hardenable dental composition containing a mixture of agglomerated and aggregated nanoparticles

专利摘要:
ABSTRACT? HARDENING DENTAL COMPOSITION CONTAINING A MIXTURE OF AGGLOMERATED AND AGGREGATED NANOPARTICLES, PARTS KIT AND ITS USE? The present invention relates to a dental composition comprising: - filler (F1) which comprises nanodimensioned aggregate particles in an amount of about 30 to about 70% by weight, - filler (F2) which comprises agglomerated particles, nanodimensions in an amount of about 1 to about 20% by weight, - hardenable component (A1) which is a urethane (meth) acrylate with a functionality of at least 2 and which has a molecular weight of about 400 to about 3,000 g / mol, - hardenable component (A2) which is a polymerizable (meth) acrylate via radical with a functionality of at least 2 which is different from component (A1), - redox curing initiator system, the dental composition does not comprise non-agglomerated, nano-sized fillers in an amount above about 10% by weight, percentage by weight with respect to the weight of the entire composition. The dental composition is particularly useful as or for the production of crowns and bridges, inlays, onlays and permanent veneers.
公开号:BR112016000433B1
申请号:R112016000433-7
申请日:2014-07-01
公开日:2020-12-08
发明作者:Reinhold Hecht；Uwe H. Hoheisel；Adrian S. Eckert；Bernhard Hofmann
申请人:3M Innovative Properties Company；
IPC主号:

专利说明:

Field of invention
[001] The present invention relates to a dental composition that is useful as a dental filling material, particularly as a bulk filling material (bulkfill), or for the production of long-lasting restorations with permanent composites such as crowns and bridges, permanent inlays, onlays and veneers. Background of the invention
[002] Composite materials are well known in dentistry and can be used as fillers, permanent cements or materials for temporary crowns and bridges. Depending on the indication, the different composite materials can be differentiated by their respective filling contents.
[003] Typically, filler composites are highly filled materials, which are characterized by their good mechanical properties such as low abrasion (low wear). Unfortunately, due to the high filler load, these materials sometimes tend to be brittle.
[004] Temporary crown and bridge materials have a lower fill content compared to filler composites. This often results in better elasticity and greater resistance to fracture, but is often accompanied by increased abrasion or wear, which prevents long-term use of these materials.
[005] The laboratory composite materials that are commercially available for the manufacture of dental restorations, such as crowns, cannot be used in a procedure in the office (in-office) or dental clinic (chairside) and need the involvement of a dental laboratory external. Alternatively, composite blocks for milling, such as Paradigm ™ MZ 100 (3M ESPE) can be used in a procedure in the dental office or clinic but require a considerably high investment in CAD / CAM (computer-aided design / computer-aided manufacturing) technology.
[006] Thus, there is a need for a material that combines the properties of the materials described above, which can be used to manufacture crowns and bridges based on composite in the office or clinic without the need for an investment in CAD / technology CAM. Additionally, there is an increasing demand from patients and dentists for aesthetic and durable dental restorations.
[007] EP 2 167 013 A1 (3M) refers to dental compositions containing a polyfunctional (meth) acrylate comprising urethane, urea or starch groups, methods of producing and using them.
[008] US 2005/0234148 A1 (Heraeus) describes agglomerated inorganic fillers for dental materials consisting of agglomerates of 0.5 to 50 pm inorganic particles from 200 to 7000 nm, whose interfaces are fused to at least one adjacent particle. WO 2012/057917 A1 (3M) describes a preformed semi-finished dental article comprising a composition for uncured dental restoration that comprises a certain resin system of at least 50% by weight of nano-agglomerated filler, the composition for uncured dental restoration it has a first shape that is malleable enough to be formed into a second shape.
[009] US 6,730,156 B1 (Windisch et al.) Refers to a filler comprising a substantially amorphous agglomerate comprising particles of non-heavy metal oxide and heavy metal oxide. The filler can be mixed in a hardenable resin to provide radiopaque dental materials that have desirable strength and aesthetic character. Description of the invention
[010] In particular, it would be desirable to have a dental composition that is available with high fracture resistance, low wear and sufficient flexibility. If possible, the dental composition should also be easy to apply. Ideally, the dental composition should also be aesthetically acceptable.
[011] This objective can be achieved with the dental composition described in this text.
[012] In one embodiment, the present invention features a dental composition comprising: -fill (F1) comprising nanodimensioned aggregate particles in an amount of about 30 to about 70% by weight, -fill (F2) which comprises particles nano-sized agglomerates in an amount of about 1 to about 20% by weight, -durable component (A1) which is a urethane (meth) acrylate with a functionality of at least 2 and which has a molecular weight above about 450 g / mol, - hardenable component (A2) which is a (meth) acrylate polymerizable via radical with a functionality of at least 2 which is different from component (A1), - redox initiator system or dark cure initiator system.
[013] The dental composition typically does not comprise a non-agglomerated, nanodimensioned filler (e.g., average particle size of about 50 nm) in an amount above about 10% by weight.
[014] The invention also relates to a kit of parts comprising the dental composition as described in this text and at least one or all of the following parts: - mixing means, - dental impression material, - dental cement.
