Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/71—Fillers
  • A61K6/74—Fillers comprising phosphorus-containing compounds
  • A61K6/75—Apatite
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/71—Fillers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/70—Preparations for dentistry comprising inorganic additives
  • A61K6/78—Pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the invention relates to the light-cured and polymerizable restorative acrylic dental composite filling materials and a new supportive phase system for producing the said dental composites, and to the production of a new acrylic dental composite filling material for the related technical field.
• Resin-based composite (RBC) materials were first reported by Bowen in 1958.
• the commercial use of resin-based composites was made possible by the author's patent titled "a vinyl-silane treated fused silica and binder" in 1962.
• the concept of chemically cured RBCs became a concept only after they were introduced to the dental market in 1970.
• these materials are frequently preferred in Grade I and Grade II Restorations.
• BisGMA has found wide use in commercial dental resin composites.
• the color stability of the monomer is insufficient, highly viscous, and could not be purified by methods such as distillation and crystallization.
• Bowen has conducted studies on isomeric crystalline dimethacrylates, which exhibit eutectic formations at room temperature and are liquid, which is a new monomeric system.
• three aromatic diesters of phthalic (P), isophthalic (I), and terephthalic (T) acids synthesized the bis(2-methacryloxyethyl)-P/l/T ester monomer and purified it by recrystallization method. It has been determined that the mechanical properties of the composites produced from these monomers are equivalent to BisGMA and the polymerization shrinkage values meet the expected property. On the other hand, these monomer systems could not provide the expected color stability in vivo.
• dimethacrylate resins tend to adsorb water in the oral environment and exhibit hygroscopic expansion. Although this expansion has some advantages, it causes various disadvantages such as decreased mechanical strength and wearing resistance in the long term. For this reason, hydrophobic monomer systems obtained by removing the hydroxyl groups in the BisGMA chains have been developed to minimize the water retention capacity of the resin. However, these systems could not meet the desired mechanical properties.
• UDM Urethane dimethacrylates
• Polymerization shrinkage is the most common problem in composite resins.
• the approximate volume shrinkage of BisGMA-based polymers is around 5% and this value can be reduced by increasing the loading amount of the supportive phase systems.
• polymerization shrinkage is one of the important parameters affecting the duration of use of the composite.
• various studies have been conducted on non-shrinkage and polymerized bicyclic compounds by the cycle opening polymerization technique. Bailey stated that various bicyclic monomers and unsaturated dicetels containing spiro orthocarbonates, spiro orthocarbonates, bicyclic keto lactones, and trioxabicyclo octanes exhibit double ring polymerization without shrinkage and/or expansion.
• Compomers are dental materials that combine the aesthetic properties of conventional composites and the fluoride release and adhesion properties of glass ionomer cement.
• compomers are separated from glass ionomer cement in two ways: firstly, glass particles are partially silanized to enable binding with resin, and secondly, the polymeric structure is formed as a result of radical polymerization reactions following the activation of monomers by light.
• silorane-based organic resin monomers One of the technological developments in dental commercial materials in recent years is the use of silorane-based organic resin monomers.
• the silorane monomer is named after the siloxane and oxirane molecules that make up its structure.
• the composite resin produced includes 78.5% by weight of clumped (aggregate) zircon ia/silica clusters with the main particle size of 5-20 nm and silica-based supportive phase systems with a particle size of 20 nm without clumping.
• quartz-tungsten-halogen light sources were first used.
• the most commonly used photoinitiator system in these systems is camphorquinone.
• the polymerization time of a 2 mm thick restoration with traditional quartz-tungsten-halogen light sources takes approximately 40-60 seconds.
• Argon laser which provides high energy output at 448 nm wavelength, has provided various advantages such as rapid polymerization in commercial dental restorative materials.
• Plasma Arc Units Another system developed to shorten the polymerization time is "Plasma Arc Units".
• short arc systems provided by the use of xenon light sources are named plasma arc light sources.
• This unit consists of spark and fluid gas systems produced by applying high energy potential between two tunnels. The system operates at 400-500 nm wavelength and polymerization takes place in less than 1 second.
