Filler and composite materials with zirconium and silica nanoparticles. RU patent 2472708.

FIELD: chemistry.

SUBSTANCE: invention relates to filler materials made of nanoparticles for use in composite materials, including dental composite materials. The filler materials contain clusters of silica and zirconium dioxide nanoparticles. The filler materials can be obtained by mixing a sol of silica nanoparticles with a sol of pre-formed crystalline particles of zirconium nano-oxide.

EFFECT: filler materials provide the desired optical properties, such as opalescence, and are useful in dental compositions.

25 cl, 4 tbl, 2 dwg

The technical field to which the invention relates.

The present invention relates to fillers of nanoparticles for use in composite materials, including dental composite materials. More specifically, the present invention relates to materials fillers with clusters of nanoparticles of silica and Zirconia, which provides desirable optical properties, such as opalescence, for use in dental compositions.

The level of technology

In the last few decades there is an increasing demand among dentists and patients dental clinics in more aesthetic dental fillings. In the dental industry is growing focus on aesthetic dentistry, which leads to the development of dental filling compositions, which are more fully mimic the appearance of natural teeth. For example, were developed in the same colour of the teeth composite resin materials that can be used instead, for example, metal amalgam fillings, with a more natural-looking dental restorations. In recent years, have become available for highly aesthetic composite materials containing nannapaneni of silica and/or Zirconia containing shielding system and having the prob is gnosti opalescence, that gives dentists the ability to create dental fillings, it has such a natural look that they are almost not recognized by the ordinary observer.

Natural tooth enamel is as opalescence, which preferably are rejected shorter (blue) wavelengths of light, creating the appearance of blue on a dark background, and more orange/yellow light on a white background. Though developed opalescent dental composites, this property is often missing in dental composites, which use the system nanofillers of silica and Zirconia. Despite the many beneficial properties offered by nannapaneni of silica and Zirconia, no opalescence can be considered as a disadvantage. Thus, there remains a need for systems, fillers, in particular in systems nanofillers of silica and Zirconia, which provide dental composites with opalescent properties, to better simulate the appearance of natural teeth while maintaining acceptable processing, rentgencontrastnoe, transparency, radiographic and other desirable properties of the dental composition.

The invention

The present invention presents fillers for use in the comp the attributes of the materials. Fillers include clusters of nanoparticles of Zirconia and silica, providing light and roentgenocontrast, along with excellent optical transparency as in reflection and transmission.

The filler can be obtained by (a) the provision of Zola Zirconia containing pre-formed crystalline nanoparticles of Zirconia with a diameter of approximately 3 nm to approximately 30 nm, (b) providing Zola silica containing silica nanoparticles with a diameter of approximately 10 nm to approximately 100 nm, (C) Association Zola Zirconia and Zola silica with formation of a mixture of nanoparticles of Zirconia and silica, and (d) heating the mixture to a temperature from about 450°C. to approximately 950°C, followed by grinding the resulting material to form a filler-containing clusters nanoparticles of silica and Zirconia with a diameter of from about 0.25 microns to about 50 microns.

Typically, the Sol of nanodioxide zirconium restore acid before mixing with the colloidal solution of nanogrammes. In some implementations, the silica nanoparticles and nanoparticles of Zirconia uniformly distributed in the resulting clusters of the nanoparticles. Optionally, the method dopolnitelnye stage of processing the surface of the clusters, nanoparticles of silica and dioxide zirconium, for example, celanova agent binding or similar processing to facilitate inclusion in the resinous component.

Fillers of silica and Zirconia in accordance with the present invention are useful in composite materials, including dental composite materials. Such composites typically contain the polymerized component, such as methacrylate or more ethylene-unsaturated compound, the system initiator and a filler containing clusters, nanoparticles of silica and Zirconia. Such composite materials typically have a value of Cab, comprising at least 15, more typically at least 18, and most typically at least 20.

Typically, dental composites in accordance with the present invention have a refractive index from about 1,44 to approximately 1,65, more typically from about 1.50 to about 1,6, most typically from about 1.50 to about 1,56. Composites also typically exhibit excellent processing characteristics, rentgencontrastnoe, low turbidity (typically less than 70, more typically less than 60, and most typically less than 55 values units) and are independent of the direction of transparency, or scanning, i.e. transparency, to a lesser extent, depends on the La, at which the light has passed through the material, which makes them useful for a variety of dental and orthodontic applications, including dental filling means (for example, the materials of the seals fluid sealing means, the pre-formed crowns and bridges, temporary filling, dental adhesives, dental cements, gaskets under seal, orthodontic adhesives, dental sealants, dental coverage, etc. Compositions and related methods can be applied to obtain dental products by curing with education, for example, dental fillings, dental milled blanks, dental crowns and bridges, dental prostheses, orthodontic devices etc.

The above brief description of the present invention is not intended to describe each exercise or every implementation in accordance with the present invention. Other implementation characteristics and advantages of the present invention will be apparent from the following detailed description of the present invention and from the formula of the present invention.

Definition

By "crystalline Zirconia" means the Zirconia exhibiting significant crystal is practical (monoclinic, tetragonal, cubic or pseudokoningii) x-ray diffraction peaks. Typically, crystalline zirconium dioxide corresponds to the crystallinity of the sols Zirconia, described in U.S. patent No. 6376590 (Kolb et al), filed October 28, 1999, or in U.S. patent No. 7429422 (Davidson et al), filed June 7, 2007, both of which are fully incorporated into this application by reference.

Under "pre-formed" crystalline nanoparticles of Zirconia mean Sol, which is used for filler enclosing particles of Zirconia, which are crystalline before drying and roasting filler.

Under the "Sol" refers to a colloid that has a continuous liquid phase in which a solid substance aspergerian in the liquid. Typically, the Sol is a stable colloidal suspension of solid particles with a diameter of 1-500 them in the liquid and particles are usually not whether or not aggregated.

As used in this application, "curing" refers to a material or composition which can be vulcanized (e.g., polymerized or cross stitched) or solidified, for example by removal of the solvent (for example, by evaporation and/or heating); heating to induce polymerization and/or cross-stitching; irradiation, in useraudit polymerization and/or cross-linking; and/or mixing of one or more components inducyruya polymerization and/or cross-stitching.

Under "dental composition" mean nonapology or filled (for example, composite material (e.g., dental or orthodontic material)capable of applying or bonding with the surface of the oral cavity. Dental compositions include, for example, adhesives (e.g., dental and/or orthodontic adhesives, cements (e.g., glass ionomer cements, modified resin glass ionomer cements and/or orthodontic cements), and base cover (for example, basic orthodontic coverage), sealing means (for example, sealing materials, gaskets, seals (e.g., orthodontic sealants and coatings. Often the dental composition can be used to bind dental products and dental structures.

By "curable dental composition" means a dental composition, such as a paste, which can be overiden with the formation of dental products.

Under "dental product" means a product which may be glued (e.g., connected) to the surface of the oral cavity (e.g., tooth structure). Typically, the dental is the logical product is restored dentition or a part of it. Examples include sealing means, repentance, tab for fillings, onlays, veneers, full and partial crowns, bridges, implants, implant abutment teeth, crowns, fillings for front teeth, fillings poteryannoi arc strip under seal, sealants, dentures, dental pins, bridge frameworks and other bridge structures, abutment teeth, orthodontic appliances and devices, and prostheses (e.g., partial or full dentures).

As used in this application, the terms "dental composition" and "dental device" is not limited to compositions and products, which are used in dentistry, but also include orthodontic composition (e.g., orthodontic adhesives) and orthodontic devices (e.g., orthodontic devices, such as plates for correction of a malocclusion, occlusal mouth guard, brackets, buccal tubes, bands, clips, plugs, lingual plates for bite, openers for occlusion, centralizers and the like), respectively.

