tetrafluoroborate.

[0102] Fillers for the catalyst paste and base paste can be inorganic or organic. The fillers can be reinforcing or non-reinforcing fillers or mixtures thereof.

[0103] Particularly for highly dispersed reinforcing fillers, at least 50m 2 Active fillers with a BET surface area of ​​10 ...

[0104] More preferably, the at least one reinforcing filler is present in the form of nanoparticles, as a fibrous or foliar filler, for example as a fibrous mineral filler or as a fibrous synthetic filler.

[0105] The proportion of the reinforcing filler in the dental material according to the present 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 weight of the dental material.

[0106] In principle, the same materials as the reinforcing fillers are suitable for the non-reinforcing fillers, except that the non-reinforcing fillers are necessarily 50m 2 / g (Technical Bulletin Pigmente Degussa Kieselsauren, p. 12, p. 5 and p. 13, p. 3). Preferred non-reinforcing fillers are materials selected from the group consisting of alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal fluorides, alkaline earth metal carbonates, in particular calcium apatite (Ca5[(F, Cl, OH, ½CO3)]|(PO4)3), especially calcium hydroxylapatite (Ca5[(OH)|(PO4)3]), titanium dioxide, zirconium oxide, aluminum hydroxide, silicon dioxide, precipitated silica, calcium carbonate and dental glasses (barium, strontium, aluminum, fluoride).

[0107] Particularly for bisphenol A-free monomer compositions that are also aromatic-free, composite non-reinforcing fillers having a refractive index of less than 1.55 are preferred. Particularly for bulk-filled composites, particle sizes of 1.5 μm or less are preferred. Of course, the above compounds can be used alone or in any combination with one another, i.e. in hydrophilic as well as hydrophobized form. Preferably, the non-reinforcing fillers used have an average particle size of greater than 0.1 μm (Ullmann Enzyklopadie der Technischen Chemie, Vol. 21, p. 523).

[0108] The proportion of the non-reinforcing filler in the dental material according to the present 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 weight of the dental material. The total amount of reinforcing and non-reinforcing fillers in the dental material according to the present invention is usually 0.1 to 80% by weight, preferably 0.5 to 80% by weight, particularly preferably 1 to 75% by weight, and particularly preferably 5 to 70% by weight, based on the total amount of the dental material.

[0109] Additionally, higher amounts of selected radiopaque fillers may be present in the at least one base paste and / or the at least one catalyst paste. Preferably, these fillers are irregularly shaped or spherical YbF3 or YF3 powders with an average primary particle size of 40 nm to 1.5 μm, particularly preferred are core-shell combination products consisting of a YF3 or YbF3 core and an SiO2 shell, particularly preferred is a silanized surface of the SiO2 shell. In particular, such core-shell bonded products have a refractive index of 1.48-1.54 measured with a particle size measuring laser diffraction instrument SALD-2001 (Schimadzu), an average particle size of the aggregates of 0.5-5 μm, and a specific BET surface area of ​​2 m, measured with a Micromeritics Tristar 3000 instrument. 2 / g~5m 2 / g. Here, the refractive index of the core-shell combination product consisting of a YbF3 core and a SiO2 shell is 1.52-1.54.

[0110] Preferably, the at least one base component and / or the at least one catalyst component contains one or more additives, preferably buffer salts, water scavengers, metal scavengers, metal complexing agents, further paste-forming agents, surfactants, active ingredients, substances allowing optical scanning, flavoring and / or odorizing agents, substances allowing diagnosis, substances capable of etching tooth material, and / or substances having an adhesive effect, such as MDP or A-MDP, fluorinating agents, bleaching agents, desensitizing agents, adhesive bond promoters, dyes, colorants, color pigments, indicators, further initiators or initiator components, stabilizers, polymerization inhibitors, thixotropic auxiliaries, and antibacterial substances or a combination of two or more thereof.

[0111] The weight portion of the additive, based on the total mass of the at least one base component and / or at least one catalyst component, is usually 0 to 20% by weight, preferably 0.0001 to 15% by weight, particularly preferably 0.001 to 10% by weight, based on the total mass of the respective components.

[0112] An advantageous use of the polymerizable dental material according to the invention is the production of core build-up materials, polymerizable composite cements and / or bulk filling composites. Specifically, the described kits also include kits which, in addition to the described components, also contain the following dental adhesion promoter compositions, in particular single-component compositions for the pretreatment of restorative surfaces (e.g., glass ceramics, oxide ceramics, metals). Preferably, these further primers consist of (i) one or more alkoxysilane monomers (e.g., MPS) and / or (ii) one or more acidic monomers (e.g., phosphate or carboxylic acid ester monomers (e.g., MDP and 4-META)) and / or (iii) one or more sulfur-containing monomers (e.g., 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol (short, VBATDT)) and / or one or more stabilizers (e.g., BHT and / or MEHQ and (V) organic solvents).

[0113] Therefore, a composition containing an organic hydroperoxide compound having five or more carbon atoms and at least one hydroperoxide group bonded to a tertiary carbon, a thiourea system, and a filler is also possible as a dental adhesive material, a dental composite resin, or a dental cement containing a radically polymerizable monomer without an acidic group, and also contains an acidic component added in an amount approximately equal to the total mass of the monomer, hydroperoxide, and thiourea system. Here, catalyst paste A contains an organic hydroperoxide, a radically polymerizable monomer, preferably methyl acrylate, and a filler, and base paste B contains thiourea, the same or another radically polymerizable monomer, preferably methyl acrylate, and a filler.

