Polymerizable dental material with a phase transfer catalyst

Abstract

The invention relates to a polymerizable dental material containing a catalyst paste (A) and a base paste (B), wherein the catalyst paste (A) contains at least one organic peroxygen compound, at least one radically polymerizable organic (meth)acrylic monomer and at least one filler, and wherein the base paste (B) contains at least one radically polymerizable organic (meth)acrylic monomer, an amine as co-initiator of the radical polymerization, at least one filler and at least one salt-like, water-soluble, powdery reduction agent dispersed therein, wherein the catalyst paste (A) and/or the base paste (B) contains at least one phase transfer catalyst that is selected from the group consisting of the ammonium, phosphonium and/or sulfonium salts that contain an inorganic or organic anion, provided that the phase transfer catalystin the event of organic anionscontains only those having 1-4 carbon atoms, and that anions of sulfinic acids are precluded.

Claims

1. A two-part dental material, containing a catalyst paste (A) and a base paste (B) separate from the catalyst paste (A), wherein the catalyst paste (A) contains at least one organic peroxygen compound, at least one radically polymerizable organic (meth)acrylic monomer selected from the group consisting of 2-hydroxyethylmethacrylate, di- and higher acrylates, di- and higher acrylamides, di- and higher methacrylates and di- and higher methacrylamides, and at least one filler, and wherein the base paste (B) contains at least one radically polymerizable organic (meth)acrylic monomer, an amine as co-initiator of the radical polymerization, at least one filler, and at least one salt-like, water-soluble and powdery reduction agent that is dispersed therein, and wherein only the catalyst paste (A) contains at least one phase transfer catalyst that is selected from the group consisting of ammonium, phosphonium, and/or sulfonium salts that contain an inorganic or organic anion, provided that the phase transfer catalystin the case of organic anionscontains only those having 1-4 carbon atoms, and that the anions of sulfinic acids are precluded.

2. The two-part dental material as recited in claim 1, wherein the at least one, salt-like, water-soluble and powdery reduction agent is selected from the group consisting of sulfites.

3. The two-part dental material as recited in claim 1, wherein the proportion of the at least one phase transfer catalyst is 0.01 to 5 percent by weight relative to the total mass of the catalyst paste (A).

4. The two-part dental material as recited in claim 1, wherein the co-initiator of the radical polymerization is a primary, secondary, or tertiary amine.

5. The two-part dental material as recited in claim 1, wherein such is dual-hardening and that additionally, at least one photoinitiator is provided in the catalyst paste (A) and/or in the base paste (B).

6. The two-part dental material as recited in claim 1, wherein the at least one radically polymerizable organic (meth)acrylic monomer is selected from the group consisting of the di and higher acrylates, di and higher acrylamides, di and higher methacrylates and di and higher methacrylamides.

7. The two-part dental material as recited in claim 1, wherein the at least one radically polymerizable organic (meth)acrylic monomer is selected from the group consisting of acrylates or methacrylates containing aromatic groups, acrylates or methacrylates containing aliphatic groups, acrylates or methacrylates containing polyether groups, acrylates or methacrylates containing polyester groups, acrylates or methacrylates containing polyurethane, or combinations of two or more of these monomers.

8. The two-part dental material as recited in claim 7, wherein the at least one radically polymerizable organic (meth)acrylic monomer is selected from the group of monomers consisting of Bisphenol A diacrylate, Bisphenol A dimethacrylate, bisphenol glycidyl acrylate, bisphenol glycidyl methacrylate (Bis-GMA), ethoxylated Bisphenol A diacrylate, ethoxylated Bisphenol A dimethacrylate, 1,6-bis(acryloxy-2-ethoxycarbonylamino)-2,4,4-trimethyl-hexane, 1,6-bis(methacryloxy-2-ethoxy-carbonylamino)-2,4,4-trimethyl-hexane (UDMA), trimethylolpropane triacrylate trimethylolpropane trimethacrylate (TMPTMA), 2-hydroxyethylacrylate, 2-hydroxyethyl methacrylate (HEMA), glycerin-1,3-acrylate, glycerin-1,3-dimethacrylate (GDMA), dodecanediol diacrylate, dodecanediol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene diacrylate, tetraethylene glycol dimethacrylate or combinations of two or more of these monomers.

