Dental composites with photoinitiators - Patent Application 20070122999

Abstract

The present invention relates to a photocurable, polymerizable dental composite material, as well as to a polymerized composite material for producing direct or indirect dentures, comprising: (i) 30 to 90% by weight of an inorganic filler component comprising at least one dental glass and, optionally, at least one amorphous metal oxide; (ii) 5 to 60% by weight of at least one urethane acrylate, urethane methacrylate, or a mixture thereof; (iii) 0.01 to 30% by weight of at least one difunctional, trifunctional, tetrafunctional, or polyfunctional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate; and (iv) 0.01 to 10% by weight of a hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazole, and at least one mercaptotetrazole as an initiator system, and optionally at least one pigment, the total composition of the composite being 100% by weight.

Description

[Technical Field]

[0001] The subject of the present invention is a photocurable polymerizable dental composite material, comprising: (i) 30 to 90 wt. % of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 5 to 60 wt. % of at least one urethane acrylate, urethane methacrylate, or mixture thereof; (iii) 0.01 to 30% by weight of at least one di-, tri-, tetra- or polyfunctional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate, in particular not a urethane methyl acrylate; (iv) 0.01 to 10 wt. % of hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazole and at least one mercaptotetrazole as an initiator system, and optionally (v) 0.01 to 10 wt. % of at least one stabilizer and optionally at least one UV additive; (vi) optionally at least one pigment; The present invention provides a dental composite material, a polymerized composite material for producing a direct or indirect denture, and a composite material for use in producing a direct or indirect denture, comprising:

[0002] Many dental composites are known that can be used universally for both direct adhesive restorations and extraoral fabrication of indirect dentures. U.S. Patent Application Publication Nos. 2017 / 0266081 and 2021 / 0161772 disclose photopolymerizable dental materials having ethylenically unsaturated functional groups and hexaarylbisimidazole derivatives.

[0003] The same specification discloses in examples the use of MMT (3-mercapto-4-methyl-4H-1,2,4-triazole), MBT (2-mercaptobenzothiazole), and DMABE (dimethylaminobenzoic acid ethyl ester) as coinitiators for various o-Cl-HABI derivatives. The examples show that good mechanical properties are obtained, but the cure depth is low (less than 3 mm, see Table 2).

[0004] Modern dental lamps emit blue light with an emission maximum in the 400-500 nm wavelength range. A typical photoinitiator (PI) that optimally absorbs and is capable of radical formation in this wavelength range is camphorquinone (CQ). However, because the photochemically formed radicals of CQ rapidly recombine, CQ exhibits extremely low activity in combination with acrylates, methacrylates, vinylenes, or other radically polymerizable double bonds. A well-established method for better utilizing the reactivity of CQ radicals within the wavelength range is the addition of tertiary amines, which form CQ radicals and tertiary amine radicals by intermolecular hydrogen radical transfer according to Norris type II. Intramolecular recombination of CQ is eliminated, and the formed radicals can be used to initiate radical polymerization of polymerizable double bonds.

[0005] As the coinitiator, preferably used is an aminobenzoate such as 2-ethylhexyl-4-(dimethylamino)benzoate, 2-butoxyethyl-4-(dimethylamino)benzoate, or others. Empirically, using these coinitiators, dental restorative composites can achieve high double bond conversion rates, high mechanical durability (flexural strength, elastic modulus, fracture toughness, etc.), and high cure depth. This was also achieved in the aforementioned US Patent Application Publication No. 2017 / 0266081 and US Patent Application Publication No. 2021 / 0161772.

[0006] Recently, however, 2-ethylhexyl-4-(dimethylamino)benzoate has been classified by the European Chemicals Agency (ECHA) as potentially harmful to fertility and has therefore been declared a Class 1B CMR substance, casting doubt on the general use of this substance class in medical products.

[0007] The use of hexaarylbisimidazoles as photoinitiators and their combination with thiols or thiol heterocycles is generally known in the literature (J. Lalevée, J.-P-Fouassier; Dyes and Chromophores in Polymer Science, Wiley; 2015; Chapter 4.1; pp. 130-131, R. Dessauer; Photochemistry, History and Commercial Applications of Hexaarylbiimidazoles: All about HABIs, Elsevier, 2006, R. Dessauer; The invention of Dylux instant-access imaging materials and the development of HABI chemistry - a personal history; Adv. Photochem., 2005, 28, 129-261 and B. M. Monroe and G. C. Weed, Photoinitiators for free radical-initiated photoimaging systems, Chem. Rev., 1993, 93, 435-448). Berdzinski and co-workers were able to demonstrate, in particular by photo-DSC, the increased reactivity of mercaptotriazoles or phenylmercaptotriazoles in combination with chlorine-substituted hexaarylbisimidazoles (o-Cl-HABI) compared to 1,6-hexanediol diacrylate (S. Berdzinski, N. Strehmel, H. Lindauer, V. Strehmel, B. Strehmel; Photochem. Photobiol. Sci., 2014, 13, 789).

[0008] The object of the present invention was to provide an alternative photoinitiator system that allows equivalent or better properties than known camphorquinone (CQ) aminobenzoate photoinitiator systems in terms of the depth of cure of the dental material and / or the resulting mechanical properties of the dental material. Therefore, a further general object was to provide an alternative photoinitiator system that has equivalent or better properties than CQ / aminobenzoate PI systems, which are good in conventional dental restorative composites. A further object was to provide a photoinitiator system that does not contain aminobenzoates. In particular, it is desirable for the initiator system to be compatible with typical dental compositions, which may have low to very high filler contents depending on the dental material, including, in particular, dental glasses and metal oxides, depending on the specific dental application. Furthermore, the object was to provide a photoinitiator system that is compatible with the monomer or monomer mixture used. A further object was to be able to keep the initiator system content as low as possible.

[0009] The subject of the present invention is a radiation-curable, polymerizable dental composite material according to any one of claims 1 to 14, a polymerized composite material according to claim 15 or 16, a use according to claim 17, and a photoinitiator system according to claim 18. The invention is described in the claims and in particular in the description and examples.

[0010] Surprisingly, it has been discovered that high cure depths can be achieved by using various aromatic mercaptotetrazoles in combination with HABI, particularly o-Cl-HABI, compared to the cure depths of 3.00 mm or less achieved with mercaptotriazole compounds in the prior art, as discussed above.

[0011] A preferred subject of the present invention is a photoinitiator system for use in a radiation-curable polymerizable composition, preferably a dental composite, which comprises at least one compound containing at least one ethylenic group, the photoinitiator system comprising: a) hexaarylbisimidazole and / or substituted hexaarylbisimidazole, b) at least one mercaptotetrazole, including phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazole, and optionally c) at least one mercaptotriazole and / or substituted mercaptotriazole; Including, Preferably, c) and b) are present in a weight ratio of 5:3 to 3:5, in particular a weight ratio of 1:3 to 3:5, particularly preferably c) and b) are present in a weight ratio of 1:3, and particularly preferably a:(b+c) is present in a weight ratio of 1.1 or more:1; Contains a photoinitiator system.

[0012] The combination of HABI and mercaptotetrazole provides significantly improved depth of cure in dental composites. The combination of HABI, mercaptotetrazole, and mercaptotriazole provides significantly improved depth of cure along with further improved mechanical properties such as improved flexural strength and improved modulus of elasticity.