[0114] Examples of radical polymerizable monomers having no acidic group are aromatic radical polymerizable monomers (having no acidic group) and aliphatic radical polymerizable monomers having no acidic group. The radically polymerizable monomers without acidic groups may be mono-, di- or trifunctional, or may be characterized by even higher functionality. Examples of monofunctional aromatic radically polymerizable monomers containing no acidic group are benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, and neopentyl glycol-(meth)acrylic acid-benzoic acid.

[0115] An example is an ester. The difunctional aromatic radical polymerizable monomer containing no acidic group has a hydroxyl group in the molecule and a hydroxyl group in the molecule.

[0116] The preferred amount of the monomer, particularly the hydrophilic monomer, in the catalyst paste and base paste is 0.1 to 20% by weight, preferably 5 to 15% by weight. Hydroperoxide compounds, preferably having five or more carbon atoms and at least one hydroperoxide group attached to a tertiary carbon, are the components used as oxidizing agents in redox polymerization initiators.

[0117] Examples of hydroperoxide compounds useful in the present invention having five or more carbon atoms and containing at least one hydroperoxide group attached to a tertiary carbon are isopropylbenzene hydroperoxide, t-amyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di-(hydroperoxy)hexane, p-diisopropylbenzene monohydroperoxide, p-menthone hydroperoxide, and pinane hydroperoxide. These may be used alone or in combination of two or more. Among these, it is preferable to use isopropylbenzene hydroperoxide, cumene hydroperoxide and / or 1,1,3,3-tetramethylbutyl hydroperoxide.

[0118] The amount of the hydroperoxide compound mixed is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, of the total mass.

[0119] Pyridylthiourea or its derivatives are preferably used as the thiourea, which acts 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. Particularly preferred is (2-pyridyl)thiourea. The amount of pyridylthiourea or a derivative thereof 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. Here too, the fillers used are those already mentioned.

[0120] It is contemplated that an acidic compound may be added to activate the hydroperoxide compound. However, if the hydroperoxide compound is too strongly activated, the storage stability and working time of the adhesive kit will be impaired. Therefore, in the present invention, the amount of mixing is limited. Examples of the acidic compound are a phosphoric acid group, a phosphoric acid monoester group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a phosphonic acid monoester group, a carboxylic acid group, an acid anhydride group, a sulfonic acid group, and sulfur. Examples are organic compounds having an acidic group (eg, an acid group), and inorganic acids (eg, hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid).

[0121] Furthermore, it is possible here to add vanadium and / or copper compounds. These polymerization catalysts are preferably present in the base paste B. Examples of vanadium compounds are vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearic acid, vanadium naphthenate, vanadium benzoylacetonate, vanadium oxalate, bis(maltobase) oxovanadium(IV), oxobis(1-phenyl-1),3-butanedionate), vanadium(IV), vanadium(V), trioxyisopropoxide, ammonium(V) metavanadate, sodium(V) metavanadate, vanadium(V) pentoxide, and ditetraoxide. Examples are vanadium(IV) and vanadyl(IV) sulfate.

[0122] The solubility of the particular compound is a prerequisite. Combinations of different vanadium compounds are possible. Preferably, the copper compound is a compound that is soluble in the radically polymerizable monomer. Specific examples thereof include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper tartrate, copper, copper oleate, copper octylate, copper octenoate, copper methacrylate, and copper 4-cyclohexylbutyrate; β-diketone coppers: copper acetylacetone, copper trifluoroacetylacetone, copper hexafluoroacetylacetone, copper 2,6,6-tetramethyl-3,5-heptanedionate, and copper benzoylacetone; β-ketoester coppers: copper acetoacetate; copper alkoxides: copper methoxide, copper ethoxide, copper isopropoxide, copper isopropoxide, and copper 2-(2-butoxyethoxy)ethoxide; and copper 2-(2-methoxyethoxyethoxy)ethoxide. Dithiocarbamic acids include copper and copper dimethyldithiocarbamate; and salts of copper and inorganic acids.

[0123] Additionally, it is also possible to use a phase transfer catalyst, as already mentioned.

[0124] In both described kit systems, it is further shown that it is preferable if an additional oxidizing agent is used. Particularly preferred here are peroxides such as alkali persulfates, for example sodium persulfate, potassium persulfate, or alkaline earth persulfates, for example calcium persulfate and ammonium persulfate. Also preferred are alkali percarbonates, such as sodium percarbonate, potassium percarbonate, or alkaline earth percarbonates or percarbonates such as ammonium percarbonate. Also preferred are perborates, such as sodium perborate, alkaline earth perborates or ammonium perborate, or alkali metal peroxides, such as lithium peroxide, sodium peroxide, potassium peroxide or alkaline earth metal peroxides.

[0125] The present invention therefore also relates to a modular system (kit of parts) comprising the above-mentioned component primer (single-component primer) and dental material (single-component or two-component complex) and optionally further primers.