• some researchers suggest that the characteristics of the final product will not be of the desired quality since polymerization takes place in such a short time.
• One of the most important cases in composite restorations is the monomer conversion percentage.
• One of the simplest methods to achieve polymerization is to apply heat. Heat reduces monomer viscosity, allowing free radicals to better diffuse into the monomer, and a higher percentage of monomer conversion is observed.
• the "postcure heating" method has been developed for photoinitiator composite systems. In this method, the composite is first cured with a conventional light source and photopolymerized and then heat is applied. This method is preferred in glass ionomer systems rather than composite filling materials.
• Resin-based composite restorations that started with methyl methacrylate resin compositions have come a long way in terms of organic resin, inorganic phase, and curing techniques.
• resin-based composite filling materials do not have a structure that can mimic the natural tooth structure and do not have sufficient features that can meet clinically necessary expectations. Therefore, considering the clinical expectation, research on the development of the properties of composite filling materials continues at an increasing rate.
• Martin et al. carried out studies on the synthesis of a urethane multimetacrylatebased monomer system, which may be an alternative to BisGMA-based composites that cause problems such as low monomer conversion and high volume shrinkage.
• they produced urethane-multimetacrylate monomer by using methacryloyloxypropylphenylmethane (BMPM) and urethane-methacryloyloxyethyl (UME) initial monomers.
• BMPM methacryloyloxypropylphenylmethane
• UAE urethane-methacryloyloxyethyl
• Liu et al. drew attention to the problems of homogeneous dispersion of Ag nanocrystals used in dental composites in organic resin to prevent secondary caries formation and loaded silver particles into composite systems by modifying them with organic agents.
• tertiary ammonium dimethacrylate compounds such as N,N-bis[2-(3-(methacryloyloxy) propanamido)ethyl]-N-methyldodecyl ammonium iodide (QADMAI-12), N,N-bis[2-(3- (methacryloyloxy)propanamido)ethyl]-N-methylhexadecyl-ammonium iodide (QADMAI-16) and N,N-bis[2-(3-(methacryloyloxy)propanamido)ethyl]-N-methyloctadesethyl ammonium iodide (QADMAI-18). They determined that the monomer conversion percentages of the produced composite were better compared to conventional composites as well as antibacterial and radio
• Liu et al. conducted studies on a light-curable biocidal dental resin composite. They have loaded the supportive phase system produced by combining poly(BisGMA)-graft-silanized whisker hydroxyapatite (PGSHW) and silanized-silica (s-SiOs) nanoparticles into bisphenol-A glycidyl methacrylate (BisGMA)/triethylene glycol dimethacrylate (TEGDMA) based dental resin.
• PGSHW poly(BisGMA)-graft-silanized whisker hydroxyapatite
• s-SiOs silanized-silica
• Wu et al. developed a self-repairing composite containing dimethylaminohexadodecyl methacrylate (DMAHDM) to provide antibacterial function and nano-sized amorphous calcium phosphate (NACP) for remineralization to find solutions to problems such as cracking and secondary caries occurring in composite restorations.
• DMAHDM dimethylaminohexadodecyl methacrylate
• NACP nano-sized amorphous calcium phosphate
• DADDM dimethylaminododecyl methacrylate
• NAg silver nanoparticles
• DADDM dimethylaminododecyl methacrylate
• DMAHM dimethylaminohexane methacrylate
• nACP loaded amorphous calcium phosphate nanoparticles
• nFA nano fluorapatite
• Liu et al. examined the morphology, loading, and mechanical properties of the composite by adding silanized hydroxyapatite (DK-sHA) particles with a morphology similar to that of sea urchin to composites containing and without BisGMA/TEGDMA organic resin structures containing silica nanoparticles. They determined that the mechanical properties of the composite could be improved by loading the DK-sHA support phase to the silica-free composite structures at 5% and 10% by weight and that the composite's elasticity modulus and microhardness values increased at loading levels of 20% to 30%, but the strength did not increase more.
