PRODUCTION OF ANTIBACTERIAL AND REGENERATIVE DENTAL COMPOSITE USING SUPPORTIVE PHASES (FILLERS) ANTIBACTERIAL AND BIOACTIVE PROPERTIES OF WHICH ARE IMPROVED

Abstract

The present invention relates to restorative purpose acrylic dental composite filling material which are curable by light and are polymerizable, and which contains only -tricalcium phosphate (-TCP), nanocrystalline cellulose (NCC), hydroxy apatite particles/fibers/whiskers, AI-Sr-OF and AI-Sr-Si-OF and/or mixtures thereof as supportive phase system for conferring regenerative and antibacterial properties to composite filling materials, and relates to production method of said dental composite filling material.

Claims

1.-29. (canceled)

30. An acrylic dental composite material comprising: an organic compound which can be cured with light and which can be polymerized as the main matrix, a photo-initiator, and a supportive phase comprising: an oxyfluoride compound, and SiO.sub.2, SiO.sub.2/Silan, Si/Zr nano-cluster, Si/Zr/Silan nano-cluster, TiO.sub.2, TiO.sub.2/Silan, ZrO.sub.2, ZrO.sub.2/Silan, 3YSZ, -tricalcium phosphate (-TCP), nano-crystalline cellulose (NCC), hydroxyl-apatite particles/fibers/whiskers, or any combination thereof, wherein the supportive phase provides regenerative and antibacterial characteristics to said composite material.

31. The acrylic dental composite material according to claim 30, wherein the organic compound comprises BisGMA between 1% and 5% by weight, HEMA between 5% and 10% by weight, UDMA between 5% and 10% by weight and TEGDMA between 1% and 5% by weight.

32. The acrylic dental composite material according to claim 30, wherein said photo-initiator is selected from the group comprising CQ, diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide, 1-phenyl-1,2-propandione, 4-EDMAB, and any combination thereof.

33. The acrylic dental composite material according to claim 32, wherein the acrylic dental composite material comprises CQ between 0.1 and 0.5 wt. %, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide between 0.1 and 0.5 wt. %, 1-phenyl-1,2-propandione between 0.1 and 0.5 wt. %, and 4-EDMAB between 0.5 and 1.0 wt. %.

34. The acrylic dental composite material according to claim 30, wherein the oxyfluoride compound is provided at a value between 1% and 40% by weight.

35. The acrylic dental composite material according to claim 30, wherein said oxyfluoride compound comprises an Al-Sr-OF compound an Al-Sr-Si-OF compound, or both.

36. The acrylic dental composite material according to claim 30, wherein the acrylic dental composite material comprises SiO.sub.2, SiO.sub.2/Silan, Si/Zr nano-cluster, Si/Zr/Silan nano-cluster, TiO.sub.2, TiO.sub.2/Silan, ZrO.sub.2, ZrO.sub.2/Silan, 3YSZ, -tricalcium phosphate (-TCP), nano-crystalline cellulose (NCC), hydroxy-appatite particles/fibers/whiskers, or any combination thereof in an amount between 1 and 90 wt. %.

37. The acrylic dental composite material according to claim 30, further comprising a pigment.

38. The acrylic dental composite material according to claim 36, wherein said pigment is selected from Duranat Yellow Iron Oxide (Pigment Yellow 42 & 43 CI 77492), Duranat Red Iron Oxide (Pigment Red 101 CI77491), Phenyl-bis (2,4,6-trimethylbenzoyl) phosphine-oxide, 1-Phenyl-1,2-propanedione, Diphenyl (2,4,6-trimethylbenzoyl) phosphine-oxide, Duranat Brown Iron Oxide (Pigment Brown), Duranat Black Iron Oxide (Pigment Black 11 CI 77499), iron oxide (Fe.sub.2O.sub.3-10 red), ferric hydroxide (FeOOH-yellow), TiO.sub.2, E171 Titanium Dioxide, Pigment White 6 CI77891, and any combination thereof.