[0013] The subject of the present invention is a photocurable polymerizable dental composite material, comprising: (i) 30 to 90 wt. % of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 5 to 60% by weight of at least one urethane acrylate, urethane alkyl acrylate, in particular urethane methacrylate, or mixtures thereof; (iii) 0.01 to 30% by weight of at least one di-, tri-, tetra- or polyfunctional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate, in particular not a urethane methacrylate; (iv) 0.01 to 10 wt. % of hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazole and at least one mercaptotetrazole as an initiator system; Including, The total composition of the composite is 100% by weight; The dental composite material may further comprise a mixture of hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazoles and a mixture of mercaptotetrazoles as an initiator system.

[0014] Preferred is a combination iv) comprising, as an initiator system, a) a hexaarylbisimidazole (HABI) and / or a substituted hexaarylbisimidazole (substituted HABI), in particular a halogen-substituted hexaarylbisimidazole, particularly preferably a chlorine-substituted hexaarylbisimidazole, and b) at least one mercaptotetrazole, including a phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazole, in particular a p-substituted phenyl-substituted mercaptotetrazole. Hexaarylbisimidazole (HABI) corresponds to 2,2'-bis(phenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole. The substituted hexaarylbisimidazoles correspond to substituted 2,2'-bis(phenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazoles, such as, in particular, halogen-, especially fluorine-, bromine- or chlorine-substituted hexaarylbisimidazoles, preferably when at least one or two phenyl groups are 2-chloro, 2,4-dichloro-substituted.

[0015] The hexaarylbisimidazole (HABI) and / or at least one substituted hexaarylbisimidazole may each be present independently as a mixture, and the at least one mercaptotetrazole, including phenyl- and / or substituted phenyl-substituted mercaptotetrazoles, may each be present independently as a mixture.

[0016] Monomers which are not urethane acrylates and / or urethane alkyl acrylates, in particular not urethane methacrylates, preferably have at least one ethylenic group, particularly preferably at least two ethylenic groups.

[0017] Preferably, the weight ratio of a) hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazole to b) mercaptotetrazole is 3:1 to 1:1, in particular 2.5:1 to 1.1:1. Furthermore, it is preferred if the initiator system (iv) is present in the dental composite material in an amount of 0.1 to 1.0 wt.%, preferably 0.1 to 0.7 wt.%.

[0018] According to a preferred alternative, the dental composite material comprises (v) 0.01 to 10% by weight, particularly 0.01 to 5% by weight, preferably 0.1 to 1% by weight, of at least one stabilizer and optionally at least one UV additive, the total composition of the composite being 100% by weight. Here, UV additives are understood to mean organic and inorganic compounds that can be used as UV filters in dental composites. The organic UV filter may be the UV additive oxybenzone. This filter primarily absorbs UVB rays and short UVA rays. Additional UV additives include at least one benzophenone derivative, preferably an alkoxy-substituted benzophenone and / or phenol derivative, such as 2-hydroxy-4-methoxybenzophenone, 2,6-bis(1,1-dimethyl)-4-methylphenol, butylphenol (MBBT), and / or tris(biphenyltriazine) (TBPT), as well as mixtures containing at least two of these UV additives. Additional UV additives known to those skilled in the art, including organic and inorganic compounds that function as UV filters, may also be used.

[0019] According to a further embodiment, the dental composite material comprises in (iv) as initiator system: a) hexaarylbisimidazoles and / or substituted hexaarylbisimidazoles, in particular chlorine-substituted hexaarylbisimidazoles, b) at least one mercaptotetrazole, including in particular at least one phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazole; c) at least one mercaptotriazole and / or at least one substituted mercaptotriazole; Preferred c) mercaptotriazoles and / or substituted mercaptotriazoles include at least one mercaptotriazole including 3-mercapto-1,2,4-triazole (MTA), 3-mercapto-4-methyl-4H-1,2,4-triazole, and / or mixtures thereof.

[0020] The present invention also relates to (iv) a dental composite material comprising, as initiator system, a) a hexaarylbisimidazole (2,2'-bis(phenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole) and / or a substituted hexaarylbisimidazole (substituted 2,2'-bis(phenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole), b) at least one mercaptotetrazole, including 1-phenylmercaptotetrazole and p-substituted 1-phenylmercaptotetrazole or mixtures of these mercaptotetrazoles, in particular those selected from the mixtures of mercaptotetrazoles mentioned above, and c) at least one mercaptotriazole.

[0021] Preferred mercaptotriazoles, particularly 1-phenylmercaptotetrazoles and p-substituted 1-phenylmercaptotetrazoles, include 5-mercapto-1-phenyl-1H-tetrazole (MPHTA), 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole (HPMTA), 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole (EPMATA), 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, 4-(5-sulfanyl-1H-1,2,3,4-tetrazol-1-yl)benzonitrile (STABN), 1-[4-(5-mercapto-1H-tetrazol-1-yl)phenyl]ethanone (MTPE), and / or mixtures comprising at least two of the foregoing tetrazoles.

[0022] The subject of the present invention is furthermore a compound selected from the group consisting of: a) at least one of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (o-Cl-HABI), 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (2,4-Cl-HABI), 2,2'-bis(3-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (3-Cl-HABI), 2,2'-bis(4 ... The dental composite material contains substituted hexaarylbisimidazoles, which may include hexaarylbisimidazoles such as 4-Cl-HABI, 2,2'-bis(phenyl)-4,4'-bi(2-chlorophenyl)-5,5'-biphenyl-1,1'-bi-1H-imidazole, 2,2'-bis(phenyl)-4,4'-biphenyl-5,5'-bi(2-chlorophenyl)-1,1'-bi-1H-imidazole, 2,2'-bis(phenyl)-4,4',5,5'-tetra(2-chlorophenyl)-1,1'-bi-1H-imidazole, and mixtures containing at least two of the aforementioned hexaarylbisimidazoles. Despite the "bis" moiety, the hexaarylbisimidazoles may include both homodimers and heterodimers. The compounds may exist as tautomers, conformers, and structural isomers.

[0023] The content of hexaarylbisimidazole and / or substituted hexaarylbisimidazole in the dental composite material may be 0.10 to 5% by weight, particularly 0.15 to 5% by weight, and all contents therebetween. A particularly preferred content of at least one hexaarylbisimidazole and / or substituted hexaarylbisimidazole in the dental composite material may be 0.12 to 0.5%, preferably 0.15 to 0.5% by weight, and particularly preferably 0.015 to 0.25% by weight.

[0024] Particularly preferred dental composite materials include b) at least one mercaptotetrazole selected from the group consisting of 5-mercapto-1-phenyl-1H-tetrazole (MPHTA), 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole (HPMTA), 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole (EPMATA), 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, 4-(5-sulfanyl-1H-1,2,3,4-tetrazol-1yl)benzonitrile (STABN), 1-[4-(5-mercapto-1H-tetrazol-1-yl)phenyl]ethanone (M and / or a mixture comprising at least two of the aforementioned tetrazoles, preferably b) comprises 5-mercapto-1-phenyl-1H-tetrazole (MPHTA), 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole (HPMTA), 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole (EPMATA), 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, 4-(5-sulfanyl-1H-1,2,3,4-tetrazol-1yl)benzonitrile (STABN), and / or a mixture of at least two of the aforementioned tetrazoles. Alternatively, the at least one mercaptotetrazole is selected from those previously mentioned. Particularly preferred mercaptotetrazoles include 5-mercapto-1-phenyl-1H-tetrazole (MPHTA), 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole (HPMTA), 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole (EPMATA), and / or a mixture of at least two of the aforementioned mercaptotetrazoles. The content of at least one mercaptotriazole may be 0.02 to 5 wt. % and all contents therebetween. A content of 0.15 to 0.5 wt. % is preferred.

