Dental composite material and mill blanks consisting of said composite material

Abstract

A polymerisable dental composite material comprising (i) 70 to 85% by weight of an inorganic filler component comprising at least one dental glass and optionally at least one amorphous metal oxide, (ii) 10 to 30% by weight of at least one monomer comprising 1,3-bis(5′-alkyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl and/or 1,3-bis(5′,9′-dialkyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl, (iii) 0.01 to 5% by weight of at least one di-, tri-, tetra- or multi-functional monomer not being a urethane (meth)acrylate, (iv) 0.01 to 10% by weight of at least one initiator, of an initiator system and optionally of at least one stabilizer and optionally of at least one pigment, wherein the total composition of the composite material amounts to 100% by weight, and a polymerized composite material having a flexural strength of greater than or equal to 190 MPa and an elastic modulus of 12 to 21 GPa for the production of indirect dentures.

Claims

1. A polymerisable dental composite material, comprising (i) 60 to 85% by weight of an inorganic filler component comprising at least one dental glass, as well as optionally at least one amorphous metal oxide, (ii) 10 to 40% by weight of at least one monomer comprising 1,3-bis(5′-alkyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl and/or 1,3-bis(5′,9′-dialkyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl, wherein the alkyl groups, each independently, are selected from C1 to C4 alkyl groups, (iii) 0.01 to 5% by weight of at least one di-, tri-, tetra- or multi-functional monomer not being a urethane (meth)acrylate, comprising bis(methacryloyloxymethyl)tetrahydrocyclopentadiene, bis(acryloyloxymethyl)tetrahydrodicyclopentadiene, as well as optionally mixtures comprising at least a 3,8-/3,9-/4,8-/ 3,10-/4,10 isomer and/or cis isomer and trans isomer of the aforementioned compounds, and optionally di-, tri-, tetra- or multi-functional (meth)acrylic esters of polyethers, (iv) 0.01 to 10% by weight of at least one initiator, of an initiator system, as well as optionally of at least one stabilizer and optionally of at least one pigment, wherein the total composition of the composite material amounts to 100% by weight.

2. The dental composite material according to claim 1, wherein ii) the monomer comprises at least one monomer of general formula II, ##STR00003## with a) R.sup.1, R.sup.4 equal to H and R.sup.2 and R.sup.3 each independently equal to C1 to C4 alkyl or b) R.sup.1, R.sup.4, R.sup.2 and R.sup.3 each independently equal to C1 to C4 alkyl.

3. The dental composite material according to claim 1, wherein the dental glass has an average particle size d.sub.50 of 0.1 to 1.0 μm.

4. The dental composite material according to claim 1, wherein the amorphous metal oxide comprises at least one non-agglomerated amorphous metal oxide having a primary particle size of 2 to 45 nm, and the amorphous metal oxide optionally comprises precipitated silicon oxide, zirconium oxide or mixed oxides.

5. The dental composite material according to claim 1, wherein the composite material comprises as (i) inorganic filler component (i.1) 70 to 84% by weight of at least one dental glass, and optionally (i.2) 1 to 15% by weight amorphous metal oxide, based on the total composition.

6. The dental composite material according to claim 1, wherein (ii) further comprises a mixture of at least two different urethane (meth)acrylates, wherein the mixture comprises at least one difunctional urethane(meth)acrylate having a bivalent alicyclic group and a difunctional urethane (meth)acrylate having a bivalent alkylene group, and optionally at least one at least tetrafunctional dendritic urethane (meth)acrylate.

7. The dental composite material according to claim 1, wherein the at least one stabilizer comprises water, at least one benzophenone derivative and/or at least one phenol derivative.

8. The dental composite material according to claim 1, wherein (ii) comprises 1,3-bis(5′-methyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl and/or 1,3-bis(5′,9′-dimethyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl, in a mixture with at least one other urethane (meth)acrylate, and/or (iii) comprises bis(methacryloyloxymethyl)tetrahydrodicyclopentadiene, bis(acryloyloxymethyl)tetrahydrodicyclopentadiene, or a mixture of these monomers with at least one di-, tri-, tetra- or multi-functional monomer not being urethane (meth)acrylate.

9. A polymerized dental composite material obtained by polymerization of the composite material according to claim 1.

10. The polymerized dental composite material according to claim 9, having i) a flexural strength of greater than or equal to 200 MPa, dry after polymerization or 7 days, dry 23° C.+/−3° C., according to EN ISO 6872:2008, and/or ii) having a flexural strength of greater than or equal to 200 MPa, 7 days, 37° C. H.sub.2O, according to EN ISO 6872:2008, and/or iii) having a flexural strength of greater than or equal to 200 MPa, 7 days, 37° C. H.sub.2O, thermocycling 5000 cycles, according to EN ISO 6872:2008.