Under the surface of the oral cavity" refers to soft or hard surfaces in the oral cavity. Solid surface typically contain dental structures, including, for example, natural and artificial tooth surface, bone, dental models, dentin, enamel, cement, etc.

Under "h what polytelis" mean the material of the particles is acceptable for use in the oral cavity. Dental fillers, in General, have an average particle size of not more than 100 micrometers.

Under the "nannapaneni" imply a filler having an average primary particle size of no more than 200 nanometers. Component of the nanofiller may be one nannapaneni or a combination of nanofillers. Typically nanopolymer contains pyrogen free and no nanoparticles or clusters of nanoparticles. Under "nanostructured" refers to a material in a form having at least one dimension, an average of no more than 200 nanometers (e.g., nano-sized particles). Thus, nanostructured materials are materials, including, for example, nanoparticles, as defined below in this application; the aggregates of nanoparticles, materials, covering the particles, where the coating has an average thickness of no more than 200 nanometers; materials applied to the aggregates of particles, where the coating has an average thickness of no more than 200 nanometers; materials infiltrated into the porous structure with an average pore size of no more than 200 nanometers; and combinations thereof. The porous structure include, for example, porous particles, porous aggregates of particles, porous coating, and combinations thereof.

As used in this application, the term "nanoparticles" is synonymous with "nano-particles" refers to particles having an average size not the m ore than 200 nanometers. As used in this application for spherical particles, "size" refers to the particle diameter. As used in this application to non-spherical particles, "size" refers to the longest size of the particles. In certain implementations, the nanoparticles consist of discrete, reaggregating and deagglomerating particles.

Under the "cluster nanoparticles" means the Association of the nanoparticles, which are assembled together by relatively weak intermolecular forces that cause them sticking together, i.e. aggregation. Typically, clusters, nanoparticles have an average size less than 10 micrometers.

As used in this application, the term "ethylene-unsaturated compound", as it implies, includes monomers, oligomers and polymers having at least one ethylene unsaturated bond.

By "polymerization" refers to the formation of high-molecular substances from the monomer or oligomer. The polymerization reaction may also include the reaction cross-stitching.

As used in this application, the term "(meth)acrylate" is a brief reference to the acrylate, methacrylate, or combinations thereof, and "(meth)acrylic" is a brief reference to acrylic, methacrylic, or combinations thereof. As used in this application, "(meth)acrylate-functional compounds" are compounds containing, among other things, meth)acrylate segment.

The terms "contains", "containing" and variations thereof do not have a limiting meaning, where these terms are included in the description and the formula of the present invention.

Reference in this application to numerical ranges by using endpoints is intended to include all numbers that fall within the given range (for example, 1-5 includes 1, 1,5, 2, 2,75, 3, 3,80, 4 and 5).

As used in this application, "a" or "an" means "at least one" or "one or more"unless specified otherwise. Additionally, the singular includes the plural, unless the context clearly requires otherwise. Thus, for example, reference to a composition containing "a compound" includes a mixture of two or more compounds.

As used in this description and the claims, which included the term "or" in General is used in the sense including "and/or", unless the context clearly requires otherwise.

Unless otherwise indicated, all numbers expressing quantities of ingredients, measurement properties, such as control ratio, etc. that are used in the description and the formula of the present invention, should be interpreted as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters listed in the above description and the claims, which is attached, t is Auda approximations, which can vary depending on the desired properties, which are believed to be obtained by experts in the field of technology when using the doctrines of the present invention. At least, not as an attempt to limit the application of the doctrine of equivalents to the scope of the formula of the present invention, each numerical parameter should be at least interpreted, taking into account the number of reported significant digits and by applying standard methods of rounding. Notwithstanding that the numerical ranges and parameters that indicate the broad scope of the present invention are approximations, the numerical values shown in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily arise from the standard deviation found in their respective testing measurements.

Brief description of drawings

FIGA and b are diagrams showing the difference between dependent angle translucent composites and are independent of the angle of the translucent composites. On FIGA composite material (2) is located on a straight line from the observer (1). In this situation, Examples E1-E3 and Comparative examples CE and SE are transparent. On FIGU composite Mat is the Rial (2) is located at an angle relative to the observer (1). In such a situation are clear Examples E1-E3, but Comparative examples CE and SE are more opaque than when they are considered in a straight line.

Detailed description of the invention

The present invention provides materials fillers consisting of nanoparticles of silica (SiO₂) and nanoparticles of Zirconia (ZiO₂). Nanoparticles of silica and Zirconia are typically glued together in the form of clusters of nanoparticles of silica and Zirconia. In some implementations in accordance with the present invention the silica nanoparticles and nanoparticles of Zirconia are evenly distributed across all clusters, nanoparticles, which can be optionally surface-treated with silane or other acceptable binding agent to improve their inclusion in resin.

Fillers with clusters of nanoparticles of silica and Zirconia in accordance with the present invention is obtained by mixing the Sol nanogrammes together with pre-formed by a Sol of particles of nanodioxide zirconium. The Sol of nanodioxide Zirconia typically consists of crystalline nanoparticles of Zirconia. Consider that the source of zirconium dioxide affects the opalescence of the resulting filler material. As demonstrated in the examples below, given in the first application, the use of pre-formed Sol nanodioxide Zirconia, under certain circumstances, provides nannapaneni of silica and Zirconia with the best opalescense properties than those obtained from zirconyl acetate. In particular, composite materials containing a filler with clusters of nanoparticles of silica and Zirconia in accordance with the present invention typically exhibit is opalescence (C_ab)of at least 15, more typically at least 18, and most typically at least 20. Fillers with clusters of nanoparticles of silica and Zirconia obtained from zirconyl acetate, typically have a lower value opalescence, or together are not opalescence.

In addition to opalescence, materials fillers with clusters of nanoparticles of silica and Zirconia in some implementations also provide roentgenocontrast, transparency and optical clarity, which are less dependent on the angle at which consider the material, compared with fillers derived from zirconyl acetate. Such optical properties provide materials that are very similar in appearance to natural teeth, and are desirable in many areas of products, including tech is having a dental filling materials, the pre-formed dental crowns and bridges, temporary dental filling materials and other dental materials.

Fillers with clusters of nanoparticles of silica and Zirconia in accordance with the present invention can be applied in many different composite materials and are particularly appropriate for use in the curable dental compositions. Such materials typically contain the polymerized component, system initiators, one or more fillers and one or more optional additives. Each of these components is discussed in more detail below.

The POLYMERIZED COMPONENT

Dental compositions in accordance with the present invention are typically cured due to the presence of the polymerized component. In some implementations, the composition can be solidified (e.g., polymerized by using traditional methods of photopolymerization and/or chemical polymerization) before applying to the surface of the oral cavity. In other implementations, the composition can be solidified (e.g., polymerized by using traditional methods of photopolymerization and/or chemical polymerization) after application to the surface of the oral cavity.

In certain implementations the composition which are photopolymerizable, i.e. compositions contain system photoinitiators, which upon irradiation actinium radiation initiates the polymerization (or hardening) of the composition. In other implementations of the composition are chemically curing, i.e. compositions contain a chemical initiator (i.e., the system initiators), which can polimerizuet, be vulcanized or otherwise cured composition regardless of the irradiation actinium radiation. Such chemically-curable composition is sometimes referred to as "simoultaniously" compositions.

The polymerized component typically contains one or more ethylene-unsaturated compounds containing or not containing an acid functional group. Examples of useful ethylene-unsaturated compounds include esters of acrylic acid, esters of methacrylic acid, hydroxyquinoline esters of acrylic acid, hydroxyquinoline esters of methacrylic acid, and combinations thereof.