[0126] In a modular system (kit of parts) or in short in each kit, it seems reasonable to use for other components, bulk fill complexes, long chain monomers to reduce stress and shrinkage, independent of the monomers used for the primer. These may consist of long-chain spacer groups (e.g., alkyl, cycloalkyl and / or aryl ether groups, polybutadiene, polyethylene glycol, polypropylene glycol, polytetrahydrofuran) to which at least one polymerizable group (e.g., (meth)acrylate, (meth)acrylamide, aryl, styrene) is attached at its side or terminal end. Furthermore, an additional linking group such as a urethane, amide, carbonate ester, or carboxylic acid ester group may be included between the spacer group and the polymerizable group. Additionally, functionality can be further increased by incorporating one or more backbone structures (table list of possible backbone structures) anywhere between the spacer, linking group and / or polymerizable group. Preferably, in all the described kits, the following are suitable as photoinitiators: alpha diketones and their derivatives, such as 9,10-phenanthrenequinone, in particular D,L-camphorquinone, 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. Additionally, organometallic photoinitiators, 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, are suitable.

[0127] The present invention also relates to a dental cured product obtained by mixing the catalyst paste (A) according to the present invention with the base paste (B) preferably in a ratio of 1:20 to 1:1, and polymerizing the polymerizable dental material.

[0128] The present invention also relates to the use of a polymerizable dental material containing at least one above-mentioned catalyst paste (A) and at least one above-mentioned base paste (B) for the production of a core build-up material, a polymerizable composite cement and / or a bulk-fill composite for the production of a core build-up, a luting fixation and / or a tooth filling.

[0129] The present invention also relates to a dental cured product obtained by mixing the catalyst paste (A) according to the present invention with the base paste (B) preferably in a ratio of 1:20 to 1:1, and polymerizing the polymerizable dental material.

[0130] The present invention also relates to hardened dental materials, in which only a single-component system is used for both the primer and the composite, for the production of core build-up materials, polymerizable composite cements and / or bulk-fill composites, for the production of core build-up, luting and / or tooth filling materials.

[0131] Further developments, advantages and possible uses of the invention also result from the following drawings and description of embodiments. All features described and / or depicted herein, by themselves or in any combination, form the subject matter of the invention independently of their abstracts in the claims or their background literature. [Example]

[0132] Preparation of the primer composition The raw materials used, BHT, DMAEMA (DMAPMA), acidic adhesive monomers (MDP, GDMAP, etc.), monofunctional monomers (HEMA, A-HEMA), and depending on the respective recipes, none or one polyfunctional monomer were weighed into a mixing can (PP 30 cup, transparent, Hauschild, Germany) according to the recipe of each example, and mixed homogeneously for 1 minute at 3500 r / min (Speedmixer DAC 150 FVZ, Hauschild, Germany). Subsequently, the amount of deionized water specified in each example was added, and the mixture was homogenized again in a Speedmixer at 3500 r / min for 1 minute. Here, the polyfunctional monomers were used in the same molar ratios, in other words, in the same amounts of material.

[0133] Sample preparation For testing of adhesive bond strength, fractured permanent molars from humans were used and near-surface dentin, i.e., dentin as close as possible to the tooth enamel, was used to keep variability as low as possible. The teeth were stored in a 0.5% aqueous solution of chloramine-T in a refrigerator at 2-8°C, and they were rinsed thoroughly with running water before preparation of the tooth surface. For sample pretreatment, the teeth are embedded in a suitable material (Vari-Kwick liquid (LOT: 2013004123)) and surface preparation is achieved by polishing with an automatic grinding machine equipped with a rotating grinding disc and an automatic water supply. For this purpose, silicon carbide abrasive paper of grit grade P400 is used in order to prepare a sufficiently large adhesive bond area according to ISO 6344-1. After polishing, the embedded tooth is thoroughly washed with water to remove any foreign matter, such as remaining abrasive particles. The prepared surface must then be used for testing within four hours.

[0134] For the test, the teeth are rinsed under running water for 10 seconds. The water is then remobilized with filter paper or by a soft / short burst of oil-free and water-free compressed air just prior to adhesive application. The adhesive is applied evenly over the entire prepared tooth surface and rubbed in for 20 seconds. The tooth is then inserted into a combination screw clamp containing a white insert for the composite cylinder with a hole diameter of (2.38±0.03) mm. The fill recess of the mold is centered over the tooth location suitable for the adhesive bonding composite, ensuring that the adhesive bonding location consists of only the intended dentin. The mold is then lowered onto the surface of the tooth. In all cases, the complex used was a complex prepared according to Example 3 of DE 102015103427 A1 (respectively composition 2).

[0135] The base paste has the following composition:

[0136] [Table 2]

[0137] The composite catalyst paste has the following composition:

[0138] [Table 3]

[0139] During this process, it is introduced into the mold, spread onto the adhesive bonding surface, and cured in a drying cabinet at 37°C for 6-7 minutes. No light curing with an external light source is performed.

[0140] Storage of the composite specimens for 24 (±2) hours is achieved in water at 37 (±2)° C. Immediately after removing the specimens from the water, the composite strength of the specimens is tested.

[0141] For each example, 10 teeth are prepared in the described manner.

