Polymerizable co-initiators

Abstract

Dental, radically polymerizable composition comprising A) one or more radically polymerizable monomers and B) comprising a photoinitiator system B1) a photoinitiator having an absorption maximum in a wavelength range of 420 to 500 nm, and B2) a co-initiator of the formula (I) where R 1 = H or Methyl, R 2 = H, C1 to C4 alkyl or halogen, R 3 / R 4 = Alkyl, and n = 0 to 4.

Description

[0001] The present invention relates to dental, radically polymerizable compositions with novel polymerizable co-initiators.

[0002] The invention is defined in the attached claims. Preferred aspects of the present invention will also become apparent from the following description, including the examples.

[0003] Where certain embodiments are designated as preferred for an aspect of the invention (composition, therapeutic application, use, or hardened product), the corresponding descriptions also apply to the other aspects of the present invention, mutatis mutandis. Preferred individual features of aspects of the invention (as defined in the claims and / or disclosed in the description) can be combined with one another and are preferably combined with one another, unless otherwise apparent to a person skilled in the art from the present text.

[0004] During dental treatment, polymerizable dental materials are typically cured by the dentist using blue light. LED lamps with a narrow wavelength range and an emission maximum in the 450 to 470 nm range have become established for this purpose.

[0005] For reliable curing, photoinitiator systems that absorb in this wavelength range are therefore necessary. α-Diketones in combination with aromatic dialkylamino co-initiators are typically used for this purpose. Camphorquinone is usually employed as the photoinitiator.

[0006] Camphorquinone is a type II photoinitiator. Irradiation in the wavelength range of 420 to 500 nm excites camphorquinone to the singlet state (S1) due to the n,π* transition of the α-dicarbonyl chromophore. This short-lived state (approx. 20 µs) can undergo non-radiative transitions, be deactivated, decay, or transition to a lower-energy triplet state (T1) via intersystem crossing (ISC). In the T1 state, camphorquinone reacts with the co-initiator amine to form an excited complex state known as an "exciplex." Within the exciplex, charge transfer from the nitrogen of the electron-donating amine to the activated carbonyl of camphorquinone generates two radical ion species.If the amine possesses an alkyl group in the α-position of the nitrogen, two free radicals are formed through intermolecular hydrogen abstraction: a reactive aminoalkyl radical and a relatively unreactive camphorquinone ketyl radical. The resulting aminoalkyl radical is responsible for initiating the photopolymerization of the monomers, while the camphorquinone ketyl radicals tend to deactivate the reaction or can even act as termination agents.

[0007] Ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate and 4-(dimethylamino)benzonitrile are widely used as co-initiators.

[0008] A disadvantage of ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl 4-(dimethylamino)benzoate, 4-(dimethylamino)benzonitrile and similar compounds is that unreacted residues are not firmly incorporated into the polymer matrix and can thus be released into the oral environment over time.

[0009] To solve this problem, several polymerizable co-initiators have already been proposed in the patent literature.

[0010] German patent DE 10 2004 011 497 A1 (Ivoclar Vivadent AG) discloses dental materials containing polymerizable thermal initiators, polymerizable photoinitiators, polymerizable co-initiators, and / or polymerizable stabilizers. These dental materials are characterized by a low proportion of soluble components (initiators, inhibitors), which has a positive effect on the material's biocompatibility.

[0011] WO 2020 / 099518 A1 (Dentsply Detrey GmbH) discloses polymerizable compositions with polymerizable co-initiators. These compositions are characterized by a significantly reduced leaching of tertiary aromatic amines.

[0012] WO 2016 / 149488 A1 (University of Kansas) discloses polymerizable compositions with polymerizable co-initiators. The co-initiators are tertiary aliphatic amines with terminal methacrylate groups. The compositions are characterized by reduced leaching of the tertiary amines.

[0013] WO 2007 / 017348 A2 (Lamberti SPA) discloses polymerizable compositions with polymerizable co-initiators. The co-initiators are 4-dialkylaminobenzoic acid esters esterified with unsaturated alcohols. These co-initiators are characterized by low extractability and low volatility.

[0014] The article “Low-Migration Compounds with Amine Functionality as Coinitiators of Radical Polymerization” (H. Chen et al., Macromolecular Rapid Communications, Vol. 45, 2024, No. 16, pp. 1–8 (2400196). ISSN 1521-3927. DOI: 10.1002 / macr.202400196) investigates amine-based co-initiators as alternatives to ethyl 4-(dimethylamino)benzoate. Co-initiators with a methacrylate group are characterized by reduced leaching.

[0015] Although several polymerizable co-initiators have already been proposed, there is still a need for co-initiators in dental dentistry that are characterized by reliable curing and low leaching.

[0016] The problem is solved comprehensively by a dental, radically polymerizable composition. A) one or more radically polymerizable monomers and B) comprising a photoinitiator system B1) a photoinitiator having an absorption maximum in a wavelength range of 420 to 500 nm, and B2) a co-initiator of the formula (I)whereby R 1 = H or Methyl, R 2 = H, C1 to C4 alkyl or halogen, R 3 / R 4 = Alkyl, and n = 0 to 4, where optional the alkyl groups R 3 and R 4 with the nitrogen atom they can also form a saturated 5- or 6-membered ring, or in the event that R 2 an alkyl group, the alkyl groups R 2 and R 4 They can also form a 5- or 6-ring.

[0017] In a preferred embodiment, the co-initiator B2 of formula (I) R 2 = H, Methyl or Ethyl, and / or (preferably “and”) R 3 / R 4 = Methyl or Ethyl, and / or (preferably “and”) n = 0.

[0018] Preferably, the co-initiator B2 is a compound of formula (II), where R 1 = H or Methyl, R 2 = H, Methyl or Ethyl, and R 3 / R 4 = Methyl or Ethyl.

[0019] In a preferred embodiment, the proportion of B2 is in the range of 0.01 to 6.0 wt.%, preferably from 0.03 to 4.0 wt.%, based on the total mass of the radically polymerizable composition.

[0020] Depending on the application and exact composition, the proportion of B2 can vary. For example, in dental composite compositions with a lower proportion of polymerizable monomers A, the proportion of B2 is in the range of 0.01 to 1.5 wt.%, preferably 0.03 to 0.8 wt.%, based on the total mass of the radically polymerizable composition. In dental adhesives with a higher proportion of polymerizable monomers A, the proportion of B1 is in the range of 0.1 to 6.0 wt.%, preferably 0.2 to 4.0 wt.%, based on the total mass of the radically polymerizable composition. Photoinitiators B1:

[0021] The photoinitiators according to the invention exhibit an absorption maximum in a wavelength range of 420 to 500 nm. α-Diketones are preferably used. Camphorquinone is particularly preferred.

