EA046296B1 - LIGHT CURING AND POLYMERIZABLE ACRYLIC DENTAL COMPOSITE FILLING MATERIAL AND METHOD FOR ITS PRODUCTION - Google Patents

Description

Field of technology to which the invention relates

The present invention relates to acrylic dental composite fillings for restorative purposes, which are light-cured and polymerized, as well as to the production of these dental composites. Dental composites primarily consist of a support phase comprising ceramic-based materials and a polymer-based organic resin. In addition, they may contain several structures called a coupling agent in the composite material, in addition to the structures of the supporting phase, and provide the ability to increase the life and improve the mechanical, chemical and physical properties of the composite material by providing chemical bonding between the supporting phase and the organic phase.

Through the invention, a restorative and antimicrobial effect is achieved by using hydroxyapatite ceramics obtained by a biomimetic method in the structure of a composite filling. Moreover, through the invention, the antimicrobial effect is achieved by using methoxyfluoride compounds such as Al-Sr-OF and Al-Sr-Si-OF in the submicron dimension in the composite structure without using melting technology.

Prior Art

Resin-based composites (RBCs) were first described by Bowen in 1958. However, commercial use of resin-based composites was allowed after the author received a patent entitled Vinylsilane-treated fused silica and coupling agent in 1962. Development of basic chemical requirements cured RBC was only marketed after they were introduced to the dental market in 1970. On the other hand, these materials were generally preferred in Class 1 and Class 2 restorations, although non-abrasive applications in extensive restorations , was limited.

Issued a patent entitled Method of Dental Restoration Using a Dart Visible Light Curable Composition in 1974 and developed Total Etch Adhesives in the 1980s. led to the introduction of light-curable RBCs through clinical use in Class 1 and 2 restorations [1].

Increasing expectations from esthetic dentistry in recent years have inevitably led to the development of resin composites with advanced physical and mechanical properties, meeting esthetic requirements and having a clinically long service life for use in direct restorations. One of the most significant improvements we are seeing in this field is that nanostructured particles are combined with nanocrystals and used in the structure of conventional resins [2].

The history of existing resin monomers is based on the discovery by the German chemist J. Redtenbacher of a new acid called acrylic acid. Beginning in the 1900s, methyl methacrylate polymers also began to be produced using polymerization techniques, as well as the synthesis of methacrylate and numerous ester derivatives. By the end of the 1930s. Polymethyl methacrylate was first used in dentistry as a resin for the base of dentures, and a few years later it began to be used as materials for indirect fillings. During World War II, following the discovery in Germany of benzoyl peroxide and tertiary amine oxidation initiator accelerator systems, it became possible to polymerize methyl methacrylate at room temperature, and thus these polymer structures could be used as direct filling materials. However, these materials could not provide the required clinical characteristics [3].

The American dentist R. L. Bowen, observing the insufficient properties of methyl methacrylate resins, developed other synthetic resins for use in dental filling materials. In this area, he conducted research on epoxy resins that polymerize at room temperature. Although epoxy resins exhibited good esthetic properties in the oral cavity, the slow curing stage prevented their use as direct filling materials [4].

In connection with the problems that exist for epoxy resins, Bowen in 1956 conducted research on a new monomer system of 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane - BisGMA. This monomer system has been found to have relatively high activity compared to methyl methacrylate systems due to the characteristics of high molecular weight, chemical structure, low volatility, low polymerization shrinkage and rapid cure [4].

Bis-GMA is widely used in commercial dental resin composites. However, the color stability of the monomer is not sufficient, it is quite viscous, and cannot be purified by methods such as distillation and crystallization. To solve this problem, Bowen conducted studies on liquid isomeric crystalline dimethacrylates, which are a new monomer system and exhibit eutectic formations at room temperature. Within the scope of three aromatic diesters of phthalic (P), isophthalic (I) and terephthalic (T) acids, a monomer was synthesized

- 1 046296 bis(2-methacryloxyethyl)-P/1/T ester and purified by recrystallization. It was found that the mechanical properties of composites prepared from these monomers are equivalent to those of Bis-GMA, and that the polymerization shrinkage values satisfy the required performance. However, these monomer systems could not provide the required color stability under in vivo conditions [5].

Depending on their polar structure, dimethacrylate resins tend to adsorb water in the oral cavity and exhibit hygroscopic expansion. Although this expansion has some advantages, it leads to various disadvantages in the long run, such as reduced mechanical strength and corrosion resistance. Therefore, to minimize the water retention capacity of the resin, hydrophobic monomer systems have been developed by removing the hydroxyl groups located on the Bis-GMA chains. However, these systems also did not have the necessary mechanical properties [3].

Since hydrophobic monomers may not have the required properties, several studies have been conducted to improve fluorocarbon-containing polymers with the characteristics of low surface energy and high hydrophobicity. Within this scope, polyfluoromonomethacrylate and octofluoropentyl methacrylate monomer systems are used in resin composites. Although these composite structures had the expected hydrophobic properties, they could not provide sufficient physical and mechanical properties, in addition, they exhibited particularly high polymerization shrinkage [3].

Urethane dimethacrylates (UDMs), which are another monomer system used in composite resins, were first synthesized from hydroxyalkyl methacrylates and diisocyanates. This monomer has a lower viscosity value, while at the same time having a molecular weight similar to Bis-GMA. Since the percentage of monomer conversion in composite systems prepared using UDM monomers is higher compared to Bis-GMA systems, biocompatibility is also increased. These systems, also depending on their economic costs, are used as an alternative to Bis-GMA monomers in commercial resin composites [3, 6].

Polymerization shrinkage is the most common problem associated with composite resins. The volumetric shrinkage of Bis-GMA based polymers is approximately 5% and this value can be reduced by increasing the loading volume of the support phase systems [7]. Since polymerization shrinkage is a significant parameter affecting the service life of a composite, several studies have been conducted on double-ring compounds exhibiting no shrinkage and polymerized by ring-opening polymerization technique. Bailey indicated that various double ring monomers containing spiroorthoesters, spiroorthocarbonates, bicycloketolactones and trioxabicyclooctanes, and unsaturated diketals exhibit double ring opening polymerization without shrinkage and/or expansion. However, it was found that at the end of the reaction, a relatively large amount of monomer remained in the environment, not participating in the polymer structure [3].