9. The two-part dental material as recited in claim 1, wherein the radically polymerizable organic (meth)acrylic monomers are free of any structural units having bisphenol A residues.

10. The two-part dental material as recited in-claim 1, wherein the organic peroxygen compound is selected from the group consisting of organic peroxides.

11. The two-part dental material as recited in claim 1, wherein the anion of the phase transfer catalyst is selected from the group consisting of halogenides, hydroxides, anions of inorganic acids, pseudo halogenide anions or halogen complexes of aluminate, silicate or phosphate, or anions of organic acids having 1-4 carbon atoms, excluding anions of sulfinic acids.

12. The two-part dental material as recited in claim 11, wherein the anion of the phase transfer catalyst is selected from the group consisting of fluoride, chloride, bromide, iodide, hydroxide, sulfate, hydrogen sulfate, dihydrogen sulfate, phosphate, phosphonate, borate, chlorate, perchlorate, nitrite, nitrate, hydrogen carbonate, carbonate, tetrafluoroborate, tetrachloroaluminate, hexafluorosilicate, hexachlorophosphate, formate, acetate, butyrate, fumarate, maleate, glutarate, lactate, malate, malonate, oxalate, pyruvate or tartrate.

13. The two-part dental material as recited in claim 1, wherein the phase transfer catalyst is an ammonium salt having the cation NR.sub.1R.sub.2R.sub.3R.sub.4, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4independent of each othermean C.sub.1 to C.sub.20 alkyl, C.sub.1 to C.sub.20 alkyl halogenide, C.sub.1 to C.sub.20 alkyloxy, C.sub.1 to C.sub.20 hydroxyalkyl, C.sub.2 to C.sub.20 alkenyl, C.sub.2 to C.sub.20 alkenyloxy, C.sub.2 to C.sub.20 alkinyl, C.sub.2 to C.sub.20 alkinyloxy, C.sub.2 to C.sub.20 alkyl ester, aryl, aryloxy, aralkyl, aralkyloxy, alkylaryl and/or alkylaryloxy.

14. The two-part dental material as recited in claim 1, wherein the phase transfer catalyst is a phosphonium salt having the cation PR.sub.1R.sub.2R.sub.3R.sub.4, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4independent of each othermean C.sub.1 to C.sub.20 alkyl, C.sub.1 to C.sub.20 alkyl halogenide, C.sub.1 to C.sub.20 alkyloxy, C.sub.2 to C.sub.20 alkenyl, C.sub.2 to C.sub.20 alkenyloxy, C.sub.2 to C.sub.20 alkinyl, C.sub.2 to C.sub.20 alkinyloxy, C.sub.2 to C.sub.20 alkyl ester, aryl, aryloxy, aralkyl, aralkyloxy, alkylaryl and/or alkylaryloxy.

15. The two-part dental material as recited in claim 1, wherein the phase transfer catalyst is a sulfonium salt having the cation SR.sub.1R.sub.2R.sub.3, wherein R.sub.1, R.sub.2 und R.sub.3independent of each othermean C.sub.1 to C.sub.20 alkyl, C.sub.1 to C.sub.20 alkyl halogenide, C.sub.1 to C.sub.20 alkyloxy, C.sub.2 to C.sub.20 alkenyl, C.sub.2 to C.sub.20 alkenyloxy, C.sub.2 to C.sub.20 alkinyl, C.sub.2 to C.sub.20 alkinyloxy, C.sub.2 to C.sub.20 alkyl ester, aryl, aryloxy, aralkyl, aralkyloxy, alkylaryl and/or alkylaryloxy.

16. The two-part dental material as recited in claim 1, wherein the phase transfer catalyst is tetrabutylammonium hydrogen sulfate, tetramethylammonium hydrogen sulfate, tetrahexylammonium hydrogen sulfate, bis[tetrakis(hydroxymethyl)-phosphonium] sulfate, tetraphenylphosphonium chloride, 1-ethyl-2,3-dimethylimidazoliumimidazolium ethylsulfate, cetyltrimethylammonium hydrogen sulfate, (vinylbenzyl) trimethylammonium chloride, tetrabutylammonium chloride and/or tetrabutylammonium tetrafluoroborate.

17. A cured dental material obtained by a method comprising providing the two-step dental material of claim 1, mixing the components A and B at a ratio of 1:20 to 1:1 and polymerizing of the resulting polymerizable dental material.