[0022] In a preferred embodiment, the proportion of B1 is in the range of 0.01 to 3.0 wt.%, preferably from 0.02 to 2.0 wt.%, based on the total mass of the radically polymerizable composition.

[0023] Depending on the application and exact composition, the proportion of B1 can vary. For example, in dental composite compositions with a lower proportion of polymerizable monomers A, the proportion of B1 is in the range of 0.01 to 1 wt.%, preferably 0.02 to 0.5 wt.%, based on the total mass of the radically polymerizable composition. In dental adhesives with a higher proportion of polymerizable monomers A, the proportion of B1 is in the range of 0.05 to 3.0 wt.%, preferably 0.1 to 2.0 wt.%, based on the total mass of the radically polymerizable composition. Radically polymerizable monomers A:

[0024] Preferably, the radically polymerizable monomers A are (meth)acrylic compounds. In this context, "(meth)acrylic" is understood to mean both "acrylic" and "methacrylic".

[0025] In a preferred embodiment, the radically polymerizable monomers A are selected from the group consisting of acrylates, methacrylates, acrylamides and methacrylamides, particularly preferably selected from the group consisting of acrylates and methacrylates.

[0026] In a further preferred embodiment, the radically polymerizable monomers A are selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tricyclo[5.2.1.0 2,6]decan-3(4),8(9)-dimethanol-di(meth)acrylat, 2-Hydroxypropyl-1,3-di(meth)acrylat, 3-Hydroxypropyl-1,2-di(meth)acrylat, Urethandi(meth)acrylat, 7,7,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 7,9,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 1,5,5-Trimethyl-1-[(2-(meth)acryloyloxy-ethyl)carbamoylmethyl]-3-(2-(meth)acryloyloxyethyl)carbamoylcyclohexan, 1,3-Bis(3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(9'-methyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1'-dimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1',9'-trimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 3(4),8(9)-Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-en)tetrahydrodicyclopentadien, 3(4),8(9)-Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-9'-methyl-decyl-9'-en)tetrahydrodicyclopentadien, Trimethylolpropandi-(meth)acrylat, Trimethylolpropantri(meth)acrylat,ethoxyliertes Trimethylolpropantri-(meth)acrylat, Ditrimethylolpropantetra(meth)acrylat, ethoxyliertes Ditrimethylolpropantetra-(meth)acrylat, Pentaerythritoldi(meth)acrylat, Pentaerythritoltri(meth)acrylat, Pentaerythritol-tetra(meth)acrylat, Dipentaerythritoltetra(meth)acrylat, Dipentaerythritolpenta(meth)acrylat, Dipentaerythritolhexa(meth)acrylat, 2,2-Bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]-phenyl]propan, 2,2-Bis[4-[2-(meth)acryloyloxy-3-hydroxypropoxy]phenyl]propan, ethoxyliertes Bisphenol-A-di(meth)acrylat, propoxyliertes Bisphenol-A-di(meth)acrylat, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxydiethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxytriethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxytetraethoxy-phenyl]propan, 2,2-Bis[4-(meth)acryloyloxypentaethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxydipropoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]-2-[4-(meth)acryloyloxydiethoxyphenyl]propan,2-[4-(Meth)acryloyloxydiethoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propan, 2-[4-(Meth)acryloyloxdipropoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propan, 2-Hydroxyethyl(meth)acrylat, 2-Hydroxypropyl-(meth)acrylat, 3-Hydroxypropyl(meth)acrylat, 1,2-Dihydroxypropyl(meth)acrylat, 1,3-Dihydroxypropyl(meth)acrylat, Methyl(meth)acrylat, Ethyl(meth)acrylat, Propyl(meth)acrylat, Butyl(meth)acrylat, Hexyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Tetrahydrofurfuryl(meth)acrylat, Isobornyl(meth)acrylat, Lauryl(meth)acrylat, Cyclohexyl(meth)acrylat, (Octahydro-4,7-methano-1H-indenyl)methyl(meth)acrylat, Benzyl(meth)acrylat, Phenoxyethyl(meth)acrylat, 10-Methacryloyloxydecyldihydrogenphosphat, 6-Methacryloyloxyhexyldihydrogenphosphat, 2-Methacryloyloxyethyldihydrogenphosphat und 2-Methacryloyloxypropyldihydrogenphosphat, bevorzugt ausgewählt aus der Gruppe bestehend aus Triethylenglycoldi(meth)acrylat, Tetraethylenglycoldi(meth)acrylat, 1,6-Hexandiol-di(meth)-acrylat, 1,10-Decandioldi(meth)acrylat, 1,12-Dodecandioldi(meth)acrylat, Tricyclo-[5.2.1.0, 2,6]decan-3(4),8(9)-dimethanol-di(meth)acrylat, 2-Hydroxypropyl-1,3-di(meth)acrylat, 3-Hydroxypropyl-1,2-di(meth)acrylat, Urethandi(meth)acrylat, 7,7,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 7,9,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 1,5,5-Trimethyl-1-[(2-(meth)-acryloyloxyethyl)carbamoylmethyl]-3-(2-(meth)acryloyloxyethyl)carbamoylcyclohexan, 1,3-Bis(3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(9'-methyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1'-dimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1',9'-trimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 3(4),8(9)-Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-en)tetrahydrodicyclopentadien, 3(4),8(9)-Bis-(4',7'-dioxa- 3',8'-dioxo-2'-aza-9'-methyl-decyl-9'-en)tetrahydrodicyclopenta-dien, 2,2-Bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propan, 2,2-Bis[4-[2-(meth)-acryloyloxy-3-hydroxypropoxy]phenyl]propan, ethoxyliertes Bisphenol-A-di(meth)acrylat, propoxyliertes Bisphenol-A-di(meth)acrylat, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]-propan, 2,2-Bis[4-(meth)acryloyloxydiethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxy-triethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxytetraethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxypentaethoxyphenyl]-propan, 2,2-Bis[4-(meth)acryloyloxydipropoxy-phenyl]propan, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]-2-[4-(meth)acryloyloxydiethoxy-phenyl]propan, 2-[4-(Meth)acryloyloxydiethoxyphenyl]-2-[4-(meth)acryloyloxytriethoxy-phenyl]propan und 2-[4-(Meth)acryloyloxydipropoxyphenyl]-2-[4-(meth)acryloyloxy-triethoxyphenyl]propan.,

[0027] In a preferred embodiment, a dental, radically polymerizable composition according to the invention comprises the monomers A in an amount ranging from 1 to 99 wt.% based on the total mass of the radically polymerizable composition. The exact proportion depends on the specific application and the corresponding presence of other components.