[0025] An alternative subject of the present invention is a light-curable polymerizable dental composite material comprising: (i) 40 to 90 wt. %, particularly 40 to 75 wt. %, of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 10 to 60% by weight, in particular 10 to 30% by weight, of at least one urethane acrylate, urethane alkyl acrylate, in particular urethane methacrylate, or mixtures thereof; (iii) 0.01 to 25% by weight, in particular 10 to 25% by weight, of at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane acrylate and / or a urethane alkyl acrylate, in particular not a urethane methacrylate; (iv) 0.01 to 10 wt. % of hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazole and at least one mercaptotetrazole as an initiator system; optionally at least one pigment; Including, The total composition of the composite is 100% by weight; The dental composite material may further comprise a mixture of hexaarylbisimidazole (HABI) and / or substituted hexaarylbisimidazoles and a mixture of mercaptotetrazoles as an initiator system.

[0026] (iv) As a) 0.1 to 0.5% by weight, in particular 0.1 to 0.3% by weight, particularly preferably 0.15 to 0.3% by weight, of hexaarylbisimidazole and / or substituted hexaarylbisimidazole and / or mixtures thereof, b) 0.02 to 0.2% by weight, preferably 0.02 to 0.15% by weight, particularly preferably 0.3 to 0.15% by weight, of at least one mercaptotetrazole, in particular comprising phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles and / or mixtures thereof, in particular p-substituted phenyl-substituted mercaptotetrazoles, c) 0.02 to 0.2% by weight, in particular 0.03 to 0.1% by weight, of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, The total composition of the composite is 100% by weight; Dental composite materials are particularly preferred.

[0027] According to a further alternative, as (iv), a) 0.15 to 0.3 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.04 to 0.2 wt. % of at least one mercaptotetrazole, particularly comprising a phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazole, in particular a p-substituted phenyl-substituted mercaptotetrazole; c) 0.03 to 0.1 wt. % of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, c) and b) are present in a weight ratio of 5:3 to 3:5, in particular in a weight ratio of 1:3 to 3:5, particularly preferably c) and b) are present in a weight ratio of 1:3, The total composition of the composite is 100% by weight; Dental composite materials are preferred. All weight ratios, for example, 5:3 to 3:5, and all further weight ratios may each independently vary by plus or minus 5%, preferably plus or minus 2.5%, particularly preferably plus or minus 1%. The presence of c) and b) in a weight ratio of 5:3 to 3:5, particularly a weight ratio of 1:3 to 3:5, refers to the weight ratio of c) to b), such as c) / b) in (wt% / wt%).

[0028] The present invention further provides, as (iv), a) 0.15 to 0.3 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.06 to 0.2 wt. %, in particular 0.1 to 0.2 wt. %, of at least one mercaptotetrazole, in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) 0.03 to 0.1 wt. % of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, c) and b) are present in a weight ratio of 5:3 to 3:5, particularly c) and b) are present in a weight ratio of 1:3 to 3:5, particularly preferably a:(b+c) is present in a weight ratio of 1:1 to 2:1, and even more preferably a:(b+c) is present in a weight ratio of 1.1 or more:1; The total composition of the composite is 100% by weight; It is a dental composite material.

[0029] Likewise, the subject of the present invention is a compound as (iv) a) 0.15 to 0.3 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.08 to 0.2 wt. %, in particular 0.1 to 0.2 wt. %, of at least one mercaptotetrazole, in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) 0.03 to 0.8 wt. % of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, c) and b) are present in a weight ratio of 1:3 to 3:5, and particularly preferably a:(b+c) is present in a weight ratio of 1.1 or more:1; The total composition of the composite is 100% by weight; It is a dental composite material.

[0030] According to a further alternative, the polymerizable composite material may optionally contain (vi) at least one pigment, dye, or mixture of pigment and dye, or similarly a mixture of pigments and / or dyes. Here, it may be more preferred if the content of (vi) is 0.001 to 5% by weight of the total composition. Dyes soluble in dental composite materials, for example according to DIN 55934, may be particularly preferred.

[0031] Furthermore, the emission maximum in the wavelength range of 440 to 550 nm and the 2 or more, preferably 1000mW / cm 2 or more, preferably 1200mW / cm 2 Polymerized dental composites, especially light-cured or polymerized composites, preferably LED-polymerized composites, having in particular the above light outputs are the subject of the present invention.

[0032] Particularly preferred polymerized dental composites have a flexural strength of 130 MPa or more and an elastic modulus of 6500 MPa or more, as determined according to DIN EN ISO 4049:2019. Similarly, for polymerized composites, an elastic modulus of 5500 MPa or more is preferred at a case depth of 8.5 mm or more, an elastic modulus of 6000 MPa or more is preferred at a case depth of 9 mm or more, and an elastic modulus of 6500 MPa or more is particularly preferred at a case depth of 9.5 mm or more, and optionally a flexural strength of 135 MPa or more, especially 140 MPa or more. Polymerization is preferably carried out using a light source such as a Translux2Wave, Translux, or LED, which has an emission maximum in the wavelength range of 400 to 550 nm, especially 440 to 480 nm, and the light output is preferably 700 mW / cm. 2 More than 1000mW / cm 2 Above, especially 1200mW / cm 2 The determination of the mechanical properties is carried out according to the standards mentioned and the polymerization is preferably carried out as described in the examples.

[0033] It is also preferred if the cure depth or polymerization depth of the polymerized composite material is 9.0 mm or more, the cure depth or polymerization depth being determined in accordance with DIN EN ISO 4049:2019, 7.10, in particular if the curing or polymerization is at an emission maximum in the wavelength range of 400 to 550 nm, in particular 440 to 480 nm, and at a wavelength of 1200 mW / cm 2 The curing and determination of the double bond conversion rate are performed for 20 seconds using a light source with a light output of 1000 to 1200 mW / cm or more, particularly an LED light source such as Translux2Wave. 2 For the determination of curing and / or mechanical properties, a Translux Wave (700 mW / cm) from Kulzer GmbH can be used. 2 Although a Translux2Wave (light output of 1000W or more) can be used, Translux2Wave is preferred.

[0034] A high filler content is advantageous for achieving very good mechanical properties of the cured composite while simultaneously reducing polymerization shrinkage that occurs during curing. These properties are also crucial for the long-term success of a denture material. However, a high filler content generally inhibits a high depth of cure or polymerization during light curing of the composite.

[0035] In the examples listed below, the conditions mentioned were adjusted: - The monomers, fillers, and additives used were the same in all experiments. - Camphorquinone (CQ) and 2-ethylhexyl 4-(dimethylamino)benzoate (EHA) were used as the reference photoinitiator system. - A new photoinitiator system, synonymous with initiator system, contains hexaarylbisimidazole (HABI-1) as a photosensitizer. Additionally, combinations of coinitiators containing various mercaptotriazoles and mercaptotetrazoles in various amounts and mixing ratios were added. The "best" coinitiators for high double bond conversion, high mechanical strength, and high cure depth were identified, as well as the best combinations of these coinitiators and their optimal mixing ratios in combination with the photosensitizer HABI, particularly o-Cl-HABI.