Compositions, particularly in photopolymerizing the implementation may contain compounds with free radical active functional groups, which may include monomers, oligomers and polymers containing one or more ethylene-unsaturated groups. Acceptable compounds contain at least one ethylene-unsaturated bond and capable of undergoing polymerization doba is ing. Such svobodnoradikal curable compounds include mono-, di - or poly-(meth)acrylates (i.e., the acrylates and methacrylates, such as methyl(meth)acrylate, acrylate, isopropyl methacrylate, n-haskil acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, the glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propandiol di(meth)acrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol Tetra(meth)acrylate, sorbitol hexarelin, tetrahydrofurfuryl (meth)acrylate, bis[1-(2-aryloxy)]-p-ethoxytrimethylsilane, bis[1-(3-akiaki-2-hydroxy)]-p-propoxybenzaldehyde, ethoxycarbonyl bisphenol a di(meth)acrylate and trihydroxide-isocyanurate trimethacrylate; (meth)acrylamide (i.e. acrylamide and methacrylamide), such as (meth)acrylamide, methylene bis-(meth)acrylamide and diacetone (meth)acrylamide; urethane(meth)acrylates; the bis-(meth)acrylates of polyethylene glycols (preferably of molecular weight 200-500), copolymerizate mixture accelerandi monomers, such as shown in U.S. patent No. 4652274 (Boettcher et al.), accelerandi oligomers, such as shown in U.S. patent No. 4642126 (Zador et al.) and poly(ethylene-unsaturated) carbarnoyl of isocyanurates, such as described in U.S. patent No. 4648843 (Mitra); and vinyl compounds such as styrene, diallyl CFT is lat, divinyl succinate, divinyl adipate and divinyl phthalate. Other acceptable svobodnoradikal curable compounds include siloxane-functional (meth)acrylates, as described, for example, in WO-00/38619 (Guggenberger et al.), WO-01/92271 (Weinmann et al.), WO-01/07444 (Guggenberger et al.), WO-00/42092 (Guggenberger et al.) and photopolymer-functional (meth)acrylates, as described, for example, in U.S. patent No. 5076844 (Fock et al.), U.S. patent No. 4356296 (Griffith et al.), EP-0373384 (Wagenknecht et al.), EP-031 0201 (Reiners et al.) and EP-0201 778 (Reiners et al.). A mixture of two or more svobodnoradikal curable compounds can be applied if desired.

Curable component may also contain hydroxyl groups and ethylene-unsaturated groups in one molecule. Examples of such materials include hydroxyalkyl(meth)acrylates, such as 2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate; glycerol mono - or di-(meth)acrylate; trimethylolpropane mono - or di-(meth)acrylate; pentaerythritol mono-, di - and tri-(meth)acrylate; sorbitol mono-, di-, tri-, Tetra - or Penta-(meth)acrylate; and 2,2-bis[4-(2-hydroxy-3-methacryloxypropyl)phenyl]propane (G). Acceptable ethylene-unsaturated compounds are also available from a wide variety of commercial sources such as Sigma-Aldrich, St. Louis. A mixture of the ethylene-unsaturated compounds can be used if desired.

In certain implementations of the polymerized component includes P Is G-DMA (polyethylene glycol dimethacrylate, having a molecular weight constituting approximately 400), G, UDMA (urethane dimethacrylate), GDMA (glycerol dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), bisema, as described in U.S. patent No. 6030606 (Holmes), and/or NPGDMA (neopentylglycol dimethacrylate). If desired, can be applied to various combinations of these curable components.

If the composition contains an ethylene-unsaturated compound without acid functional group, it is in General present in the amount of at least 5% by weight, more typically at least 10% by weight, and most typically at least 15% by weight of the ethylene-unsaturated compounds without acid functional groups based on the total weight of the unfilled composition. Compositions in accordance with the present invention typically contain no more than 95% by weight, more typically not more than 90 mass%, and most typically not more than 80% by weight of ethylene-ninasimone compounds without acid functional groups based on the total weight of the unfilled composition.

In some implementations of the polymerized component may contain one or more ethylene-unsaturated compounds with acid functional group. As used in this application, the ethylene-unsaturated compounds with acid functional group", as it implies, include monomers, oligomers and polymers, operasie ethylene unsaturated bond and an acid and/or preceding the acid functional group. Prior to the acid functional groups include, for example, anhydrides, halide acids and pyrophosphates. The acid functional group may include carboxylic acid functional group, a phosphoric acid functional group, fosfonovoi acid functional group, a sulfonic acid functional group, or combinations thereof.

The ethylene-unsaturated compounds with acid functional group include, for example, α,β-unsaturated acid compounds, for example glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl(meth)acrylate (e.g., DUMB) phosphate, bis((meth)aryloxides) phosphate, ((meth)Acrylonitrile) phosphate, bis((meth)Acrylonitrile) phosphate, bis((meth)aryloxy)propyloxy phosphate, (meth)aryloxyalkyl phosphate, bis((meth)aryloxyalkyl) phosphate, (meth)aryloxyalkyl phosphate, bis((meth)aryloxyalkyl) phosphate, (meth)acrylamidoethyl phosphate, bis((meth)acrylamidoethyl) phosphate, caprolactone methacrylate phosphate, di - or tri-methacrylates citric acid, poly(meth)acelerando oligomannose acid, poly(meth)acelerando primulinum acid, poly(meth)acelerando poly(meth)acrylic acid, poly(meth)acelerando polycarboxylate acid, poly(meth)acelerando polychloroprene acid, poly(meth)atilirovanie polysulfone, the Oli(meth)acelerando pribornoy acid and the like, can be used as components in the curable component systems. Can also be applied to the monomers, oligomers and polymers of unsaturated carboxylic acids such as (meth)acrylic acid, aromatic (meth)calironia acid (for example, metallisoundia trimellitate acid and their anhydrides. Certain preferred compositions in accordance with the present invention include ethylene-unsaturated compound with acid functional group containing at least one P-Oh fragment.

Some of these compounds get, for example, as reaction products between isocyanatomethyl (meth)acrylates and carbolic acids. Additional compounds of this type include both acid-functional, and the ethylene-unsaturated components, and are described in U.S. patent No. 4872936 (Engelbrecht) and 5130347 (Mitra). Can be used with a wide variety of such compounds containing the ethylene-unsaturated and acid fragments. If desired, there may be used mixtures of such compounds.

Additional ethylene-unsaturated compounds with acid functional group include, for example, polymerized bisphosphonate acid, as described, for example, in the provisional application U.S. No. 60/437106, filed December 30, 2002; AA:CA:EM (copolymer of acrylic acid:itacon the howling acid linked methacrylate, obtained by the reaction of AA:THE copolymer with a sufficient amount of 2-isocyanatoacetate with the transformation of part of the acid groups of the copolymer in related methacrylate groups, as described, for example, in Example 11 of U.S. patent No. 5130347 (Mitra)); and the examples in U.S. patent No. 4259075 (Yamauchi et al), 4499251 (Omura et al), 4537940 (Omura et al), 4539382 (Omura et al.), 5530038 (Yamamoto et al.), 6458868 (Okada et al.), and in the European publication number EP 712622 (Tokuyama Corp.) and ER 1051961 (Kuraray Co., Ltd.).

Compositions in accordance with the present invention may also contain a combination of ethylene-unsaturated compounds with acid functional group, as described, for example, in published patent application U.S. No. 2007/0248927 (Luchterhandt et al.), filed August 11, 2004, the Composition may also contain a mixture of ethylene-unsaturated compounds with acid functional group, and without it.

If the composition contains an ethylene-unsaturated compound with acid functional group, it is in General present in the amount of at least 1% by weight, more typically at least 3% by weight, and most typically at least 5% by weight of the ethylene-unsaturated compounds with acid functional group based on the total weight of the unfilled composition. Compositions in accordance with the present invention typically contain not more than 80 mass%, more typically not more than 70 mass%, naibolee typically no more than 60% by weight of the ethylene-unsaturated compounds with acid functional group based on the total weight of the unfilled composition.