[0028] Thus, the proportion of A in dental composite compositions is preferably in the range of 7 to 39 wt.%, preferably from 9 to 29 wt.%, based on the total mass of the radically polymerizable composition.

[0029] In dental adhesive compositions, the proportion of A is in the range of 20 to 85 wt.%, preferably 30 to 80 wt.%, based on the total mass of the radically polymerizable composition.

[0030] Due to their positive properties, the co-initiators according to the invention are suitable for use in a variety of dental compositions. They can be advantageously used both in filler-containing dental composite materials such as filling materials, core build-up materials, crown and bridge materials, fissure sealants or luting composites, and in dental adhesives. Dental composite materials:

[0031] The advantages of the co-initiators according to the invention, such as reliable curing in combination with very low leaching, are particularly advantageous in composite materials.

[0032] In a preferred embodiment, the dental, radically polymerizable composition according to the invention is a dental filling material.

[0033] Inventive dental, radically polymerizable composite compositions comprise, in addition to components A, B1 and B2, the following: C) Inhibitors, and / or D) inorganic fillers, and / or E) Colouring agents. Inhibitors / stabilizers (C):

[0034] Inhibitors or stabilizers ensure that the compositions have sufficient storage stability.

[0035] In a preferred embodiment, a composition according to the invention contains 0.001 to 1.0 wt.%, preferably 0.01 to 0.5 wt.%, particularly preferably 0.01 to 0.3 wt.%, in each case based on the total mass of the polymerizable composition, of one or more inhibitors (C).

[0036] Preferably (C) is selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroxyanisole and 2,2,6,6-tetramethyl-piperidine-1-oxyl. Inorganic fillers (D):

[0037] In a preferred embodiment, a composite composition according to the invention contains 60 to 92 wt.%, preferably 70 to 90 wt.%, of inorganic fillers (D).

[0038] The total quantity of inorganic fillers preferably comprises D1) a subset of inorganic fillers with an average particle size in the range of 0.4 µm to 10 µm, preferably in the range of 0.5 µm to 5 µm, and D2) a subset of inorganic fillers with an average particle size in the range of 5 nm to 100 nm, preferably in the range of 10 nm to 80 nm.

[0039] Preferably, the inorganic fillers D1 comprise dental glasses, ytterbium(III) fluoride, zirconium dioxide, aluminium oxide or silicon dioxide.

[0040] Dental glass refers to glass suitable for use in dentistry. It is characterized, among other things, by high purity and contains no toxic components (e.g., lead or arsenic). Such dental glasses are commercially available in different particle sizes from SCHOTT under the designations G018-307, G018-163, G018-093, GM39923, GM32087, G018-308, GM27884, GM31685, G018-053, 8235, G018-186, GM31684, G018-310, G018-159, G018-161, GM35429, G018-090 and G018-117 or from FERRO under the designations IS 50 1101, IS 50 1102 and IS 50 1103.

[0041] Preferably, D1 is selected from the group consisting of barium silicate glasses, barium aluminum silicate glasses, barium borosilicate glasses, barium boroaluminium silicate glasses, barium borofluoroaluminium silicate glasses, strontium silicate glasses, strontium aluminum silicate glasses, strontium borosilicate glasses, strontium boroaluminium silicate glasses, strontium borofluoroaluminium silicate glasses, zirconium silicate glasses, ytterbium(III) fluoride, zirconium dioxide, aluminum oxide and silicon oxide, preferably selected from the group consisting of barium aluminum silicate glasses, barium borosilicate glasses, barium boroaluminium silicate glasses and ytterbium(III) fluoride.

[0042] The mean particle size for D1 refers to d50 values ​​determined by static light scattering in volume-weighted evaluation.

[0043] In another preferred embodiment, D1 is organically surface-modified, preferably with 3-methacryloxypropyl(trimethoxy)silane.

[0044] The subset D1 preferably includes D1a) a subset of inorganic fillers with an average particle size in the range of 1 µm to 10 µm, preferably in the range of 1 µm to 5 µm, and D1b) a subset of inorganic fillers with an average particle size in the range of 0.4 µm to <1 µm, preferably in the range of 0.5 µm to 0.9 µm. Preferably, the ratio of the total mass of subset D1a to the total mass of subset D1b is in the range of 1 : 1 to 12 : 1, preferably in the range of 1.5 : 1 to 8 : 1.

[0045] Preferably, the ratio of the mean particle size of the inorganic fillers D1a to the mean particle size of the inorganic fillers D1b is in the range of 1.5 : 1 to 10 : 1, preferably in the range of 2 : 1 to 5 : 1.

[0046] Preferably, the d25 value of D1a is greater than the d75 value of D1b, each determined by static light scattering with volume-weighted evaluation.

[0047] Preferably, the inorganic fillers D2 are selected from the group consisting of ytterbium(III) fluoride, yttrium(III) fluoride, zirconium dioxide and silicon dioxide, preferably selected from the group consisting of ytterbium(III) fluoride and silicon dioxide.

[0048] In a further preferred embodiment, D2 is organically surface-modified. Ytterbium(III) fluoride, yttrium(III) fluoride, and zirconium dioxide particles are preferably organically surface-modified with 10-methacryloyloxydecyl dihydrogen phosphate. Silicon dioxide particles are preferably organically surface-modified with 3-methacryloxypropyl(trimethoxy)silane.

[0049] Preferably, the particles of the inorganic fillers D2 are non-aggregated and non-agglomerated.

[0050] The mean particle size for D2 refers to d50 values ​​determined by dynamic light scattering in volume-weighted evaluation.

[0051] Preferably, the ratio of the total mass of subset D1 to the total mass of subset D2 is in the range of 1 : 1 to 10 : 1, preferably in the range of 1.5 : 1 to 6 : 1. Colouring agent (E):

[0052] To adjust the color of the material for the desired application, a composition according to the invention can additionally contain one or more colorants (E). Inorganic color pigments as well as organic color pigments or dyes can be used as colorants. Preferred colorants are titanium dioxide and iron oxides.

[0053] In a preferred embodiment, a composition according to the invention contains 0.0001 to 1 wt.%, preferably 0.0001 to 0.5 wt.%, particularly preferably 0.0001 to 0.1 wt.%, in each case based on the total mass of the polymerizable composition, of one or more colorants (E).