[0142] Thermal cycle Five of the ten teeth were subsequently subjected to a temperature-change stress test, in which the five specimens were subjected to 5000 cycles of thermomechanical loading in a thermal cycling machine (Thermocycler THE 1200, SD Mechatronik GmbH, Feldkirchen-Westerham, Germany) in alternating baths between cold water at 5 (±1) °C and hot water at 55 (±1) °C. Here, the specimen remained in each of both baths for 30 seconds, with a 5 second drip-off period in between.

[0143] Adhesion value measurement The measured adhesion values ​​were determined by means of a shear test method that can measure the combined shear strength between the dental material and the dental tissue, which method is described for dental adhesives in standard DIN EN ISO 29022.

[0144] The test equipment used was a "shear-off device with a concave blade" (Zwick Universal Testing Machine, Zwick, Ulm, Germany). Immediately after removal from the water, the composite specimen was clamped in a metal sample holder. A load was applied to the specimen at a transverse main speed of 1.0 mm / min until the specimen broke, and the maximum force (F) before the composite broke was recorded. The shear bond strength (shear stress) is calculated using the following formula:

[0145] σ = F 2 A -1 where: σ: shear stress in MPa (megapascals) F: Maximum measured force (N) A:mm 2 Unit adhesive area

[0146] With a given diameter of 2.38 mm for the composite cylinder, the adhesive bond area was 4.45 mm for all measurements performed. 2 is.

[0147] Measurements were performed on five of the ten teeth immediately after the storage period described to determine the initial bond value, and on the five previously thermally cycled teeth in the same manner. A single value for shear bond strength, as well as the mean and standard deviation of all five measurements, were determined and recorded. Here, a variation in measurement accuracy of approximately 4 MPa is shown. The following values ​​in the examples represent in each case the average value over the five samples in question.

[0148] Example 1 No polyfunctional compounds are used, and therefore Example 1 is not in accordance with the present invention. In the described manner, 20% by weight of MDP has the following structure: [ka] 49.7% by weight of HEMA with the following structure [ka] 0.1% BHT (butyl oxytoluene) with the following structure [ka] and 0.2% by weight of 2-(dimethylamino)ethyl methyl acrylate having the following structure: [ka] However, it is mixed first alone and then with 30% by weight of water.

[0149] The average adhesion value was initially 18.0 MPa, but decreased to 8.0 MPa after the described thermal cycling. This decreased value indicates that the adhesive bond is not suitable for permanent use in the patient's mouth and that sufficient adhesive effectiveness, if any, cannot be guaranteed.

[0150] Example 2 As polyfunctional compound, glycerol propoxylate triacrylate is used, which has the following structural formula: [ka] In the described method, 20 wt. % MDP, 47.2 wt. % HEMA, 0.1 wt. % BHT, and 0.2 wt. % 2-(dimethylamino)ethyl methyl acrylate and 2.5 wt. % glyceryl propoxy triacrylate are mixed as triacrylates, first alone and then together with 30 wt. % water. The average adhesion value was initially 10.4 MPa and increased to a value of 12.2 MPa after the thermal cycling described. Here, the adhesive bond is not only guaranteed in the long term, but is even improved over simulated aging cycles.

[0151] Example 3 As the polyfunctional compound pentaerythritol dimethyl acrylate, a mixture of about 25% by weight of mono-, 50% by weight of di-, and 25% by weight of trimethacrylate with the following structural formula is used: [ka] mono-, [ka] J-, [ka] Trimethacrylate In the described method, 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 are mixed as dimethacrylates, first alone and then together with 30 wt. % water. The average adhesion value was initially 12.8 MPa and increased to a value of 14.4 MPa after the thermal cycling described. Also here, the adhesive bond is not only guaranteed in the long term, but is even improved over simulated aging cycles.

[0152] Example 4 As polyfunctional compound, trimethylpropane trimethacrylate is used, which has the following structural formula: [ka] In the described manner, 20 wt. % MDP, 47.7 wt. % HEMA, 0.1 wt. % BHT, and 0.2 wt. % 2-(dimethylamino)ethyl trimethacrylate as well as 2 wt. % trimethylpropane trimethacrylate are mixed first alone and then with 30 wt. % water. The average adhesion value was initially 20.1 MPa and then decreased slightly to a value of 17.1 MPa after the described thermal cycling. These adhesion values ​​are considerably better than the normally applied limit value of 10 MPa, so that these values ​​also very much guarantee a good adhesive bond between tooth and polymerizable dental material over the long term.

[0153] Example 5 As polyfunctional compound, trimethylolpropane trimethacrylate is used, which has the following structural formula: [ka] Deviating from Example 4, MDP is replaced by GDMAP and in the manner described, 19.1 wt. % GDMAP, 48.6 wt. % HEMA, 0.1 wt. % BHT and 0.2 wt. % 2-(dimethylamino)ethyl methyl acrylate and 2 wt. % trimethylpropane trimethacrylate as the trimethacrylate are mixed first alone and then together with 30 wt. % water. The average adhesion value was initially 12.7 MPa and then increased after thermal cycling to a value of 15.7 MPa.