The development of the organic resin structure was accompanied by the production of composites known as compomers, which were modified with polyacids, in 1994. These composite substances were prepared by embedding systems of supporting phases, such as calcium-aluminum fluorosilicate glasses, into the polymer resin. Compomers are dental materials that combine the esthetic properties of conventional composites with the fluoride release and adhesion properties of glass ionomer cements. It should be noted that compomers differ from glass ionomer cement in two aspects: firstly, the glass particles are partially silanized to ensure binding to the resin, and secondly, the polymer structure is formed as a result of radical polymerization reactions after activation of the monomers with light [8].

In 1984, hybrid structures from organic and inorganic polymers were synthesized, which Schmidt designated as ormosils (organically modified silicates) and then as ormocers (organically modified ceramics). In ormoceras, organic and inorganic compounds are combined on a nanoscopic, that is, molecular scale. Thus, these substances have the characteristics of organic and inorganic components found in their structures, in which they exhibit unique features, the basis of which has not yet been established [9]. The use of ormocers in dentistry began in 1998, and especially in recent years, ormocers have found commercial application in the field of restorative materials.

The use of silorane-based organic resin monomers is one of the latest technological developments in dental commercial materials. The monomer is called silorane after the siloxane and oxirane that make up its structure. To provide composite materials that are believed to be an alternative to methacrylate-based monomers and that maintain mechanical strength and also reduce polymerization shrinkage, silorane monomers developed within 3M ESPE have rapidly achieved commercial use due to the fact that they correspond to clinical expectations [10].

In addition to reducing polymerization shrinkage, another feature that needs to be added to monomer systems is an antibacterial effect. In this volume we obtain mo

- 2 046296 numbers with antibacterial properties, without adding fluoride-releasing compounds to the structure. Within this framework, the most promising monomer is methacrylyldododecylpyridinium bromide (MDPB), obtained by the reaction of the antibacterial agent dodecylpyridinium bromide and the methacryl group. Several studies have found that composite systems obtained by copolymerizing conventional dental monomers and methacrylyl dodecylpyridinium (MDP) have the effect of inhibiting the growth of bacteria on their surfaces. However, in commercial composite systems currently produced, the antibacterial effect is provided by fluoride-releasing particles of the supporting phase, rather than by monomer systems of this type [11, 12].

Three main components, such as a monomer, a silane-treated support phase and an initiator, were used in the first composite resin structure in the 1960s. The support phase used by Bowen in 1963 consists of ground quartz particles that have an average size in the range of 8-12 µm (8000-12000 nm). Due to the limitations of macrophilic composite in esthetic restorations (such as problems with surface polishing), in the 1970s. minifill composites have been developed. Support phase systems obtained by pyrogenic methods increased the polishing ability, allowing composites to be loaded with a maximum value of 55%, while they significantly reduced the mechanical strength [2].

Testing of support phase systems in the form of mixtures only became possible in the 1980s and 1990s. Restorative materials having a particle size of 600-2000 nm containing these hybrid support phase systems were commercialized as hybrid, microhybrid and intensified (with filamentary structure) composites. Although its mechanical strength can be significantly increased with these products, their polishing ability is still limited. The maximum load in these products reached 70-77% by weight. However, the particle size values of conventional composites cannot adequately match the hydroxyapatite crystals, dentinal tubules, and enamel cores contained in the natural tooth structure. Consequently, the potential to provide the required retention between the macroscopic material and the nanoscopic (1-10 nm) tooth structure cannot be achieved [13].

Since it is not possible to obtain a supporting phase smaller than 100 nm by grinding, the use of nanotechnological methods in obtaining the supporting phase is an innovative method in this field of technology, providing properties such as controlled crystal growth, a homogeneous finished product in terms of structure and size. At the beginning of this century, Filtek Supreme (3MESPE, St. Paul, USA) became a commercial milestone for the application of nanotechnology in operative dentistry. The composite resin obtained in this context contains aggregated zirconia/silica groups, which have a main particle size of 5-20 nm and in an amount of 78.5 wt.%, and silica-based support phase systems, which are not subject to aggregation and have particle size 20 nm [2].

Recently, composite systems containing microhybrid and nanofill composites together have been produced on a commercial scale. This new composition made it possible to increase the loading proportions of support phase systems to 87 wt.% depending on the formation of gaps of the filler with support phase content between larger and smaller particles [2].

In addition, the curing techniques used to polymerize composites have undergone time improvements based on improvements in the support phase and monomer systems. As mentioned above, the first composite filling materials used in the field of dentistry were polymerized using redox reactions at room temperature. The polymerization reactions of these products, packaged as two different materials, were initiated by mixing the products and required a long period of time, such as 8 min, to complete the polymerization correctly [14].

Duration-dependent composite systems (Nuva; Dentsplay/Caulk) that could be photopolymerized were developed in the late 1970s. This type of polymerization method provided dentists with the advantage of rapid cure after product placement and the ability to achieve the desired contour. First of all, these systems use quartz lamps with a wavelength of 354 nm as a source of ultraviolet light; the polymerization reaction occurs with the formation of free radicals. Although this system was advantageous in the beginning, in subsequent periods, in such cases where the application is in large volume, some problems such as incomplete polymerization and very rapid depletion of the light source occurred. Therefore, in subsequent periods, visible light energy began to be used in the wavelength range of 400-500 nm instead of UV light for photopolymerization [15]. At first, visible light systems used quartz-tungsten-halogen light sources. The most used photoinitiator in these systems is camphor-quinone [14]. The polymerization time for a 2 mm thick restoration is approximately 40-60 s on traditional quartz-tungsten-halogen sources

- 3 046296 light. Although these systems are more advantageous for polymerization compared to self-curing systems, the search continues for new methods where the light energy at the surface of the composite is more intense compared to the areas below, and the light penetrates into the areas below with less intensity [16].

Along with the development of laser technology that provides high light intensity within the energy range required for photopolymerization in dental materials, dental applications have also been developed. The argon laser, which provides high output power at 448 nm, has several advantages such as rapid polymerization in commercial dental restorative materials [17].

Another system designed to reduce curing time is Plasma Arc Unites. Short arc systems provided by the use of a xenon light source in this context are called a plasma arc light source. This unit consists of a spark generated by applying a high energy potential between two tungsten electrodes and liquid gas systems. The system operates at a wavelength of 400-500 nm and polymerization is completed in less than 1 s. However, some researchers suggest that the final product may not have the required quality due to the completion of polymerization in such a short time [18].

Manufacturers have developed the present system, providing high energy output and short run time, similar to plasma arc systems, to keep the quartz tungsten halogen lamp in the market. In contrast, concerns about polymerization shrinkage have arisen based on the development of rapid cure conditions [18].