[0036] Furthermore, the ratio of hexaarylbisimidazole (HABI), a photosensitizer, especially substituted hexaarylbisimidazole, was evaluated in terms of high mechanical strength and high cure depth.

[0037] Depending on the filler content required, the particle size distribution may be relatively wide for high filler packing density and excellent mechanical properties, or may be designed to be relatively narrow for specific applications. The mean value of the particle size distribution may be in the range of 0.1 μm to 30 μm, preferably in the range of 0.5 μm to 20 μm. Here, the particle size distribution is defined as the particle size distribution d of the dental glass fraction in the range of 0.7 to 2.0 μm, especially 1.2 to 2.0 μm (micrometers), based on the total composition. 50 Preferably, the d of 1.8 μm, plus or minus 0.25 μm, is based on a content of 5 to 75% by weight of dental glass having 50 and particularly preferably d of 20 μm or less 99 or d less than 10 μm 99 In an alternative embodiment, additional dental glass fractions with different smaller and / or larger particle size distributions can be added to optimally adjust the packing density. The adjusted packing density allows optimal adjustment of the mechanical properties and reduced shrinkage. The particle size distribution can be determined by laser diffraction.

[0038] Generally, particle size is determined by laser diffraction, for example by a Mastersizer 3000E, by measuring the intensity of scattered light from a laser beam as it passes through a sample of dispersed particles. This analysis can be performed by Mie scattering and Fraunhofer scattering.

[0039] In this analysis, the particle size is calculated from the generated diffraction pattern based on the identified data. This is done by analyzing the data of the angle-dependent scattered light intensity and forming the basis for calculating the size of the particles involved in the diffraction pattern according to Mie's theory. The particle size is expressed as the diameter of a sphere of equal volume. Therefore, the disclosed particle size distribution can be understood as the particle size distribution of a sphere of equal volume.

[0040] The urethane acrylate preferably comprises a difunctional urethane acrylate, preferably selected from difunctional urethane acrylates having a divalent alkylene group, preferably comprising a difunctional urethane alkyl acrylate having a divalent alkylene group with alkyl of 1 to 10 C atoms and alkylene of 3 to 20 C atoms.

[0041] Photochemically polymerizable dental composites are understood to mean composites that can be polymerized by UV radiation and / or visible light (VIS radiation), preferably by a radiation source having an emission maximum in the spectral range of 400 nm to 530 nm, preferably at least one maximum or maximum in the spectral range of 440 to 500 nm. Particularly preferably, the irradiation of the composite is carried out for at least 10 seconds per projection area of ​​the radiation source. Irradiation for at least 15 seconds to 5 minutes, preferably 10 to 30 seconds per projection area of ​​the radiation source, is even more preferred. In principle, radiation sources are those with emission wavelengths, preferably with an emission maximum in the spectral range of 440 to 480 nm and a power of 500 mW / cm , as are used in particular in the dental field. 2 Ultra, especially 1200mW / cm 2Any common radiation source having the above intensities is suitable. Radiation sources with LED illuminators are particularly preferred.

[0042] The subject of the present invention is also a dental composite material obtainable by polymerization using a UV beam source and / or a Vis beam source, preferably with a Vis beam source having an emission maximum in the spectral range from 380 nm to 530 nm, preferably with at least one maximum or maximum in the spectral range from 400 to 500 nm.

[0043] In one variant, it is particularly preferred if the inorganic filler component is composed of at least one dental glass, or a mixture of a dental glass with the aforementioned average particle size, and an amorphous metal oxide, particularly a non-aggregated amorphous metal oxide, preferably a silanized amorphous metal oxide.The dental glass can preferably be silanized as well.The silanization preferably includes acrylic functionalization.The amorphous metal oxide can include silicon dioxide, precipitated silicon dioxide, pyrogenic silica, zirconium oxide, mixed oxides, or mixtures thereof, and in particular the metal oxide is silanized.

[0044] Dental glasses that may be used include aluminum silicate glasses or fluoroaluminum silicate glasses, fluoroaluminum silicate glasses containing boron, barium aluminum silicate, strontium silicate, strontium borosilicate, lithium silicate, and / or lithium aluminum silicate, as well as mixtures of at least two of the aforementioned dental glasses. As amorphous metal oxides or mixtures of amorphous metal oxides, amorphous oxide-based or mixed oxide-based spherical fillers can be used, such as amorphous SiO2, ZrO2, or similar mixed oxides of SiO2 and ZrO2.

[0045] The subject of the present invention is also a) Average particle size d of 1.8 μm plus / minus 0.25 μm 50 and preferably d of 20 μm or less 99, especially d below 10 μm 99 dental glass, or b) i) optionally a d of 2 to 8 μm, plus or minus 0.5 μm, in particular d of 4 to 6 μm, plus or minus 0.25 μm 50 ii) d of 1.0 to 2.0 μm, optionally plus / minus 0.25 μm, in particular 1.2 to 2.0 μm, optionally plus / minus 0.5 μm, preferably 1.5 μm, optionally plus / minus 0.15 μm 50 and iii) optionally a d between 0.5 μm and 1.2 μm with plus / minus 0.15 μm, optionally between 0.7 and 0.9 μm with plus / minus 0.5 μm. 50 wherein the ratio of i), ii) and iii) is 1-4:1:4-8, in particular 2-3:1:6-7. i) optionally having a d of 5 μm, plus or minus 0.5 μm; 50 ii) optionally a d of 1.8 μm, plus or minus 0.25 μm 50 and iii) optionally a d of 0.85 μm, plus or minus 0.15 μm 50 is particularly preferred, and the ratio of i), ii), and iii) is 1-4:1:4-8, particularly 2-3:1:6-7.

[0046] According to a preferred embodiment, the dental composite material has an average particle size d of 1.2 to 2.0 μm. 50 , preferably having an average particle size of 1.35 to 1.95 μm, in particular d of 1.8 μm, optionally plus / minus 0.15 μm 50 Preferably, d is 10 μm or less 99 Particularly preferred is at least one dental glass, in particular a radiopaque dental glass, having a d of about 0.85 μm, optionally plus / minus 0.1 μm, in particular plus / minus 0.05 μm, preferably plus / minus 0.03 μm. 50 Preferably, the average particle size is 10 μm or less. 99There is further provided a dental glass having the following structure. Particularly preferred dental glasses include barium aluminum borosilicate glasses. Furthermore, barium aluminum silicate glasses having a refractive index of n=1.52 to 1.55, preferably 1.53, are particularly preferred. Particularly preferred particle size distributions include a d of 0.2 μm or more. 10 d of 20 μm or less, preferably 7.5 μm or less 99 , preferably d of 0.4 μm or more 10 d less than ~7.5μm 99 , and an average diameter d of 0.7 to 7.5 μm 50 It may be in the range of.

[0047] According to a preferred embodiment, the dental composite material comprises (i) 70-85 wt. % of at least one inorganic filler component, with an average particle size d of 0.7-2.0 μm. 50 The at least one dental glass is present in a 100% by weight total composition in an amount of from 50% to 80% by weight, in particular from 55% to 76% by weight, preferably from 60% to 75% by weight, particularly preferably from 60% to 71% by weight, based on the composite material having a total composition of 100% by weight, and more preferably in combination with 4 to 7.5% by weight of amorphous silicon dioxide in the total composition.