39. The acrylic dental composite material according to claim 37, wherein an amount of pigment in the composite material is in range from 0.01 and 1 wt. %.

40. An acrylic dental composite filling material production method with restorative purpose and cured with light and which can be polymerized and which shows antimicrobial effect, the method comprising: a) mixing BisGMA (1%-5% by weight) in ultrasonic water bath and adding HEMA (5%-10% by weight), UDMA (5%-10% by weight) and TEGDMA (1%-5% by weight) therein and preparing organic matrix of the composite structure, b) adding SiO.sub.2, SiO.sub.2/Silan, Si/Zr nano-cluster, Si/Zr/Silan nano-cluster, TiO.sub.2, TiO.sub.2/Silan, ZrO.sub.2, ZrO.sub.2/Silan, 3YSZ, -tricalcium phosphate -TCP), nano-crystalline cellulose (NCC), hydroxyl-apatite particles/fibers/whiskers, Al-Sr-OF and Al-Sr-Si-OF with changing proportions between 50%-90% by weight and/or the supportive phase system comprising the mixtures thereof to the prepared organic matrix mixture and mixing in ultrasonic water bath or speed mixer until a homogeneous mixture is obtained, c) adding camphorcinone or diphenyl (2,4,6-trimethyl-benzoil) phosphine oxide or phenyl bis(2,4,6-trimethyl-benzoyl) phosphine oxide or 1-phenyl-1,2-propandione (0.2% by weight) and 4-EDMAB (0.8% by weight) to the prepared mixture and mixing thereof in ultrasonic bath, d) waiting 30 minutes in vacuumed stove in order to remove air bubbles which may remain in the mixture structure, e) bringing the prepared composite matrix to room temperature before application and mixing by means of cement spatula and placing thereof to a Teflon mold, f) placing a glass plate to each side of the Teflon mold and compressing by applying pressure, g) processing the samples by means of blue-LED light device.

41. The dental composite filling production method according to claim 40, wherein in the process step a), said mixing process is realized for duration of 10 minutes at 40 C.

42. The dental composite filling production method according to claim 40, wherein in the process step b), said supportive phase system is added at a proportion of at least 70% by weight.

43. The dental composite filling production method according to claim 40, wherein in the process step b), said mixing process is realized for duration of 1 day.

44. The dental composite filling production method according to claim 40, wherein in the process step c), said mixing process is realized for 3 hours.

45. The dental composite filling production method according to claim 40, wherein in the process step d), said waiting process is realized for 30 minutes at temperature of 37 C.

46. The dental composite filling production method according to claim 40, wherein in the process step g), the process of subjecting to said blue-LED light device is realized for 20 seconds.

47. The dental composite filling material obtained by means of the method according to claim 40.

Description

DETAILED DESCRIPTION OF THE INVENTION

1. Synthesis of Supportive Phase Systems

1.1. Biomimetic Hydroxyapatite Synthesis

[0051] Firstly, Synthetic Body Fluid (SBF) solution is prepared for biomimetic hydroxyapatite (BHA) synthesis. The SBF solution prepared by Tas [60] and having a composition which is the most similar one to human plasm among the solutions of the literature is used.

[0052] Hydroxyapatite (HA) widely preferred in hard tissue applications is produced by using Ca(NO.sub.3).sub.2.4H.sub.2O or Ca(OH).sub.2 or Ca(CH.sub.3COO).sub.2 or CaCl.sub.2 as calcium source, and (NH.sub.4).sub.2HPO.sub.4 or NH.sub.4H.sub.2PO.sub.4 or K.sub.2HPO.sub.4 or H.sub.3PO.sub.4 as phosphor source, at 37 C. inside the synthetic body fluid (SBF) with pH of 7.4 according to the reaction of the Equation 1. Amounts of the materials used in synthesizing of BHA ceramic powders are adjusted such that Ca/P proportion of the resulting product is between 1.5 and 1.8, for example is 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8.