The improvements seen in light emitting diode (LED) technology have made the use of these light sources inevitable in the dental industry. The emission range of blue LED light sources corresponds to the wavelength range of photoinitiator systems. The main advantages of this light source can be defined as follows: transportability, minimal maintenance requirements, long service life and emission only at the wavelength required to activate the photoinitiator [14].

Another curing method, especially used in cement technology, is the dual curing method. In the chemical curing method, the additional initiator remaining in the environment must be removed from it, and a long waiting time is required until the product is completely set, these problems are attempted to be solved by the light curing method. It should be noted that when curing with light, complete polymerization cannot be ensured due to the fact that the light cannot be intense enough at deeper points. To overcome these problems, dual-cure resin cement systems are developed using both chemical and photoinitiator systems within the products [19-21].

One of the most important considerations in composite restorations is the percentage of monomer conversion. One of the simplest methods is the use of heat to ensure polymerization. Heating provides better diffusion of free radicals into the monomer by reducing the viscosity of the monomer and thus a higher percentage of monomer conversion is observed. Based on this principle, a post-curing heating method has been developed for composite systems with a photoinitiator. In this method, photopolymerization is carried out by curing the composite first with a conventional light source and then by providing heat [22]. This method is preferred in glass ionomer systems rather than composite restorative materials.

Resin-based composite restorations, which began with the use of methyl methacrylate resin compositions, have come quite a long way to date in terms of the use of organic resins, inorganic phases and curing techniques. However, resin-based composite filling materials do not have a structure that can mimic natural tooth structure and properties that are sufficient to meet the required expectations. Therefore, given clinical expectations, research to improve the properties of composite restorative materials continues at an increasing rate.

In 2014, Martin et al. [23] conducted research on the synthesis of a monomer system based on urethane multimethacrylate, which could be an alternative to Bis-GMA-based composites associated with problems such as low monomer conversion and high volumetric shrinkage. In this context, they prepared a urethane multimethacrylate monomer using the starting monomers methacryloyloxypropylphenylmethane (BMPM) and urethane methacryloyloxyethyl (UME). They found that the resulting composite exhibited lower polymerization shrinkage and higher flexural strength compared to conventional composites, and the physicochemical and mechanical properties of the composite were specifically stable when silicate support phase particles were loaded into the monomer system.

Liu et al. [24] pointed out the problems of homogeneous mixing of Ag nanocrystals, which are used in dental composites to prevent secondary caries within organic resin, and loaded silver particles into composite systems through modification with organic

- 4 046296 agents. Within this field, they investigated the mechanical and antibacterial properties of dental resin composites by coating Ag nanoparticles with oleic acid. They found that modified silver nanoparticles significantly improved the mechanical and antibacterial properties of the composite, such as flexural strength, elastic modulus, and compressive strength, compared to unmodified particles.

Not et al. [25] conducted studies on the synthesis of antibacterial and radiopaque dimethacrylate monomers for use with dental resin composites. Within this field, they synthesized tertiary ammonium dimethacrylate compounds such as N,N-6uc[2(3-(methacryloxy)propanamido)ethyl]-Nmethyldodecylammonium iodide (QADMAI-12), N,N-6uc[2-(3 (methacryloxy)propanamido)ethyl]-Nmethylhexadecylammonium iodide (QADMAI-16) and N,N-6uc[2(3-(methacryloxy)propanamido)ethyl]-Nmethyloctadylammonium iodide (QADMAI-18). They also determined that the percentage of monomer conversion in the resulting composite was improved compared to conventional composites in addition to antibacterial and opacity properties. However, they observed that the flexural strength and elastic modulus values of the composites were lower compared to conventional composites.

Liu et al. [26] conducted studies on a bioactive dental resin composite that was light cured. They loaded a system of support phases that they produced by combining nanoparticles of poly(Bis-OMA)-silanized hydroxyapatite whiskers (PGSHW) and silanized silica (s-SiO ₂ ) in a bisphenol-A-glycidyl methacrylate (Bis-OMAUTriethylene glycol dimethacrylate) dental resin (TEGDMA) They determined that their produced composites containing a hybrid PGSHW/sSiO2 support phase system significantly improved mechanical properties and monomer conversion percentage values such as flexural strength, elastic modulus, compressive strength and toughness compared to composites incorporating hydroxyapatite nanoparticles.In addition, they showed that the resulting composite in in vitro biological activity tests was capable of forming apatite.

Wu et al. [27] developed a composite that contains dimethylaminohexadodecyl methacrylate (DMAHDM) for antibacterial function and nanosized amorphous calcium phosphate (NACP) for remineralization, and which provides self-healing, with the aim of finding a solution to problems such as cracks and secondary caries formation noted with composite restorations. . They found that the composite structure created as a result of their work, for the first time in the literature, has the ability to repair cracks, has an antibacterial effect and the ability to remineralize after crack formation.

Chan et al. [28] conducted studies on composite systems exhibiting antimicrobial effects, similar to Wu et al. [27]. They loaded nanoscale amorphous calcium phosphate ceramics and dimethylaminododecyl methacrylate (DMADDM) monomeric structures into organic resin systems made from conventional composites. As a result of their work, they suggested that the use of these substances in composite materials as support phase systems may be appropriate, determining that the release of Ca and P ions increases in accordance with the decrease in pH as a result of bacterial growth, and that the DMADDM monomer inhibits bacterial growth. exhibiting an antimicrobial effect.

Zhang et. al [29], as did Chan et al. [28], used silver nanoparticles (NAg) also as a support phase system in addition to dimethylaminododecyl methacrylate (DMADDM), amorphous calcium phosphate nanoparticles with antimicrobial effect, and determined that the antimicrobial effect was longer lasting compared to other composites.

Zhou et al. [30] developed a new antimicrobial monomer system and loaded amorphous calcium phosphate nanoparticles into this system to prevent the formation of biofilm observed on the composite structure and consequently avoid the occurrence of secondary caries. They synthesized dimethylaminododecyl methacrylate monomers (DMADDM) containing 12 carbon chains, similar to the studies of Chan [28] and Zhang [29] using dimethylaminohexane methacrylate monomer (DMAHM) containing 6 carbon chains as antimicrobial monomers and loaded nanoamorphous calcium phosphate (nACP) particles. by spray drying as an auxiliary step in this structure. As a result of the research, they found that the DMADDM monomer showed a greater antimicrobial effect compared to the DMAHM monomer. They determined that DMADDM-NACP nanocomposites had similar strength values compared to systems using tertiary ammonium dimethacrylates, while they reduced biofilm formation on the composite by only 5%. Taking into account their results, they suggested that the carbon chain length of the monomer was sufficiently effective for antimicrobial activity.