[0054] In a preferred embodiment, a dental composite composition according to the invention comprises one that is radically polymerizable. A) in an amount in the range of 7 to 39 wt.%, preferably from 9 to 29 wt.%, B1) in an amount in the range of 0.01 to 1 wt.%, preferably from 0.02 to 0.5 wt.%, B2) in an amount in the range of 0.01 to 1.5 wt.%, preferably from 0.03 to 0.8 wt.% C) in an amount in the range of 0.001 to 1 wt.%, preferably from 0.01 to 0.5 wt.%, D) in an amount in the range of 60 to 92 wt.%, preferably 70 to 90 wt.%, and E) in an amount in the range of 0.0001 to 1 wt.%, preferably from 0.0001 to 0.5 wt.%, in each case based on the total mass of the radically polymerizable composition. Additive F:

[0055] In a further preferred embodiment, a dental, radically polymerizable composite composition according to the invention comprises additives F. The proportion of additives F is 0.01 to 5 wt.%, preferably 0.02 to 1.0 wt.%, based on the total mass of the radically polymerizable composition.

[0056] Preferred additives F are UV and daylight stabilizers or molecular weight regulators. Dental adhesives:

[0057] The advantages of the co-initiators according to the invention, such as reliable curing in combination with very low leaching, are particularly advantageous in the case of adhesives.

[0058] In a preferred embodiment, the dental, radically polymerizable composition according to the invention is a dental adhesive.

[0059] Inventive dental, radically polymerizable adhesive compositions comprise, in addition to components A, B1 and B2, the following: C) Inhibitors, and / or G) Solvents.

[0060] Depending on the specific application, dental, radically polymerizable adhesive compositions according to the invention additionally include H) inorganic fillers and / or I) Filmmakers. Inhibitors / stabilizers (C):

[0061] Inhibitors or stabilizers ensure that the compositions have sufficient storage stability.

[0062] In a preferred embodiment, a composition according to the invention contains 0.001 to 1.0 wt.%, preferably 0.01 to 0.5 wt.%, particularly preferably 0.01 to 0.3 wt.%, in each case based on the total mass of the polymerizable composition, of one or more inhibitors (C).

[0063] Preferably (C) is selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroxyanisole and 2,2,6,6-tetramethyl-piperidine-1-oxyl. Solvent (G):

[0064] In a preferred embodiment, a composition according to the invention contains 5 to 70 wt.%, preferably 15 to 65 wt.%, particularly preferably 10 to 40 wt.%, in each case based on the total mass of the polymerizable composition, of one or more solvents (G).

[0065] Preferably (G) is selected from the group consisting of water, ethanol, isopropanol and acetone. H) Inorganic fillers:

[0066] Preferably, the inorganic fillers H are selected from the group consisting of ytterbium(III) fluoride, yttrium(III) fluoride, zirconium dioxide and silicon dioxide, preferably selected from the group consisting of ytterbium(III) fluoride and silicon dioxide.

[0067] In a further preferred embodiment, H is organically surface-modified. Ytterbium(III) fluoride, yttrium(III) fluoride, and zirconium dioxide particles are preferably organically surface-modified with 10-methacryloyloxydecyl dihydrogen phosphate. Silicon dioxide particles are preferably organically surface-modified with 3-methacryloxypropyl(trimethoxy)silane.

[0068] Preferably, the inorganic fillers H have a mean particle size in the range of 5 nm to 100 nm, more preferably in the range of 10 nm to 80 nm. The mean particle size for H refers to d50 values ​​determined by dynamic light scattering using volume-weighted analysis.

[0069] Preferably, the particles of the inorganic fillers H are non-aggregated and non-agglomerated.

[0070] In another preferred embodiment, the inorganic fillers are H pyrogenic silicas. I) Filmmakers:

[0071] The use of film formers has a positive effect on surface quality and homogeneity and improves flow behavior. Furthermore, film formers provide initial tackiness, thus facilitating the subsequent application of composite materials.

[0072] Preferred film formers are (meth)acrylic-functionalized (co)polymers. Suitable functionalized polyacrylic acids and copoly(acrylic acid / itaconic acid) are described in EP 0 323 120 A2. Other suitable polymers are described in US 10,449,125 B2 and DE 10 2023 123 022.0.

[0073] In a preferred adhesive composition, the total amount of radically polymerizable monomers comprises (A) A1) a subset of radically polymerizable monomers without an acid group and A2) a subset of radically polymerizable monomers with an acid group.

[0074] Preferably, the acid group is selected from the group consisting of phosphoric acid, phosphonic acid, and carboxylic acid. Phosphoric acid groups are particularly preferred.

[0075] Vorzugsweise sind die säuregruppenhaltigen radikalisch polymerisierbaren Monomere (A2) ausgewählt aus der Gruppe bestehend aus 10-(Meth)acryloyloxydecyldihydrogenphosphat (10-MDP), 2-(Meth)acryloyloxyethyldihydrogenphosphat, 2-(Meth)acryloyloxypropyldi-hydrogenphosphat, 6-(Meth)acryloyloxyhexyldihydrogenphosphat, 4-(Meth)acryloyloxy-butyldihydrogenphosphat, 8-(Meth)acryloyloxyoctyldihydrogenphosphat, 9-(Meth)-acryloyl-oxynonyldihydrogenphosphat, 11-(Meth)acryloyloxyundecyldihydrogenphosphat, 20-(Meth)acryloyloxyeicosyldihydrogenphosphat, 1,3-Di(meth)acyloyloxypropyl-2-dihydrogenphosphat, 2-(Meth)acryloyloxyethylphenyldihydrogenphosphat, Di(2-(meth)acyloyloxy-ethyl)pyrophosphat, Di(2-(meth)acyloyloxypropyl)pyrophosphat, Di(2-(meth)acyloyloxy-butyl)pyrophosphat, Di(2-(meth)acyloyloxypentyl)pyrophosphat, Di(2-(meth)acyloyloxy-hexyl)pyrophosphat, Di(2-(meth)acyloyloxydecyl)pyrophosphat, Glyceryldimethacrylatphosphat, Pentaerythritoltrimethacrylatphosphat,Dipentaerythritol pentaacrylate phosphate, tetramethacryloxyethyl pyrophosphate, trimellitic acid 4-methacryloyloxyethyl ester (4-MET), trimellitic anhydride 4-methacryloyloxyethyl ester (4-META), pyromellitic acid dimethacrylate, pyromellitic acid glycerol dimethacrylate, methacryloyloxyethyl phthalate, methacryloyloxyethyl maleate, methacryloyloxyethyl succinate, 1,3-glycerol dimethacrylate maleate and dioxyethoxymethacrylic acid ethylenediaminetetraacetic acid ester, preferably selected from the group consisting of 10-methacryloyloxydecyl dihydrogen phosphate, 6-methacryloyloxyhexyl dihydrogen phosphate, 2-methacryloyloxyethyl dihydrogen phosphate and 2-methacryloyloxypropyl dihydrogen phosphate.

[0076] In a preferred embodiment, an adhesive composition A2 according to the invention comprises an amount of 1 to 10 wt.%, preferably 3 to 7 wt.%, based on the total mass of the radically polymerizable composition.