[0048] The present invention also provides a dental composite material comprising (i) at least one dental glass, in particular a silanized barium aluminum borosilicate glass, a barium aluminum borofluorosilicate glass, preferably functionalized with methacryloxypropyl groups, and optionally 70 to 85% by weight of at least one inorganic filler component, in particular at least one non-agglomerated amorphous metal oxide having a primary particle size of 2 to 150 nm, in particular 2 to 100 nm, preferably 2 to 45 nm, wherein the amorphous metal oxide comprises silicon dioxide, precipitated silicon dioxide, pyrogenic silica, zirconium oxide, mixed oxides, or mixtures thereof, in particular wherein the metal oxide is silanized.

[0049] Preferably, the dental composite material contains, as inorganic filler components, (i.1) 66 to 84 wt. %, particularly 68 to 78 wt. %, or 75 to 78 wt. % of at least one dental glass, and optionally (i.2) 2 to 10 wt. % of an amorphous metal oxide, particularly 3 to less than 10 wt. %, preferably 4 to 8 wt. % of an amorphous metal oxide. The ratio of the dental glass to the amorphous metal oxide is preferably 20:1 to 7:1, more preferably 15:1 to 10:1. The total composition including (i), (ii), (iii), and (iv) is 100 wt. %; or, optionally, the total composition including (i), (ii), (iii), (iv), and optionally (v), and optionally (vi) is 100 wt. %.

[0050] In a preferred alternative, the composite material may contain a polymeric particulate filler content in addition to the inorganic filler component. The total content of such polymeric particulate fillers may be 0.01 to 15% by weight, preferably 0.5 to 10% by weight, based on the total composition of the composite material (100% by weight). The particle size of the polymeric filler is preferably in the range of 10 to 200 micrometers, in particular 30 to 90 micrometers, and particularly preferably 20 to 50 micrometers. The polymeric particulate filler is preferably non-spherical. Preferably, the polymeric particulate filler is present in the form of a segmented polymer.

[0051] Di- to deca-functional urethane acrylates or di- to deca-functional urethane alkyl acrylates are used as monomers and do not contain peroxy groups.

[0052] According to a particularly preferred variant, the dental composite comprises as (ii) at least one difunctional urethane acrylate having a divalent alkylene group and / or a urethane alkyl acrylate having a divalent alkylene group with alkyl of 1 to 10 C atoms, preferably methyl, and alkylene of 3 to 20 C atoms, preferably from three different urethane(alkyl)acrylates, and optionally at least one at least tetrafunctional dendritic urethane(alkyl)acrylate, preferably at least one hexafunctional dendritic urethane(alkyl)acrylate, in particular a urethane(meth)acrylate Includes:

[0053] According to a particularly preferred variant, the dental composite material comprises (ii) a mixture of at least two different urethane (meth)acrylates, preferably a mixture of three different urethane (meth)acrylates.

[0054] The notation (alkyl)acrylate or (meth)acrylate or urethane(alkyl)acrylate with (alkyl) in parentheses or urethane(meth)acrylate with (meth) in parentheses means that this notation may include acrylate or urethane acrylate, regardless of whether an alkyl group or a methyl group is present. The alkyl group preferably contains 1 to 10 C atoms, preferably 1 to 2 C atoms, in the urethane alkyl acrylates mentioned. The alkyl group preferably contains 1 to 10 C atoms, preferably 1 to 2 C atoms, in the (alkyl)acrylates mentioned.

[0055] Monomers which are not urethane acrylates or urethane alkyl acrylates are generally understood to be monomers which contain at least one ethylene group, in particular at least two ethylene groups.

[0056] The difunctional urethane acrylate, urethane(alkyl)acrylate, urethane(alkyl)acrylate having a divalent alkylene group, or urethane(meth)acrylate having a divalent alkylene group is preferably selected from linear or branched urethane dimethacrylates functionalized with divalent alkylene groups, urethane dimethacrylate-functionalized polyethers having alkylene groups, such as bis(methacryloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, also known as UDMA, also known as HEMA-TDMI. Bis(methacryloxy-2-ethoxycarbonylamino)alkylene is preferred, where alkylene is linear or branched C3 to C20, preferably C3 to C6, and particularly preferably methyl-substituted alkylene, such as HEMA-TMDI. The divalent alkylene preferably includes 2,2,4-trimethylhexamethylene and / or 2,4,4-trimethylhexamethylene.

[0057] The at least tetrafunctional dendritic urethane methacrylates include tetrafunctional to decafunctional dendritic urethane methacrylates.

[0058] According to a further preferred embodiment, the dental composite material comprises as component (iii) 0.01 to 15 wt. % of at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane(alkyl)acrylate and which may be selected from di(meth)acrylic esters, di(meth)acrylic esters of polyethers, bis(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene and / or bis-(2'-oxa-3'-oxopentyl-4'-methyl-4'-ene)tetrahydrodicyclopentadiene and their isomers, and tri-, tetra- or polyfunctional methacrylic esters of polyethers.

[0059] Preferably, the content of component (iii) may be 0.15 to 25% by weight, particularly 0.15 to 20% by weight, or particularly preferably 10 to 25% by weight. Component (iii) preferably comprises a dimethacrylic ester of a polyether, such as dimethacrylated polyethylene glycol, dimethacrylated polypropylene glycol. Dimethacrylated triethylene glycol (TEGDMA), diethylene glycol dimethacrylate (DEGMA), dimethacrylated tetraethylene glycol (TEDMA), bis-GMA, and / or ethoxylated bis-GMA are particularly preferred.

[0060] Water can be added as a stabilizer to dental composite materials to improve consistency and flowability for processability. Stabilizers are preferably added to the composite materials to prevent premature polymerization and provide the materials with a certain shelf life. As a preferred stabilizer, the composite materials contain at least one stabilizer containing water or a mixture of three stabilizers in component (iv). The stabilizer is preferably present in an amount of 0.01 to 10% by weight, particularly preferably 0.7 to 10% by weight, and especially preferably 0.5 to 2% by weight, of the total composition. Furthermore, it is preferred if the composite materials contain 0.01 to 2% by weight of water as a stabilizer, preferably 0.1 to 1.0% by weight.

[0061] To optimally adjust the color and natural aesthetics of the polymerized composite material, at least one pigment is added to the composite material, including at least one fluorescent pigment and optionally at least one organic color pigment and / or at least one inorganic color pigment, in particular a non-fluorescent color pigment. The at least one fluorescent pigment is preferably an organic fluorescent pigment, in particular a non-polymerizable organic fluorescent pigment, optionally containing an aryl carboxylic acid ester, an aryl carboxylic acid, a coumarin, a rhodamine, a naphthalimide, or a derivative of each substance. The inorganic fluorescent pigment is preferably CaAl4O7:Mn 2+ , (Ba0.98Eu0.02)MgAl 10 O 17 , BaMgF4:Eu 2+, Y(1.995)Ce(0.005)SiO5.

[0062] The pigments, especially color pigments, that can be used in the composite include organic and inorganic pigments such as diethyl-2,5-dihydroxyterephthalate, N,N'-bis(3,5-xylyl)perylene-3,4:9,10-bis(dicarbimidyl), copper phthalocyanine, titanate pigments, especially chromium antimony titanate (rutile structure), spinel black, especially pigments based on iron oxide black (Fe3O4) in which iron (Fe) is partially substituted by chromium and copper or nickel and chromium or manganese, zinc iron chrome spinel, brown spinel, ((Zn,Fe)(Fe,Cr)2O4) cobalt zinc aluminate blue spinel, and / or titanium dioxide. The pigments, including fluorescent and color pigments, are preferably present in an amount of 0.01 to 10% by weight, particularly preferably 0.01 to 5% by weight, and more preferably 0.01 to 1% by weight, of the total composition.