Jan et al. [31] conducted research on polymerization shrinkage, which is one of the most common problems in dental restoration, and was designed to reduce polymerization shrinkage and increase the hardness values of the composite structure by modifying dimethacrylate monomers with diisocyanate side groups. As a result of the research

It has been found that polymerization shrinkage can be reduced and the surface hardness of the composite can be increased depending on the use of diisocyanate side groups and chain length.

Khan et al. [32] carried out work to strengthen the bond between the filling material and the tooth surface, as well as to ensure the release of fluoride. In this context, they coupled fluorapatite nanoparticles (nFA) produced by the sol-gel method to an organic resin composed of urethane monomer structures through diisocyanate side chains. They found that the resulting composite exhibited better bonding to tooth structure compared to conventional composites and that fluoride release was realized over a long period of time, and suggested that the composite structure could be used as a filling material.

Liu et al. [33] investigated the morphological, loading and mechanical characteristics of composites containing Bis-GMA/TEGDMA organic resin structures with and without silica nanoparticles by adding silanized hydroxyapatite (DK-sHA) particles having a sea urchin-like morphology to the composite. They found that the mechanical properties of the composite could be improved by loading 5 and 10 wt% DK-sHA support phase into silica-free composite structures and determined that although the elastic modulus and microhardness values of the composite were increased at loading levels from 20 to 30%, the strength remained the same. They determined that DK-sHA was embedded in the resin and was homogeneously distributed within the composite compared to silanized amorphous hydroxyapatite and filamentous hydroxyapatite. When loaded into composite systems that also contained silica particles, it was determined that the strength and elastic modulus values of the composite could be significantly improved.

Taubock et al. [34] studied the effect of alkaline bioactive glass nanoparticles (SiO ₂ -Na ₂ OCaO-P ₂ O ₅ -Bi ₂ Oz) loaded into dental resin on the properties of the composite. They found that loading at 20% was not effective on microhardness, but it significantly increased the percentage of monomer conversion.

Hojati et al. [35] loaded ZnO nanoparticles into a composite material to enhance the antimicrobial effect of dental restorative materials and evaluated the antimicrobial effect of the composite against Streptococcus mutans bacteria, as well as the physical and mechanical properties of the material. They determined that bacterial growth was significantly reduced by increasing the loading of ZnO nanoparticles and that the values of flexural strength, compressive modulus, and monomer conversion were unchanged compared to conventional composite systems.

Jan et. al [36] modified Bis-GMA monomers and added toluene-2,4-diisocyanate (TDI) and 1,6-hexamethylene diisocyanate (HDI) functional side groups to this monomer system to find a solution to the shrinkage problem in the polymerization of dental composites. They found that the resin containing a large number of functional pendant groups and modified with TDI exhibited less cytotoxic effect compared to the HDI-modified resin. In addition, they suggested that the TDI modified resin caused less toxic effect compared to Bis-GMA monomers depending on the compression of the toxic resin monomers within the structure.

In summary, recent studies of existing commercial dental composites indicate that restorative restorative materials now provide sufficient physical and mechanical strength. Thus, research on resin-based composite restorative materials in the past three years has intensively focused on improving the chemical properties of the composite, such as reducing polymerization shrinkage and increasing the percentage of monomer conversion, as well as improving the biological properties of the composite, such as antimicrobial and remineralizing properties. Effect.

Objective of the present invention

This invention includes the production of composite restorative materials suitable for clinical needs for use in conservative dental treatment. Results required in this area:

1) Improving marginal compatibility and inhibiting secondary caries by reducing shrinkage during polymerization;

2) Inhibition of secondary caries using maintenance phase systems containing fluoride;

3) Improving remineralizing properties with bioactive ceramics such as hydroxyapatite;

4) Preservation of mechanical properties while enhancing antibacterial and biological properties.

To achieve these results, a light-curing and polymerizable acrylic dental composite filling material is proposed, including an organic compound, a photoinitiator and a supporting phase, in which said acrylic dental composite filling material contains at least one of the following compounds: SiO ₂ , SiO ₂ /silane, Si nanocluster /Zr, Si/Zr/silane nanocluster, TiO ₂ , TiO ₂ /silane, ZrO ₂ , ZrO ₂ /silane, 3YSZ to ensure the strength of the supporting phase; at least one of the following

- 6 046296: hydroxyapatite or β-tricalcium phosphate (β-TCP) to ensure the regenerative properties of the maintenance phase; at least one of the following metaloxyfluoride compounds: Al-SrOF or Al-Sr-Si-OF to provide antibacterial properties of the support phase; mixtures of bisphenol A glycidyl methacrylate (Bis-GMA), hydroxyethyl methacrylate (HEMA), urethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) as an organic compound; at least one of the following compounds: camphor quinone (CQ), diphenyl (2,4,6trimethylbenzoyl)phosphine oxide, 1-phenyl-1,2-propanedione, ethyl 4-dimethylaminobenzoate (4-EDMAB) as a photoinitiator. The organic compound of the acrylic dental composite filling material preferably contains bisphenol A glycidyl methacrylate (Bis-GMA) from 1 to 5 wt.%, hydroxyethyl methacrylate (HEMA) from 5 to 10 wt.%, urethane dimethacrylate (UDMA) from 5 to 10 wt.% and triethylene glycol dimethacrylate (TEGDMA) from 1 to 5 wt.%. The photoinitiator contains a CQ compound from 0.1 to 0.5 wt.%, a diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide compound from 0.1 to 0.5 wt.%, a 1-phenyl-1,2-propanedione compound from 0.1 to 0.5 wt.%, or the 4-EDMAB compound from 0.5 to 1.0 wt.%, the metal oxyfluoride compound is contained in an amount from 1 to 40 wt.%.

The acrylic dental composite filling material further contains a pigment that is selected from the group consisting of Duranat Yellow iron oxide, Duranat Red iron oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-phenyl-1,2-propanedione 98 %, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Duranat Brown iron oxide, Duranat Black iron oxide, iron oxide, ferric hydroxide, TiO ₂ , titanium dioxide E171; white pigment 6 CI 77891 or mixtures thereof, in a mass amount of 0.01 to 1 wt.%.