[0077] In a preferred embodiment, a dental, radically polymerizable adhesive composition comprises A) in an amount in the range of 20 to 85 wt.%, preferably from 30 to 80 wt.%, B1) in an amount in the range of 0.05 to 3.0 wt.%, preferably from 0.1 to 2.0 wt.%, B2) in an amount in the range of 0.1 to 6.0 wt.%, preferably from 0.2 to 4.0 wt.% C) in an amount in the range of 0.001 to 1.0 wt.%, preferably from 0.01 to 0.5 wt.%, and G) in an amount in the range of 5 to 70 wt.%, preferably 15 to 65 wt.%, in each case based on the total mass of the radically polymerizable composition.

[0078] Another embodiment is a dental, radically polymerizable composition according to the invention for use in a therapeutic procedure as a dental filling material or as a dental adhesive.

[0079] A further component of the invention is the use of the above-described co-initiators B2 of formulas (I) or (II) in combination with photoinitiators B1 for the radical polymerization of radically polymerizable monomers A. The embodiments preferred above in connection with the dental radically polymerizable compositions according to the invention are also preferred for use.

[0080] Another component of the invention is a hardened product obtained by radical polymerization of a composition according to the invention comprising radically polymerizable monomers A, photoinitiators B1 and co-initiators B2 of formulas (I) or (II). The embodiments preferred above in connection with the dental radically polymerizable composition according to the invention are also preferred for the hardened product. Examples: Determination methods:

[0081] Particle size (D1): The particle size distributions of the microscale fillers D1a and D1b were determined by static light scattering on a Beckman Coulter LS 13 320. The particle sizes given are the d50 values ​​based on volume-weighted analysis.

[0082] Particle size (D2): The particle size distribution of the nanoscale fillers D2 was determined using dynamic light scattering on a Malvern ZetaSizer Nano ZS. For this purpose, the nanoparticles under investigation were finely dispersed in a suitable solvent using ultrasound and then measured at a wavelength of 633 nm. The resulting volume-weighted particle size distribution data were evaluated and displayed using ZetaSizer software V7.13. The particle sizes given are the d50 values ​​for volume-weighted analysis.

[0083] Depth of cure: The depth of cure (DHT) (polymerization depth) was determined according to the method described in ISO 4049:2019 under Polymerization Depth using a Celalux 2 light-curing unit (VOCO GmbH, Cuxhaven, Germany). Measurements were taken with light from the LED of the Celalux light-curing unit, with a radiation flux maximum at a wavelength in the range of 420 to 490 nm, an irradiation duration of 10 s, 20 s, or 40 s, and an irradiation intensity of 1000 mW / cm². 2 carried out.

[0084] Flexural strength: The flexural strength was determined by manufacturing and curing test specimens with dimensions of 2×2×25 mm, analogous to the procedure described in ISO 4049:2019. The measurement, in which the test specimens were subjected to a three-point bending test until fracture, was carried out on a universal testing machine according to the specifications of the standard, as was the evaluation.

[0085] E-modulus: The modulus of elasticity (E-modulus) was determined from the obtained stress-strain diagram of the flexural strength measurement based on the slope in the linear-elastic region of the graph.

[0086] Shear bond strength: The test compositions obtained were each subjected to a shear test. Unless otherwise specified, the shear bond strength tests were performed according to ISO 29022:2013 - Dentistry - Adhesion - Testing of shear bond strength with a recessed blade. Details can be found in the following text:

[0087] Bovine front teeth were embedded in an epoxy matrix in the form of a ring with a diameter d = 2.5 cm, exposing the dentin surface.

[0088] The tooth surfaces were prepared using a standardized process: coarse grinding with P120 sandpaper (average grit size 125 ± 1 µm) followed by fine grinding with P400 sandpaper (average grit size 35 ± 1 µm). The prepared tooth surfaces were then rinsed under running deionized water to remove impurities and subsequently dried with a short burst of air or by gently dabbing with a paper towel to remove excess water. The teeth were not over-dried, thus preventing any morphological changes to the tooth structure.

[0089] The respective test composition (the respective adhesive) was applied to the prepared tooth surface and massaged into the surface for 20 seconds. The solvents contained in the test composition (in the adhesive) were removed by blasting with oil- and water-free compressed air for 5 seconds, followed by light curing for 10 seconds (Celalux 2, 420–490 nm, 1000 W / cm²). 2 ).

[0090] After the adhesive layer had cured, the embedded tooth specimen was inserted into a composite screw clamp including a insertion mold (from ISO 29022:2013 - Ultradent Products, South Jordan).

[0091] The filling cavity of the insert was placed on the surface of the tooth and checked for a sufficient fit. The appliance was then fixed in place with screws.

[0092] Inserting the composite into the recess of the insert mold: The composite (GrandioSO A1, manufacturer: VOCO GmbH, Cuxhaven) was applied to the bonding surface using a suitable packing instrument (composite packer) and a tight contact without air bubbles was achieved. After filling the cylindrical part of the insert mold, the composite was light-cured for 20 seconds (Celalux 2, 420–490 nm, 1000 W / cm²). 2 ). While avoiding stresses that could negatively affect the bond (tension, torsion, shear, etc.), the composite test specimen fitted with a composite cylinder was carefully removed from the insertion mold and the clamping device.

[0093] The composite specimen was transferred to a specimen holder and clamped in place. A fixture for the recessed shear blade (crosshead construction with recessed blade) was installed in a universal testing machine (Zwick, Roell). The composite specimen, secured in its holding device, was aligned in the holder under the crosshead with the recessed blade, centered on the composite cylinder and in contact with the tooth, and positioned so that the recess of the crosshead and the composite cylinder to be sheared slid into each other without generating stress. Abbreviations: BisGMA bisphenol A glycidyl dimethacrylate (CAS 1565-94-2) Bis-EMA ethoxylated bisphenol A dimethacrylate (CAS 41637-38-1) TEGDMA triethylene glycol dimethacrylate (CAS 109-16-0) TCDDMA 3(4),8(9)-Bis(methacryloyloxymethyl)tricyclo[5.2.1.0 2,6 decane (CAS 43048-08-4) HEMA 2-Hydroxyethyl Methacrylate (CAS 868-77-9) CQ DL-Camphorquinone (CAS 10373-78-1) EDB Ethyl 4-dimethylaminobenzoate (CAS 10287-53-3) EHDB 2-Ethylhexyl-4-dimethylaminobenzoate (CAS 21245-02-3) DMAB 4-(Dimethylamino)benzonitrile (CAS 1197-19-9) EMBO-MA 2-(Methacryloyloxyethyl)-4-dimethylaminobenzoate (CAS 79984-80-8, synthesis according to DE 10 2004 011 497 A1, paragraph