[015] The invention also relates to the use of the dental composition described in the present text as or for the production of crown (s), bridge (s), inlay (s), veneer (s) and as filler in bulk ( bulkfill). Definitions
[016] Unless defined differently, for this description the following terms must have the same meaning:
[017] A "dental composition" or "composition for dental use" or "composition for use in the dental field" is any composition that can be used in the dental field. On this subject, the composition should not be harmful to the health of the patients and, therefore, free of dangers and the toxic components capable of being extracted from the composition. Examples of dental compositions include temporary and permanent bridge and crown materials, artificial crowns, anterior or posterior filling materials, adhesives, grinding blanks, laboratory materials and orthodontic devices. Dental compositions are typically curable compositions, which can be cured under ambient conditions, which include a temperature range of about 15 to 50 ° C or about 20 to 40 ° C within a period of about 30, 20 or 10 minutes. Higher temperatures are not recommended as they could cause pain to the patient and can be harmful to the patient's health. Dental compositions are typically supplied to the practitioner in comparable small volumes, that is, volumes in the range of about 0.1 to about 100 ml or from about 0.5 to about 50 ml or from about 1 to about 30 ml. Thus, the storage volume of useful packaging devices is within these ranges.
[018] A “curable material or component” or “polymerizable component” is any component that can be cured or solidified, for example, by heating, to cause radiation-induced polymerization, chemical cross-linking, polymerization or cross-linking through the use of a redox initiator. A curable compound can contain only one, two, three or more polymerizable groups. Typical examples of polymerizable groups include unsaturated carbon groups, such as a vinyl group present, that is, in a (methyl) acrylate group. An "initiator" is a substance that is able to initiate the curing process of a hardenable composition.
[019] A "monomer" is any chemical substance that can be CHARACTERIZED by a chemical formula, which has polymerizable groups (including (meth) acrylate groups) that can be polymerized into oligomers or polymers thereby increasing molecular weight. The molecular weight of monomers can usually and simply be calculated based on the given chemical formula.
[020] As used in the present invention, the term "(meth) acryl" is an abbreviation that refers to "acryl" and / or "methacryl". For example, a “(meth) acryloxy” group is an abbreviation that refers to an acryloxy group (that is, CH2 = CH- C (O) -O-) and / or a methacryloxy group (that is, CH2 = C (CH3) -C (O) -O-).
[021] The terms “curing, hardening or solidifying reaction” are used interchangeably and refer to a reaction in which the physical properties, such as viscosity and hardness, of a composition change over time due to a chemical reaction between the individual components.
[022] The term "polymerizable component comprising an acid group" is intended to include monomers, oligomers and polymers having ethylenic unsaturation and acidic and / or acid precursor functionality. Acid precursor features include, for example, acid halides and pyrophosphates. The acid group preferably comprises one or more carboxylic acid residues, such as - COOH or -CO-O-CO-, phosphoric acid residues, such as -OP (O) (OH) OH, phosphonic acid residues, such as CP (O) (OH) OH, sulfonic acid residues, such as -SO3H or sulfinic acid residues, such as -SO2H.
[023] A "powder" means a dry bulk solid composed of a large amount of very fine particles that can flow freely when agitated or tilted.
[024] A "particle" means a substance that is a solid and has a shape that can be geometrically determined. Particles can typically be analyzed for, for example, grain size or diameter.
[025] The average particle size of a powder can be obtained from the cumulative curve of the grain size distribution and is defined as the arithmetic mean of the measured grain sizes of a certain powder mixture. The respective measurements can be made using granulometers available for sale (for example, the CILAS Laser Diffraction Particle Size Analysis Instrument (laser diffraction particle size analyzer)).
[026] A "nanodimensioned filler" is a filler, the individual particles of which have a size in the nanometer region, for example, an average particle diameter less than about 200 nm or less than about 100 nm or less than about 50 nm. Useful examples are presented in US 6,899,948 and US 6,572,693, the contents of which, especially with reference to nanodimensioned silica particles, are hereby incorporated by reference.
[027] The measurement of the size of the nanoparticles is preferably based on a TEM (transmission electron microscopy) method, by which a population is analyzed to obtain an average particle diameter. A preferred method for measuring the particle diameter can be described as follows:
[028] Samples approximately 80 nm thick are placed on 200 mesh copper grids with carbon stabilized substrates (SPI Supplies - a division of Structure Probe, Inc., West Chester, PA, USA). A transmission electron micrograph (TEM) is made, using JEOL 200CX (JEOL, Ltd. from Akishima, Japan and sold by JEOL USA, Inc.) at 200 Kv. A population size of about 50 to 100 particles can be measured and an average diameter is determined.
[029] "Agglomerate" is the description of a weak association of particles normally held together through charge or polarity and that can be broken into smaller entities. The specific surface of agglomerated particles does not deviate essentially from the specific surface of the primary particles that make up the agglomerate (cf. DIN 53206; 1972).
[030] Agglomerated fillers are available for sale from Degussa, Cabot Corp or Wacker under the trade name Aerosil ™, CAB-O-SIL ™ and HDK.