[0154] Example 6 As polyfunctional monomer, pentaerythritol trimethacrylate is used, which has the following structural formula: [ka] In the described manner, 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 are mixed with 2% by weight of pentaerythritol trimethacrylate as the trimethacrylate, first alone and then together with 30% by weight of water. The average adhesion value was initially 22.3 MPa and then decreased to a value of 16.9 MPa after the described thermal cycle. These adhesion values ​​are significantly better than the normally applied limit value of 10 MPa, so these values ​​also guarantee a very good adhesive bond between the tooth and the polymerizable dental material over the long term.

[0155] Example 7 As polyfunctional compound, sorbitol pentamethacrylate is used, which has the following structural formula: [ka] In the described manner, 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 the pentamethacrylate are mixed first alone and then with 30 wt. % water. The average adhesion value was initially 16.9 MPa and then increased to a value of 17.3 MPa after the described thermal cycle. Both of these adhesion values ​​are significantly higher than the limit value of 10 MPa, so that this system also guarantees a very good adhesive effect.

[0156] Example 8 As polyfunctional compound, an aliphatic urethane hexaacrylate (GENOMER* 4691® RahnAG) having the following hypothetical structural formula is used: [ka] In the described method, 20 wt. % MDP, 45.9 wt. % HEMA, 0.1 wt. % BHT, and 0.2 wt. % 2-(dimethylamino)ethyl methyl acrylate and 3.8 wt. % aliphatic urethane hexaacrylate are mixed first alone and then together with 30 wt. % water. The average adhesion value was initially 14.9 MPa and then 18.3 MPa after the described thermal cycle, thus again ensuring very good permanent adhesion.

[0157] Table 3 summarizes the different adhesion values ​​for different multifunctional compounds: [Table 4]

[0158] Example 9 As polyfunctional compound, tetrafunctional alkoxylated pentaerythritol tetramethacrylate is used, which has the following structural formula: [ka] In the described manner, 20% by weight of MDP, 46.1% by weight of HEMA, 0.1% by weight of BHT, and 0.2% by weight of 2-(dimethylamino)ethylmethylacrylic acid and 3.6% by weight of tetrafunctional alkoxylated pentaerythritol tetramethylacrylic acid as tetramethylacrylic acid are mixed first alone and then with 30% by weight of water. The average adhesion value was initially 11.0 MPa and after the described thermal cycle was 12.3 MPa, where the adhesive bond is not only guaranteed in the long term but also improves over the simulated aging cycle.

[0159] Example 10 As the same polyfunctional compound as in Example 4, trimethylolpropane trimethacrylate having the following hypothetical structural formula is used: [ka] This test series demonstrates the effect of the proportion of phosphate 10-methacryloyloxydecyl dihydrogen phosphate (MDP) and / or accelerator 2-(dimethylamino)ethyl methacrylate (DMAEMA) on the adhesive effectiveness of the resulting composite. For 100%, the proportion of 2-hydroxyethyl methacrylate (HEMA) was adjusted accordingly. The results are summarized in Table 3 below. [Table 5]

[0160] The presence of 2-(dimethylamino)ethyl methacrylate has been shown to have a positive effect on adhesive effectiveness, both initially and after thermal cycling. Best results are achieved with approximately 20-30% 10-methacryloyloxydecyl dihydrogen phosphate.

[0161] Example 11 As the same polyfunctional compound as in Example 4, trimethylolpropane trimethacrylate having the following hypothetical structural formula is used: [ka] In the described method, 20 wt. % MDP, 47.7 wt. % HEMA, 0.1 wt. % BHT, and 0.2 wt. % 2-(dimethylamino)ethyl methyl acrylate, and 2 wt. % trimethylpropane trimethacrylate as the trimethacrylate are mixed first alone and then together with 30 wt. % water. The primers were then tested with the above-described base / catalyst pastes 1-4. The results are summarized in Table 4 below.

[0162] [Table 6]

[0163] In contrast to the relatively hydrophobic base / catalyst paste 1, the average initial adhesion values ​​for the strongly hydrophilic composites 3 and 4 are shown to increase significantly. The average adhesion value was initially 14.9 MPa and after the described thermal cycle (TC) was 18.3 MPa. Thus, here too, a very good permanent bond is guaranteed. The influence of the hydrophilicity is clearly visible, especially after the described thermal cycle.

[0164] Example 12 As the same polyfunctional compound as in Example 4, trimethylolpropane trimethacrylate having the following hypothetical structural formula is used: [ka] This test series shows the influence of the accelerators copper(II) acetylacetonate and iron(III) EDTA in the presence of sodium persulfate on the adhesive effectiveness of the resulting composites. For 100%, the portion of 2-hydroxyethyl methacrylate (HEMA) was adjusted accordingly. Copper-containing primer (Cu): In the manner described, 20 wt. % MDP, 47.2 wt. % HEMA, 0.1 wt. % BHT, 0.2 wt. % 2-(dimethylamino)ethyl methyl acrylate, and 2 wt. % trimethylpropane tri-methacrylate as the trimethacrylate, and 0.5 wt. % copper(II) acetylacetonate are mixed first alone and then together with 30 wt. % 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 wt. % trimethylpropane tri-methacrylate as trimethacrylates, and 0.7 wt. % iron(III) EDTA are mixed first alone and then with 30 wt. % water.