A method for producing a light-curing and polymerizable acrylic dental composite filling material includes the stages:

a) mixing Bis-GMA from 1 to 5 wt.% in an ultrasonic water bath with the addition of HEMA from 5 to 10 wt.%, UDMA from 5 to 10 wt.% and TEGDMA from 1 to 5 wt.% to obtain an organic matrix composite structures;

b) adding SiO ₂ , SiO ₂ /silane, Si/Zr nanocluster, Si/Zr/silane nanocluster, TiO ₂ , TiO ₂ /silane, ZrO ₂ , ZrO ₂ /silane, 3YSZ, β-tricalcium phosphate (β-TCP) , particles/fibers/threads of hydroxyapatite, Al-SrOF and Al-Sr-Si-OF in an amount of 50-90 wt.% and/or mixtures thereof, to the resulting organic matrix, and stirring in an ultrasonic water bath or using a high-speed mixer until obtaining a homogeneous mixture;

c) adding camphor-quinone or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide or phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide or 0.2 wt.% 1-phenyl-1,2-propanedione and 0.8 wt.% 4EDMAB to the prepared mixture and stirring in an ultrasonic bath;

d) keeping the samples in a vacuum oven to remove any air bubbles that may be present in the mixture structure;

e) bringing the prepared composite matrix to room temperature before use and mixing with a cement spatula, and placing in Teflon molds;

f) placing sheets of glass on both sides of the molds and compressing them by applying pressure;

g) processing of samples using a blue LED light apparatus. Stirring in step (a) is carried out for 10 minutes at 40°C, in step (b) the system of supporting phases is added in an amount of at least 70 wt.%, in step (b) stirring is carried out for one day, in step ( c) stirring is carried out for three hours, in step (d) the samples are kept for 30 minutes at 37°C, in step (g) treatment with a blue LED light apparatus is carried out for 20 seconds.

Detailed Description of the Invention

1. Synthesis of systems of supporting phases

1.1. Biomimetic synthesis of hydroxyapatite

First, a solution of Synthetic Biological Fluid (SBF) was prepared for the synthesis of biomimetic hydroxyapatite (BHA). We used the SBF solution prepared by Ta§ [60] and having a composition that is most similar to human blood plasma among the solutions described in the literature.

Hydroxyapatite (HA), usually preferably used in hard tissues, is prepared using Ca^NOs^^^O or Ca(OH) ₂ or Ca(CH ₃ COO) ₂ or CaCl ₂ as a source of calcium, and (NH ₄ ) ₂ HPO ₄ or NH4H2PO4 or K2HPO4 or H3PO4 as a source of phosphorus, at 37°C in synthetic biological fluid (SBF) with pH 7.4 according to the reaction of Equation 1. The amount of materials used in the synthesis of BHA ceramic powders is adjusted in this way, so that the Ca/P ratio in the resulting product is from 1.5 to 1.8, for example 1.5; 1.55; 1.6; 1.65; 1.7; 1.75; 1.8.

Ca(NO ₃ ) _{2.4H 2} O + 6(NH ₄ ) ₂ HPO ₄ Sayu(PO ₄ ) ₆ (OH) ₂ + 12 NH ₄ NO ₃ + 8 HNO ₃ (1)

- 7 046296

1. The first stage includes the preparation of stock solutions. In this step, 1 M Ca(NO3)2.4H2O and 1.2 M (NH ₄ ) ₂ HPO ₄ are added to 1000 and 500 ml of SBF solution respectively and dissolved using a magnetic stirrer with a heater at 500 rpm and 37°C.

2. The pH value of the Ca(NO ₃ ) ₂ .4H ₂ O solution is adjusted to 8 using a SVS:NH ₃ solution in a 2:1 ratio.

3. After adjusting the pH, the (NH ₄ ) ₂ HPO ₄ solution is added to the Ca(NO ₃ ) ₂ .4H ₂ O solution at a rate of 3-5 ml/min and stirred for 1-2 hours.

4. This mixture is maintained by keeping at 37°C for 24-48 hours and then filtered using blue tape filter paper using vacuum filtration method.

5. The resulting white and viscous precipitates are dried at 80°C and crushed in an agate mortar, calcined for 1 hour at 900°C in a muffle furnace.

6. The resulting biomimetic hydroxyapatite ceramic powder is abbreviated as BHA.

1.2. Synthesis of zirconium dioxide

Zirconium dioxide nanoparticles can be synthesized by various methods such as sol-gel, precipitation, combustion, condensation and thermal fragmentation of zirconium compounds. The most common method today is the sol-gel method of methods for the synthesis of such types of nanoceramics as zirconium dioxide. The crystalline phase, crystal size and other properties of zirconia nanoparticles are based on several parameters such as the type of starting compound, the pH value of the solution during hydrolysis and the thermal process. In the sol-gel method, various parameters such as purity, homogeneity and physical properties of zirconia can be controlled at low temperatures [61].

In the present work, zirconia is synthesized using sol-gel technology from zirconium oxynitrate salt as the starting material and the following experimental steps:

1. A 2.5 M aqueous solution of ZrO(NO ₃ ) ₂ .xH ₂ O is dissolved in a ratio of 3:5 (v/v) in ethanol to 400 ml.

2. Add 120 ml of HNO ₃ to the solution.

3. To prevent aggregation by forming a complex with the metal salt and ensuring uniform distribution [61], a PEG solution at a ratio of 1 wt.% is added to the resulting acid solution, and the sol solution is obtained by hydrolysis of the zirconia salt.

4. The mixture is dried at 200°C using a magnetic stirrer with a heater, and then dried in an oven at 150°C for one night, and thus a gel is obtained by condensation reactions.

5. The dried mixture is calcined for 1 hour in a muffle furnace at 1100°C.

6. The resulting ceramic zirconium dioxide powder is designated as ZrO2.

1.3. Synthesis of tetragonal zirconia doped with yttrium, 3 mol.%

The substance exists in three different crystalline forms under atmospheric conditions: monoclinic (up to 1170°C), tetragonal (at 1170-2370°C) and cubic zirconia (at 2370-2680°C) [64]. Zirconium dioxide, which is in the monoclinic phase at room temperature [65], transforms into cubic and tetragonal phases at high temperatures. On the other hand, in order for these phases formed at high temperatures to be stable at room temperature, substances such as CaO, MgO, Y ₂ O ₃ and CeO ₂ must be placed in the zirconium dioxide lattice [66]. While zirconia containing Y ₂ O ₃ in a molar ratio of 8% or more is in the cubic phase at room temperature, zirconia containing Y ₂ O ₃ in a molar ratio of 3% is in the tetragonal phase at room temperature. In a charge made at a ratio of 3-8 mol.%, zirconium dioxide includes cubic and tetragonal phases in its structure [67]. In this work, 3 mol% yttrium doped tetragonal zirconia is synthesized using sol-gel technology, similar to the synthesis of zirconia

1) 1.15 M aqueous solution of ZrO(NO ₃ ) ₂ .xH ₂ O is dissolved in ethanol in a ratio of 1:5 (v/v) to 250 ml.