11. The polymerized dental composite material according to claim 9, wherein i) the elastic modulus amounts to greater than or equal to 12 to 21 GPa dry after polymerization or 7 days, dry 23° C.+/−3° C., according to EN ISO 6872:2008, and/or ii) the elastic modulus amounts to greater than or equal to 12 to 20 GPa, 7 days, 37° C. H.sub.2O, according to EN ISO 6872:2008, and/or iii) the elastic modulus amounts to greater than or equal to 12 to 20 GPa, 7 days, 37° C. H.sub.2O, thermocycling 5000 cycles, according to EN ISO 6872:2008.

12. A polymerized dental composite material comprising 60 to 85% by weight of at least one inorganic filler compound comprising at least one dental glass of an average particle size d.sub.50 of 0.1 to 1.0 μm, as well as optionally at least one amorphous silanised metal oxide of a primary particle size of 2 to 45 nm, 10 to 40% by weight of at least one polymer being based on at least one monomer comprising (a) at least one monomer comprising 1,3-bis(5′-methyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl and/or 1,3-bis(5′,9′-dimethyl-3′,8′-dioxo-2′-aza-4′,7′-dioxa-decyl-9′-en)phenyl, (b) bis(methacryloyloxymethyl)tetrahydrodicyc lopenta diene and/or bis(acryloyloxymethyl)tetrahydrodicyc lopenta diene, and (c) optionally at least one di-urethane (meth)acrylate having a bivalent alkylene group, (d) at least one tetra- to decafunctional dendritic urethane methacrylate, and (e) optionally at least one di-, tri-, tetra- or multi-functional (meth)acrylic ester of polyethers, and 0.01 to 10% by weight of at least one pigment wherein the total composition of the composite material amounts to 100% by weight.

13. A polymerized dental composite material according to claim 9, wherein the polymerized dental composite material is present in the form of a block of material, a block of material that is present as a three-dimensional geometrical moulded body, a block material as a milling blank without an adapter, or as a milling blank with an adapter for fastening in an automated device to remove material.

14. Method of using a dental composite material according to claim 1 for the production of dental prosthetic restorations in a material-removing process or for the production of direct adhesive dental restorations.

15. Method according to claim 14 for the production of dental prosthetic restorations comprising crowns, inlay, onlays, superstructures, artificial teeth, dental bridges, dental bars, spacers, abutments or veneers.

16. Polymerized dental composite material according to claim 9 obtained by polymerization at a pressure of 50 to 300 MPa and/or elevated temperature at 90 to 150° C.

17. The polymerised dental composite material according to claim 12, wherein the polymerised dental composite material is present in the form of a block of material.

18. Method of using a dental composite material according to claim 9 for the production of dental prosthetic restorations in a material-removing process, or for the production of direct adhesive dental restorations.

19. Method of using dental composite material according to claim 12 for the production of dental prosthetic restorations in a material-removing process, or for the production of direct adhesive dental restorations.

Description

EXECUTION EXAMPLES

(1) Three-Point Bending Flexural Test

(2) Flexural properties were determined using a three-point bending flexural test according to ISO 6872:2008 (ISO 6872:2008. Dentistry—Ceramic materials, 3rd ed, International Organization for Standardization, Geneva, 2008). The rod-shaped specimens, 4.0 mm wide, 14.0 mm long and 1.2 mm thick, were produced with a low-speed diamond saw (Isomet, Buehler, Lake Bluff, Ill., USA). All specimens were wet ground and polished with a #600 and #1000 diamond wheel (Maruto, Tokyo, Japan) and #1000 diamond blades (Maruto) mounted on a metallographic lapping machine (Dia-Lap, ML-150P, Maruto) to achieve the required dimensions of 4.0±0.2×14.0±0.2×1.2±0.2 mm. In order to minimize edge breaks in the rod-shaped specimens during the bending test, an edge chamfer, 0.15 mm wide, was incorporated using the lapping machine with a #1000 diamond blade. After polishing, all specimens were stored in a silica gel desiccator for 7 days prior to the bending flexural test. Three groups of ten specimens each were randomly produced from each CAD/CAM block. Specimens of the first group were stored under dry conditions at ambient room temperature (23±2° C.) for 7 days. The second group was stored in 37° C. deionized water for 7 days, while the third group was stored in 37° C. deionized water for 7 days followed by 5000 thermal cycles (thermocycling 5° C. to 55° C., retention time 30 s) using a thermocyclic device (HA-K178, Tokyo Giken Inc., Tokyo, Japan). The width and thickness of each specimen were measured using a digital micrometer (MDC-25M, Mitsutoyo Co., Tokyo, Japan, minimum value: 0.001 mm). A three-point bending flexural test with a support span of 12.0 mm and a traverse speed of 1.0 mm/min was performed at ambient room temperature (23±2° C.) by means of a universal testing machine (AG-X, Shimadzu Corp., Kyoto, Japan). The flexural strength and the flexural modulus were calculated by use of software (TRAPEZIUM X, Shimadzu Corp., Kyoto, Japan). The flexural modulus (E) was calculated according to the following formula:
E=FL.sup.3/4bh.sup.3d
wherein F represents the load at an appropriate point in the linear part of the spring characteristics, L the support span (12.00 mm), b the width of the specimen, h the thickness of the specimen and d the bending at a load F. The flexural strength (σ) was calculated with the following formula:
σ=3F.sub.1L/2bh.sup.2

(3) wherein F.sub.1 represents the maximal load during the bending flexural test.