18. The cured dental material as recited in claim 17, in the form of a core buildup material, a cement composite and/or a bulk fill composite.

19. A method for making a dental material selected from a core buildup material, a polymerizable composite cement and a bulk fill composite for producing core structures, mountings and/or tooth fillings, the method comprising providing the two-part dental material of claim 1, and including the components A and B in the dental material.

20. An add-on system (kit of parts) comprising the two-part dental material as recited in claim 1 and a dental adhesive.

21. The two-part dental material of claim 7, wherein the at least one radically polymerizable organic (meth)acrylic monomer has at least two acrylate and/or methacrylate groups.

22. The two-part dental material of claim 1, wherein the phase transfer catalyst is an ammonium salt having at least one C4 residue.

23. The two-part dental material of claim 1, wherein the phase transfer catalyst has an organic anion having 1-4 carbon atoms.

24. The two-part dental material of claim 1, wherein the phase transfer catalyst has an inorganic anion selected from hydroxides, anions of inorganic acids, pseudohalogenide anions and halogen complexes of aluminate, borate, silicate and phosphate.

Description

EXECUTION EXAMPLES

(1) To produce the 1-step, 1-component light-curing, self-etching and self-adhesive bonding, the ingredients listed in the following tables 1 and 2 are used. All ingredients except water and ethanol were weighed into a beaker and homogenized with a centrifugal mixer (Hauschild DAC 150 FVZ). Subsequently, these were dispersed with a three-roll mill, Exakt 80E. After the dispersion, water and ethanol are added; the material was homogenized again in the centrifugal mixer and refilled into black 10 ml dropping bottles (manufactured by Transcodent).

(2) To produce the dual-hardening core build-up composites and composite cements, the ingredients listed in the following tables 3 through 21 were used.

(3) All ingredients are weighed into a beaker and homogenized in a centrifugal mixer (Hauschild DAC 150 FVZ). Subsequently, the dispersion is performed at room temperature using a three-roll mill (Exakt 80E). Afterward, the pastes are homogenized once more in the centrifugal mixer.

(4) TABLE-US-00001 TABLE 1 1-Step, 1-Component Light-Curing Bonding without DHEPT - Corresponds to Bonding I (Production Example I); Based on EP 2 554 154 A1, Comparative Example 2 Amount Ingredient [% by weight] BisGMA.sup.7) 28.85 HEMA.sup.8) 22.50 GDMA.sup.9) 4.50 CQ.sup.2) 1.80 EPD.sup.1) 0.90 MDP.sup.14) 9.00 BHT.sup.3) 0.05 HDK H2000 4.50 Water 13.50 Ethanol 13.50 BAPO.sup.13) 0.90 DHEPT.sup.11) 0.00 Total: 100.00

(5) TABLE-US-00002 TABLE 2 1-Step, 1-Component Light-Curing Bonding with DHEPT - Corresponds to Bonding II (Production Example II); Based on EP 2 554 154 A1, Example 5 Amount Ingredient [% by weight] BisGMA.sup.7) 27.05 HEMA.sup.8) 22.50 GDMA.sup.9) 4.50 CQ.sup.2) 1.80 EPD.sup.1) 0.90 MDP.sup.14) 9.00 BHT.sup.3) 0.05 HDK H2000 4.50 Water 13.50 Ethanol 13.50 BAPO.sup.13) 0.90 DHEPT.sup.11) 1.80 Total: 100.00

(6) TABLE-US-00003 TABLE 3 Polymerizable Dental Material Catalyst Paste (Production Example 1) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 4.50 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 41.61 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Total: 100.00

(7) TABLE-US-00004 TABLE 4 Polymerizable Dental Material Base Paste (Production Example 2) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 4.50 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 41.10 DHEPT.sup.11) 0.90 EPD.sup.1) 0.20 CQ.sup.2) 0.09 BHT.sup.3) 0.01 HMBP.sup.12) 0.20 Total: 100.00

(8) TABLE-US-00005 TABLE 5 Polymerizable Dental Material Base Paste (Production Example 3) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 4.50 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 39.10 DHEPT.sup.11) 0.90 EPD.sup.1) 0.20 CQ.sup.2) 0.09 Sodium sulfite (5 m) 2.00 BHT.sup.3) 0.01 HMBP.sup.12) 0.20 Total: 100.00