[0165] The primers were then tested with the above base pastes 2B and 3B, and the corresponding catalyst pastes 2 and 3. The results are summarized in Table 5 below.

[0166] [Table 7]

[0167] The presence of copper(II) acetylacetonate and sodium persulfate has been shown to result in lower average initial adhesion values ​​for the relatively hydrophobic Base / Catalyst Paste 2B / 2 compared to the reference Base / Catalyst Paste 2 / 2. On the other hand, when copper- or iron-containing primers were used in the presence of sodium persulfate with the fairly hydrophilic base / catalyst paste 3B / 3, higher average initial adhesion values ​​compared to the baseline and a tendency for improved adhesion values ​​after thermal cycling could also be seen. In particular, the Cu-primer / 3B / 3 combination shows an increase in the average adhesion value from 24.1 MPa to 25.3 MPa after thermal cycling and therefore also shows a high resistance in the case of simulated aging.

Claims

1. a polymerizable (meth)acrylate or (meth)acrylamide monomer having (i) at least one acidic group and (ii) at least one hydrophilic group, wherein the at least one hydrophilic group is at least a hydroxyl, amino, amine, thiol, hydrochloride, or polyether group, preferably a polyhydroxyl group, a polyamine group, and a chain-linked polyether group; or two (meth)acrylate or (meth)acrylamide monomers, one of which (i) has at least one acidic group and the other of which (ii) has at least one hydrophilic group, said at least one hydrophilic group being a hydroxyl, amine or polyether group; 1. A liquid dental primer composition comprising: The polymerizable (meth)acrylate or (meth)acrylamide monomer having (i) at least one acidic group and / or (ii) at least one hydrophilic group is characterized in that (iii) it comprises 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-polyfunctionality; characterized in that photoinitiators, polymerization catalysts and organic solvents are absent, A liquid dental primer composition.

2. a polymerizable (meth)acrylate or (meth)acrylamide monomer having (i) at least one acidic group and (ii) at least one hydrophilic group, wherein the at least one hydrophilic group is at least a hydroxyl, amino, amine, thiol, hydrochloride, or polyether group, preferably a polyhydroxyl group, a polyamine group, and a chain-linked polyether group; or two (meth)acrylate or (meth)acrylamide monomers, one of which (i) has at least one acidic group and the other of which (ii) has at least one hydrophilic group, said hydrophilic group being a hydroxyl, amine or polyether group; 1. A liquid dental primer composition comprising: and wherein the (meth)acrylate or (meth)acrylamide monomer comprises (iii) 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-polyfunctionality; characterized in that photoinitiators, polymerization catalysts and organic solvents are absent, A liquid dental primer composition.

3. at least one acid group is a carbonate, sulfate, phosphate, phosphonate, or phosphinate; Or the monomer having an acidic group is MDP, PENTA, GDMAP, MAC, 4-META, A-MDP, or PMGDM; or (poly)vinyl carboxylic acid is included; 3. The composition according to claim 1 or claim 2, characterized in that:

4. 4. The composition according to claim 1, wherein the hydrophilic groups are terminal or side-linked hydroxyls, or terminal or side-linked amino groups, or main-chain linked polyether groups.

5. 5. The composition according to claim 1, wherein the 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-polyfunctional (meth)acrylate or (meth)acrylamide monomer (iii) contains the corresponding number of functional groups in the form of (meth)acrylate, (meth)acrylamide, styrene and / or aryl groups.

6. The composition according to any one of claims 1 to 5, characterized in that the polyfunctional monomer comprises a backbone having a structure selected from the group consisting of glycerin, trimethylolpropane, pentaerythriol, xylitol, triglycerol, dipentaerythritol, sorbitol, hydrocarbons, cycloalkanes, aliphatic polyethers, PEG, PPG, PTMEG, paraformaldehyde, and unbranched or branched hydrocarbons.

7. 7. Composition according to any one of claims 1 to 6, characterized by the absence of vanadium compounds, aromatic amines, sulfonates and / or aromatic sulfonates, sulfinates and / or aromatic sulfinates.

8. The dental primer composition according to any one of claims 1 to 7, characterized in that it is a single-component composition.

9. 9. Composition according to any one of claims 1 to 8, characterized in that the pH value of the composition is ≦3.5 and ≧1.

0.

10. Composition according to any one of claims 1 to 9, characterized in that the portion of polyfunctional monomers is between 0.1 and 10% by weight.

11. 11. The composition according to claim 1, wherein MDP is contained in an amount of 15 to 35% by weight, HEMA is contained in an amount of 35 to 60% by weight, and water is contained in an amount of 20 to 50% by weight.

12. 12. The composition of claim 11, wherein the polyfunctional monomer is present in the composition in dissolved form.

13. 13. Composition according to any one of claims 1 to 12, characterized in that it contains 0.005 to 1% by weight of BHT and / or hydroquinone monomethyl ether (MEHQ), pyrocatechol derivatives and / or HALS (sterically hindered amines) and / or 0.05 to 5% by weight of 2-(dimethylamino)ethyl methacrylate.

14. The composition according to any one of claims 1 to 13, further comprising at least one inorganic or organic peroxide compound.