SYSTEM INITIATORS

In certain implementations, the composition in accordance with the present invention are photopolymerizable, i.e. compositions contain photopolymerizing component and system photoinitiators, which after irradiation actinium radiation initiates the polymerization (or hardening) of the composition. Such photopolymerizable composition can be svobodnoradikal polymerized and cation polymerized.

Acceptable photoinitiator (i.e. photoinitiator system containing one or more compounds for polymerization svobodnoradikal photopolymerizing compositions include binary and ternary systems. Typical triple photoinitiator include salt iodone, photosensitizer and an electron-donating compound, as described in U.S. patent No. 5545676 (Palazzotto et al). Acceptable salt iodone are dianiline salt iodone, such as diphenyliodonium, defamiliarisation, diphenylethylenediamine, telelcommunications(pentafluorophenyl)borate. Acceptable photosensitizers are monoketones and diketones, which absorb some amount of light in the range from 400 nm to 520 nm (preferably from 450 nm to 500). Especially acceptable compounds include alpha-diketones, which absorb light in the range from 400 nm to 520 nm (dazh is more preferable, from 450 to 500 nm). Acceptable connections are camporgiano, benzyl, fullam, 3,3,6,6-tetramethylcyclopentadiene, phenanthraquinone, 1-phenyl-1,2-propanedione and other 1-aryl-2-alkyl-1,2-ethionamid and cyclic alpha-diketones. Acceptable electron-donating compounds include substituted amines, such as ethyldimethylamine. Other acceptable tertiary system photoinitiators useful for photopolymerization cation curable resins described, for example, in U.S. patent No. 6765036 (Dede et al.).

Other useful photoinitiator for polymerization svobodnoradikal photopolymerizing compositions include the class of phosphine oxides, which typically have a functional wavelength range from 380 nm to 1200 nm. Preferred phosphinoxide free radical initiators with a functional wavelength range from 380 nm to 450 nm are acyl and bysally the phosphine oxides, such as described in patnah U.S. No. 4298738 (Lechtken et al.), 4324744 (Lechtken et al.), 4385109 (Lechtken et al.), 4710523 (Lechtken et al.) and 4737593 (Ellrich et al.), 6251963 (Kohler et al.); and the application EP No. 0173567 A2 (Ying).

Commercially available phosphinoxide photoinitiator capable of free-radical initiation when irradiated at wavelengths in the range of greater than 380 nm - 450 nm include bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide (IRGACURE 819, Ciba Specialty Chemicals, Tarrytown, NY), bis(2,6-dimethoxybenzoyl)-(2,4,4-Tr is methylpentyl) phosphine oxide (CGI 403, Ciba Specialty Chemicals), 25:75 mixture, by weight, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl of phosphine oxide and 2-hydroxy-2-methyl-1-phenylpropane-1-it (IRGACURE 1700, Ciba Specialty Chemicals), a 1:1 mixture, by weight, of bis(2,4,6-trimethylbenzoyl)feel of phosphine oxide and 2-hydroxy-2-methyl-1-paperpaper-1-it (DAROCUR 4265, Ciba Specialty Chemicals) and ITIL,4,6-trimethylbenzoyl phosphinate (LUCIRIN LR8893X, BASF Corp., Charlotte, NC).

Typically, phosphinoxide initiator is present in photopolymerizable composition in catalytically effective amounts, for example, from 0.1 mass% to 5.0 mass% based on the total weight of the unfilled composition.

Tertiary amine reducing agents can be used in combination with allposters.com. Illustrative tertiary amines useful in the present invention include ethyl-4-(N,N-dimethylamino)benzoate and N,N-dimethylaminoethylmethacrylate. In the case of the presence of amine reducing agent is present in photopolymerizable compositions in amounts of from 0.1 mass% to 5.0 mass% based on the total mass anapolina composition. Useful amounts of other initiators well known to specialists in this field of technology.

In certain implementations of the arrangement in accordance with the present invention are chemically curing, i.e. compositions contain chemically curing, componenti chemical initiator (i.e. system initiators)that can polimerizuet, be vulcanized or otherwise cured composition regardless of the irradiation actinium radiation. Such chemically-curable composition is sometimes referred to as "simoultaniously" compositions.

Chemically curable composition may contain a redox vulcanizing system containing curable component (for example, ethylene-unsaturated curable component) and redox agents containing oxidizing agent and reducing agent. Acceptable curable components, redox agents, optional acid-functional components, and optional fillers that are useful in the present invention, described in the publications U.S. patent No. 2003/0166740 (Mitra et al.) and 2003/0195273 (Mitra et al).

Reducing and oxidizing agents should react or otherwise interact with each other with obtaining free radicals capable of initiating polymerization of the resin system (for example, ethylene-unsaturated component). This type of vulcanization is a reaction in the dark, that is not dependent on the presence of light and can occur in the absence of light. Reducing and oxidizing agents are preferably sufficiently with abiline to collapse and do not have undesirable staining, that allows their storage and use in a typical dental conditions. They should be sufficiently miscible with the resin system (and preferably water-soluble)to allow easy dissolution in (and poor separation from the other components of the composition.

Useful reducing agents include ascorbic acid, derivatives of ascorbic acid and metal complexes with ascorbic acid, as described in U.S. patent No. 5501727 (Wang et al.); amines, in particular tertiary amines, such as 4-tert-butyldimethylsilyl; salts of aromatic Sultanovich acids, such as p-toluensulfonate salt and benzazocine salts, thiourea, such as 1-ethyl-2-thiourea, tetradecylthioacetic, tetramethylrhodamine, 1,1-dibutil thiourea and 1,3-dibutil thiourea; and mixtures thereof. Other secondary reducing agents may include chloride cobalt (II)chloride iron (II)sulfate iron (II), hydrazine, hydroxylamine (depending on the choice of oxidizing agent), salt dithionite or sulfite anion and mixtures thereof. Preferably, the reducing agent is an amine.

Acceptable oxidizing agents will be well known to experts in the art and include, but are not limited to the above, perennou acid and its salts, for example sodium, potassium, ammonium the Yu, cesium and alkylammonium salt. Additional oxidizing agents include peroxides, such as benzoyl peroxides, hydroperoxides, such as cumylhydroperoxide, t-butylhydroperoxide and AMYLPEROXY, as well as salts of transition metals such as cobalt chloride (III) and iron chloride (II)sulfate, cerium (IV), perborate acid and its salts, permanganate acid and its salts, perfactory acid and its salts, and mixtures thereof.

It may be desirable to use more than one oxidizing agent or more than one reducing agent. Small amounts of transition metal compounds can also be added to increase the speed auxiliare recovery vulcanization. In some implementations it may be preferable to enable the secondary ionic salt to enhance the stability of the curable composition as described in published patent application U.S. No. 2003/0195273 (Mitra et al).

Reducing and oxidizing agents are present in amounts sufficient to allow the appropriate rate of free radical reactions. It can be estimated by combining all ingredients of the composition, with the exception of an optional filler, and observing whether the obtained cured mass.

Typically, the reducing agent, if used, is present in Ko is Icesave, which at least 0.01% by weight, and more typically at least 0.1% by weight based on the total weight (including water) of the components of the composition. Typically, the reducing agent is present in an amount of not more than 10 mass%, and more typically not more than 5% by weight based on the total weight (including water) of the components of the unfilled composition.

Typically, the oxidizing agent, if used, is present in the amount of which shall be at least 0.01% by weight, and more typically at least 0,10% by mass based on the total weight (including water) of the components of the composition. Typically, the oxidizing agent is present in an amount of not more than 10 mass%, and more typically not more than 5% by weight based on the total weight (including water) of the components of the unfilled composition.

Reducing or oxidizing agents can be microcapsular, as described in U.S. patent No. 5154762 (Mitra et al.). This will increase the shelf life of the composition and, if necessary, will allow packaging of the reducing and oxidizing agents together. For example, through appropriate selection encapsulates regenerating agent, oxidizing agents can be combined with the acid-functional component and an optional filler, and can be stored in a state that is stable during storage. Similarly, by properly using the RA water-insoluble encapsulating agent regenerating and oxidizing agents can be connected with FAS glass and water and kept in a state stable when stored.