[031] A “non-agglomerated filler” means that the filler particles are present in the resin at an unassociated and distinct stage (ie, not agglomerated and not aggregated). If desired, this can be verified by TEM microscopy.
[032] Non-agglomerated, nanodimensioned silicas are commercially available, for example, from Nalco Chemical Co., Naperville, IL., USA, under the trade name “NALCO COLLOIDAL SILICA”, for example, as NALCO # 1040, 1042 products, 1050, 1060, 2327 and 2329. Non-agglomerated fillers are used and described, for example, in EP 2 167 013 B1 (3M). The content of that reference is hereby incorporated by reference.
[033] "Aggregate", as used in the present invention, is the description of a strong association of particles often linked to each other through, for example, residual chemical treatment or partial sintering. The specific surface of the aggregate particles is typically smaller than the specific surface of the primary particles that make up the aggregate (cf. DIN 53206; 1972).
[034] Additional decomposition of the aggregates into smaller entities can occur during a polishing step applied to the surface of a composition containing the aggregate filler but not during the dispersion of the aggregated particles in a resin.
[035] Aggregate fillers and processes for their production and surface treatment are described, for example, in WO 01/30304 and US 6,730,156 (3M). The content of these references is hereby incorporated by reference.
[036] "Dispersed in the resin" means that the filler particles are present in the resin as agglomerated or aggregated or distinct particles (that is, not associated, not agglomerated and not aggregated).
[037] A "urethane group" is a group that has the "-NH-CO-O-" structure.
[038] A "urea group is a group that has the structure" -NH-CO-NH- ".
[039] An “amide group is a group that has the structure“ -NH-CO- ”.
[040] A "unit" is a simple structural unit of a chemical molecule or substrate thereof. Simple units are connected to each other. Typical units include: CH3-, -CH2-, -O-, -S-, -NR1-, -CO-, -CR1 =,
-N =, -cR1R2-, with 1 and R2 independently selected from hydrogen, linear alkyl groups (including groups c1, c2, c3, c4, c5, c6), substituted alkyl groups (including groups c1, c2, c3, c4, c5, c6), alkenyl groups (including groups c1, c2, c3, c4, c5, c6), cycloalkyl groups (including groups c4 to c14), substituted cycloalkyl groups (including groups c4 to c14), aryl alkyl groups (including c7 to c20), aryl groups (including c6 to c14) or substituted aryl groups (including c7 to c20). These units may form linear, branched or cyclic structures, such as alkyl, cycloalkyl, aryl, ester, urethane or amide groups.
[041] A "connector element" is an element that acts as a center that connects the individual side chains containing (meth) acrylate. The connector element can have a cyclic or branched structure. The connector element can even be a single atom, including N. If the connector element has a cyclic structure, it can be a saturated, unsaturated or aromatic homocyclic, that is, it comprises only hydrocarbon or substituted hydrocarbon units, or it can be a saturated, unsaturated or aromatic heterocyclic, that is, it comprises hydrocarbon or substituted hydrocarbon units and at least one heteroatom, which includes -O-, -N =, -NH-, -NR1- and / or -S-. If the connector element has a branched structure, it comprises a central atom such as C or N from which at least three or four individual side chains containing (meth) acrylate extend. Regardless of the chemical structure of the connector element, the arrangement of the individual side chains containing (meth) acrylate with respect to the connector element can be symmetrical or asymmetric.
[042] A "spacer group" is a group that connects at least two other groups in a chemically defined molecule. This group can be a substituted or unsubstituted carbon chain, which can additionally contain hetero atoms (including O, N and S) or functions like carbonyl groups.
[043] A “dental impression material”, in the meaning of the invention, is a material used to make impressions of the dental structure that include the gum. A dental impression material is usually applied on a dental modeling tray. dental can be produced with different chemical and cross-linking substances through various chemical reactions (including addition curing and condensation curing materials). Typical examples include silicone based printing materials (e.g., VPS materials) and polyether based printing materials and mixtures thereof.
[044] A “material for temporary crowns and bridges” is a hardenable material used for making dental crowns and bridges. These materials are typically used for as long as it takes for the dental technician to manufacture a permanent prosthesis, such as a crown or bridge. These time periods can last from a few days (1 to about 6 days), a few weeks (1 to about 4 weeks) or a few months (1 to about 6 months). A long-lasting bridge and crown material is typically used over a period of about 6 to about 24 months.
[045] In contrast to a long-lasting bridge and crown material, a “permanent bridge and crown material” can be used for a period of time longer than 2 years and specifically longer than 5 years. The term "visible light" is used to refer to light that has a wavelength of about 400 to about 800 nanometers (nm).
[046] "Ambient conditions" means the conditions to which the composition of the invention is usually subject during storage and handling. Ambient conditions can, for example, be a pressure of about 90 to about 110 kPa (about 900 to 1100 mbar), a temperature of about -10 to about 60 ° C and a relative humidity of about 10 to about 100%. In the laboratory, the ambient conditions are adjusted to about 23 ° C and about 101.3 kPa (1013 mbar). In the orthodontic and dental field, ambient conditions are reasonably understood as a pressure of about 95 to about 105 kPa (950 to about 1050 mbar), a temperature of about 15 to about 40 ° C and a relative humidity of about 20 about 80%.