10Ca(NO.sub.3).sub.2.4H.sub.2O+6(NH.sub.4).sub.2HPO.sub.4.fwdarw.Ca.sub.10(PO.sub.4).sub.6(OH).sub.2+12NH.sub.4NO.sub.3+8HNO.sub.3 (1)

[0053] 1. The first stage includes preparation of starting solutions. In this stage, 1M Ca(NO.sub.3).sub.2.4H.sub.2O and 1.2M (NH.sub.4).sub.2HPO.sub.4 are added respectively into 1000 ml and 500 ml SBF solution and are dissolved by using magnetic stirrer with heater at 500 rpm and 37 C.

[0054] 2. PH value of Ca(NO.sub.3).sub.2.4H.sub.2O solution is adjusted to 8 by using SVS:NH.sub.3 solution in proportion of 2:1.

[0055] 3. Following the pH adjustment, (NH.sub.4).sub.2HPO.sub.4 solution is added to Ca(NO.sub.3).sub.2.4H.sub.2O solution at a speed of 3-5 ml/min and is stirred for about 1-2 hours.

[0056] 4. The present mixture is aged by incubating at 37 C. for 24-48 hours and then filtered by using blue band filter paper by vacuumed filtration method.

[0057] 5. Resulting white and viscous precipitation is dried at 80 C. and ground in agate mortar by being calcined for 1 hour at 900 C. in muffle furnace.

[0058] 6. Resulting biomimetic hydroxyapatite ceramic powder is abbreviated as BHA.

1.2. Zirconia Synthesis

[0059] Zirconia nanoparticles can be synthesized by various methods such as sol-gel, precipitation, burning, condensation and thermal fragmentation of zirconium compounds The most common method today is sol-gel method among those methods for synthesizing of Nano ceramics as zirconia. Crystal phase, crystal size and other properties of zirconia nanoparticles are based on several parameters such as starter type, pH value of solution during hydrolyze and thermal process. In sol-gel method, various parameters such as purity, homogeneity and physical properties of zirconia ceramic can be controlled at low temperatures [61]

[0060] In the present work, zirconia ceramic is synthesized by using sol-gel technique and zirconium oxy nitrate metal salt as starting material and steps of experimental works are as follows:

[0061] 1. 2.5 M ZrO(NO.sub.3).sub.2.xH.sub.2O, water in proportion to 400 ml 3:5 (v/v) is dissolved inside ethanol.

[0062] 2. 120 ml of HNO.sub.3 is added to the solution.

[0063] 3. In order to prevent aggregation by forming complex with metal salt and to provide a homogenous distribution [61] PEG solution in ratio of 1% by weight is added to resulting acidic solution and sol solution is obtained by making zirconia salt be hydrolyzed.

[0064] 4. The mixture is dried at 200 C. by using magnetic stirrer with heater and also dried in incubator at 150 C. for one night and thus the gel is obtained by resulting condensation reactions.

[0065] 5. The dried mixture is calcined for 1 hour in muffle furnace at 1100 C.

[0066] 6. Resulting zirconia ceramic powder is abbreviated as ZrO.sub.2.

1.3 3% Mole Yttria Doped Tetragonal Zirconia Synthesis

[0067] It is in three different crystal form in atmospheric conditions as zirconia monoclinic (up to 1170 C.), tetragonal (between 1170-2370 C.) and cubic (between 2370-2680 C.) [64]. Zirconia being in monoclinic phase at room temperature [65] transforms into cubic and tetragonal phase at high temperatures. On the other hand, in order for those phases formed at high temperatures to be stable at room temperatures, agents such as CaO, MgO, Y.sub.2O.sub.3 and CeO.sub.2 should be placed into the zirconia lattice [66]. While zirconia containing Y.sub.2O.sub.3 in the mole ratio of 8% or more is in cubic phase at room temperature, zirconia containing Y.sub.2O.sub.3 in the mole ratio of 3% is in tetragonal phase at room temperature. In loading made in the ratio between 3-8% mole, zirconia involves cubic and tetragonal phases in its structure [67]. In the present work, 3% mole yttria doped tetragonal zirconia ceramic is synthesized by using sol-gel technique likewise zirconia synthesis:

[0068] 1. 1.15 M ZrO(NO.sub.3).sub.2.xH.sub.2O, water in proportion to 250 ml 1:5 (v/v) is dissolved inside ethanol.