(9) TABLE-US-00006 TABLE 6 Polymerizable Dental Material Catalyst Paste (Production Example 4) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.93 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetraethylammonium ptoluenesulfonate (phase transfer 0.18 catalyst not according to the invention) Total: 100.00

(10) TABLE-US-00007 TABLE 7 Polymerizable Dental Material Catalyst Paste (Production Example 5) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.91 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium chloride (phase transfer catalyst 0.20 according to the invention) Total: 100.00

(11) TABLE-US-00008 TABLE 8 Polymerizable Dental Material Catalyst Paste (Production Example 6) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m mit methacrylate silane) 43.91 BPO.sup.10) 0.80 BHT.sup.3) 0.09 (Vinylbenzyl)trimethylammonium chloride (phase 0.20 transfer catalyst according to the invention) Total: 100.00

(12) TABLE-US-00009 TABLE 9 Polymerizable Dental Material Catalyst Paste (Production Example 7) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.91 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium hydrogen sulfate (phase transfer 0.20 catalyst according to the invention) Total: 100.00

(13) TABLE-US-00010 TABLE 10 Polymerizable Dental Material Catalyst Paste (Production Example 8) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 44.01 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium hydrogen sulfate (phase transfer 0.10 catalyst according to the invention) Total: 100.00

(14) TABLE-US-00011 TABLE 11 Polymerizable Dental Material Catalyst Paste (Production Example 9) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.71 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium hydrogen sulfate (phase transfer 0.40 catalyst according to the invention) Total: 100.00

(15) TABLE-US-00012 TABLE 12 Polymerizable Dental Material Catalyst Paste (Production Example 10) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 44.01 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetramethylammonium hydrogen sulfate (phase transfer 0.10 catalyst according to the invention) Total: 100.00

(16) TABLE-US-00013 TABLE 13 Polymerizable Dental Material Catalyst Paste (Production Example 11) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.84 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrahexylammonium hydrogen sulfate (phase transfer 0.27 catalyst according to the invention) Total: 100.00

(17) TABLE-US-00014 TABLE 14 Polymerizable Dental Material Catalyst Paste (Production Example 12) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.88 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Cetyltrimethylammonium hydrogen sulfate (phase 0.23 transfer catalyst according to the invention) Total: 100.00

(18) TABLE-US-00015 TABLE 15 Polymerizable Dental Material Catalyst Paste (Production Example 13) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.93 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium acetate (phase transfer catalyst 0.18 according to the invention) Total: 100.00

(19) TABLE-US-00016 TABLE 16 Polymerizable Dental Material Catalyst Paste (Production Example 14) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.91 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium tetrafluoroborate (phase transfer 0.20 catalyst according to the invention) Total: 100.00

(20) TABLE-US-00017 TABLE 17 Polymerizable Dental Material Catalyst Paste (Production Example 15) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.88 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetrabutylammonium hexafluorophosphate (phase 0.23 transfer catalyst according to the invention) Total: 100.00

(21) TABLE-US-00018 TABLE 18 Polymerizable Dental Material Catalyst Paste (Production Example 16) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.91 BPO.sup.10) 0.80 BHT.sup.3) 0.09 1-Ethyl-2,3-dimethyl imidazoliumethylsulfate (phase 0.20 transfer catalyst according to the invention) Total: 100.00

(22) TABLE-US-00019 TABLE 19 Polymerizable Dental Material Catalyst Paste (Production Example 17) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.87 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Bis[tetrakis(hydroxymethyl)phosphonium]sulfate (phase 0.24 transfer catalyst according to the invention) Total: 100.00

(23) TABLE-US-00020 TABLE 20 Polymerizable Dental Material Catalyst Paste (Production Example 18) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.89 BPO.sup.10) 0.80 BHT.sup.3) 0.09 Tetraphenylphosphonium chloride (phase transfer catalyst 0.22 according to the invention) Total: 100.00

(24) TABLE-US-00021 TABLE 21 Polymerizable Dental Material Catalyst Paste (Production Example 19) Amount Ingredient [% by weight] UDMA.sup.4) 24.75 DDDDMA.sup.5) 6.25 TMPTMA.sup.6) 2.00 HDK H2000 2.00 YbF.sub.3 (100 nm) 20.00 Cristobalite powder (6 m with methacrylate silane) 43.88 BPO.sup.10) 0.80 BHT.sup.3) 0.09 (4-Methylthiophenyl)methyl phenyl sulfonium triflate 0.23 (phase transfer catalyst according to the invention) Total: 100.00

(25) .sup.1) EPD is ethyl-4-dimethylaminobenzoate.