[047] As used in the present invention, "one", "one", "o", "a", "at least one", "at least one", "one or more" and "one or more" are used interchangeably. The terms "understand" or "contain" and variations thereof do not have a limiting meaning in the way in which these terms appear in the description and claims. The term "which comprises" also includes the more limited expression "which consists essentially of" and "consists of".
[048] As used in the present invention, mentions of numeric ranges with extremes include all numbers contained in that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4 , 5, etc.). Adding an “(s)” to a term means that the term must include the singular and plural form. For example, the term "additives (s)" means an additive and more additives (for example, 2, 3, 4, etc.).
[049] Except where otherwise indicated, all numbers that express quantities of ingredients, measurement of physical properties such as those described below and so on used in the specification and in the claims should be understood as being modified in all instances by the term “ about". Detailed description of the invention
[050] It has been found that the composition described in this text meets the needs of dental professionals especially with respect to the balance of properties such as high abrasion resistance (ie, low wear), sufficient flexibility and high fracture resistance. The combination of different fillers in the right quantities in combination with a certain resin matrix allows the production of a composition that has, on the one hand, a high filling load and, on the other hand, good handling properties combined with well-balanced physical properties.
[051] This is usually difficult to achieve. A high filling load is typically accompanied by difficult mixing properties and insufficient flexibility of the cured composition. On the other hand, a low filler load typically facilitates mixing and can contribute to better flexibility, but usually produces insufficient abrasion resistance.
[052] Due to its viscosity properties, the composition is also easy to apply as it can be mixed and dispensed from known mixing and dispensing systems. If desired, this can be verified with an extrusion test as further described detail below. The composition described in this text allows the dental professional to provide the patient with a dental restoration that can be used for a longer period of time compared to existing temporary or long-term bridge and crown materials. The composition can be used not only to produce long-lasting crowns and bridges, but also inlays, onlays and composite-based veneers. Its use as a bulk filling material is also possible.
[053] Additionally, dental restoration can be produced in the dental clinic, that is, without involving a dental laboratory. In addition, there is no need to invest in expensive CAD / CAM technology. The dental composition described in this text comprises at least two types of fillers, filling (F1) and filling (F2). The dental composition is CHARACTERIZED by a comparatively high filling load. For comparison, the filler load for typical temporary crowns and bridges is in the range of about 30 to about 40% by weight with respect to the weight of the entire composition. It has been found that a high filler is beneficial for increasing wear resistance, thereby allowing the production of a dental material that can be used for a long time in a patient's mouth. The filling (F1) comprises nanodimensioned aggregate particles. The chemical nature of the filler (F1) is not particularly limited unless the purpose for which it is intended cannot be achieved.
[054] According to one modality, the filler (F1) can be characterized by at least one or all of the following characteristics: -Specific surface: from about 50 to about 400 or from 60 to about 300 or 80 at about 250 m2 / g, - comprises SiO2, ZrO2 particles and their mixtures.
[055] If desired, the specific surface can be determined according to BET (Brunauer, Emmet eTeller) using a device (Monosorb) available from Quantachrome.
[056] If desired, the average particle size can be determined by scattering light using, for example, a Malvern Mastersizer 2000 device available from Malvern Instruments. The filler (F1) can be produced according to the processes described, for example, in WO 01/30304 or US 6,730,156.
[057] The filler (F1) can be prepared from a suitable sol and one or more precursors of solutions of heavy metal compound containing oxygen, which can be salts, suns, solutions, or nanodimensioned particles; preferably suns. For the purposes of this invention, a sol is defined as a stable dispersion of solid colloidal particles in a liquid. Solid particles are typically denser than the surrounding liquid and small enough that dispersion forces are greater than the gravitational force. In addition, the particles are small enough so that there is usually no visible light refraction. The careful choice of precursor suns results in a desired degree of visual opacity, resistance. etc. The factors that will determine the choice of suns will depend on the combination of the following properties: a) the average size of the individual particles, which is preferably less than 100 nm in diameter, b) the acidity: the pH of the sun should be preferably below 6 and more preferably below about 4, and c) the sun must be free of impurities that cause undue aggregation (during the filling preparation process) of the individual, distinct particles during the subsequent steps, as spray drying or calcination, in larger particles that may have low dispersibility and mobility and, therefore, with less translucency and low polishability.
[058] If the starting sol is basic, it must be acidified, for example, by adding nitric acid or another suitable acid to lower the pH. However, the choice of a basic starting sol is less desirable since this requires an additional step and can lead to the introduction of unwanted impurities. Typical impurities that are preferably avoided are metal salts, particularly alkali metal salts, for example, sodium.
[059] The non-heavy metal sol and the heavy metal oxide precursors are mixed together, preferably in a molar ratio to correspond to the refractive index of the hardenable resin. This gives a low and desirable visual opacity. Preferably, the molar ratios between non-heavy metal oxide (“non-HMO”, non-heavy metal oxide) and heavy metal oxide (“HMO, heavy metal oxide), expressed as“ non-HMO: HMO ”are in the range about 0.5: 1 to about 10: 1, more preferably about 3: 1 to about 9: 1, and most preferably about 4: 1 to 7: 1.