15. A dental adhesive material kit comprising the liquid dental primer composition according to any one of claims 1 to 14 and a paste-like polymerizable two-component dental material containing a catalyst paste (A) and a base paste (B), The catalyst paste (A) contains at least one organic peroxygen compound, at least one radically polymerizable organic (meth)acrylate monomer, and at least one filler; The dental adhesive material kit includes the base paste (B), which contains at least one radically polymerizable organic (meth)acrylate monomer, an amine as a coinitiator for radical polymerization, at least one filler, and at least one salt-like, water-soluble, and powdery reducing agent dispersed therein.

16. A liquid dental primer composition according to any one of claims 1 to 14, and a polymerizable two-component dental material in paste form containing a catalyst paste (A) and a base paste (B), The catalyst paste (A) contains at least one organic peroxygen compound, at least one radically polymerizable organic (meth)acrylate monomer, and at least one filler; The base paste (B) is a dental adhesive material kit containing at least one radically polymerizable organic (meth)acrylate monomer, an amine as a coinitiator 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) contain at least one phase transfer catalyst selected from the group consisting of ammonium, phosphonium and / or sulfonium salts containing inorganic or organic anions, However, in the case of organic anions, the phase transfer catalysts include only those having 1 to 4 carbon atoms, and anions of sulfinic and sulfonic acids are excluded. Dental adhesive material kit.

17. 17. Dental adhesive material kit according to claim 15 or claim 16, characterized in that the phase transfer catalyst is present only in the catalyst paste (A) and / or the portion of the at least one phase transfer catalyst is 0.01 to 5 wt.-%, based on the total mass of the catalyst paste (A) and / or the base paste (B).

18. at least one salt-like, water-soluble and powdered reducing agent is selected from the group of sulfites, and / or the salt-like, water-soluble and powdered oxidizing agent is an alkali percarbonate and / or an alkali perborate; and / or The dental adhesive material kit according to any one of claims 15 to 17, characterized in that the coinitiator of the radical polymerization is a primary, secondary or tertiary amine.

19. 19. Dental adhesive material kit according to any one of claims 15 to 18, characterized in that it is dual curing and furthermore at least one photoinitiator is provided in the catalyst paste (A) and / or the base paste (B).

20. 20. The dental adhesive material kit according to claim 15, wherein the (meth)acrylate monomer is provided in the catalyst paste (A) and / or the base paste (B) in an amount of 10 to 80 wt.-%, further comprising a proportion of hydrophilic (meth)acrylate monomer of 0.1 to 20 wt.-%.

21. the at least one radically polymerizable organic (meth)acrylate monomer is selected from the group consisting of diacrylates or acrylates having three or more acroyl groups, diacrylamides or acrylamides having three or more acroyl groups, dimethacrylates or methacrylates having three or more acroyl groups, and / or dimethacrylamides or methacrylamides having three or more acroyl groups; or at least one radically polymerizable organic (meth)acrylate monomer is selected from aromatic group containing acrylate or methacrylate, aliphatic group containing acrylate or methacrylate, polyether group containing acrylate or methacrylate, hydroxyl and / or amino group containing aliphatic or aromatic (meth)acrylate monomers, polyester group containing acrylate or methacrylate, polyurethane group containing acrylate or methacrylate, or a combination of two or more of these monomers; or the at least one radically polymerizable organic (meth)acrylic acid monomer is bisphenol A diacrylate, bisphenol A dimethacrylate, 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-ethoxycarbonylamino)-2,4,4-trimethylhexane (UDMA), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethyl acrylate, 3-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, glycerin-1,3-acrylate selected from the group of monomers: glycerin-1,3-dimethacrylate (GDMA), 1,2-ethanediylbis(oxy-2-hydroxy-3,1-propanediyl)-bis(2-methylacrylate), 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene diacrylate, tetraethylene glycol dimethacrylate or a combination of two or more of these monomers; or the radically polymerizable organic (meth)acrylate monomer does not contain a structural unit having an aromatic group; The dental adhesive material kit according to any one of claims 15 to 20,

22. The dental adhesive material kit according to any one of claims 15 to 21, characterized in that the organic peroxide compound is selected from the group consisting of peroxides, peroxide esters, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyketones, hydroperoxides, and hydrogen peroxide.

23. 23. Dental adhesive material kit according to any one of claims 15 to 22, characterized in that the anion of the phase transfer catalyst is selected from the group of halides, hydroxides, anions of organic acids, pseudohalogen anions, or halogen complexes of aluminates, silicates or phosphates, or anions of organic acids having 1 to 4 carbon atoms (excluding anions of sulfinic and sulfonic acids).

24. A dental adhesive material kit comprising the liquid dental primer composition according to any one of claims 1 to 14 and a paste-like polymerizable two-component dental material containing a catalyst paste (A) and a base paste (B), the catalyst paste (A) contains at least one organic hydroperoxide, at least one radically polymerizable organic (meth)acrylate monomer, and at least one filler; The base paste (B) contains at least one radically polymerizable organic (meth)acrylate monomer, thiourea as a coinitiator of the radical polymerization, and at least one filler. Dental adhesive material kit.

25. 25. The dental adhesive material kit according to claim 24, wherein the organic hydroperoxide is cumene hydroperoxide and / or isopropylbenzene hydroperoxide and / or the thiourea is (2-pyridyl)thiourea and / or acetylthiourea.