• DK-sHA silanized hydroxyapatite
• Hojati et al. loaded ZnO nanoparticles on the composite material to improve the antimicrobial effect of dental restorative materials and evaluated the physical and mechanical properties of the material with the antimicrobial effect of the composite on Streptococcus mutans bacteria. They determined that the bacterial development decreased significantly with the increasing loading of ZnO nanoparticles and that the flexural strength, compressive modulus, and monomer transformation values did not change compared to traditional composite systems.
• Teeth are organs involved in many systems such as aesthetic appearance, pronunciation, and digestion. Diseases in the teeth are described as problems that directly affect the quality of life of individuals. Health problems that occur in teeth, especially in caries, can negatively affect the fulfillment of life functions, as well as affect the economy of individuals and countries. Caries are one of the most common diseases in the dental and oral environment from the past to the present. According to the data of the World Health Organization, caries is described as the most common non-communicable disease globally after the common cold. In the treatment of caries, the degraded tissue is removed from the structure and replaced with filling materials that can perform the functions of the tooth such as biting and chewing.
• the invention relates to a new supportive phase system for the production of light-cured and polymerizable restorative acrylic dental composite filling materials and the said dental composite filling materials in order to eliminate the existing disadvantages in the related technical field and to offer additional technical advantages and solutions for the related technical field.
• the main object of the invention is to provide an acrylic dental composite filling material in which edge compatibility is improved by reducing polymerization shrinkage.
• Another main object of the invention is to present an acrylic dental composite filling material with improved antibacterial and bioactive properties.
• the invention is to provide an acrylic dental composite filling material that minimizes the formation of secondary caries in patients.
• the invention is to provide an acrylic dental composite filling material with improved regenerative properties in one aspect.
• the subject of the invention relates to a new supportive phase system for the production of light-cured and polymerizable restorative acrylic dental composite filling material and the said dental composite filling material and is explained with examples that do not have any limiting effect only for a better understanding of the subject.
• the invention relates to the dental filling material to provide all these benefits mentioned for the related technical field.
• the said dental filling material is a composite material.
• a composite filling material that can be used as a dental filling material comprises a matrix comprising at least one organic component(s) within the filling material, and a supportive phase system comprising components to provide antibacterial, regenerative, and bioactive properties for the final product.
• the supportive phase system within the acrylic dental composite filling material of the invention provides antibacterial properties for the final product and also contains components with high mechanical properties.
• the acrylic dental composite filling material of the invention contains biomimetic hydroxyapatite, AI-Sr-OF, and AI-Si-Sr-OF compounds and silica components as the supportive phase.
• the components included in the supportive phase system of the invention have nanoflower morphology, unlike the present art.
• the supportive phase system obtained from components with the nanoflower morphology has a high surface area/volume property.
• the supportive phase system has a high surface reactivity thanks to the presence of components with these properties.
• the supportive phase system developed in this way ensures that the performance of the acrylic dental composite filling material to be obtained is increased to very high levels.
• the supportive phase system of the invention makes it possible to obtain acrylic dental composite filling material with high antibacterial properties thanks to the AI-Sr-OF and Al-Si- Sr-OF components with nanoflower morphology. These components prevent the formation of secondary caries that can be seen in patients thanks to the fluorides they contain.
• the supportive phase system of the invention makes it possible to obtain acrylic dental composite filling material with high biocompatibility and regenerative properties thanks to the biomimetic hydroxyapatite component with nanoflower morphology.
• the biomimetic hydroxyapatite component contributes to the improvement of the properties of flexural strength, compressive strength, hardness, curing depth, and polymerization shrinkage for the final product acrylic composite filling material.
• the inventors provide methods for the production of each component within the supportive phase in nanoflower morphology.
• the supportive phase system of the invention is in the range of 50% to 90% by weight in the dental composite filling material.
• the inventors can use three different methods for the production of the biomimetic hydroxyapatite component within the supportive phase system. Microwave irradiation, sonochemical and hydrothermal synthesis are used as the said methods. Under this heading, detailed explanations are made for the production of the hydroxyapatite component in the nanoflower morphology with the said production methods.