Redox vulcanizing system can be combined with other vulcanizing systems, including systems of photoinitiators, or composition, such as described in U.S. patent No. 5154762 (Mitra et al.).

CLUSTERS of NANOPARTICLES of SILICA AND ZIRCONIA

The composition in accordance with the present invention contains a filler with clusters of nanoparticles of silica and Zirconia, giving the song opalescence. I think that the effect of opalescence occurs, at least partially, due to the use of pre-formed particles nanodioxide zirconium in the formation of cluster of silica and Zirconia. The use of such pre-formed particles provides filler with excellent light compared to the light you get, if you start with other precursors, such as, for example, acetate salt.

Clusters of nanoparticles can be obtained by combining Zola nanoparticles of silica Sol pre-formed crystalline nanoparticles of Zirconia. The Sol of silica typically contains silica particles having an average diameter from about 10 nm to about 100 nm, more typically from about 15 nm to about 60 nm, most ti is icno from about 15 nm to about 35 nm, with an average diameter of particles constituting approximately 20 nm, which is particularly well suited for obtaining clusters of nanoparticles. The Sol of Zirconia typically contains particles of Zirconia, which are small enough not to dissipate a large part of visible light, but large enough to bend the shorter wavelengths of blue light, causing the effect of opalescence. The Sol of zirconium dioxide with an average particle size from about 3 nm to about 30 nm, is acceptable for the formation of clusters of nanoparticles. Typically, the particles of zirconium dioxide in the ashes have an average particle diameter from about 5 nm to about 15 nm, more typically from about 6 nm to about 12 nm, and most typically from about 7 nm to about 10 nm. When mixed together in acidic conditions where the ash mixture is stable, for example, when the value of pH 2 or below, the pre-formed nanoparticles of Zirconia form a structure with nanoparticles of silica during relativeiy and drying, which leads to the desired opalescence while maintaining a high level of optical transparency of the target composite material.

Can be applied Sol of silica NALCO 1042 (Nalco Chemical Company, Naperville, IL) or other commercially available colloid is haunted silica sols. When using stable base Zola, typically, it will first be subjected to ion exchange to remove sodium, for example, by using ion-exchange resin Amberlite IR-120, or pH regulate nitric acid. Is usually desirable to adjust the pH value of the silica is lower than 1.2, typically from approximately 0.8 to approximately 1.0, and then thereto is added slowly zirconium dioxide to prevent local gelatinization and agglomeration. The pH value of the resulting mixture typically ranges from approximately 1.1 to approximately 1.2. Acceptable colloidal silica sols are available from many manufacturers, including Nalco (Ondeo-Nalco, Grace chemical), ..Stark, Nissan Chemical (Snowtex), Nyacol and Ludox (DuPont). Selected Sol must have silica particles being discrete and having a corresponding size specified in the application. The silica Sol can be processed with providing high acid Sol of silica (for example, stable nitrate), which can be mixed with a Sol of zirconium dioxide without gelatinization.

The Sol of Zirconia can be obtained using the method described in U.S. patent No. 6376590 (Kolb, et al), which was filed on October 28, 1999, or in U.S. patent No. 7429422 (Davidson et al.), which was filed June 7, 2007, As used in this application, the term "Zirconia" relates the I to the various stechiometry for oxides of zirconium, most typically ZrO₂and can be also known as zirconium oxide or zirconium dioxide. The Zirconia may contain up to 30 weight percent of other chemical fragments, such as, for example, Y₂About₃and organic matter.

Clusters of nanoparticles of silica and Zirconia can be obtained by mixing together Zola of nanogrammes and Sol nanodioxide zirconium and heating the mixture to at least 450°C. Typically, the mixture is heated for from 4 to 24 hours at a temperature of from about 400 to about 1000°C., more typically from about 450 to about 950°C. to remove water, organic compounds and other volatile components, and potentially weaker aggregation of particles (not necessarily). Alternatively, or additionally, the ash mixture can be cast to different stages of processing to remove water and volatile substances. The resulting material can be ground or crushed and sorted to remove large aggregates. The surface of the filler may then be processed, for example, silane, before mixing with the resin.

The amount of filler used in the composite material will depend on the particular application, as described in more detail in this application below. Typically, for dental plombires is cnyh compositions of the content of the filler is from about 40 weight percent to 90 weight percent of the composition. In some implementations it is also desirable that the refractive index (RI) of the filler essentially match the refractive index of the resin (i.e. RI filler differed from RI resin only at a value of from about 0.02 to about 0.05 RI units).

As used in this application, the "refractive index" refers to the absolute refractive index of a material (e.g., monomer), which implies, is the ratio of the speed of electromagnetic radiation in free space and speed of the radiation in the material. The refractive index can be measured using known methods, for example by means of Abbe Refractometer in the visible light range (commercially available, for example, from Fisher Instruments, Pittsburgh, Pa.). In General, will appreciate that the measured refractive index may somewhat vary depending on the device. Measurements are typically carried out in accordance with the recommendations of the manufacturer of the device and good laboratory practice. The values of the refractive index can be measured by the variance of the test sample (typically at room temperature) in the optical liquids with different known specific refractive indices. For this purpose, a set of calibrated optical liquids from Cargille Laboratories, Cedar Grove, N.J.). Observed what I dispersions conducted on an optical microscope. The refractive index of solids can be determined by using the line of the Beck as a band of light that appear along the outer edge of dispersed particles when examined with a microscope. The line of the Beck indicates the relative difference or equivalence of the refractive indices of the solid substance and the optical fluid.

ADDITIONAL FILLER(S)

In addition to the filler with clusters of nanoparticles of silica and Zirconia, compositions in accordance with the present invention may optionally contain one or more other fillers. Such fillers can be selected from one or more of a wide variety of substances that are acceptable for inclusion in the compositions used in dental purposes, for example fillers currently used in dental restorative compositions, etc.

The choice of filler affects important properties of dental composite, such as its appearance, roentgenocontrast and physical and mechanical properties. The appearance of partially affected by the regulation of the quantities and relative refractive indices of the ingredients of the composite, thus allowing the change of scanning, Mat or perlamutrovogo composite. Thus, the appearance of the dental material, etc is desired, to be created such that it almost will not differ from the natural dentition.

Roentgenocontrast is a measure of the ability of the dental composite to the detection of the x-ray inspection. Often radioupravlyaemye dental composite is desirable, for example, to allow the dentist to determine whether the dental filling sound or not. In other circumstances it may be desirable meridionality composite. Acceptable fillers Radioservice compositions described in EP-A2-0189540, ER-IN-0238025 and U.S. patent No. 6306926 B1.

The amount of filler included in the composite, this application is called "load level" and expressed as mass percentage based on the total mass of the dental material, and will vary depending on the type of filler, of a vulcanized resin and other components of the composition, and intended use of the composite.

For some dental materials, such as seals, compositions in accordance with the present invention can be easily filled (for example, have a level load, comprising less than about 40 mass percent) or nannapaneni. In such implementations, the viscosity dental material is low enough to allow penetration increased the surveillance and depression occlusal surfaces of the teeth, and in the etched region of the enamel, thus contributing to the conservation of the dental material. In those applications, which are desired high strength or durability (for example, sealing means for the front or side of teeth, dentures, cements for crowns and bridges, artificial crowns, artificial teeth and dentures), the load level may be about 95 weight percent. For most dental restorative and prosthetic applications, the load level is at least 40 mass% and more typically from about 60 to 90 weight percent.