[0063] Pigment selection must be tailored specifically to the dental composite composition to allow for the tailoring of a uniform color in both the polymerizable and polymerized composites. The production of large material blocks also requires tailoring of both pigment selection and concentration to avoid undesirable discoloration due to the size of the polymerized material block.

[0064] According to a further preferred embodiment, the composite material may comprise (iv) 0.01 to 2% by weight of an initiator system, in particular for the UV range and / or VIS range (visible light), and 0.01 to 2% by weight of a stabilizer.

[0065] Furthermore, the subject of the present invention is a polymerized dental composite material, obtainable by i) polymerization of the composite material with a UV and / or VIS beam source, preferably with a VIS beam source having an emission maximum in the spectral range of 400 nm to 530 nm, preferably with at least one maximum or maximum in the spectral range of 440 to 500 nm.

[0066] A polymerized dental composite material, in particular for producing direct or indirect dentures, (i) 30 to 90 wt. %, particularly 40 to 90 wt. %, of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 5 to 60% by weight, in particular 10 to 60% by weight, of at least one polymer based on at least one urethane acrylate, urethane methacrylate, or a mixture thereof, (iii) 0.01 to 30% by weight, in particular 0.01 to 25% by weight, of at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane acrylate and / or urethane alkyl acrylate, in particular not a urethane methacrylate, and optionally (iv) 0.01 to 10 wt. % of a hexaarylbisimidazole and / or substituted hexaarylbisimidazole and at least one mercaptotetrazole as an initiator system; optionally at least one pigment, and optionally at least one stabilizer, and optionally at least one UV additive; Including, The total composition of the composite is 100% by weight; Dental composite materials are preferred. Here, it is particularly preferred if the modulus of elasticity is 6500 [MPa] or more, determined according to DIN EN ISO 4049:2019 and / or a bending strength of 130 [MPa] or more, and in particular if the modulus of elasticity is 6700 [MPa] or more, determined according to DIN EN ISO 4049:2019 and / or a bending strength of 130 [MPa] or more, and the hardening depth or polymerization depth is 9.5 mm or more, determined according to DIN EN ISO 4049:2019. In this case, polymerization can be carried out according to the conditions listed above and below.

[0067] According to a further embodiment, the present invention relates to the use of dental composite materials for the production of dental filling materials, dental prosthetic supplies as composite materials for the production of directly bonded dental restorations, as hoof repair materials, as bone cements, as bone cements for cementing artificial joint prostheses, as orthodontic appliances and devices, by moulding methods (DIN 8580), additive methods and / or material removal methods, in particular methods in which the polymerised composite material is removed by mechanical production methods such as milling, cutting such as laser cutting, grinding, crushing, chipping and / or drilling, in particular not in the patient, i.e. not in a surgical, therapeutic or diagnostic method, preferably with CAD / CAM methods, or in particular not in the patient, i.e. in a non-surgical, non-therapeutic or non-diagnostic method, preferably with CAD / CAM methods. Particularly preferably, the composite material can be used for the production of medical, veterinary, or dental prostheses, including crowns, inlays, onlays, superstructures, artificial teeth, dental bridges, dental bars, spacers, abutments, or veneers. Furthermore, the polymerized composite material can be used for the production of direct dentures, indirect dentures, prosthetic teeth, dental bridges, and / or milling blanks. Additive methods (additive manufacturing) or, synonymously, rapid technology or generative manufacturing, include in particular all 3D printing methods (3D printing), such as stereolithography (SLA), digital light processing (DLP), continuous liquid interface manufacturing (CLIP), daylight polymer printing (DPP), digital light synthesis (DLS), two-photon lithography (2PP), material jetting, powder bed fusion, such as electron beam melting, selective laser melting (SLM), selective laser sintering (SLM), selective heat sintering (SHS), and further additive methods known to those skilled in the art that allow composite materials to be constructed. Composite materials can also be applied by bonding methods, such as adhesives, or coating methods, and are not particularly applicable for surgical, therapeutic, or diagnostic procedures.

[0068] Likewise, the urethane (meth)acrylate according to the present invention preferably includes (ii) at least one urethane (meth)acrylate, in particular a urethane dimethacrylate, preferably a bis(methacryloxy-2-ethoxycarbonylamino)alkylene, a diurethane acrylate oligomer, an alkyl-functional urethane dimethacrylate oligomer, an aromatic-functionalized urethane dimethacrylate oligomer, an aliphatic unsaturated urethane acrylate, a bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyether, an aromatic urethane diacrylate oligomer, an aliphatic urethane diacrylate oligomer, an aliphatic urethane diacrylate, a hexafunctional aliphatic urethane resin, an aliphatic urethane triacrylate, an aliphatic urethane acrylate oligomer, or an unsaturated aliphatic urethane acrylate. Di- and polyfunctional urethane (meth)acrylates, such as especially urethane di(meth)acrylates, are preferred, and particularly preferably the at least one (iii) urethane dimethacrylate is selected from linear or branched alkyl-functionalized urethane dimethacrylates, urethane dimethacrylate-functionalized polyethers, especially bis(methacryloxy-2-ethoxycarbonylamino)alkylenes, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane.Suitable urethane (meth)acrylates are available under the trade names Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (diurethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomer), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165, Actilane 250, Genomer 1122 (monofunctional urethane acrylate), Photomer 6210 (cas no. 52404-33-8, aliphatic urethane diacrylate), Photomer 6623 (hexafunctional aliphatic urethane resin), Photomer 6891 (aliphatic urethane triacrylate), UDMA, Roskydal LS 2258 (aliphatic urethane acrylate oligomer), Roskydal XP 2513 (unsaturated aliphatic urethane acrylate). The urethane (meth)acrylate may preferably be selected from the urethane (meth)acrylates described above or from a mixture of at least two different, preferably at least three different, urethane (meth)acrylates described above.

[0069] (iii) The at least one di-, tri-, tetra- or polyfunctional monomer which is not a urethane(alkyl)acrylate, in particular not a urethane(meth)acrylate, is preferably selected from at least one of the following monomers, in particular bis-(2'-oxa-3'-oxo-pentyl-4'-ene)tetrahydrodicyclopentadiene (tricyclo[5.2.1. 02,6 ] ester of decanedimethanol with two acrylates) or bis-(2'-oxa-3'-oxo-pentyl-4'-methyl-4'-ene)tetrahydrodicyclopentadiene (tricyclo[5.2.1. 02,6] Esters of decanedimethanol and two methacrylates) and their isomers, 1,4-butanediol dimethacrylate (1,4-BDMA) or pentaerythritol tetraacrylate, bis-GMA monomer (bisphenyl-A-glycidyl methacrylate), triethylene glycol dimethacrylate (TEGDMA) and diethylene glycol dimethacrylate (DEGMA), tetraethylene glycol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and mixtures of monomers including butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated / propoxylated bisphenol-A-di(meth)acrylate, mixtures containing at least one of these (meth)acrylates, and / or copolymers comprising one or at least two of the aforementioned monomers.