(26) .sup.2) CQ is DL-camphorquinone.

(27) .sup.3) BHT is 2,6-di-tert-butyl-4-methylphenol.

(28) .sup.4) UDMA is an isomer mixture consisting of di-2-methacryloxyethyl-2,2,4-trimethyl hexamethylene dicarbamate and di-2-(meth)acryl-oxyethyl-2,4,4-trimethyl-hexamethylene dicarbamate corresponding to Formula (I).

(29) ##STR00001##

(30) .sup.5) DDDDMA is 1,12-dodecanediol dimethacrylate.

(31) .sup.6) TMPTMA is trimethylolpropane trimethacrylate.

(32) .sup.7) BisGMA is bisphenol-A-glycidyl methacrylate.

(33) .sup.8) HEMA is 2-hydoxyethyl methacrylate.

(34) .sup.9) GDMA is glycerin-1,3-dimethacrylate.

(35) .sup.10) BPO is dibenzoyl peroxide.

(36) .sup.11) DHEPT is p-tolyl-diethanol amine.

(37) .sup.12) HMBP is 2-hydroxy-4-methoxy-benzophenone.

(38) .sup.13) BAPO is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, that functions as auxiliary initiator for light-curing.

(39) .sup.14) MDP is 10-methacryloyloxdecyl dihydrogen phosphate.

(40) To produce the patent and comparative examples, the catalyst paste and the base paste formulations were filled into 5 ml double syringes of the type Mixpac 1:1 SDL X05-01-52 (Sulzer), corresponding to the combinations listed in Table 19. For testing, the dental masses were discharged through a root canal-tip of the type IOR 209-20, via a static mixer of the type Mixpac MLT 2.5-10-D (Sulzer).

(41) TABLE-US-00022 TABLE 22 Combination of the Production Examples Catalyst Paste Base Paste Combination Production Example 1 Production Example 2 Comparative Example 1 Production Example 1 Production Example 3 Comparative Example 2 Production Example 4 Production Example 3 Comparative Example 3 Production Example 5 Production Example 3 Patent Example 1 Production Example 6 Production Example 3 Patent Example 2 Production Example 7 Production Example 3 Patent Example 3 Production Example 8 Production Example 3 Patent Example 4 Production Example 9 Production Example 3 Patent Example 5 Production Example 10 Production Example 3 Patent Example 6 Production Example 11 Production Example 3 Patent Example 7 Production Example 12 Production Example 3 Patent Example 8 Production Example 13 Production Example 3 Patent Example 9 Production Example 14 Production Example 3 Patent Example 10 Production Example 15 Production Example 3 Patent Example 11 Production Example 16 Production Example 3 Patent Example 12 Production Example 17 Production Example 3 Patent Example 13 Production Example 18 Production Example 3 Patent Example 14 Production Example 19 Production Example 3 Patent Example 15

(42) To test the bonding strength, the core build-up materials in Comparative Examples 1 through 3 and Patent Examples 1 through 15, and the comparative material LuxaCore Smartmix Dual (DMG, LOT 707376) were combined with Bonding I and II. The experiments were performed using human dentin based on the ISO 29022 standard.

(43) For this purpose, human teeth were embedded in cold-mounting materials (VariKwick, manufactured by Bhler) and the dentin was exposed by grinding the surface. The bonding was applied to the test specimens treated in this way and 10 s light-cured (Superlite 1100, made by M+W Dental). Subsequently, the test specimens were inserted into a bonding clamp (Bonding Clamp, manufactured by Ultradent), that contains a plug-in mold for the core build-up cylinder to be attached (Bonding Mold Insert, manufactured by Ultradent). The fill cavity in the mold was positioned in the center of the tooth at a location suitable for the composite and lowered. Next, the core build-up material was applied to the composite surface and stored in the dark for seven minutes at 37 C. in self-curing mode. Upon the elapse of this time, the test specimens were removed from the mold and placed in water for another 24 hours at 37 C.