[060] In a preferred embodiment in which the nanodimensioned aggregate particles contain compounds containing silica and zirconium, the method of preparation begins with a mixture of silica sol and zirconyl acetate, in a molar ratio of about 5.5: 1.
[061] Before mixing the non-heavy metal oxide sol with the heavy metal oxide precursor, the pH of the non-heavy metal oxide sol is preferably reduced to provide an acid solution having a pH of about 1.5 to about 4.0. The non-heavy metal oxide sol is then slowly mixed with the solution containing the heavy metal oxide precursor and vigorously stirred. Vigorous stirring is preferably carried out throughout the mixing process. The solution is then dried to remove water and other volatile components. Drying can be done in several ways, including, for example, tray drying, fluidized bed and spray drying. In the preferred method in which zirconyl acetate is used, drying is by spraying.
[062] The resulting dry material is preferably composed of small substantially spherical particles as well as hollow sphere fragments. These fragments are then calcined in batches for additional removal of organic residues. The removal of organic residues allows the filling to become more brittle, which results in a more efficient reduction in particle size. During calcination, the plateau temperature is preferably adjusted to about 200 ° C to about 800 ° C, more preferably about 300 ° C to 600 ° C. Sintering is done for about 0.5 hours to about 8 hours, depending on the amount of material to be calcined. It is preferred that the landing time of the calcination step is such that a plateau surface area is obtained. It is preferred that the time and temperature are chosen so that the resulting filler is white, free from black, gray or amber colored particles, as determined by visual inspection.
[063] The calcined material is then preferably ground to an average particle size of less than about 5 pm, preferably less than 2 pm (on a volumetric basis), as can be determined using a Sedigraph 5100 (Micrometrics , Norcross, Ga., USA). The determination of the particle size can be done by first obtaining the specific density of the filling using an Accuracy 1330 picometer (Micrometrics, Norcross, Ga., USA). Grinding can be carried out by various methods including, for example, agitation, grinding, vibrating grinding, fluid energy grinding, jet grinding, and ball grinding. Ball grinding is the preferred method.
[064] The resulting fillers comprise, contain, essentially consist of or consist of nanodimensioned aggregate particles. If desired, this can be tested by TEM (transmission electron microscopy (TEM) microscopy. The surface of the filler particles (F1) can be treated The surface treatment can be done in the same way as described in more detail for the filler particles (F2) below or according to a process as described in US 6,730,156 or WO 01/30304.
[065] Once dispersed in the resin, the filler (F1) remains in an aggregate stage. That is, during the dispersion stage, the particles do not decompose into separate (that is, individual) and unassociated (that is, not agglomerated, not aggregated) particles. The filler (F1) is typically present in an amount of at least about 30 or at least about 35 or at least about 40% by weight with respect to the weight of the entire composition. The filler (F1) is typically present in an amount of at most about 70 or at most about 60 or at most about 50% by weight with respect to the weight of the entire composition. Thus, the filler (F1) is typically present in an amount of about 30 to about 70, or about 35 to about 60, or about 40 to about 50% by weight with respect to the weight of the entire composition.
[066] The dental composition can contain only one type of filler (F1) or more types of fillers (F1), for example, two, three or four different types. Without the desire to stick to a specific theory, it is believed that the filling (F1) contributes to the polishability of the dental composition described in this text. It has been found that aggregates of the filler particles (F1) can break during a polishing step contributing to a smooth surface and a lower light scatter compared to a rough surface. From a clinical point of view, this typically results in high gloss retention and color stability.
[067] However, it has been found that the use of non-agglomerated fillers, such as those used in the examples of EP 2 167 013 (A1), is not suitable for achieving the desired abrasion resistance.
[068] In addition, the use of non-agglomerated filler is often accompanied by an increase in viscosity. A high viscosity, however, adversely affects the forces required to mix and extrude dental material from a manually operated dispenser. In addition, due to the very specific surface, incorporating a large amount (for example, greater than about 40% by weight) of non-agglomerated filler in the resin matrix is often not possible.
[069] Thus, it was discovered that the use of nano-sized aggregate fillers contributes to a better resistance to abrasion of the dental composition, allows a greater filling load in the resin matrix of the dental composition, facilitates the production of pastes due to the better properties of wetting of the filler and contributes to better handling properties.
[070] The dental composition can contain only one type of filler (F2) or more types of fillers (F2), for example, two, three or four different types. The filling (F2) comprises nanodimensioned aggregate particles. The chemical nature of the filler (F2) is not particularly limited unless the purpose for which it is intended cannot be achieved. The size of the filler particles must be such that a homogeneous mixture with the hardenable component (A1) that forms the resin matrix can be obtained.
[071] According to one modality, the filling (F2) can be characterized by at least one or all of the following characteristics: - Specific surface of the agglomerated particles, nanodimensioned (BET according to Brunauer, Emmet and Teller): about from 30 to about 400 or from 50 to about 300 or from 70 to about 250 m2 / g; - comprises particles of SiO2, ZrO2, Al2O3 and their mixtures.