[0069] 2. 80 ml of HNO.sub.3 is added to the solution.

[0070] 3. 0.35M Y(NO.sub.3).sub.3.6H.sub.2O is added to resulting acidic solution.

[0071] 4. In order to prevent aggregation by forming complex with metal salt and to provide a homogenous distribution [61] PEG solution in ratio of 1% by weight is added to resulting acidic solution and sol solution is obtained by making metal salts be hydrolyzed.

[0072] 5. The mixture is dried at 200 C. by using magnetic stirrer with heater and also dried in incubator at 150 C. for one night and thus the gel is obtained by resulting condensation reactions.

[0073] 6. The dried mixture is calcined for 1 hour in muffle furnace at 1100 C.

[0074] 7. Resulting 3% mole yttria doped tetragonal zirconia ceramic powder is abbreviated as 3YSZ.

1.4. Silica Synthesis

[0075] Silica powders to be used as supportive phase in the present work is obtained from commercial LUDOX HS-40; LUDOX AM; LUDOX AS-40; LUDOX TM-50; LUDOX AS-30; LUDOX TMA; LUDOX CL; LUDOX SM; LUDOX HS-30; LUDOX TM-40; LUDOX LS; LUDOX CL-X colloidal silica solutions:

Method 1

[0076] 1. Colloidal silica solution is dried in incubator at 80 C.

[0077] 2. Dried powders are ground for one (1) day long in ball mill.

[0078] 3. Ground powders are sifted through a sieve with mesh of maximum 250.

[0079] 4. Resulting silica ceramic powder is abbreviated as SiO.sub.2.

Method 2

[0080] 1. Water of colloidal silica solution is evaporated in rotary evaporator at 80 C.

[0081] 2. Then the silica is dried in vacuumed incubator at 80 C.

[0082] 3. Dried powders are ground for one (1) day long in ball mill.

[0083] 4. Ground powders are sifted through a sieve with mesh of 250.

[0084] 5. Resulting silica ceramic powder is abbreviated as SiO.sub.2.

Method 3

[0085] 1. Colloidal silica solution is dried first by using freeze dryer then in vacuumed incubator at 80 C.

[0086] 2. Dried powders are ground for one (1) day long in ball mill.

[0087] 3. Ground powders are sifted through a sieve with mesh of 250.

[0088] 4. Resulting silica ceramic powder is abbreviated as SiO.sub.2.

1.5. Silica/Zirconia Group Synthesis

[0089] One of the most essential properties demanded by dentist and patient in dental composites in the recent years is that the composites can fulfil aesthetic expectation. At this point, dental composite structures are desired to imitate view of the natural tooth as much as possible. Silica/zirconia Nanoclusters are quite attractive supportive phase systems in fulfilling aesthetic expectation thanks to optical features they have and outstanding mechanical features they brought in dental composites [68]. Silica/zirconia Nanoclusters which are a metal oxide can be synthesized by various methods such as wet impregnation, sol-gel, chemical precipitation and sol-gel at low temperatures [69]. By means of those methods, Zr ions are arranged into silica lattice and a structure containing mixture of metal oxides is formed [70]. In the present work, silica/zirconia Nanoclusters are synthesized on the basis of wet impregnation [71] but drying and calcination process is done likewise sol-gel method without applying filtration process after sedimentation. In Si/Zr Nanocluster structure to be obtained, the ratio of Si/Zr varies between 1 and 20 depending on intended opacity value [69].

[0090] 1. pH value of 500 ml colloidal silica solution is adjusted to 2.5 by diluted HNO.sub.3 solution.

[0091] 2. That solution is slowly added to solution of 230.65 ml zirconyl acetate and stirred for 1 hour.

[0092] 3. The mixture is dried in incubator or in rotary evaporator at 80 C. and calcined in muffle furnace for 4 hours at 550 C.