(44) Upon the elapse of this time, a shearing test was performed using a universal testing machine (Zwicki Universal Testing Machine Z0.5 TN) with a corresponding set-up. To do so, the composite test specimens were clamped into a test clamp (Test Base Clamp, manufactured by Ultradent). In the clamp, the test specimens were aligned abutting at the tooth under a cross head with recessed blade (Crosshead Assembly, manufactured by Ultradent) in the center of the composite cylinder. The test specimens were stress-tested up to breaking at a testing speed of 1.0 mm/min. The results are shown in Table 23.

(45) TABLE-US-00023 TABLE 23 Results Bonding Strength at Dentin* Polymerizable Dental Material Adhesive [MPa] Examples Not According to the Invention: LuxaCore Smartmix Dual LOT 707376 white Production Example I: Bonding I 7.6 LuxaCore Smartmix Dual LOT 707376 white Production Example II: Bonding II 3.9 Comparative Example 1: Polymerizable Dental Material Production Example I: Bonding I 7.3 Comparative Example 1: Polymerizable Dental Material Production Example II: Bonding II 3.8 Comparative Example 2: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) Production Example I: Bonding I 8.3 Comparative Example 2: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) Production Example II: Bonding II 9.5 Comparative Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) Production Example I: Bonding I 8.6 and Tetraethylammonium p-toluenesulfonate (0.59 mmol; Phase Transfer Catalyst) Examples According to the Invention Using Ammonium Salts as Phase Transfer Catalysts: Patent Example 1: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 18.3 Tetrabutylammonium Chloride (0.72 mmol; Phase Transfer Catalyst) Patent Example 2: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 12.8 (Vinylbenzyl)trimethylammonium Chloride (0.94 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 15.3 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 15.7 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) After 15 Months Storage at 23 1 C. Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example II: Bonding II 14.6 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 13.3 Tetrabutylammonium Hydrogen Sulfate (0.30 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 15.8 Tetrabutylammonium Hydrogen Sulfate (1.18 mmol; Phase Transfer Catalyst) Patent Example 6: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 14.5 Tetramethylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 7: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 13.4 Tetrahexylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 8: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 12.8 Cetyltrimethylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 9: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 13.0 Tetrabutylammonium Acetate (0.59 mmol; Phase Transfer Catalyst) Patent Example 10: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 14.4 Tetrabutylammonium Tetrafluoroborate (0.61 mmol; Phase Transfer Catalyst) Patent Example 11: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 10.5 Tetrabutylammonium Hexafluorophosphate (0.59 mmol; Phase Transfer Catalyst) Examples According to the Invention Using Heterocyclic Ammonium Salt as Phase Transfer Catalyst: Patent Example 12: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 11.2 1-Ethyl-2,3-dimethyl-imidazoliumethyl Sulfate (0.8 mmol; Phase Transfer Catalyst) Examples According to the Invention Using Phosphonium Salts as Phase Transfer Catalysts: Patent Example 13: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 11.7 Bis[tetrakis(hydroxymethyl)phosphonium]sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 14: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Production Example I: Bonding I 10.5 Tetraphenylphosphonium Chloride (0.59 mmol; Phase Transfer Catalyst) Examples According to the Invention Using Sulfonium Salts as Phase Transfer Catalysts: Patent Example 15: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and (4- Production Example I: Bonding I 14.0 Methylthiophenyl)methyl Phenyl Sulfonium Triflate (0.59 mmol; Phase Transfer Catalyst) Example According to the Invention Using Various Commercial All-in-One Adhesives: Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Clearfil S3 Bond Plus (Kuraray) 19.5 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Clearfil Universal Bond (Kuraray) 14.9 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Scotchbond Universal (3M Espe) 16.2 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and Xeno Select (Dentsply) 11.6 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and All Bond Universal (Bisco) 11.0 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) Patent Example 3: Polymerizable Dental Material - contains Sodium Sulfite (15.87 mmol) and iBond Universal (Heraeus Kulzer) 10.1 Tetrabutylammonium Hydrogen Sulfate (0.59 mmol; Phase Transfer Catalyst) *The number of non-adhering test specimens was included at a value of zero.