26. 26. The dental adhesive material kit according to claim 24 or claim 25, wherein the (meth)acrylate monomer in the catalyst paste (A) and / or the base paste (B) is provided in an amount of 10 to 80 wt. %, and further, the proportion of hydrophilic (meth)acrylate monomer is 0.1 to 20 wt. %.

27. the at least one radically polymerizable organic (meth)acrylate monomer is selected from the group consisting of diacrylates or acrylates having three or more acroyl groups, diacrylamides or acrylamides having three or more acroyl groups, dimethacrylates or methacrylates having three or more acroyl groups, and / or dimethacrylamides or methacrylamides having three or more acroyl groups; or at least one radically polymerizable organic (meth)acrylate monomer is selected from aromatic group containing acrylate or methacrylate, aliphatic group containing acrylate or methacrylate, polyether group containing acrylate or methacrylate, hydroxyl and / or amino group containing aliphatic or aromatic (meth)acrylate monomers, polyester group containing acrylate or methacrylate, polyurethane group containing acrylate or methacrylate, or a combination of two or more of these monomers; or the at least one radically polymerizable organic (meth)acrylic acid monomer is bisphenol A diacrylate, bisphenol A dimethacrylate, 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-ethoxycarbonylamino)-2,4,4-trimethylhexane (UDMA), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethyl acrylate, 3-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, glycerin-1,3-acrylate selected from the group of monomers: glycerin-1,3-dimethacrylate (GDMA), 1,2-ethanediylbis(oxy-2-hydroxy-3,1-propanediyl)-bis(2-methylacrylate), 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene diacrylate, tetraethylene glycol dimethacrylate or a combination of two or more of these monomers; or the radically polymerizable organic (meth)acrylate monomer does not contain a structural unit having an aromatic group; The dental adhesive material kit according to any one of claims 24 to 26,

28. Dental adhesive kit according to any one of claims 24 to 27, characterized in that vanadium and / or copper compounds are provided in the catalyst paste (A) and / or the base paste (B).

29. at least one salt-like, water-soluble and powdered reducing agent is selected from the group of sulfites, and / or Dental adhesive material kit according to any one of claims 24 to 27, characterized in that the salt-like, water-soluble and powdered oxidizing agent is an alkali percarbonate and / or an alkali perborate.

30. 30. The dental adhesive material kit according to any one of claims 24 to 29, characterized in that the catalyst paste (A) and / or the base paste (B) contain at least one phase transfer catalyst selected from the group of ammonium, phosphonium and / or sulfonium salts containing inorganic or organic anions, with the proviso that in the case of organic anions, phase transfer catalysts only include those having 1 to 4 carbon atoms, and anions of sulfinic and sulfonic acids are excluded.

31. 31. Dental adhesive material kit according to any one of claims 24 to 30, characterized in that it is dual curing and further at least one photoinitiator is provided in the catalyst paste (A) and / or the base paste (B).

32. A paste-like single-component composite composition comprising the single-component primer composition according to any one of claims 1 to 14, and at least one radically polymerizable organic (meth)acrylate monomer, at least one filler, and at least one photoinitiator. Dental adhesive material kit.

33. the at least one radically polymerizable organic (meth)acrylate monomer is selected from the group consisting of diacrylates or acrylates having three or more acroyl groups, diacrylamides or acrylamides having three or more acroyl groups, dimethacrylates or methacrylates having three or more acroyl groups, and / or dimethacrylamides or methacrylamides having three or more acroyl groups; or at least one radically polymerizable organic (meth)acrylate monomer is selected from aromatic group containing acrylate or methacrylate, aliphatic group containing acrylate or methacrylate, polyether group containing acrylate or methacrylate, hydroxyl and / or amino group containing aliphatic or aromatic (meth)acrylate monomers, polyester group containing acrylate or methacrylate, polyurethane group containing acrylate or methacrylate, or a combination of two or more of these monomers; or the at least one radically polymerizable organic (meth)acrylic acid monomer is bisphenol A diacrylate, bisphenol A dimethacrylate, 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-ethoxycarbonylamino)-2,4,4-trimethylhexane (UDMA), trimethylolpropane triacrylate, trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethyl acrylate, 3-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA), 3-hydroxypropyl methacrylate, glycerin-1,3-acrylate selected from the group of monomers: glycerin-1,3-dimethacrylate (GDMA), 1,2-ethanediylbis(oxy-2-hydroxy-3,1-propanediyl)-bis(2-methylacrylate), 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene diacrylate, tetraethylene glycol dimethacrylate or a combination of two or more of these monomers; or the radically polymerizable organic (meth)acrylate monomer does not contain a structural unit having an aromatic group; 33. The dental adhesive material kit according to claim 32,

34. 34. The dental adhesive material kit according to claim 32 or 33, comprising a phase transfer catalyst and a reducing agent selected from the group of sulfites and / or an oxidizing agent.

35. Use of a kit according to any one of claims 15 to 34 for producing and bonding a core build-up material, a polymerizable composite cement and / or a bulk fill composite for the production of a core build-up, a luting fixation and / or a tooth filling material on at least one tooth.

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