The filler(s)used in the compositions in accordance with the present invention, is typically fine. The filler(s) can be unimodal or multimodal (e.g. bimodal) distribution of particle sizes. The maximum particle size (the largest size particles, in General, the diameter or volume average value) of the filler(s) is typically less than 50 micrometers, more typically less than 10 micrometers, and most typically less than 5 micrometers. In some implementations, the average particle size of the filler(s) is typically less than 0.5 micrometers, and more typically less than 0.2 micrometer, but in other implementations the medium is nd the particle size may be large, and the material may include particles with a maximum particle size of about 40 micrometers.

Napoletani(s) may be inorganic. It may also be cross stitched organic matter, insoluble resinous system and optionally filled with inorganic filler. The filler(s) shall in any case be non-toxic and acceptable for use in the oral cavity. The filler(s) may be Radioservice or radioprogramas. The filler is typically essentially insoluble in water.

In addition to the SiO₂-ZrO₂clusters, nanoparticles, examples of other acceptable inorganic fillers that can be included in the composition, occur in nature or are synthetic materials, including, but not limited to the above: quartz (i.e. silica SiO₂); nitrides (e.g. silicon nitride), glasses derived from, for example, Zr, Sr, CE, Sb, Sn, Ba, Zn and Al; feldspar; borosilicate glass; kaolin; talc; titanium dioxide; fillers with low hardness ILAC, for example, described in U.S. patent No. 4695251 (Randklev); and submicron silica particles (e.g., pyrogenic silica, such as available under the trade name AEROSIL, including "OX 50," "130," "150" and "200" silicas from Degussa Corp., Akron, HE and CAB-O-SIL M5 silica from Cabot Corp., Tuscola, IL). In some implementation, eniah silica particles or nanogrammes are pyrogen free and no i.e. contain unweighted silica. Examples of acceptable particles of the organic filler include filled or unfilled polarisavenue polycarbonates, polyepoxides etc. Additional filler(s) can react with acids do not react with acids or their combination.

May also include metal fillers, for example, a metal filler particle, obtained from pure metal, such as a metal of Groups IVA, VA, VIA, VIIA, VIII, IB or IIB, aluminum, indium and thallium of Group IIIB and tin and lead of Group IVB, or their alloys. Can also be optionally included traditional dental amalgam powders of alloys, typically a mixture of silver, tin, copper and zinc. The metal filler particles preferably has an average particle size from about 1 micron to about 100 microns, more preferably from 1 micron to about 50 microns. Also covered in a mixture of such fillers and combinations of fillers derived from organic and inorganic materials. Particularly preferred are foruminformation glass fillers, raw or processed by silanols. Such glass fillers have the added advantage consisting in the release of fluoride in the dental works on the Le space in the oral cavity.

In some implementations, the composition may contain reactive acid filler. Acceptable reacting with acid fillers include metal oxides, glass, and metal salts. Typical metal oxides include barium oxide, calcium oxide, magnesium oxide and zinc oxide. Typical glass include borate glass, phosphate glass and foruminformation ("FAS") glass. FAS glass are particularly preferred. The FAS glass, if present, typically contains enough eluruume cations, so that the cured dental composition can be formed by mixing glass with components of the curable composition. Glass also typically contains enough eluruume fluoride ions, so that the cured composition will have kristalicheskie properties. Such glass can be obtained from a melt containing fluoride, aluminum oxide and other stekloobrazuyuschego ingredients, using methods known to experts in the field of production of glass FAS. The FAS glass, if present, is typically in the form of particles that are sufficiently finely chopped to allow their easy mixing with other cement components and have good performance when using the resulting mixture in the mouth.

In General, the average R is setting the log file name particles (typically, diameter) glass FAS used in such compositions, does not exceed approximately 12 micrometers, typically not more than 10 micrometers, and more typically less than 5 micrometers, according to measurements carried out using, for example, sedimentation analyzer. Acceptable glass FAS are known to experts in the art and available from a wide variety of commercial sources, and many of them found in existing currently available glass ionomer cements, for example, commercially available under the trade names VITREMER, VITREBOND, RELY X LUTING CEMENT, RELY X LUTING PLUS CEMENT, PHOTAC-FIL QUICK, KETAC-MOLAR and KETAC-FIL PLUS (3M ESPE Dental Products, St. Paul, MN), FUJI II LC and FUJI IX (G-C Dental Industrial Corp., Tokyo, Japan) and CHEMFIL Superior (Dentsply International, York, PA). If desired, can be used a mixture of fillers.

The surface of the particulate fillers may also be processed by the binding agent to improve the bonding between the filler and resin. Acceptable binding agents include gamma-methacryloxypropyltrimethoxysilane, gamma mercaptopropionylglycine, gamma aminopropyltrimethoxysilane etc. the silane Treated fillers and nannapaneni Zirconia and silica (ZrO₂-SiO₂), the silane treated fillers and nannapaneni of silica, the silane treated fillers and nannapaneni from Dixi is and cycnia and combinations thereof, are particularly acceptable for some restorative compositions. Other acceptable excipients are described in U.S. patent No. 6387981 (Zhang et al); 6572693 (Wu et al); 6730156 (Windisch); and 6899948 (Zhang); and international publication no WO 03/063804 (Wu et al.). Components of the fillers described in these references include nanosized silica particles, nanosized metal oxide particles, and combinations thereof. Nannapaneni also described in the publication of U.S. patent No. 2005/0252413 (Kangas et al.); 2005/0252414 (Craig et al.); and 2005/0256223 (Kolb et al.).

For some realizations of the present invention, which include a filler (for example, a dental adhesive composition, the composition typically contains at least 1% by weight, more typically at least 2% by weight, and most typically at least 5% by weight of filler based on the total weight of the composition. For such implementations compositions in accordance with the present invention typically contain not more than 40 mass%, more typically not more than 20 mass%, and most typically not more than 15% by weight of filler based on the total weight of the composition.

For other implementations (for example, where the composition is a dental restorative or orthodontic adhesives) compositions in accordance with the present invention typically contain at least 40% by weight, more than ipino, at least 45% by weight, and most typically at least 50% by weight of filler based on the total weight of the composition. For such implementations compositions in accordance with the present invention typically contain not more than 90 mass%, more typically not more than 80 mass%, even more typically no more than 70% by weight filler, and most typically not more than 50% by weight filler based on the total weight of the composition.

OTHER ADDITIVES

Optionally, the compositions in accordance with the present invention may contain solvents (such as alcohols (e.g., propanol, ethanol), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate), other non-aqueous solvents (e.g. dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrrolidinone)) or mixtures thereof.

In some implementations in accordance with the present invention compositions are non-aqueous. In another implementation, the composition may optionally contain water. Water can be distilled, deionized, or tap water. If available, the amount of water should be sufficient to ensure adequate operational and mixing properties and/or to allow the transport of ions, especially in the reaction of the filler-acid. In such implementations, the water is contained in the number, IU the greater extent, approximately 1 wt.%, and more preferably at least about 5 wt.%, of the total weight of ingredients used for the formation of a curable composition. In General, the water is contained in an amount of not more than about 75 wt.%, and more preferably not more than about 50 wt.% of the total weight of ingredients used for the formation of a curable composition.

If desired, the compositions in accordance with the present invention may contain additives such as indicators, dyes (including potootvedeniya dyes), pigments, inhibitors, accelerators, viscosity modifiers, moisturizing agents, antioxidants, tartaric acid, chelating drugs, buferiruemoi agents, stabilizers, thinners, and other similar ingredients that will be apparent to experts in the given field of technology. Surfactants, for example nonionic surfactants, cationic surfactants, anionic surfactants, and combinations thereof, may be optionally used in the compositions. Useful surfactants include polimerizuet and the polymerized surfactants. Additionally, medicines and other medicines can be optionally added in the dental composition. Examples of clucalc, but not limited to the above, sources of fluoride, whitening agents, anti-caries (e.g., xylitol), teeth re-mineralizing agents (for example, compounds of calcium phosphate and other calcium sources and sources of phosphate), enzymes, breath fresheners, anesthetics, coagulation means, acid neutralizers, chemotherapeutic agents, immune response modifiers, thixotropic means, polyols, anti-inflammatory agents, antimicrobial agents, antifungal agents, agents for treating xerostomia, desensibilization and the like, of the type often used in dental compositions. Also can be applied to any combination of the above additives. The choice and number of any of these additives may be selected by the specialist in the art to achieve the desired result without performing unnecessary experiments.