[0093] 4. Calcined powder is ground in ball mill for one day long and sifted through 450 mesh sieve.

[0094] 5. Resulting silica/zirconia Nanocluster ceramic powder is abbreviated as Si/Zr Nanocluster.

1.6. Titanium Oxide

[0095] Titanium oxide is purchased commercially and used as supportive phase system without subjecting to any process.

1.7. Methoxyfluoride Synthesis

[0096] Metal-oxyfluoride systems also called as acid reactive supportive phase system are used in dental composites as fluorine emission agent. Main object of those structures used in dental composite systems arises due to preventing secondary decay formation in areas where restoration is made. Metal oxides, metallic salts and glass systems constitute acid-reactive supportive phase systems group. Floro-alumino-silicate (FAS) glasses are examples of metal-oxyfluoride systems. While these systems are prepared by melting technique, high particle dimension they have restricts their use as supportive phase system in dental composites. Metal oxides which are produced as alternative to those systems and contain a trivalent metal, oxygen, fluorine, alkali metal and preferably silicon can be used in dental composite depending on their controllable surface area values. Oxygen and fluorine atom in these structures bind to same atom. For example, aluminum binds to oxygen and fluorine aluminum in the structure in which it is present as trivalent atom and is together with Al.sub.2O.sub.3 and AlF.sub.3 structures within the same lattice form. Typically preferred structure in these structure as alkali earth metal is strontium metal. Proportion of trivalent metal and alkali earth metal in oxyfluoride material influences the properties of the composite as chemical and curing efficiency. For instance, using alkali earth metal in the structure at high proportion increases reactivity of the composite and leads to emission of undesired other materials as well as fluorine [184]. In the present work, metal-oxyfluoride systems prepared by precipitation technique as alternative to FAS glasses which are used as fluorine emission agent in dental composites are used. In this context, two different fluorine emission agents as Al-Sr-oxyfluoride and Al-Sr-Si-oxyfluoride not containing silicon are produced as supportive phase system. Experimental steps are sorted as follows:

Production of Al-Sr-Oxyfluoride Supportive Phase Systems

[0097] 1. 2M and 80 mL Al(NO.sub.3).sub.3.9H.sub.2O solution is mixed with 2M and 20 mL Sr(NO.sub.3).sub.2 solution. Prepared solution is called as cation solution.

[0098] 2. 2M and 720 mL NH.sub.4OH solution is mixed with 2M and 180 mL NH.sub.4F solution and prepared solution is called as anion solution.

[0099] 3. Cation solution is added to anion solution under strong stirring and stirred for 1 hour.

[0100] 4. White and viscous precipitation resulted at the end of 1 hour stirring is filtered by vacuumed filtration method and rinsed with purified water.

[0101] 5. Precipitations are dried in incubator at 100 C. for one night and subsequently kept for 1 hour at 250 C.

[0102] 6. Dried powders are ground in ball mill for three hours and sifted through 250 mesh sieve.

Production of Al-Sr-Si Oxyfluoride Supportive Phase Systems

[0103] 1. 2M and 67 mL Al(NO.sub.3).sub.3.9H.sub.2O solution is mixed with 2M and 33 mL Sr(NO.sub.3).sub.2 solution. Prepared solution is called as cation solution.

[0104] 2. 2M and 67 mL Na.sub.2SiO.sub.3 solution, 2M and 653 mL NH.sub.4OH solution and 2M and 180 mL NH.sub.4F solution are mixed with each other and prepared solution is called as base solution.

[0105] 3. Cation solution is added to base solution under strong stirring and stirred for 1 hour.

[0106] 4. White and viscous precipitation resulted at the end of 1 hour stirring is filtered by vacuumed filtration method and rinsed with purified water.

[0107] 5. Precipitations are dried in incubator at 100 C. for one night and subsequently kept for 1 hour at 250 C.

[0108] 6. Dried powders are ground in ball mill for three hours and sifted through 250 mesh sieve.