[072] If desired, the specific surface can be determined as described above.
[073] Suitable agglomerated nanoparticles include pyrolysed silicas, such as products sold under the Aerosil ™ trade name, for example, Aerosil OX-130, -150, and -200, Aerosil R8200 available from Degussa AG, (Hanau, Germany), CAB-O-SIL ™ M5 available from Cabot Corp (Tuscola, Ill., USA), and HDK ™, for example, HDK-H 2000, HDK H15; HDK H18, HDK H20 and HDK H30 available from Wacker.
[074] The surface of the filler filler particles (F2) can be treated with a resin-compatible surface treatment agent. Particularly preferred surface modifying or surface treatment agents include silane treatment agents capable of polymerization with a resin. The preferred silane treatment agent includes Y-methacryloxypropyltrimethoxysilane, available commercially under the trade name A-174, from Witco OSi Specialties (Danbury, CT, USA) and Y-glycidoxypropyltrimethoxysilane, a product available under the trade name G6720, available from United Chemical Technologies (Bristol, PA, USA).
[075] Alternatively, a combination of surface modifying agents may be useful, with at least one of the agents having a copolymerizable functional group with a curable resin. For example, the polymerizing group may be ethylenically unsaturated or a cyclic function subjected to ring opening polymerization. An ethylenically unsaturated polymerization group can be, for example, an acrylate, methacrylate or vinyl group. A cyclic functional group undergoing ring-opening polymerization generally contains a heteroatom such as oxygen, sulfur or nitrogen and is preferably a 3-membered ring containing oxygen as an epoxide. Other surface modifying agents that generally do not react with hardenable resins can be included to improve rheological properties or dispersibility. Examples of silane of this type include, for example, functional silanes of alkyl or aryl polyethers, alkyl, cycloalkyl, hydroxyalkyl, aryl , hydroxy aryl or aminoalkyl.
[076] Without the desire to stick to a specific theory, it is believed that the filling (F2) contributes to the rheological behavior of the dental composition described in this text. The use of this type of filling allows the supply of a high filling dental composition, which, however, is still mixable with the use of static mixing tips. From a clinical point of view, this typically results in improved handling properties, such as easy mixing of pastes and low extrusion forces from cartridge systems. The filler (F2) is typically present in an amount of at least about 1 or at least about 3 or at least about 5% by weight with respect to the weight of the entire composition. The filler (F2) is typically present in an amount of at most about 20 or at most about 15 or at most about 10% by weight with respect to the weight of the entire composition. Thus, the filler (F2) is typically present in an amount of about 1 to about 20, or about 3 to about 15, or about 5 to about 10% by weight with respect to the weight of the entire composition.
[077] The dental composition described in this text comprises at least two types of hardenable components, component (A1) and component (A2). Component (A1) and component (A2) are components of the resin matrix of the dark curable dental composition. The dental composition comprises at least one curable component (A1) which is a urethane (meth) acrylate with a functionality of at least 2.
[078] If desired, the dental composition can comprise at least two, three, or four different types of hardenable component (A1). The molecular weight of the curable component (A1) is at least about 450 or at least about 800 or at least about 1,000. Useful ranges include from about 450 to about 3,000 or from about 800 to about 2,700 or from about 1,000 to about 2,500. Molecules that have a molecular weight above about 450 g / mol or above about 1000 g / mol are normally less volatile than molecules that have a lower molecular weight and, thus, can contribute to providing a biocompatible composition .
[079] In addition, if the molecular weight is not high enough, the desired fracture resistance of the hardened dental composition may not be achieved.
[080] The urethane (meth) acrylates used in the composition described in this text are typically formed by reacting an NCO-terminated compound with a suitable monofunctional (meth) acrylate monomer, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate preferably hydroxyethyl and hydroxypropyl methacrylate.
[081] Urethane (meth) acrylates can be obtained by various processes known to the person skilled in the art. For example, a polyisocyanate and a polyol can be reacted to form an isocyanate-terminated urethane prepolymer which is subsequently reacted with a (meth) acrylate, such as 2-hydroxyethyl (meth) acrylate. These types of reactions can be carried out at room temperature or at higher temperatures, optionally in the presence of catalysts, such as tin catalysts, tertiary amines and the like.
[082] The polyisocyanates that can be used to form the isocyanate-functionalized urethane prepolymers can be any organic isocyanate having at least two free isocyanate groups. Aliphatic, cycloaliphatic, aromatic and araliphatic isocyanates are included.
[083] Any of the known polyisocyanates, such as alkyl and alkylene polyisocyanates, cycloalkyl and cycloalkylene polyisocyanates and combinations such as alkylene and cycloalkylene polyisocyanates can be used.
[084] Preferably, diisocyanates having the formula X (NCO) 2 are used where X represents an aliphatic hydrocarbon radical with 2 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical with 5 to 18 carbon atoms, a hydrocarbon radical aromatic with 6 to 16 carbon atoms or an araliphatic hydrocarbon radical with 7 to 15 carbon atoms.