Preparation AND APPLICATION of DENTAL COMPOSITIONS CONTAINING a FILLER OF SILICA AND ZIRCONIA

Dental compositions in accordance with the present invention can be obtained by combining all of the various components using conventional mixing methods. The resulting composition may optionally contain fillers, solvents, water and other additives, as is isano in this application. Typically, photopolymerizable compositions in accordance with the present invention is obtained by simple mixing, in conditions of "safe light", the components of the composition in accordance with the present invention. Acceptable inert solvents can be used, if desired, when exposed to this mixture. Can be used any solvent which does not react appreciably with the components of the compositions in accordance with the present invention. Examples of acceptable solvents include acetone, dichloromethane, acetonitrile and lactones. The liquid material is subject to polymerization, can be used as a solvent for other liquid or solid material that is subjected to polymerization. Solvent-free compositions can be obtained by simple dissolution (optional) complex salt iodone, activator and an electron donor in the polymerized resin, with or without the application of moderate heating to facilitate dissolution.

The amounts and types of each of the ingredients in the dental material should be adjusted to provide the desired physical and performance properties before and after curing. For example, the rate of polymerization, the polymerization stability, fluidity, compressive strength, tensile strength and durable the th dental material typically regulate, partially, by changing the kinds and amounts of initiator(s) of polymerization and the load and the size distribution of the filler particles. Such regulation is typically carried out empirically, based on previous experience with dental materials. When applying a dental material to a tooth, the tooth may be optionally pre-treated base coating and/or adhesive using methods known to experts in this field of technology.

The composition can be provided in many forms, including single-system and multi-component systems, for example two-component system powder/liquid, paste/liquid, paste/powder and pasta/pasta. Other forms used multicomponent combinations (i.e. combinations of two or more parts, each of which is in the form of powder, liquid, gel, or it is also possible to paste. The various components of the composition can be divided into separate parts in any desired manner; however, in auxiliare-regenerative multi-component system, one part typically contains the oxidizing agent and the other part typically contains the reducing agent, although it is possible to connect the reducing agent and oxidizing agent in one part of the system, if the components are stored separately, for example through use the of microencapsulation. Also, for those implementations in which the dental composition is in the form of resin-modified glass ionomer (RMGI), policestate reacting with acid filler and water, in General, will not all be present in the same part, although any two of them can be grouped together in the same part, along with any combination of other components.

The components of the composition can be included in the set, where the content of the composition is Packed in order to allow storage of the components until they are needed.

The components of the composition can be mixed and clinically applied using traditional methods. To initiate photopolymerizing compositions, in General, necessary curing light. The composition can be in the form of composites or tonics, which are very well bonded to the dentin and/or enamel. Optional, can be used a base layer of the tooth cloth, on which is applied curable composition.

The present invention encompasses a wide variety of dental compositions. Illustrative of dental materials include dental filling means (e.g., composites, seals, gaskets, tab for fillings, onlays, crowns and bridges, orthodontic devices and orthodontic ADH is the Ziva. Such dental materials include direct aesthetic restorative materials (for example, sealing means for anterior and posterior teeth, dentures, adhesives and base coatings for hard tissue of the oral cavity, sealants, veneers, gaskets under the seal of orthodontic brittnye adhesives for use in all types of braces (such as metal, plastic and ceramic), cement for crowns and bridges, artificial crowns, artificial teeth, dentures, etc. Such dental materials used in the mouth and placed next to natural teeth. The expression "placed next to"as used in this application refers to the placement of dental material in a temporary or permanent contact link (e.g., adhesive) or contact (e.g., occlusal or proximal) with the natural tooth.

The characteristics and advantages of the present invention is additionally illustrated by the following examples which are not intended to limit the present invention. The particular materials and amounts listed in these examples, as well as other conditions and details, should not be construed as needlecases way limiting the present invention. Unless otherwise indicated, all parts and percentages are given n is a mass basis, all the water is deionized water, and all molecular weights are average molecular weights.

Examples

Unless otherwise noted, reagents and solvents were obtained from Sigma-Aldrich Corp., St. Louis, MO.

As used in this application,

"G" refers to 2,2-bis[4-(2-hydroxy-3-methacryloxypropyl)phenyl]propane;

"TEGDMA" refers to the triethylene glycol dimethacrylate, obtained from Sartomer Co., Inc., Exton, PA;

"UDMA" refers to diuretin the dimethacrylate obtained under the trademark "ROHAMERE 6661-0" from Rohm America LLC, Piscataway, NJ;

"Becema" refers to ethoxylated bisphenol a to dimethacrylate, obtained from Sartomer Co., Inc., Exton, PA;

"BHT" refers to butilirovannogo hydroxytoluene;

"BZT" refers to 2-(2-hydroxy-5-methacryloxyethyl)-2H-benzotriazole obtained from Ciba, Inc., Tarrytown, NY;

"EHMAP" refers to ethyl-(N-methyl-N-phenyl)aminopropionic synthesized using known methods, such as described Adamson, et al.; JCSOA9; J. Chem. Soc; 1949; spl. 144, 152, which are incorporated in this application by reference;

"CPQ" refers to camporgiano;

"Irgacure 819" refers to bis(2,4,6-trimethylbenzoyl)phenylphosphine obtained from Ciba, Inc., Tarrytown, NY;

"PEG 600 DM" refers to the polyethylene glycol dimethacrylate, the average molecular mass of ~600, available from Sartomer Co., Inc., Exton, PA; and

"GENIOSIL GF-31" or "GF-31" refers to the composition of 3-metacello is dipropyltryptamine, available from Wacker Chemie AG, Munich, Germany.

Obtaining resin And

The resin was prepared by mixing together the components in the relative amounts listed in Table 1 below (all quantities are given as mass fractions):

Getting Filler And:

Filler And received by weighing 105,24 grams of NALCO 1042 Zola silica, added what I 3.15 grams of 70 wt.% NGO ₃solution and add to this 45,16 grams of the recovered acid Sol of zirconium dioxide (obtained essentially as described in U.S. patent No. 7429422 (Davidson et al), filed June 7, 2007). This resulted in the receipt of an oxide mixture of about 73 wt.% silica and 27 wt.% zirconium dioxide based on the weight of oxides. To this mixture was added 100 grams of granulated sugar. The resulting Sol was poured into the ceramic vessel and prozharivali at 625°C to remove volatile and organic substances. The resulting roasted material essentially grinded using mortar and pestle and passed through a nylon sieve size 75 μm to remove large agglomerates. The material is then treated with silane by mixing together 25,000 grams of the resulting milled oxide, 3,270 grams GF-31 silane, 27.4 grams of ethyl acetate and 0,447 grams of 30% NH₄OH solution. They were allowed to mix for approximately 4 hours before distillation of the ethyl acetate in pyrexia tray and then was heated at 90°C for 30 minutes.

Getting Filler (without sugar):

The filler was obtained by weighing 45,16 grams of the recovered acid Sol of zirconium dioxide (obtained essentially as described in U.S. patent No. 7429422, (Davidson, et al.), submitted June 7, 2007), and to which was added a mixture of 105,65 grams of the NALCO 1042 Zola silica and 1.19 grams of 70 wt.% solution of nitric acid. The mixture was poured directly into a ceramic vessel for roasting and prozharivali at 625°C for 4 hours to remove water and volatile organic substances. The resulting oxide contained about 73 wt.% silica and 27 wt.% Zirconia. The resulting filler was ground using a mortar and pestle, passed through a nylon sieve size 75 μm to remove large agglomerates. 40 grams of this material was added to 6,02 grams GF-31 silane, 49 grams of ethyl acetate and 0,76 grams 30% NH₄OH solution. The reaction lasted for 3 hours, the solvent drove on pyrexia the tray and the material was prozharivali at 90°C for 30 minutes to obtain the desired filler.