[0109] Steps (method 1) of a method used in the scope of experimental works, comprising functionalization by using A174, of supportive phase systems of biomimetic hydroxyapatite (BHA), zirconia (ZrO.sub.2), silica (SiO.sub.2), silica/zirconia nanocluster (Si/Zr nanocluster) and commercially available titania (TiO.sub.2) produced as supportive phase system in the present work are sorted as follows:

[0110] 1. Suitable amount of A174 is added to 380 ml ethanol:water (1:3) in a glass bottle that is capped and pH value of the solution is adjusted to 3.5 by acetic acid solution and stirred for 30 minutes.

[0111] 2. Then supportive phase system to be modified under strong stirring is added to this solution and stirred for 30 minutes in magnetic stirrer with heater and stirred for 10 minutes in ultrasonic water bath.

[0112] 3. After stirring, it is treated for 3 hours at 80 C. in condenser.

[0113] 4. The mixture filtered by vacuumed filtration is rinsed in ethanol/water solution for removing silanizing agent that is not reacting.

[0114] 5. Finally, resulting precipitations are dried for 24 hours at 60 C. in vacuumed incubator.

[0115] Steps (method 2) of another method used in the scope of experimental works, comprising functionalization by using A174, of supportive phase systems of biomimetic hydroxyapatite (BHA), zirconia (ZrO.sub.2), silica (SiO.sub.2), silica/zirconia nanocluster (Si/Zr nanocluster) and commercially available titania (TiO.sub.2) produced as supportive phase system in the present work are sorted as follows:

[0116] 1. Suitable amount of A174 is added to 380 ml ethanol:water (1:3) located inside closed system reactor and in inert environment.

[0117] 2. PH value of the solution is adjusted between 2-4 by acetic acid and stirred for 30 minutes.

[0118] 3. Supportive phase system to be modified under strong stirring is added and stirred.

[0119] 4. It is treated for 1-3 hours at 60-80 C. in inert gas environment under condenser. Filtered mixture is rinsed inside ethanol/water solution to remove reaction residue.

[0120] 5. It is dried in clay incubator or in vacuumed incubator at 60-80 C.

[0121] The proportion between silane amount (X) to be used as binding agent and supportive phase amount to be treated was suggested and determined with the following formula [75]:

X=Af/(7)

[0122] X: Binding agent amount (g), f: Supportive phase amount (g), A: Surface area of supportive phase (m2/g), : Wetting surface of silane (314 m.sup.2/g)

Production of Composite Filling Materials (Method 1)

[0123] 1. BisGMA (1-5%) is stirred in ultrasonic water bath for 10 minutes at 40 C. Organic resin part of the composite structure is prepared by adding HEMA (5-10%), UDMA (5-10%) and TEGDMA (1-5%) therein.

[0124] 2. Only SiO.sub.2, SiO.sub.2/Silane, Si/Zr nanocluster, Si/Zr/Silane nanocluster, TiO.sub.2, TiO.sub.2/Silane, ZrO.sub.2, ZrO.sub.2/Silane, 3YSZ, -tricalcium phosphate (-TCP), nanocrystalline cellulose (NCC), hydroxyapatite particles/fibers/whiskers, Al-Sr-OF and Al-Sr-Si-OF in proportion varying between 50-90% by weight and/or supportive phase system containing the mixture of these materials are added to prepared resin mixture and stirred for one day in ultrasonic water bath or by speed mixer until a homogenous mixture is obtained.

[0125] 3. Camphoquinone or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide or phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide or 1-phenyl-1,2-propanedione (0.2%) and 4-EDMAB (0.8%) is added to prepared mixture and stirred for 3 hours in ultrasonic bath.

Production of Composite Filling Materials (Method 2)

[0126] 1. BisGMA (1-5%) is stirred in ultrasonic water bath for 10 minutes at 40 C. and organic part of the composite structure is prepared by adding HEMA (5-10%), UDMA (5-10%) and TEGDMA (1-5%) therein.