2) Add 80 ml of HNO3 to the solution.

3) Add 0.35M Y(NO ₃ ) ₃ .6H ₂ C to the resulting acid solution.

4) To prevent aggregation by forming a complex with the metal salt and ensuring homogeneous distribution [61], a PEG solution at a ratio of 1 wt.% is added to the resulting acid solution, and the sol solution is obtained by hydrolysis of the metal salts.

5) The mixture is dried at 200°C using a magnetic stirrer with a heater and then dried in an oven at 150°C for one night and thus the gel is obtained through condensation reactions.

6) The dried mixture is calcined for 1 hour in a muffle furnace at 1100°C.

7) The resulting ceramic powder of tetragonal zirconia doped with 3 mol% yttrium is designated as 3YSZ.

1.4. Silicon dioxide synthesis

- 8 046296

The silica powders to be used as the supporting phase in this work are commercial solutions of colloidal silica 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.

Method 1.

1. The colloidal solution of silicon dioxide is dried in a thermostat at 80°C.

2. The dried powders are ground for one (1) day in a ball mill.

3. The ground powders are sieved through a sieve with a maximum size of <250 mesh.

4. The resulting ceramic silica powder is abbreviated as SiO ₂ .

Method 2.

1. Water from a colloidal solution of silicon dioxide is evaporated in a rotary evaporator at 80°C.

2. Then the silicon dioxide is dried in a vacuum thermostat at 80°C.

3. The dried powders are ground for one (1) day in a ball mill.

4. The ground powders are sifted through a <250 mesh screen.

5. The resulting ceramic silica powder is abbreviated as SiO ₂ .

Method 3.

1. The colloidal solution of silicon dioxide is dried first using a freeze dryer, then in a vacuum thermostat at 80°C.

2. The dried powders are ground for one (1) day in a ball mill.

3. The ground powders are sifted through a <250 mesh screen.

4. The resulting silicon dioxide powder is abbreviated as SiO ₂ .

1.5. Combined synthesis of silicon dioxide/zirconia

In recent years, one of the most important properties in dental composites required by the dentist and the patient is the compliance of the composites with esthetic expectations. At this stage, it is necessary that the dental composite structures mimic the appearance of a natural tooth as closely as possible. Silica/zirconia nanoclusters are highly attractive support phase systems to meet esthetic expectations due to the optical characteristics they have and the outstanding mechanical properties they bring to dental composites [68]. Silicon dioxide/zirconia nanoclusters, which are metal oxide, can be synthesized by various methods such as impregnation, sol-gel, chemical deposition and sol-gel at low temperatures [69]. Using these methods, Zr ions are located in the silicon dioxide lattice and a structure containing a mixture of metal oxides is formed [70]. In this work, silica/zirconia nanoclusters are synthesized based on impregnation [71], but the drying and calcination process is carried out similarly to the sol-gel method without using a filtration process after deposition. In the resulting Si/Zr nanocluster structure, the Si/Zr ratio varies from 1 to 20 depending on the assumed opacity value [69].

1. The pH value of 500 ml of colloidal silicon dioxide solution is adjusted to 2.5 with a dilute HNO ₃ solution.

2. This solution is slowly added to the 230.65 ml zirconyl acetate solution and stirred for 1 hour.

3. The mixture is dried in a thermostat or rotary evaporator at 80°C and calcined in a muffle furnace for 4 hours at 550°C.

4. The calcined powder is ground in a ball mill for one day and sieved through a <450 mesh sieve.

5. The resulting silica/zirconia nanocluster ceramic powder is designated as Si/Zr nanocluster.

1.6. Titanium oxide

Titanium oxide is commercial and is used as an auxiliary phase system without any process.

1.7. Synthesis of methoxyfluorides

Metal-oxyfluoride systems, also called acid-reactive supporting phase systems, are used in dental composites as a fluoride releasing agent. The main objective of those structures that are used in dental composite systems is to prevent secondary caries in the areas where the restoration is made. Metal oxides, metal salts and glass systems constitute the acid-reactive group of support phase systems. Fluoroaluminosilicate (FAS) glasses are examples of metal-oxyfluoride systems. Although these systems are prepared by melting, they have a large particle size, which limits their use as a supporting phase system in dental composites. Metal oxides,

- 9 046296 which are produced as an alternative to these systems and contain trivalent metal, oxygen, fluorine, alkali metal and preferably silicon, can be used in a dental composite depending on their controlled surface area values. The oxygen and fluorine atom in these structures are bonded to the same atom. For example, aluminum binds with oxygen and aluminum fluorine in a structure in which it is present as a trivalent atom, and, together with the structures of Al2O3 and AlF3, is in the same lattice form. Typically, the preferred structure in these structures as the alkaline earth metal is strontium metal. The proportion of trivalent metal and alkaline earth metal in the oxyfluoride material affects both the chemical properties of the composite and the cure efficiency. For example, using a high proportion of alkaline earth metal in the structure increases the reactivity of the composite and leads to the release of undesirable other materials as well as fluorine [184]. This work uses metal-oxyfluoride systems produced by deposition as an alternative to FAS glasses, which are used as a fluoride-releasing agent in dental composites. In this context, two different fluorine-containing agents such as silicon-free Al-Sr-oxyfluoride and AlSr-Si-oxyfluoride are prepared as support phase systems. The following experimental steps are presented.

Preparation of Al-Sr-oxyfluoride systems of supporting phases

1. 80 ml of a 2M solution of A1(NO ₃ ) _{3.9H 2} O is mixed with 20 ml of a 2M solution of Sr(NO ₃ )2. The prepared solution is called a cationic solution.

2. 720 ml of 2M NH ₄ OH solution is mixed with 180 ml of 2M NH ₄ F solution, and the prepared solution is called an anionic solution.

3. The cationic solution is added to the anionic solution with vigorous stirring and stirred for 1 hour.

4. The white and viscous precipitates obtained after stirring at the end of 1 hour are filtered by vacuum filtration and washed with purified water.

5. The sediments are dried in a thermostat at 100°C for one night and then kept for 1 hour at 250°C.

6. The dried powders are ball milled for 3 hours and sifted through a <250 mesh sieve.

Preparation of Al-Sr-Si oxyfluoride systems of supporting phases

1. 67 ml of a 2M solution of A1( _NO3 ) _{3.9H2O is} mixed with 33 ml of a 2M solution of Sr( _NO3 ) ₂ . The prepared solution is called a cationic solution.