• the hydroxyapatite component first comprises the following process steps: i. 50 ml of Ca(NC>3)2.4H2O and 0.1 M EDTA mixture in the range of 0.05 to 0.15 M is added to 50 ml (NFU ⁇ HPC solution in the range of 0.03 to 0.08 M. ii. NaOH is added to the solutions taken into SVS and the pH value is increased to 9-13 in a controlled manner and mixed for a few minutes.
• the solution obtained in the process step ii is treated in a microwave oven so that it is open for at least 6 hours and closed for at least 10 hours; preferably, an oven of 700 W power is used as the said microwave.
• the mixture obtained by applying process step iii is cooled to room temperature and washed with deionized water.
• the mixture obtained by applying the process step iv is dried for at least 2 hours in a vacuum oven with a temperature of at least 70°C.
• the mixture obtained in process step ii is subjected to the mixing process before being placed in the hydrothermal reactor; the said mixing process is preferably carried out at a speed of at least 300 rpm for 10 minutes.
• the mixture obtained in process step iii is placed in the hydrothermal reactor and the hydrothermal reaction is carried out; the said hydrothermal reaction is carried out for at least 12 hours and in the temperature range of 150 to 220°C. v.
• the mixture is then expected to drop to room temperature.
• the precipitate removed from the reactor is rinsed with distilled water. vii. It is dried in an oven at 60°C for 24 hours.
• the mentioned production methods provide hydroxyapatite compounds in nanoflower morphology. Subsequently, hydroxyapatite compounds are used as components in the supportive phase system in the nanoflower morphology.
• the supportive phase system of the invention comprises AI-Sr-OF and AI-Si-Sr-OF compounds as fluorine release agents. These supportive phase systems, which are generally obtained by the melting method, are limited in use as supportive phase systems since they have a large grain size.
• AI-Sr-OF and AI-Si-Sr-OF metaloxyfluorides with nanoflower morphology produced by the inventors in the invention have been used as supportive phase systems together with hydroxyapatite in nanoflower morphology thanks to their superior mechanical properties.
• AI-Sr-OF and AI-Si-Sr-OF compounds can be produced by three different methods similar to the production of hydroxyapatite compounds.
• preliminary preparation processes are applied for the production of AI-Sr-OF and AI-Si-Sr-OF compounds.
• the said process steps are as follows: i.
• the cation solution is prepared by mixing 80 mL of AI(NO3).9H2O in the range of 0.1 to 0.3 M, 20 mL Sr(NOs)2 in the range of, 0.1 to 0.3 M, and 0.1 M EDTA solutions.
• the anion solution is prepared by mixing 720 mL NFLOH in the range of 0.1 M to 0.3 M and 180 mL NF F in the range of 0.1 to 0.3 M.
• iii The cation solution is added to the anion solution under strong stirring.
• the solution obtained by the application of process step iii is subjected to stirring for at least 90 minutes at room temperature in the ultrasonic sonicator device, followed by the synthesis of AI-Sr-OF compounds in the nanoflower morphology. It is preferred that the said ultrasonic sonicator device is at least 28 kHz frequency and 200 W power.
• the mixture obtained in process step iii is placed in the hydrothermal reactor and the hydrothermal reaction is carried out.
• the said hydrothermal reaction is carried out for at least 12 hours and at a value in the temperature range of 150 to 220°C.
• AI-Si-Sr-OF Synthesis with Nanoflower Morphology i The cation solution is prepared by mixing 60 to 70 mL of AI(NC>3)3.9H2O in the range of 0.1 to 0.3 M and 30 to 40 mL of Sr(NOs)2 and 0.1 M EDTA solutions in the range of 0.1 to 0.3 M. ii.
• the anion solution is prepared by mixing 60 to 70 mL of NasSiOs solution in the range of 0.1 to 0.3 M, 600 to 700 mL of NFUOH solution in the range of 0.1 to 0.3 M, and 2M 180 mL NH4F solutions.