(4) The hardness test was carried out using a Zwick universal device: The measured values of the specimens according to the invention are in the range of 800 to 850.

(5) In the following, comparative examples of light-curing products Venus Diamond (VD) and Venus Pearl (VP) are measured according to ISO 4049 and ISO 6872 (The exposure was carried out point by point according to the method described in EN ISO 4049:2009 7.11 using a Translux 2Wave (1200 mW/cm.sup.2) by means of an exposure time of respectively 20 seconds per exposure point) and compared with Example 1 according to the invention.

(6) TABLE-US-00002 TABLE 2 Comparison Ex. 1 with Venus products Comparative examples Venus Venus Diamond Pearl Example 1 (VD) (VP) Flexural strength [MPa] 182 MPa 195 MPa according to EN ISO 6872 (dry) Elastic modulus [GPa] 15.6 GPa 15.8 GPa according to EN ISO 6872 (dry) Flexural strength [MPa] 174 MPa 149 MPa according to EN ISO 4049 (24 h/water) Elastic modulus [GPa] 12.0 GPa 11.4 GPa according to EN ISO 4049 (24 h/water)

(7) TABLE-US-00003 TABLE 3 Examples 1 to 4: Example 1 Example 2 Example 3 and 4 average 0.4 μm 0.4 μm 0.85 μm diameter % by % by % by dental glass d.sub.50 weight g weight g weight g dental glass barium- 74.31 74.31 74.31 74.31 73.31 73.31 aluminum- borofluorsilicate glass (silanised) urethane 1,3-bis(5′- 22.76 22.76 22.77 22.77 23.63 23.63 (meth)- methyl-3′,8′- acrylates dioxo-2′-aza- 4′,7′-dioxa- decyl-9′- en)phenyl (formulal I) TCD ester TCD-dimethyl- 1.26 1.26 1.27 1.27 1.31 1.31 diacrylate ester initiator tert.- 0.36 0.36 0.36 0.36 0.40 0.40 butylperoxy-2- ethylhexanoate 2,4,6- 0.13 0.13 0.13 0.13 0.13 0.13 trimethylbenzo ylphenylphos- phinic acid ethylester N,N-dimethyl- 0.07 0.07 0.07 0.07 0.08 0.08 4- aminobenzoic acid 2- butoxyethyl- ester stabilizer 2,6-bis(1,1- 0.03 0.03 0.03 0.03 0.03 0.03 dimethylethyl)- 4-methyl- phenol glycerin 0.55 0.55 0.54 0.54 0.56 0.56 2-hydroxy-4- 0.16 0.16 0.16 0.16 0.17 0.17 methoxy- benzophenone 2-(2H-benzo- 0.10 0.10 0.10 0.10 0.11 0.11 triazol-2-yl)-6- dodecyl-4- methyl-phenol water 0.25 0.25 0.25 0.25 0.26 0.26 pigments diethyl-2,5- 0.02 0.02 0.01 0.01 0.01 0.01 and others dihydroxy- terephthalate, color pigments, titanium dioxide

(8) Polymerization: 3 hours at 95° C.

(9) TABLE-US-00004 TABLE 4a Flexural strengths and e-modulus (according to EN ISO 6872) without storage flexural strength e-modulus Example 1 244 MPa 18.2 GPa Example 2 248 MPa 17.7 GPa Example 3 243 MPa 14.6 GPa Example 4 234 MPa 14.6 GPa

(10) TABLE-US-00005 TABLE 4b Flexural strengths and e-modulus (elastic modulus) (according to EN ISO 6872) 7 days RTdry flexural strength e-modulus Example 1 234 MPa 14.9 GPa Example 2 216 MPa 15.5 GPa Example 3 261 MPa 16.1 GPa Example 4 281 MPa 17.8 GPa

(11) TABLE-US-00006 TABLE 4c Flexural strengths and e-modulus (EN ISO 6872) flexural strength E-Modul storage conditions Example 3 244 MPa 14.8 GPa 7 days, 37° C. H.sub.2O Example 3 216 MPa 13.6 GPa 7 days, 37° C. H.sub.2O, thermocycling 5000 cycles Example 4 232 MPa 15.9 GPa 7 days, 37° C. H.sub.2O Example 4 219 MPa 15.3 GPa 7 days, 37° C. H.sub.2O, thermocycling 5000 cycles