[0056] ) DMADA 4-(Dimethylamino)-N,N-di-2-propen-1-ylbenzamide (CAS 1789739-75-8, synthesis according to WO 2020 / 099518 A1, page 59, example 1 MAB 2-121-1) BHT 2,6-Di-tert-butyl-4-methylphenol (CAS 128-37-0) BZT 2-(2H-Benzotriazol-2-yl)-4-methyl-phenol (CAS 2440-22-4) Dental glass 1 GM27884 UF2.0 (surface coated with MPS) Dental glass 2 GM27884 UF0.7 (surface coated with MPS) YbF3 Ytterbium(III) fluoride (20 nm, surface-coated with MDP) MPS Methacryloxypropyltrimethoxysilane (CAS 2530-85-0) MDP 10-Methacryloyloxydecyl dihydrogen phosphate (CAS 85590-00-7) FS yellow iron oxide yellow (CI Pigment Yellow 42, CAS 51274-00-1) FS red iron oxide red (CI Pigment Red 101, CAS 1309-37-1) FS black iron oxide black (CI Pigment Black 11, CAS 1317-61-9) FS white titanium dioxide (CI Pigment White 6, CAS 13463-67-7)

[0094] Example 1 (Synthesis Co-Initiator):

[0095] 3-(Dimethylamino)phenol (1.00 g, 7.45 mmol, 1 eq) was dissolved in 10 mL of CHCl3 in a two-necked flask. Methacrylic anhydride (1.30 mL, 8.94 mmol, 1.2 eq) and triethylamine (1.21 mL, 8.94 mmol, 1.2 eq) were added dropwise at 0 °C using a dropping funnel. The reaction mixture was stirred at 0 °C until the starting material was completely dissolved (approx. 10 min). The mixture was then warmed to room temperature and stirred overnight. After completion of the reaction, the organic phase was washed successively with distilled water (30 mL), 1 N HCl (30 mL), and 1 N NaHCO3 (30 mL). The organic phase was then dried over anhydrous MgSO4, filtered, and evaporated under reduced pressure. The reaction mixture was purified by silica gel flash chromatography using a 1:10 mixture of acetone and cyclohexane as eluent, yielding the product as a bright red oil (1.33 g, 89% yield). 1H NMR (300 MHz, DMSO): δ (ppm) 7.22 (t, 1H), 6.63 (dd, 1H), 6.45 (dd, 2H), 6.28 (s, 1H), 5.90 (m, 1H), 2.92 (s, 6H), 2.02 (s, 3H). Example 2 (Conversion & Polymerization Rate):

[0096] In a mixture of BisGMA (70 wt%) and TEGDMA (30 wt%), 1.8*10 -3 mol% camphorquinone and 3.1*10 -3 mol% co-initiator dissolved.

[0097] The curing of the mixtures was investigated using real-time Fourier-transform infrared spectrometry (RT-FTIR) (JASCO FTIR 4100). For this purpose, the samples (shape: diameter 12.5 mm, thickness 2 mm) were exposed to an LED (470 nm, I0 = 70 mW / cm²) for 300 seconds. 2 ) irradiated and thereby the conversion of the methacrylate band (6165 cm -1 ) as well as the maximum polymerization rate (based on the initial double bond concentration [M0]). Table 1 (Example 2): Example 2a Example 2b (comparison) Co-initiator from example 1 EDB Conversion (@300 s) 69% 70% maximum polymerization rate Rp / [M0] x100 (s- 1 ) 5,5 5,7 DHT (10 s) [mm] 5 5 DHT (20 s) [mm] 7 7 DHT (40 s) [mm] 10 10 Example 3 (Leaching):

[0098] The respective co-initiators (B2), CQ (B1), and resins (Bis-GMA / TEGDMA, 70:30 w / w) were weighed out in the mass ratios specified in Table 2. The mixture was stirred at room temperature for 60 minutes until the solids were completely dissolved. To prepare the specimens, the compositions were poured into round molds (height = 2 mm, diameter = 10 mm). The molds were covered with PET release film to prevent the formation of oxygen inhibition layers. The specimens were then cured for 60 minutes under blue light irradiation (Individo Light Box, VOCO GmbH, Cuxhaven, Germany). The specimens were examined for irregularities, and their respective weights were recorded. The specimens were then transferred to containers with 10.0 ml of ethanol or water. After defined times (1 d, 7 d) aliquots of 1.0 mL were taken, the solvent was evaporated and the residue was dissolved in 1.0 mL of acetonitrile.The solution containing the extracted components was then analyzed by HPLC using an Agilent 1260 Infinity HPLC system in combination with OpenLab ChemStation. The amount of extractable components was quantified based on the predefined extinction coefficients for monomers and amines. The percentages given refer to the theoretically present (weighed) amount of the respective substances in the sample bodies. Table 2 (Example 3): Example 3a 3b (Comparison) 3c (Comparison) 3D (comparison) (A) Bis-GMA 70,00 70,00 70,00 70,00 TEGDMA 30,00 30,00 30,00 30,00 (B1) CQ 0,30 0,30 0,30 0,30 (B2) Co-initiator from Example 1 0,60 EDB 0,60 EHDB 0,60 DMAB 0,60 1d(Ethanol) Amin (B2) and 6,40% 6,45% 6,66% TEGDMA 1,68% 1,66% 1,66% 1,72% BisGMA 0,85% 0,95% 0,96% 1,00% 7d(Ethanol) Amin (B2) and 25,67% 25,58% 27,30% TEGDMA 2,72% 2,90% 2,92% 3,01% BisGMA 1,62% 1,97% 1,99% 2,13% 1d(water) Amin (B2) and and and and TEGDMA 0,13% 0,25% 0,25% 0,27% BisGMA and and and and 7d(Water) Amin (B2) and and and and TEGDMA 0,40% 0,46% 0,45% 0,48% BisGMA 0,006% 0,005% 0,006% 0,007% nd - not detectable Example 4 (Dental composite compositions):