[0127] 2. Only SiO.sub.2, SiO.sub.2/Silane, Si/Zr nanocluster, Si/Zr/Silane nanocluster, TiO.sub.2, TiO.sub.2/Silane, ZrO.sub.2, ZrO.sub.2/Silane, 3YSZ, -tricalcium phosphate (-TCP), nanocrystalline cellulose (NCC), hydroxyapatite particles/fibers/whiskers, Al-Sr-OF and Al-Sr-Si-OF in proportion varying between 50-90% by weight and/or supportive phase system containing the mixture of these materials and camphoquinone or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide or phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide or 1-phenyl-1,2-propanedione and 4-EDMAB in proportion of 0.5-1.0% by weight is added to organic matrix mixture and stirred by speed mixer.

[0128] 3. The samples are kept in vacuumed incubator for 30 minutes at 37 C. for removing air bubbles which could be present in the structure of mixture.

[0129] Compositions of the dental composites are given in the following.

Organic Resin

[0130]

TABLE-US-00001 TABLE 1 Organic composition of dental composites Constituent Amount (% by Weight) BisGMA 1-5 HEMA 5-10 UDMA 5-10 TEGDMA 1-5 CQ 0.1-0.5 Diphenyl(2,4,6- 0.1-0.5 trimethylbenzoyl)phosphine oxide phenyl bis(2,4,6- 0.1-0.5 trimethylbenzoyl)phosphine oxide 1-phenyl-1,2-propanedione 0.1-0.5 4-EDMAB 0.5-1.0

Supportive Phase

[0131]

TABLE-US-00002 TABLE 2 Supportive phase systems used in dental composites and their proportions by weight Amount (% by Constituent Feature Weight) SiO.sub.2 Main Phase 10-90 SiO.sub.2/Silane Main Phase 10-90 Si/Zr nanocluster Main Phase 10-90 Si/Zr/Silane nanocluster Main Phase 10-90 TiO.sub.2 Opacifier and antimicrobial agent 0.1-20 TiO.sub.2/Silane Opacifier and antimicrobial agent 0.1-20 ZrO.sub.2 Opacifier 0.1-20 ZrO.sub.2/Silane Opacifier 0.1-20 3YSZ Opacifier 0.1-20 -tricalcium phosphate Antimicrobial and regenerative .sup.1-40 (-TCP) phase hydroxyapatite Antimicrobial and regenerative .sup.1-40 particles/fibers/whiskers phase nanocrystalline cellulose Antimicrobial phase .sup.1-40 (NCC) AlSrOF Antimicrobial phase .sup.1-40 AlSrSiOF Antimicrobial phase .sup.1-40

[0132] Dental composites should be in conformity with natural tooth color. In this context, pigments used in structures of dental composites are essential. These pigments should be stable in mouth environment and should not exhibit color change. Generally, oxide pigments such as iron oxide (Fe.sub.2O.sub.3-red) or ferric hydroxide (FeOOH-yellow) are used in dental composites [31]. In the scope of present patent application, composite products given in Table 1 can be in following color groups in accordance with Vita Classic (Vita Zahnfabrik, Bad Sackingen, Germany);

[0133] A (Yellow-red)A1, A2, A3, A3.5

[0134] B (Yellow)B1, B2, B3

[0135] C (Gray)C1, C2, C3

[0136] D (Red-Gray)D2, D3, D4.

[0137] In order to provide respective colors, Duranat Yellow Iron Oxide (Pigment Yellow 42 & 43 Cl 77492), Duranat Red Iron Oxide (Pigment Red 101 Cl 77491), Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-Phenyl-1,2-propanedione 98%, Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, Duranat Brown Iron Oxide (Pigment Brown), Duranat Black Iron Oxide (Pigment Black 11 Cl 77499), iron oxide (Fe.sub.2O.sub.3-red), ferric hydroxide (FeOOH-yellow) or mixtures thereof in the proportion of 0.01-1% by weight can be used in composites.

[0138] In order to obtain opaque products in composite fillings, color pigments (E171 Titanium Dioxide; Pigment White 6 Cl 77891;) containing TiO.sub.2 and/or TiO.sub.2can be used in structure.

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