2. 67 ml of 2M Na ₂ SiO ₃ solution, 653 ml of 2M NH4OH solution and 180 ml of 2M NH4F solution are mixed with each other, and the prepared solution is called stock solution.

3. The cationic solution is added to the main solution with vigorous stirring and stirred for 1 hour.

4. The white and viscous precipitates obtained after stirring at the end of 1 hour are filtered by vacuum filtration and washed with purified water.

5. The sediments are dried in a thermostat at 100°C for one night and then kept for 1 hour at 250°C.

6. The dried powders are ball milled for 3 hours and sifted through a <250 mesh sieve.

Method steps (Method 1) used in the scope of experimental work, including functionalization using A174, support phase systems of biomimetic hydroxyapatite (BHA), zirconia (ZrO ₂ ), silica (SiO ₂ ), silica/zirconia nanocluster ( Si/Zr nanocluster) and commercial titanium dioxide (TiO ₂ ) obtained as the supporting phase system in this work are as follows.

1. A suitable amount of A174 is added to 380 ml of ethanol:water (1:3) mixture in a capped glass bottle and the pH value of the solution is adjusted to 3.5 with acetic acid solution and stirred for 30 min.

2. Then the system of supporting phases to be modified is added to this solution, with strong stirring, stirred for 30 minutes with a magnetic stirrer with a heater, and stirred for 10 minutes in an ultrasonic water bath.

3. After mixing, treatment is carried out for 3 hours at a temperature of 80°C in a condenser.

4. The vacuum-filtered mixture is washed in ethanol/water solution to remove unreacted silanizer.

5. Finally, the resulting precipitates are dried for 24 hours at 60°C in a vacuum thermostat.

Steps of another method (Method 2) used in the scope of experimental work, including functionalization using A174, support phase systems of biomimetic hydroxyapatite (BHA), zirconia (ZrO2), silica (SiO2), silica/zirconia nanocluster (nanocluster Si/Zr) and commercial titanium dioxide (TiO ₂ ) obtained in

- 10 046296 as a system of supporting phases in this work are as follows.

1. A suitable amount of A174 is added to 380 ml of ethanol:water (1:3) mixture inside a closed system reactor and in an inert environment.

2. The pH value of the solution is adjusted to 2-4 with acetic acid and stirred for 30 minutes.

3. Add and mix the system of supporting phases to be modified with vigorous stirring.

4. The treatment is carried out for 1-3 hours at a temperature of 60-80°C in an inert gas environment under a condenser. The filtered mixture is washed in ethanol/water solution to remove reaction residue.

5. Dry in a clay thermostat or in a vacuum thermostat at 60-80°C. The ratio of the amount of silane (X) used as a coupling agent and the amount of supporting phase to be treated has been proposed and determined using the following formula [75]:

X=Axf/ ω(7)

X is the amount of binding agent (g),

F - amount of supporting phase (g),

A is the surface area of the supporting phase (m ² /g), ω is the wetting surface of silane (314 m ² /g).

Production of composite filling materials (method 1)

1) Bis-GMA (1-5%) is stirred in an ultrasonic water bath for 10 minutes at 40°C. The organic resin part of the composite structure is prepared by adding HEMA (5-10%), UDMA (5-10%) and TEGDMA (1-5%) to it.

2) Only SiO ₂ , SiO ₂ /silane, Si/Zr nanocluster, Si/Zr/silane nanocluster, TiO ₂ , TiO ₂ /silane, ZrO ₂ , ZrO ₂ /silane, 3YSZ, β-tricalcium phosphate (β-TCP) , nanocrystalline cellulose (NCC), hydroxyapatite particles/fibers/threads, Al-Sr-OF and Al-Sr-Si-OF in an amount of 50 to 90 wt.% and/or a mixture of these materials are added to the prepared resin mixture and mixed in for one day in an ultrasonic water bath or using a high-speed mixer until a homogeneous mixture is obtained.

3) Camphoquinone or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide or phenyl-bis(2,4,6trimethylbenzoyl)phosphineoxide, or 1-phenyl-1,2-propanedione (0.2%) and 4-EDMAB (0 .8%) is added to the prepared mixture and stirred for 3 hours in an ultrasonic bath.

Preparation of composite fillers (method 2)

1. Bis-GMA (1-5%) is stirred in an ultrasonic water bath for 10 min at 40°C and the organic part of the composite structure is prepared by adding HEMA (5-10%), UDMA (5-10%) and TEGDMA ( 1-5%).

2. Only SiO ₂ , SiO ₂ /silane, Si/Zr nanocluster, Si/Zr/silane nanocluster, TiO ₂ , TiO ₂ /silane, ZrO ₂ , ZrO ₂ /silane, 3YSZ, β-tricalcium phosphate (β-TCP) , nanocrystalline cellulose (NCC), hydroxyapatite particles/fibers/threads, Al-Sr-OF and Al-Sr-Si-OF in an amount between 50-90% by weight and/or a mixture of these materials and camphoquinone or diphenyl(2,4 ,6-trimethylbenzoyl)phosphine oxide or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide or 1-phenyl-1,2-propanedione and 4-EDMAB in a proportion of 0.51.0 wt.% are added to the organic matrix mixture and stirred for speed mixer.

3. The samples are kept in a vacuum thermostat for 30 minutes at 37°C to remove any air bubbles that may be present in the structure of the mixture.

The compositions of dental composites are given below.

Organic resin:

Table 1. Organic composition of dental composites

Component Amount (in mass%) Bis-GMA 1-5 NEMA 5-10 UDMA 5-10 TEGDMA 1-5 C.Q. 0.1-0.5 Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide 0.1-0.5 Phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide 0.1-0.5 1-phenyl-1,2-propanedione 0.1-0.5 4-EDMAB 0.5-1.0

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Maintenance phase

Table 2. Maintenance phase systems used in dental compositions and

their content in mass percent Component SiO ₂ SiCh/silane Nanocluster Si/Zr Nanocluster Si/Zr/silane TiO ₂ Т1О ₂ /Silane ZrO ₂ ZrO ₂ /cimaH 3YSZ Characteristic Main phase Main phase Main phase Main phase Opacifier and antimicrobial agent Opacifier and antimicrobial agent Opacifier Opacifier Opacifier Amount (in mass%) 10-90 10-90 10-90 10-90 0.1-20 0.1-20 0.1-20 0.1-20 0.1-20 β-tricalcium phosphate (βTCP) Antimicrobial and reducing phase 1-40 Hydroxyapatite particles/fibers/threads Antimicrobial and reducing phase 1-40 Nanocrystalline cellulose (MCC) Antimicrobial phase 1-40 Al-Sr-OF Antimicrobial phase 1-40 Al-Sr-Si-OF Antimicrobial phase 1-40

Dental composites should match the natural color of the teeth. In this context, pigments used in dental composite material structures are important. These pigments must be stable in the mouth and not show color changes. Typically, oxide pigments such as iron oxide (FeOOH-red) or iron hydroxide (FeOOH-yellow) are used in dental composites [31]. In the scope of this patent application, the composite products shown in table. 1 may belong to the following color groups according to Vita Classic (Vita Zahnfabrik, Bad Säckingen, Germany).