(46) Table 23 shows the following findings: The commercially available and in Germany, the leading core build-up material LuxaCore Smartmix Dual exhibits a low bonding strength with both bonding variants (Bonding I, according to EP 2 554 154 A1, Comparative Example 2, page 19; Bonding II, according to EP 2 554 154 A1, Example 5, page 31). Hereby, the bonding strength with Bonding II is once again significantly lower than in the case of Bonding I, which can be explained thereby, that in Bonding II, some of the etching effect of the phosphoric acid methacrylate is neutralized by the aromatic amine DHEPT it also contains. The polymerizable dental material described in Comparative Example 1 (initiator composition without the water-soluble reduction agent comparable with Comparative Example 3, page 28, of EP 2 554 154 A1) exhibits a low bonding strength with both bonding variants, completely analogous to Luxacore Smartmix Dual. Here as well, the bonding strength with Bonding II is once again significantly lower compared to that with Bonding I. This shows that the composition with respect to the monomers and fillers relative to the bonding strength that was used in all examples is comparable with other commercially available core build-up materials. The polymerizable dental material described in Comparative Example 2 (initiator composition with the water-soluble reduction agent comparable with Example 5, page 17, of EP 2 554 154 A1) shows, in particular, in connection with Bonding II, a significantly higher bonding strength compared with the polymerizable dental material in Comparative Example 1. In this case, the bonding strength with Bonding I is significantly lower than with Bonding II. This leads to two conclusions: a) The use of a water-soluble reducing compound in the curable dental material does not lead to the desired success for hydrophobic compositions that are suitable for core build-up materials, in contrast to the hydrophilic bonding agents of EP 1 780 223 B1 b) If Bonding II is used with a reducing amine according to the invention in EP 2 554 154 A1, the use of a water-soluble reducing compound in the curable composition of the composite improves the bonding strength significantly. This confirms the invention disclosed in EP 2 554 154 A1 with a special adhesive containing an amine as reduction agent. However, the advantage over prior art that was presented there is clearly achieved only by using the special adhesive contained in the kit. The polymerizable dental material described in Comparative Example 3 (contains the phase transfer catalyst tetraethylammonium p-toluene sulfonatenot according to the invention) shows a comparable bonding strength to that of Bonding I with the composition of Comparative Example 2, in which no phase transfer catalyst was used. This confirms that phase transfer catalysts with relatively hydrophobic anions having more than 4 C atoms are ineffective. The polymerizable dental materials described in Patent Examples 1 through 15 exhibit a high degree of bonding strength with Bonding I that is more than 10 MPa. This confirms that by using the phase transfer catalysts according to the invention, the bonding strength can be improved significantly, whereby ammonium cations with different substituents, different anions with no more than 4 C-atoms and different concentrations of the phase transfer catalyst can be used. Further, phase transfer catalysts based on ammonium salts, as well as those based on heterocyclic ammonium derivatives are suitable, such the imidazolium derivative used in Patent Example 12, the phase transfer catalysts based on phosphonium salts (Patent Example 13 and 14) and also the phase transfer catalysts based on sulfonium salts (Patent Example 15). The applied polymerizable dental materials showed a good shelf life. Storage over 15 months did not result in a reduction of the bonding strength. With Bonding II according to the invention disclosed in EP 2 554 154 A1as is shown with the core build-up material in Patent Example 3the bonding strength cannot be improved any further, i.e. using a special adhesive that contains an amine as reduction agent is therefore not required in the curable composite when using a phase transfer catalyst according to this patent specification. The polymerizable dental material in Patent Example 3 was also tested with several commercially available light-curing, all-in-one adhesives from various manufacturers. It was possible to achieve a high degree of bonding strength in each case.

(47) Additionally, micro-tensile tests were conducted using commercially available core build-up materials in combination with various commercially available adhesives.

(48) For this test, 300 intact, non-carious, unrestored human third molars were stored in an aqueous solution of 0.5% chloramine T at 4 C. for up to 30 days. The teeth were debrided of residual plaque and calculus, and examined under a light microscope at 20 magnification to ensure that they were free of defects. Standardized Class I cavity preparations (4 mm in width and length, 4 mm in depth) were performed. Cavities were cut using coarse diamond burs under profuse water cooling (80 m, Two-Striper Prep-Set, Premier, St. Paul, USA), and finished with a 25 m finishing diamond. Inner angles of the cavities were rounded and the margins were not bevelled. To guarantee a rectangular relation between the bonded interface and the direction of the later cut -TBS beam, the cusps were flattened 2 mm and then the cavity floor was prepared parallel to the flattened cusps.