• the solution obtained by the application of the process step ii is subjected to stirring for at least 90 minutes at room temperature in the ultrasonic sonicator device, followed by the synthesis of AI-Si-Sr-OF compounds in the nanoflower morphology. It is preferred that the said ultrasonic sonicator device is at least 28 kHz frequency and 200 W power.
• the mixture obtained in process step ii is placed in the hydrothermal reactor and the hydrothermal reaction is carried out.
• the said hydrothermal reaction is carried out for at least 12 hours and at a value in the temperature range of 150 to 220°C.
• Silica Synthesis Silica powders were obtained in the rotary evaporator using Ludox HS-40, a colloidal silica solution for commercial use in the supportive phase system.
• the experimental stages carried out are outlined below: i. 100 mL of colloidal silica solution is placed in the 250 mL glass chamber of the rotary evaporator, ii. During the drying process, the temperature is gradually reduced from 160°C to 40°C, iii. After the temperature is fixed at 40°C, drying continues for 3 hours, iv. Dried silica powders are mechanically ground with the help of a ball mill for 24 hours, v. The ground powders are passed through a 250 mesh sieve and used as a supportive phase.
• the supportive phase system of the invention is preferably subjected to silanization processes and the silanized supportive phase system is allowed to be obtained. It is a preferred embodiment of the invention that the supportive phase components powders obtained by the production methods given in the invention are combined and subjected to silanization processes.
• Silanization of the supportive phase system is performed in the nitrogen atmosphere by following the steps below, respectively.
• a sealed glass bottle 5% to 10% by weight of 3methacryloyloxy-propyl- trimethoxysilane is added to the ethanol: water solution in the ratio of 4:1 to 10:1 by weight, and the pH of the solution is adjusted to a value in the range of 3 to 4 pH with the acetic acid solution and mixed at room temperature for 1 hour.
• the supportive phase system to be modified under strong stirring is then added to this solution and stirred at room temperature for 24 hours.
• the reaction mixture is filtered and rinsed with ethanol to remove the physically adsorbed silanes.
• the dental filling material of the invention is a composite material and contains at least one supportive phase and matrix component.
• the components used as matrix components in the invention are entirely obtained from organic compounds.
• Camphorquinone in the range of 0.05% to 0.2% by weight and Diphenyl(2,4,6- trimethylbenzoyljphosphine oxide compound in the range of 0.05% to 0.2% by weight are added to the organic resin mixture obtained in the process step ii) as photoinitiator and 4-EDMAB compound in the range of 0.5% to 1% by weight as an activator and then the mixture is heated for 10 minutes, iv.
• the supportive phase system in the ratio of 50-90% by weight to the organic resin mixture obtained in the process step iii) and the composite filling materials are obtained as a result of the mixing process in the ultrasonic water bath or by means of a speed mixer for at least one day until a homogeneous mixture is obtained, the said supportive phase system comprises the hydroxyapatite compound with nanoflower morphology, the AI-Si-Sr-OF compound with nanoflower morphology, the AI-Sr-OF compound with nanoflower morphology, and the silica compound, v.
• the composite filling materials obtained in process step iv are placed in the teflon molds with the spatula by bringing them to room temperature, then curing processes are applied using a blue-LED light device.
• hydroxyapatite, AI-Sr-OF, and AI-Si-Sr-OF supportive phase systems with nanoflower morphology in restorative dental composites is new in the relevant technical field, separately and together.
• a composite filling material with high biocompatibility, antibacterial and improved mechanical properties compared to the dental composites in the present art Nanodimensional supportive phase systems with high surface reactivity and surface area/volume ratio are obtained with nanoflower morphology obtained with more sensitive process steps compared to the current methods.

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• Health & Medical Sciences (AREA)
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• Oral & Maxillofacial Surgery (AREA)
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• Epidemiology (AREA)
• Animal Behavior & Ethology (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
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• Inorganic Chemistry (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Biophysics (AREA)
• Dental Preparations (AREA)

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• 2022
  • 2022-12-05 EP EP22847431.8A patent/EP4456860A1/de active Pending

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