[0070] Typical difunctional monomers, especially (iii), also referred to as crosslinkers or multiple crosslinkers, are tri- or tetraethylene glycol di(meth)acrylate, BDMA, 1,4-butanediol dimethacrylate (1,4-BDMA), bis-GMA monomer (bisphenyl-A-glycidyl methacrylate, an addition product of methacrylic acid and bisphenol-A-diglycidyl ether), diethylene glycol di(meth)acrylate, bisphenol-A-di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth)acrylate, as well as butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, ethoxylated / propoxylated bisphenol-A-di(meth)acrylate. Tri- and tetrafunctional monomers or multiple crosslinkers can also be added as diluents (low viscosity acrylates), including the following difunctional monomers: trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol tetraacrylate.

[0071] The present invention also relates to a composite material that preferably further contains at least one substance selected from the group consisting of fillers, pigments, stabilizers, control agents, antimicrobial additives, UV absorbers, thixotropic agents, catalysts, and crosslinkers. Additives such as pigments, stabilizers, and control agents are used in relatively small amounts, for example, a total of 0.01 to 3.0, especially 0.01 to 1.0, weight percent based on the total composition of the composite material. Suitable stabilizers include, for example, hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol (BHT).

[0072] Typical UV additives may also include 2,6-di-tert-butyl-4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ), 2-hydroxy-4-methoxybenzophenone, HALS (hindered amine light stabilizers), benzotriazole ultraviolet absorbers (UVA), and hydroxyphenyltriazine (HPT). Particularly suitable stabilizers are, for example, oxybenzone, hydroquinone monomethyl ether, and / or 2,6-di-tert-butyl-4-methylphenol (BHT).

[0073] The following examples are intended to clarify the invention without limiting it to these examples.

[0074] Working Example: method Composite paste manufacturing The monomer, initiator, and additives were weighed and mixed, and the mixture was mixed at 1500 rpm (rpm) at atmospheric pressure using a speed mixer (Hauschild-DAC 600.1 FVZ). -1 The filler is subsequently metered into the monomer mixture and the mixture is homogenized in a speed mixer at atmospheric pressure and 1500 rpm / min. -1 The composite is then homogenized again using a three-roll mill. The composite is then homogenized again using a speed mixer under vacuum for 700 min. -1 Degas again for 5 minutes at RT.

[0075] Determination of flexural strength and modulus of elasticity The manufacture of the bending rods and the determination of the bending strength and modulus of elasticity (elastic modulus) were carried out in accordance with DIN EN ISO 4049:2019, 7.11 (sample piece: 25 ± 2 mm × 2.0 ± 0.1 mm × (2.0 ± 0.1) mm, light source: Kulzer, Translux Wave, 700 mW / cm 2 , 20 seconds). Full reference is made to DIN EN ISO 4049:2019. Before testing, the polymerized sample pieces are stored in water at (37±1)°C for 24 hours.

[0076] Determination of case depth The determination of the cure depth / polymerization depth is carried out according to DIN EN ISO 4049:2019, 7.10 (sample piece: diameter 4 mm, minimum length ≥ 15 mm, light source: Translux 2Wave, 1000-1200 mW / cm 2 , 20 seconds). Full reference to DIN EN ISO 4049:2019.

[0077] Determination of double bond conversion rate U The double bond conversion rate U is determined using ATR-IR. Here, the material sample is placed in a cylindrical mold with a depth of 2 mm. The cylindrical mold filled with the composite is placed on the ATR crystal, so that the ATR crystal is located below the material sample. IR spectrum (wavelength range: 4000 cm) -1 ~700cm -1 Then, the composite material was placed on the upper side and covered with a transparent film, and a light source (light source: Translux 2 Wave, 1200 mW / cm 2 , 20 s) and 10 min after the end of photopolymerization, further IR spectra are recorded. -1 ) gives the residual double bond content, from which the double bond conversion U in % can be determined.

[0078] U = 100 - (total non-polymerized area / total polymerized area · 100)

[0079] [Table 1-1] [Table 1-2]

[0080] Evaluation of HABI-1 with different coinitiator ratios Camphorquinone was replaced by HABI-1 in an equimolar ratio. EHA was replaced by MTA, MPHTA, HPMTA, and EPMTA in the same weight ratio (see Table 2). The PI system HABI-1 / MTA is characterized by high double bond conversion, as well as high flexural strength and high modulus, but has a lower cure depth compared to the reference (see Table 3b). In contrast, the HABI-1 system combined with MPHTA, HPMTA, or EPMTA is characterized by somewhat lower flexural strength and modulus, but has a higher cure depth compared to HABI-1 / MTA (see Table 3a and Tables 4a and 4b).

[0081] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4]

[0082] [Table 3-1] [Table 3-2]

[0083] It can be seen that the depth of cure of the HABI / tetrazole combination is higher than that of the HABI / triazole combination.Compared to the reference (CQ / EHA), significantly better mechanical properties can be obtained for the dental composites according to the invention with the photoinitiators according to the invention.

[0084] The coinitiator MTA alone in combination with HABI-1 (0.2 wt%) leads to increased mechanical strength of the cured composite. Only the combinations with the mercaptotetrazoles MPHTA, EPMTA, and HPMTA achieve significantly higher cure depths compared to MTA. Tables 4a and 4b list the mixing ratios of MTA to MPHTA and EPMTA to HPMTA.

[0085] [Table 4-1] [Table 4-2]

[0086] When the concentration of mercaptotriazole in combination with HABI is 0.1 wt % or more, a cure depth of 10 mm or more can be achieved, especially for dental composites according to the invention having fillers.

[0087] Based on the data in Tables 3-4b, the optimal mixing ratio of mercaptotriazole / mercaptotetrazole (wt%) can be determined to be 1:3 or 3:5, with a weight percentage of HABI-1 of approximately 0.2 wt%. In this way, standard dental composites can achieve comparable mechanical strength in terms of flexural strength and modulus of elasticity (flexural strength up to 149 MPa and modulus of elasticity up to 6900 MPa) as well as acceptable cure depths (up to 10.2 mm). Furthermore, the comparable high double bond conversion rate after a standard exposure time of 20 seconds confirms the qualitatively good polymerization quality of the photoinitiator system. A high double bond conversion rate leads to a high crosslink density in the material and reduces the soluble fraction of the medical product.

Claims

1. 1. A light-curable polymerizable dental composite material comprising: (i) 30 to 90 wt. % of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 5 to 60 weight percent of at least one urethane acrylate, urethane methacrylate, or mixture thereof; (iii) 0.01 to 30% by weight of at least one di-, tri-, tetra- or polyfunctional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate; (iv) 0.01 to 10% by weight of hexaarylbisimidazole and / or substituted hexaarylbisimidazole and at least one mercaptotetrazole as an initiator system; Including, the total composition of the composite material is 100% by weight; Dental composite materials.

2. The dental composite material (v) 0.01 to 10 wt. % of at least one stabilizer and optionally at least one UV additive; The total composition of the composite material is 100% by weight 2. The dental composite material according to claim 1, wherein the composite material is a hydroxyapatite or hydroxyapatite.