(49) Cavities were overfilled 5 mm in bulk with different adhesives and core build-up materials under elevated room temperature (30 C. for simulation of intraoral temperature). Adhesives (separately cured according to the instructions of the manufacturers) and build-up resin composite were polymerized with a Bluephase light-curing unit (Ivoclar Vivadent) in accordance to the manufacturers' recommendations. The intensity of the light was checked periodically with a radiometer (Demetron Research Corp, Danbury, Conn., USA) to ensure that 1200 mW/cm.sup.2 was always exceeded during the experiments.

(50) After 24 h of water storage at 37 C. and 2,500 thermocycles (5 C./55 C.), the peripheral areas of the reconstructed/filled teeth were removed, remaining specimens were sectioned into slices in apical direction, which were sectioned again to receive resin-dentin beams. The saw was adjusted to steps of 1 mm, due to the thickness of the blade (300 m) resulting in sticks with a cross-sectional area of 700700 m (0.5 mm.sup.2). From the resulting sticks of each group, 20 were selected (n=20). These 20 sticks had to have a remaining dentin thickness to the pulp of 2.00.5 mm. If more than 20 beams were collected with the correct remaining dentin thickness, 20 sticks were randomly selected. For the case that one or more of the selected sticks failed due to the sectioning process, the percentage of prematurely failed specimens in relation to the total number of selected specimens was recorded. The same (or approximated) percentage of the 20 final specimens received 0 MPa as final -TBS result. The -TBS sticks were stored in distilled water for 24 hours at 37 C. and then fractured according to a well-suited protocol, following: Frankenberger R, Pashley D H, Reich S M, Lohbauer U, Petschelt A, Tay F R. Characterisation of resin-dentine interfaces by compressive cyclic loading. Biomaterials 2005; 26:2043-2052.

(51) The following table shows the bonding strengths in MPa for core build-up materials using various combinations of adhesives.

(52) TABLE-US-00024 Bonding Strength Core Build-up Material Adhesive (MPa) According to Patent Example 3 Adhese Universal 5.2 According to Patent Example 3 All-Bond Universal 7.4 According to Patent Example 3 Clearfill S.sup.3 Bond Plus 20.3 According to Patent Example 3 Clearfill SE Bond 21.3 According to Patent Example 3 Futurabond U 5.2 According to Patent Example 3 i-Bond 5.5 According to Patent Example 3 Scotchbond Universal 9.4 According to Patent Example 3 Xeno Select 11.2 MultiCore Flow Adhese Universal 0 MultiCore Flow All-Bond Universal 0 MultiCore Flow Clearfill S.sup.3 Bond Plus 0 MultiCore Flow Clearfill SE Bond 0 MultiCore Flow Futurabond U 0 MultiCore Flow i-Bond 0 MultiCore Flow Scotchbond Universal 0 MultiCore Flow Xeno Select 0 Rebilda DC Adhese Universal 0 Rebilda DC All-Bond Universal 0 Rebilda DC Clearfill S.sup.3 Bond Plus 0 Rebilda DC Clearfill SE Bond 0 Rebilda DC Futurabond U 0 Rebilda DC i-Bond 0 Rebilda DC Scotchbond Universal 0 Rebilda DC Xeno Select 0 LuxaCore Dual Adhese Universal 0 LuxaCore Dual All-Bond Universal 0 LuxaCore Dual Clearfill S.sup.3 Bond Plus 0 LuxaCore Dual Clearfill SE Bond 0 LuxaCore Dual Futurabond U 0 LuxaCore Dual i-Bond 0 LuxaCore Dual Scotchbond Universal 0 LuxaCore Dual Xeno Select 0 Core Paste XP Adhese Universal 0 Core Paste XP All-Bond Universal 0 Core Paste XP Clearfill S.sup.3 Bond Plus 0 Core Paste XP Clearfill SE Bond 0 Core Paste XP Futurabond U 0 Core Paste XP i-Bond 0 Core Paste XP Scotchbond Universal 0 Core Paste XP Xeno Select 0