Getting Filler With:

The filler was received with the same proportions of materials as described above in this application for Filler Century Filler was heated to 825°C for 8 hours (instead of 625°C) and grinded by ball mill instead of a mortar and pestle, and the filler was treated with silane by dispersion in 1-methoxy-2-propanol and heated to 80°C for 3 hours at pH 8.75 (regulated NH₄OH) loading 11% GF-31 to the weight of the filler, and the material is then dried.

Getting Filler D (negative control):

The silane treated filler of silica/Zirconia obtained and zirconyl acetate at a ratio of approximately 73% of silica and 27% Zirconia was obtained essentially as described in Examples of the preparation and of U.S. patent No. 6730156, except that the filler was again calcined after grinding at 713°C for 11 hours before silverbeam to remove additional residue.

Examples E1-E3 and Comparative examples CE-CE

Several different pastes were obtained by mixing the components together, as shown in Table 2 below.

Paste E1, E2, E3 and SE showed significant light, visible to the naked eye, which seemed to be orange/yellow on a white background, and blue/white on a black background. Paste SE did not show opalescence, visible to the naked eye, which seemed to be yellow in both the black and white background, to the naked eye. All pastes were translucent and transparent.

Opalescence was measured quantitatively for pastes, E1, E3, SE and SE on the spectrophotometer HunterLab Ultrascan XE (Hunter Associates Laboratory, Inc., Reston VA, USA) with a value of C_ab(opalescence), measured by determining the difference, as described below, between the values of a* and b*measured in reflection compared to a black background, and mode of transmission. This is the difference vector in the plane a-b color space to two dimensions. The results are shown in Table 3.

The samples were obtained by performing the metal ring of the optical disk of the composites (~1.3 grams each), 1 inch diameter and 1 mm thick (+/-0,02 mm) of the composite disk by compressing disks in preparation for vulcanization under the Mylar film with XL 3000 dental curing light across the surface of the disc 9 overlapping points for 20 seconds each to ensure complete cure. These disks were collected in block hunter, and after calibration for use in large samples (1 inch) is opening large holes were measured reection with respect to the black background. The instrument was re-calibrated for measurement of light transmittance, and readings were taken in the measurement mode and the measurement mode were measured turbidity. Were registered L*, a*, b* coordinates (reflection and transmission) and values of turbidity (for transmission). With_abwas calculated by the formula C_ab=((b*_ref-b*_trans)²+(a*_ref-and*t_rans)²)^1/2

As can be seen in Table 3, the samples containing the Filler and the Filler, where clusters of nanoparticles of silica and Zirconia formed from pre-formed particles of Zirconia, more light, than paste containing a filler of silica/Zirconia obtained from zirconyl acetate (SE). Opalescence was also in the range is the area, very similar to the range for a semi-transparent tint FILTEK SUPREME PLUS^TM(CE2) (silica), which is very desirable and is similar to natural enamel.

Turbidity measurements for E3 and SE were produced directly from measurements of the transmission device and are provided in Table 4. Sample containing opalescent filler, showed significantly lower turbidity than the sample containing the filler of their silica/Zirconia obtained from zirconyl acetate (SE).

The paste obtained with this opalescent filler of silica and Zirconia (E1, E2, and E3), also had an interesting optical effect, consisting in less dependence on the angle of light transmission. This effect, illustrated in figure 1, has the potential for more living similar to natural teeth, fillings for use in dental restorative means. New materials are also able to transfer from the interests of more clearly than with additional removal from the facility, with consideration for them than regular pasta.

Various modifications and changes of the present invention will be obvious to experts in the art, without departing from the scope and essence of the present invention. It should be clear that the present invention is not intended to improperly limiting illustrative implementations and examples presented in this application, and that such examples and implementation are presented only as an example in the scope of the present invention and are intended to limit only the formula of the present invention described in this application.

Full descriptions of the patents, patent documents, and publications cited in this application are fully incorporated by reference as if each was incorporated individually.

1. A method of producing a filler for a composite material including a stage on which:
(a) provide a Sol of zirconium dioxide containing the pre-formed crystalline nanoparticles of zirconium dioxide with an average diameter from about 3 nm to about 30 nm,
(b) provide a silica Sol containing silica nanoparticles with an average diameter from about 10 nm to about 100 nm,
(c) combine the Sol of zirconium dioxide and zo is ü silica with formation of a mixture of nanoparticles of Zirconia and silica,
(d) heating the mixture to a temperature from about 400°to about 1000°C and
(e) grind the heated mixture with the formation of filler-containing clusters, nanoparticles of silica and Zirconia.

2. The method according to claim 1, characterized in that the clusters of the nanoparticles have an average volume diameter of from about 0.5 to about 10 microns.

3. The method according to claim 1, wherein the silica nanoparticles have an average diameter of from about 15 nm to about 60 nm.

4. The method according to claim 1, characterized in that the nanoparticles of zirconium dioxide have an average diameter from about 5 nm to about 15 nm.

5. The method according to claim 1, characterized in that the silica nanoparticles and nanoparticles of Zirconia are evenly distributed in clusters of nanoparticles.

6. The method according to claim 1, characterized in that it further includes lowering the pH of the Sol of silica to values lower than 1.2 before mixing with the Sol of Zirconia.

7. The method according to claim 1, characterized in that it further includes a step of surface treatment of the filler celanova agent binding.

8. The method according to claim 1, characterized in that the filler of silica and zirconium dioxide has a refractive index from about 1,44 to approximately 1,65.

9. The method according to claim 1, characterized in that the Sol of Zirconia restore Ki is lotai.

10. Curable dental composition comprising:
(a) a curable component,
(b) the system initiators and
(c) a filler containing clusters of nanoparticles of Zirconia and silica nanoparticles,
when this composition is set With_abaverage of at least 15, when the measurements are carried out in accordance with the method of analysis opalescence.

11. The composition according to claim 10, characterized in that the clusters of the nanoparticles have an average volume diameter of from about 0.5 to about 10 microns.

12. The composition of claim 10, wherein the silica nanoparticles have an average diameter of from about 15 nm to about 60 nm.

13. The composition according to claim 10, characterized in that the nanoparticles of zirconium dioxide have an average diameter from about 5 nm to about 15 nm.

14. Composition according to any one of PP-13, characterized in that the silica nanoparticles and nanoparticles of Zirconia are evenly distributed in clusters of nanoparticles.

15. Composition according to any one of PP-13, characterized in that it has a value With_abconstituting at least 18, when the measurements are carried out in accordance with the method of analysis opalescence.

16. Composition according to any one of PP-13, characterized in that it has a value With_abcomprising at least 20, when the measurements are carried out in soo is according to the method of analysis opalescence.

17. Composition according to any one of PP-13, characterized in that it has a turbidity of less than 70 values of units.

18. Composition according to any one of PP-13, characterized in that the clusters of nanoparticles are treated surface.

19. The composition according to p, characterized in that the surface of the clusters, nanoparticles treated with silane.

20. Composition according to any one of PP-13, characterized in that the curable component contains ethylene-unsaturated compound.

21. The composition according to claim 20, characterized in that the curable component contains a (meth)acrylate.

22. Composition according to any one of PP-13, characterized in that it has a refractive index from about 1,44 to approximately 1,65.

23. The composition according to claim 10, characterized in that the filler obtained in accordance with the method according to any one of claims 1 to 9.

24. Dental filling material containing a dental composition according to any one of PP-13.

25. Dental filling material according to paragraph 24, wherein the material is a material of the seal pre-formed bridge or crown flowable filling material or temporary filling material.