[085] Examples of suitable polyisocyanates include 2,2,4-trimethylhexamethylene-1,6-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), cyclohexyl-1,4-di -isocyanate, 4,4'methylene-bis (cyclohexylisocyanate), 1,1'-methylenebis (4-isocyanate) cyclohexane, isophorone diisocyanate, 4,4'-methylene diphenyl diisocyanate, 1 , 4-tetramethylene diisocicanate, meta- and para-tetramethylxylene diisocicanate, 1,4-phenylene diisocicanate, 2,6-and 2,4-toluene diisocicanate, 1,5-naphthylene diisocyanate, 2,4 'and 4,4-diphenylmethane diisocicanate and mixtures thereof.
[086] It is also possible to use higher functional polyisocyanates known from the chemistry of polyurethanes or other modified polyisocyanates, for example, containing carbodiimide groups, allophanate groups, isocyanurate groups and / or biuret groups. Particularly preferred isocyanates are isophorone diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and higher functional polyisocyanates with isocyanurate structure.
[087] The isocyanate-terminated urethane compound is blocked with a (meth) acrylate to produce a urethane (meth) acrylate compound. In general, any blocking agent of the (meth) acrylate type having a terminal hydroxyl group and also having an acrylic or methacrylic moiety can be used, preferably the methacrylic moiety.
[088] Examples of suitable blocking agents include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate and / or trimethylolpropane di (meth) acrylate. Particularly preferred are 2-hydroxyethyl methacrylate (HEMA) and 2-hydroxyethyl acrylate (HEA).
[089] The equivalent ratio between isocyanate groups and reactive compounds vis-à-vis isocyanate groups is 1.1: 1 to 8: 1, preferably 1.5: 1 to 4: 1. The polyaddition reaction of isocyanate can take place in the presence of known catalysts from polyurethane chemistry, for example, organotin compounds, such as benzyl tin or amine dilaurate catalysts, such as diazabicyclo [2.2.2] octane. In addition, the synthesis can take place in the molten material or in a suitable solvent, which can be added before or during the preparation of the prepolymer. Suitable solvents are, for example, acetone, 2-butanone, tetrahydrofuran, dioxane, dimethylformamide, N-methyl-2-pyrrolidone (NMP), ethyl acetate, ethyl and propylene glycol alkyl ethers and aromatic hydrocarbons. The use of ethyl acetate as a solvent is particularly preferred.
[090] Suitable examples of urethane (meth) acrylates include 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diaza-hexadecane-1,16-dioxo-dimethacrylate (for example, Plex 666-1, Rohm), 7,7,9-trimethyl-4,13-dioxo-5,12-diaza-hexadecane- 1,16-dioxy-dimethacrylate (UDMA), urethane (methacrylates) derived from 1 , 4 and 1,3-Bis (1-isocyanate-1-methylethyl) bezene (for example, as described in EP 0934926 A1) and mixtures thereof.
[091] According to one embodiment, the hardenable component (A1) can be characterized as follows: structure A - (- S1-U-S2-MA) n, withA being a connector element comprising at least one unit, S1 being a spacer group comprising at least 4 units connected to each other, S2 being a spacer group comprising at least 4 units connected to each other, the units of A, S1 and S2 being independently selected from CH3-, -CH2-, -O-, - S-, -NR1-, -CO-, -CR1 =,
with R1 and R2 independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, cycloalkyl, substituted cycloalkyl, arylalkyl, aria or substituted aryl, and these units can form linear, branched or cyclic structures, such as alkyl, cycloalkyl, ester aryl groups, urethane or amide, U being a urethane group that connects the spacer groups S1 and S2, MA being an acrylate or methacrylate group and being 3 to 6.
[092] According to one embodiment, the curable component (A1) of the composition can be presented by structure A - (- S1-U-S2-MA) n with A being a connector element comprising at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 units, S1 being a spacer group comprised of units connected to each other and comprising at least about 4, 5, 6, 7, 8, 9 or 10 units, S2 being a spacer group comprised of units connected to each other and comprising at least about 4, 5, 6, 7, 8, 9, 10, 12, 15, 20 or 25 units, U being a urethane group that connects the spacer groups S1 and S2, MA being an acrylate or methacrylate group and n being about 3 to 6 or about 4 to 6 or about 5 to 6.
[093] This may be preferable, if A has a cyclic structure and comprises at least about 6 units.
[094] This may still be preferable, if S1 has a linear or branched structure and comprises at least about 4 or about 6 units.
[095] This may still be preferable, if S2 has a linear or branched structure and comprises at least about 6 or about 8 units.
[096] A hardenable compound (A1) may also be preferred where A has a cyclic structure and comprises at least about 6 units and S1 has a linear structure and comprises at least about 4 units and S2 has a linear structure and comprises at least about 8 units and U is a urethane group.
[097] None of the atoms of the urethane group connecting S1 or S2 or the atoms of the (meth) acrylic group belong to the spacer group S1 or S2. Thus, the atoms of the urethane group do not count as units of the spacer groups S1 or S2.
[098] The nature and structure of the connector element are not particularly limited. The connector element can contain saturated (no double bonds) or unsaturated (at least one or two double bonds), aromatic or heteroaromatic units (aromatic structure containing atoms including N, O and S).