3. (iv) as an initiator system a) hexaarylbisimidazole, substituted hexaarylbisimidazole, and / or mixtures thereof; b) at least one mercaptotetrazole, including phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles or mixtures thereof; 3. The dental composite material according to claim 1, comprising:

4. (iv) as an initiator system a) hexaarylbisimidazoles, in particular 2,2′-bis(phenyl)-4,4′,5,5′-tetraphenyl-1,1′-bi-1H-imidazole, and / or substituted hexaarylbisimidazoles, b) at least one mercaptotetrazole, including in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) at least one mercaptotriazole and / or substituted mercaptotriazole; 4. A dental composite material according to claim 1, comprising:

5. (iv) as an initiator system a) hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) at least one mercaptotetrazole selected from 1-phenylmercaptotetrazole and p-substituted 1-phenylmercaptotetrazoles; c) at least one mercaptotriazole; 5. A dental composite material according to claim 1, comprising:

6. a) the substituted hexaarylbisimidazole is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (o-Cl-HABI), 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (2,4-Cl-HABI), 2,2'-bis(3-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (3-Cl-HABI), 2,2'-bis(4-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bi-1H-imidazole (4-Cl-HABI), 2,2'-bis(phenyl)-4,4'-bi(2-chlorophenyl)-5,5'-biphenyl-1,1'-bi-1H-imidazole, 2,2'-bis(phenyl)-4,4'-biphenyl-5,5'-bi(2-chlorophenyl)-1,1'-bi-1H-imidazole, 2,2'-bis(phenyl)-4,4',5,5'-tetra(2-chlorophenyl)-1,1'-bi-1H-imidazole, and a mixture containing at least two of the aforementioned hexaarylbisimidazoles 6. A dental composite material according to claim 1, comprising:

7. 7. Dental composite material according to claim 1, characterized in that the at least one mercaptotetrazole is selected from the group consisting of 5-mercapto-1-phenyl-1H-tetrazole (MPHTA), 1-(4-hydroxyphenyl)-5-mercapto-1H-tetrazole (HPMTA), 1-(4-ethoxyphenyl)-5-mercapto-1H-tetrazole (EPMATA), 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, 4-(5-sulfanyl-1H-1,2,3,4-tetrazol-1-yl)benzonitrile (STABN), 1-[4-(5-mercapto-1H-tetrazol-1-yl)-phenyl]ethanone (MTPE), and / or a mixture comprising at least two of the aforementioned tetrazoles.

8. 8. The dental composite material according to claim 4, wherein the at least one mercaptotriazole comprises 3-mercapto-1,2,4-triazole (MTA), 3-mercapto-4-methyl-4H-1,2,4-triazole, and / or mixtures thereof.

9. (iv) is a) 0.1 to 0.5 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.02 to 0.2 wt. % of at least one mercaptotetrazole, including in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) 0.02 to 0.2% by weight of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, The total composition of the composite material is 100% by weight 9. Dental composite material according to any one of claims 4 to 8, characterized in that it is

10. (iv) is a) 0.15 to 0.3 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.04 to 0.2 wt. % of at least one mercaptotetrazole, including in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) 0.03 to 0.1% by weight of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, In particular, c) and b) are present in a weight ratio of 5:3 to 3:5, preferably in a weight ratio of 1:3 to 3:5, particularly preferably c) and b) are present in a weight ratio of 1:3, The total composition of the composite material is 100% by weight 10. Dental composite material according to any one of claims 4 to 9, characterized in that it is

11. (iv) is a) 0.15 to 0.3 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.06 to 0.2 wt. % of at least one mercaptotetrazole, including in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) 0.03 to 0.1% by weight of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, In particular, c) and b) are present in a weight ratio of 5:3 to 3:5, preferably c) and b) are present in a weight ratio of 1:3 to 3:5, particularly preferably a:(b+c) is present in a weight ratio of 1:1 to 2:1, even more preferably a:(b+c) is present in a weight ratio of 1.1:1 or more, The total composition of the composite material is 100% by weight 11. Dental composite material according to any one of claims 4 to 10, characterized in that it is

12. (iv) is a) 0.15 to 0.3 wt. % of hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) 0.08 to 0.2 wt. % of at least one mercaptotetrazole, including in particular phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazoles; c) 0.03 to 0.8% by weight of at least one mercaptotriazole and / or substituted mercaptotriazole; Including, c) and b) are present in a weight ratio of 1:3 to 3:5, particularly preferably a:(b+c) is present in a weight ratio of 1.1 or more:1, The total composition of the composite material is 100% by weight 12. Dental composite material according to any one of claims 1 to 11, characterized in that it is

13. 13. The dental composite material according to claim 4, wherein the polymerized composite material has a flexural strength of at least 130 MPa and an elastic modulus of at least 6500 MPa, determined according to DIN EN ISO 4049:2019.

14. The polymerized composite material has a cure depth or polymerization depth in mm of 9.0 mm or more, the cure depth or polymerization depth being determined in accordance with DIN EN ISO 4049:2019, 7.10, in particular, curing or polymerization is performed with an emission maximum in the wavelength range of 440 to 480 nm and an emission intensity of 1000 mW / cm ２ 14. Dental composite material according to claim 1, characterized in that the treatment is carried out for 20 seconds using a light source, in particular an LED light source, having a light output of at least 100 ohms.

15. i) A polymerized dental composite material obtainable by polymerization of the composite material according to any one of claims 1 to 14 with a UV and / or VIS beam source, preferably with a VIS beam source having an emission maximum in the spectral range of 400 nm to 530 nm, preferably with at least one maximum or maximum in the spectral range of 440 to 500 nm.

16. (i) 30 to 90 wt. % of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide; (ii) 5 to 60% by weight of at least one polymer based on at least one urethane acrylate, urethane methacrylate, or mixtures thereof; (iii) 0.01 to 30% by weight of at least one di-, tri-, tetra- or polyfunctional monomer that is not a urethane acrylate and / or a urethane alkyl acrylate, and optionally (iv) 0.01 to 10% by weight of a hexaarylbisimidazole and / or substituted hexaarylbisimidazole and at least one mercaptotetrazole as an initiator system; optionally at least one pigment, and optionally at least one stabilizer, and optionally at least one UV additive; Including, the total composition of the composite material is 100% by weight; Polymerized dental composite material, especially according to claim 15.

17. 17. Use of a dental composite material according to any one of claims 1 to 16 for producing a dental filling material, a dental prosthetic supply in additive and / or material removal methods, in particular methods in which the polymerized composite material is removed by milling, cutting, grinding, fracturing, chipping and / or drilling, in particular with CAD / CAM methods, or in non-surgical, non-therapeutic or non-diagnostic methods, preferably with CAD / CAM methods, for producing a composite material for the production of directly bonded dental restorations, or as a composite material for the production of directly bonded dental restorations, as a hoof repair material, as a bone cement, as a bone cement for cementing artificial joint prostheses, as orthodontic appliances and devices, and / or in coating or bonding methods.

18. 1. A photoinitiator system for use in a light-curable polymerizable composition, preferably a dental composite, comprising at least one compound containing at least one ethylenic group, the photoinitiator system comprising: a) hexaarylbisimidazole and / or substituted hexaarylbisimidazole; b) at least one mercaptotetrazole, including phenyl-substituted and / or substituted phenyl-substituted mercaptotetrazole, and optionally c) at least one mercaptotriazole and / or substituted mercaptotriazole; Including, Preferably, c) and b) are present in a weight ratio of 5:3 to 3:5, in particular in a weight ratio of 1:3 to 3:5, particularly preferably c) and b) are present in a weight ratio of 1:3, and particularly preferably a:(b+c) is present in a weight ratio of 1.1 or more:1; Photoinitiator systems.

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