[0099] For the preparation of the individual dental light-curable composite compositions (Examples 4a to 4f), the respective radically polymerizable monomers A were dissolved in each other by stirring. The inorganic nanoparticles D2 were then added as a colloidal solution in alcohol, the resulting mixture was homogenized by stirring, and the solvent was removed using a rotary evaporator. Next, the photoinitiators B1, the respective co-initiators B2, and the additives F were added and dissolved by stirring. Finally, the inorganic filler particles D1a and D1b, as well as the color pigments E, were added, and the resulting mixture was homogenized using a Hauschild AM 501 mixer (4 x 12 s). The homogeneous, pasty masses were then deaerated for 10 min at 50 rpm and -0.85 bar in a laboratory mixer with beam stirrers (PC Laborsystem, Magden, CH). Table 3 (Example 4): Example 4a 4b (Comparison) 4c (Comparison) (A) BisGMA 2,54 2,54 2,54 TCDDMA 0,44 0,44 0,44 Bis-EMA 10,62 10,62 10,62 (B1) CQ 0,04 0,04 0,04 (B2) Co-initiator from Example 1 0,06 EDB 0,06 EHDB 0,06 (C) BHT 0,04 0,04 0,04 (D1a) Dental glass 1 46,76 46,76 46,76 (D1b) Dental glass 2 9,57 9,57 9,57 (D2) YbF3 29,82 29,82 29,82 (E) FS black 0,003 0,003 0,003 FS knows 0,01 0,01 0,01 FS yellow 0,03 0,03 0,03 FS red 0,004 0,004 0,004 (F) BZT 0,07 0,07 0,07 DHT (10 s) [mm] 3,77 3,75 3,74 DHT (20 s) [mm] 4,08 4,07 4,05 Flexural strength [MPa] 165 163 163 E-modulus [GPa] 12,4 12,4 12,4 Table 4 (Example 4 - continued): Example 4d (comparison) 4e (Comparison) 4f (Comparison) (A) BisGMA 2,54 2,54 2,54 TCDDMA 0,44 0,44 0,44 Bis-EMA 10,62 10,62 10,62 (B1) CQ 0,04 0,04 0,04 (B2) DMAB 0,06 EMBO-MA 0,06 DMADA 0,06 (C) BHT 0,04 0,04 0,04 (D1a) Dental glass 1 46,76 46,76 46,76 (D1b) Dental glass 2 9,57 9,57 9,57 (D2) YbF3 29,82 29,82 29,82 (E) FS black 0,003 0,003 0,003 FS knows 0,01 0,01 0,01 FS yellow 0,03 0,03 0,03 FS red 0,004 0,004 0,004 (F) BZT 0,07 0,07 0,07 DHT (10 s) [mm] 3,73 3,51 3,46 DHT (20 s) [mm] 4,05 3,89 3,81 Flexural strength [MPa] 155 129 126 E-modulus [GPa] 12,3 10,4 10,2 Example 5 (Dental adhesive compositions):

[0100] For the preparation of the individual dental adhesive compositions (Examples 5a to 5f), monomers, initiators, co-initiators, inhibitors, and solvents were weighed out according to the proportions specified in Tables 5 and 6, combined, and stirred at room temperature for four hours until the solids were completely dissolved. The shear bond strengths were then determined for each adhesive composition. Table 5 (Example 5): Example 5a 5b (Comparison) 5c (Comparison) (A1) BisGMA 40,80 40,80 40,80 TEGDMA 10,00 10,00 10,00 HEMA 25,00 25,00 25,00 (A2) MDP 4,00 4,00 4,00 (B1) CQ 1,00 1,00 1,00 (B2) Co-initiator from Example 1 1,00 EDB 1,00 EHDB 1,00 (C) BHT 0,20 0,20 0,20 (G) Water 8,00 8,00 8,00 Ethanol 10,00 10,00 10,00 Shear bond strength [MPa] 18,35 17,82 17,69 Table 6 (Example 5 - continued): Example 5d (comparison) 5e (Comparison) 5f (Comparison) (A1) BisGMA 40,80 40,80 40,80 TEGDMA 10,00 10,00 10,00 HEMA 25,00 25,00 25,00 (A2) MDP 4,00 4,00 4,00 (B1) CQ 1,00 1,00 1,00 (B2) DMAB 1,00 EMBO-MA 1,00 DMADA 1,00 (C) BHT 0,20 0,20 0,20 (G) Water 8,00 8,00 8,00 Ethanol 10,00 10,00 10,00 Shear bond strength [MPa] 17,55 14,32 13,18