A (yellow-red) - A1, A2, A3, A3.5

B (yellow) - B1, B2, B3

C (gray) - C1, C2, C3

D (red-gray) - D2, D3, D4.

To obtain the appropriate colors, Duranat Yellow iron oxide (pigment yellow 42 and 43 CI 77492), Duranat Red iron oxide (pigment red 101 CI 77491), phenylbis(2,4,6trimethylbenzoyl)phosphine oxide, 1-phenyl-1,2-propanedione 98%, biphenyl (2,4,6-trimethylbenzoyl)phosphine oxide, iron oxide Duranat Brown (brown pigment), iron oxide Duranat Black (black pigment 11 CI 77499), iron oxide (Fe2O ₃ red), ferric hydroxide (FeOOH yellow ) or mixtures thereof in a proportion of 0.01-1 wt.% can be used in composites.

To obtain opaque products in composite fillers, colored pigments (titanium dioxide E171; white pigment 6 CI 77891) containing TiO ₂ and/or TiO ₂ can be used in the structure.

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Claims (14)

1. A light-curing and polymerizable acrylic dental composite filling material, including an organic compound, a photoinitiator and a supporting phase, in which the specified acrylic dental composite filling material contains at least one of the following compounds: SiO ₂ , SiO ₂ /silane, Si/Zr nanocluster, Si/Zr/silane nanocluster, TiO ₂ , TiO ₂ /silane, ZrO ₂ , ZrO ₂ /cmiaH, 3YSZ to ensure the strength of the supporting phase; at least one of the following compounds: hydroxyapatite or β-tricalcium phosphate (β-TCP) to provide the regenerative properties of the maintenance phase; at least one of the following metaloxyfluoride compounds: Al-Sr-OF or Al-Sr-Si-OF to provide antibacterial properties of the support phase; mixtures of bisphenol A glycidyl methacrylate (Bis-GMA), hydroxyethyl methacrylate (HEMA), urethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) as an organic compound; at least one of the following: camphor quinone (CQ), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-phenyl-1,2-propanedione, ethyl 4-dimethylaminobenzoate (4-EDMAB) as a photoinitiator . 2. Acrylic dental composite filling material according to claim 1, in which the specified organic compound contains bisphenol A glycidyl methacrylate (Bis-GMA) from 1 to 5 wt.%, hydroxyethyl methacrylate (HEMA) from 5 to 10 wt.%, urethane dimethacrylate (UDMA) from 5 to 10 wt.% and triethylene glycol dimethacrylate (TEGDMA) from 1 to 5 wt.%. 3. Acrylic dental composite filling material according to claim 1, in which the photoinitiator contains a CQ compound from 0.1 to 0.5 wt.%, a diphenyl(2,4,6trimethylbenzoyl)phosphine oxide compound from 0.1 to 0.5 wt. %, 1-phenyl-1,2-propanedione compound from 0.1 to 0.5 wt.%, or 4-EDMAB compound from 0.5 to 1.0 wt.%. 4. Acrylic dental composite filling material according to claim 1, in which the metal oxyfluoride compound is contained in an amount from 1 to 40 wt.%. 5. Acrylic dental composite filling material according to claim 1, which additionally contains pigment. 6. The acrylic dental composite filling material according to claim 5, wherein said pigment is selected from the group consisting of Duranat Yellow iron oxide, Duranat Red iron oxide, phenyl-bis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-phenyl-1 ,2-propanedione 98%, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, Duranat Brown iron oxide, Duranat Black iron oxide, iron oxide, ferric hydroxide, TiO ₂ , titanium dioxide E171; white pigment 6 CI 77891 or mixtures thereof. 7. Acrylic dental composite filling material according to claim 6, which contains pigment in a mass amount of 0.01 to 1 wt.%. 8. A method for producing a light-curing and polymerizable acrylic dental composite filling material according to any one of claims 1-7, including the stages: a) mixing Bis-GMA from 1 to 5 wt.% in an ultrasonic water bath with the addition of HEMA from 5 to 10 wt.%, UDMA from 5 to 10 wt.% and TEGDMA from 1 to 5 wt.% to obtain an organic matrix composite structures; b) adding SiO ₂ , SiO ₂ /silane, Si/Zr nanocluster, Si/Zr/silane nanocluster, TiO ₂ , TiO ₂ /silane, ZrO ₂ , ZrO ₂ /silane, 3YSZ, β-tricalcium phosphate (β-TCP) , particles/fibers/threads of hydroxyapatite, Al-SrOF and Al-Sr-Si-OF in an amount of 50-90 wt.%, and/or mixtures thereof, to the resulting organic matrix, and mixing in an ultrasonic water bath or using a high-speed mixer until a homogeneous mixture is obtained; c) adding camphor-quinone or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide or phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide or 0.2 wt.% 1-phenyl-1,2-propanedione and 0.8 wt.% 4EDMAB to the prepared mixture and stirring in an ultrasonic bath; d) keeping the samples in a vacuum oven to remove any air bubbles that may be present in the mixture structure; e) bringing the prepared composite matrix to room temperature before use, mixing with a cement spatula and placing in Teflon molds; f) placing sheets of glass on both sides of the molds and compressing them by applying pressure; g) processing of samples using a blue LED light apparatus. 9. The method for producing acrylic dental composite filling material according to claim 8, where in step (a) mixing is carried out for 10 minutes at 40°C. 10. The method for producing an acrylic dental composite filling material according to claim 8, wherein in step (b) the system of supporting phases is added in an amount of at least 70 wt.%. 11. The method for producing acrylic dental composite filling material according to claim 8, wherein in step (b) mixing is carried out for one day. - 16 046296 12. The method for producing acrylic dental composite filling material according to claim 8, where in step (c) mixing is performed for 3 hours. 13. The method for producing acrylic dental composite filling material according to claim 8, where at stage (d) the samples are kept for 30 minutes at 37°C. 14. The method for producing an acrylic dental composite filling material according to claim 8, wherein in step (g), treatment using a blue LED light apparatus is performed for 20 seconds.