Claims

[1] Dental, radically polymerizable composition comprising A) one or more radically polymerizable monomers and B) comprising a photoinitiator system B1) a photoinitiator having an absorption maximum in a wavelength range of 420 to 500 nm, and B2) a co-initiator of the formula (I) where R 1 = H or Methyl, R 2 = H, C1 to C4 alkyl or halogen, R 3 / R 4 = Alkyl, and n = 0 to 4. [2] Dental, radically polymerizable composition according to claim 1, wherein R 2 = H, Methyl or Ethyl, and / or R 3 / R 4 = Methyl or Ethyl, and / or n = 0. [3] Dental, radically polymerizable composition according to any one of the preceding claims, wherein B1 is an α-dicarbonyl compound, preferably camphorquinone. [4] Dental, radically polymerizable composition according to any one of the preceding claims, wherein the radically polymerizable monomers A are selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, Tri-cyclo[5.2.1.0 2,6]decan-3(4),8(9)-dimethanol-di(meth)acrylat, 2-Hydroxypropyl-1,3-di-(meth)acrylat, 3-Hydroxypropyl-1,2-di(meth)acrylat, Urethandi(meth)acrylat, 7,7,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 7,9,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 1,5,5-Trimethyl-1-[(2-(meth)acryloyloxyethyl)carbamoylmethyl]-3-(2-(meth)acryloyl-oxyethyl)carbamoylcyclohexan, 1,3-Bis(3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)-phenyl, 1,3-Bis(9'-methyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1'-dimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1',9'-trimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 3(4),8(9)-Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-en)tetrahydrodicyclopentadien, 3(4),8(9)-Bis-(4',7'-dioxa- 3',8'-dioxo-2'-aza-9'-methyl-decyl-9'-en)tetrahydrodicyclopentadien, Trimethylolpropandi(meth)acrylat, Trimethylolpropantri(meth)acrylat,ethoxyliertes Trimethylolpropantri(meth)acrylat, Ditrimethylolpropantetra(meth)acrylat, ethoxyliertes Ditrimethylolpropantetra(meth)-acrylat, Pentaerythritoldi(meth)acrylat, Pentaerythritoltri(meth)acrylat, Pentaerythritol-tetra(meth)acrylat, Dipentaerythritoltetra(meth)acrylat, Dipentaerythritolpenta(meth)-acrylat, Dipentaerythritolhexa(meth)acrylat, 2,2-Bis[4-[3-(meth)acryloyloxy-2-hydroxy-propoxy]phenyl]propan, 2,2-Bis[4-[2-(meth)acryloyloxy-3-hydroxypropoxy]phenyl]-propan, ethoxyliertes Bisphenol-A-di(meth)acrylat, propoxyliertes Bisphenol-A-di(meth)acrylat, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]propan, 2,2-Bis[4-(meth)-acryloyloxydiethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxytriethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxytetraethoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxy-pentaethoxyphenyl]-propan, 2,2-Bis[4-(meth)acryloyloxydipropoxyphenyl]propan, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]-2-[4-(meth)acryloyloxydiethoxyphenyl]propan,2-[4-(Meth)acryloyloxydiethoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propan, 2-[4-(Meth)acryloyloxdipropoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propan, 2-Hydroxyethyl(meth)acrylat, 2-Hydroxypropyl(meth)acrylat, 3-Hydroxypropyl(meth)-acrylat, 1,2-Dihydroxypropyl(meth)acrylat, 1,3-Dihydroxypropyl(meth)acrylat, Methyl-(meth)acrylat, Ethyl(meth)acrylat, Propyl(meth)acrylat, Butyl(meth)acrylat, Hexyl-(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Tetrahydrofurfuryl(meth)acrylat, Isobornyl-(meth)acrylat, Lauryl(meth)acrylat, Cyclohexyl(meth)acrylat, (Octahydro-4,7-methano-1H-indenyl)methyl(meth)acrylat, Benzyl(meth)acrylat, Phenoxyethyl(meth)acrylat, 10-Methacryloyloxydecyldihydrogenphosphat, 6-Methacryloyloxyhexyldihydrogenphosphat, 2-Methacryloyloxyethyldihydrogenphosphat und 2-Methacryloyloxypropyldihydrogenphosphat, bevorzugt ausgewählt aus der Gruppe bestehend aus Triethylenglycoldi(meth)acrylat, Tetraethylenglycoldi(meth)acrylat, 1,6-Hexan-diol-di(meth)acrylat, 1,10-Decandioldi(meth)acrylat, 1,12-Dodecandioldi(meth)acrylat, Tricyclo[5.2.1.0, 2,6]decan-3(4),8(9)-dimethanol-di(meth)acrylat, 2-Hydroxypropyl-1,3-di-(meth)acrylat, 3-Hydroxypropyl-1,2-di(meth)acrylat, Urethandi(meth)acrylat, 7,7,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)acrylat, 7,9,9-Trimethyl-3,14-dioxa-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydi(meth)-acrylat, 1,5,5-Trimethyl-1-[(2-(meth)acryloyloxyethyl)carbamoylmethyl]-3-(2-(meth)-acryloyloxyethyl)carbamoylcyclohexan, 1,3-Bis(3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(9'-methyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1'-dimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 1,3-Bis(1',1',9'-trimethyl-3',8'-dioxo-2'-aza-4',7'-dioxa-decyl-9'-en)phenyl, 3(4),8(9)-Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-decyl-9'-en)tetrahydrodicyclopentadien, 3(4),8(9)-Bis-(4',7'-dioxa-3',8'-dioxo-2'-aza-9'-methyl-decyl-9'-en)tetrahydrodicyclopentadien, 2,2-Bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propan, 2,2-Bis[4-[2-(meth)acryloyloxy-3-hydroxypropoxy]phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(meth)acryloyloxyethoxy-phenyl]propane, 2,2-bis[4-(meth)acryloyloxydiethoxyphenyl]propane, 2,2-Bis[4-(meth)acryloyloxytriethoxyphenyl]propane, 2,2-Bis[4-(meth)acryloyloxytetraethoxyphenyl]propane, 2,2-Bis[4-(meth)acryloyloxypentaethoxyphenyl]propane, 2,2-Bis[4-(meth)acryloyloxydipropoxyphenyl]propane, 2,2-Bis[4-(meth)acryloyloxyethoxyphenyl]-2-[4-(meth)acryloyloxydiethoxyphenyl]propane, 2-[4-(meth)acryloyloxydiethoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propane and 2-[4-(Meth)acryloyloxy-dipropoxyphenyl]-2-[4-(meth)acryloyloxytriethoxyphenyl]propane., [5] Dental, radically polymerizable composition according to any of the preceding claims, wherein the dental, radically polymerizable composition is a dental filling material. [6] Dental, radically polymerizable composition according to any one of the preceding claims, further comprising C) Inhibitors, and / or D) inorganic fillers, and / or E) Colouring agents. [7] Dental, radically polymerizable composition according to claim 6, wherein the total amount of inorganic fillers comprises D D1) a subset of inorganic fillers with an average particle size in the range of 0.4 µm to 10 µm, preferably in the range of 0.5 µm to 5 µm, and D2) a subset of inorganic fillers with an average particle size in the range of 5 nm to 100 nm, preferably in the range of 10 nm to 80 nm. [8] Dental, radically polymerizable composition according to claim 7, wherein the subset of inorganic fillers comprises D1 D1a) a subset of inorganic fillers with an average particle size in the range of 1 µm to 10 µm, preferably in the range of 1 µm to 5 µm, and D1b) a subset of inorganic fillers with an average particle size in the range of 0.4 µm to <1 µm, preferably in the range of 0.5 µm to 0.9 µm. [9] Dental, radically polymerizable composition according to claim 6, comprising A) in an amount in the range of 7 to 39 wt.%, preferably from 9 to 29 wt.%, B1) in an amount in the range of 0.01 to 1 wt.%, preferably from 0.02 to 0.5 wt.% B2) in an amount in the range of 0.01 to 1.5 wt.%, preferably from 0.03 to 0.8 wt.%, C) in an amount in the range of 0.001 to 1 wt.%, preferably from 0.01 to 0.5 wt.% D) in an amount in the range of 60 to 92 wt.%, preferably 70 to 90 wt.%, and E) in an amount in the range of 0.0001 to 1 wt.%, preferably from 0.0001 to 0.5 wt.%, each based on the total mass of the radically polymerizable composition. [10] Dental, radically polymerizable composition according to any one of claims 1 to 4, wherein the dental, radically polymerizable composition is a dental adhesive. [11] Dental, radically polymerizable composition according to claim 10, further comprising C) Inhibitors, and / or G) Solvents. [12] Dental, radically polymerizable composition according to claim 11, comprising A) in an amount in the range of 20 to 85 wt.%, preferably from 30 to 80 wt.%, B1) in an amount in the range of 0.05 to 3.0 wt.%, preferably from 0.1 to 2.0 wt.%, B2) in an amount in the range of 0.1 to 6.0 wt.%, preferably from 0.2 to 4.0 wt.% C) in an amount in the range of 0.001 to 1.0 wt.%, preferably from 0.01 to 0.5 wt.%, and G) in an amount in the range of 5 to 70 wt.%, preferably 15 to 65 wt.%, in each case based on the total mass of the radically polymerizable composition. [13] Dental, radically polymerizable composition according to any of the preceding claims for use in a therapeutic procedure as a dental filling material or as a dental adhesive.