[099] Specific examples of connector element A having a cyclic structure include:

[0100] Specific examples of connector element A having a non-cyclic but branched structure include:


[0101] The dotted lines indicate the connections to the spacer group S1.
[0102] The nature and structure of the spacer groups S1 or S2 are also not particularly limited.
[0103] Spacer groups are comprised of units connected with each other. Typical units include: CH3-, -CH2-, -O-, -S-, -NR1-, -CO-, - CR1 =,
-N =, -CR1R2-, with R1 and R2 independently selected from hydrogen, alkyl, substituted alkyl. alkenyl, cycloalkyl, substituted cycloalkyl, arylalkyl, aryl or substituted aryl.
[0104] These units can form linear, branched or cyclic structures, such as alkyl, cycloalkyl, aryl, ester, urethane or amide groups.
[0105] The structure of S1 can be identical to the structure of S2. However, in some modalities, the structure of S1 is different from S2. In a specific modality, the number of units present in S1 is less than or equal to the number of units present in S2.
[0106] In a specific modality, S1 may have saturated hydrocarbon.
[0107] In another specific modality, S2 may have saturated hydrocarbon. include:
[0108] Typical examples of spacer groups useful for S1 include:

[0109] The dotted lines indicate the chemical bond to group A or to group U.
[0110] Typical examples of spacer groups useful for S2 include:

[0111] The dotted lines indicate the chemical bond to the (meth) acrylate group or to the U group. The number of units to be counted according to the invention is given in brackets.
[0112] Specific examples of hardenable component (A1) include:

[0113] Suitable additional urethane (meth) acrylates are based on, w-terminated poly (meth) acrylates (as described in EP 1242493 B1) or may be a polyester, polyether, polybutadiene or urethane (meth) acrylate polycarbonate (for example , as described in US 6936642 B2).
[0114] The curable component (A1) is typically present in an amount of at least about 1 or at least about 3 or at least about 4.5% by weight with respect to the weight of the entire composition.
[0115] The curable component (A1) is typically present in an amount of at most about 20 or at most about 15 or at most about 10% by weight with respect to the weight of the entire composition.
[0116] Thus, the curable component (A1) is typically present in an amount of about 1 to about 20, or about 3 to about 15, or about 4.5 to about 10% in weight with respect to the weight of the entire composition.
[0117] It has been found that the use of a curable urethane (meth) acrylate component and more particularly, of the components described above, is beneficial in providing the curable composition with sufficient flexibility and functions as a type of toughness agent useful for improving toughness fracture of the cured dental composition.
[0118] The dental composition comprises at least one curable component (A2) which is a radical polymerizable methacrylate with a functionality of at least 2. The curable component (A2) is different from the component (A1, for example, with respect to functionality, chemical moieties, molecular weight, or combinations thereof.The hardenable component (A2) typically does not comprise a urethane moiety.
[0119] If desired, the dental composition can comprise at least two, three, or four different types of curable component (A2). The molecular weight of the curable component (A2) is at least about 170 or at least about 200 or at least about 300 g / mol.
[0120] The molecular weight of the curable component (A2) is typically in the range of about 170 to about 3,000, or from about 200 to about 2,500 or from about 300 to about 2,000 g / mol.
[0121] The hardenable component (A2) has radically free active functional groups and includes monomers, oligomers and polymers having two or more ethylenically unsaturated groups.
[0122] Such polymerizable materials via free radicals include di- or poly-acrylates and methacrylates, such as glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propan diacrylate , 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanotriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetra-acrylate, pentaerythracrylate hexane, pentaerythracrylate hexagon , bis [1- (2-acryloxy)] - p-ethoxyphenyldimethylmethane, bis [1- (3-acryloxy-2-hydroxy)] - p-propoxyphenyldimethylmethane; the bis-acrylates and bis-methacrylates of poly (ethylene glycols) of molecular weight 200 to 500, copolymerizable mixtures of acrylated monomers such as those in US 4,652,274, and acrylated oligomers, such as those of US 4,642,126; and vinyl compounds such as diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate.
[0123] Preferred ethylenically unsaturated monomers are methacrylate and acrylate monomers, such as propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol, ethyl (poly) glycol di (meth) acrylates, poly (glycyl) acrylates and poly (propylene glycols), bisphenol A ethoxylate di (meth) acrylates, for example, 2,2'-bis (4- (meth) acryloxytetraethoxyphenyl) propanes, and (meth) acrylamides. The monomers used can additionally be esters of [alpha] -cyanoacrylic acid, crotonic acid, cinnamic acid and ascorbic acid.
[0124] It is also possible to use the methacrylic esters mentioned in EP 0235826, such as [3 [4] -methacryl-oxymethyl-8 (9) -tricycle [5.2.1.02,6decylmethyl triglycolate]. Particularly suitable are 2,2-bis-4 (3-methacryloxy-2-hydroxypropoxy) phenylpropane (Bis-GMA), 2,2-bis-4 (3-methacryloxypropoxy) phenylpropane, triethylene glycol dimethacrylate (TEGDMA), and di (meth) acrylates of bishydroxymethyltricyclo (5.2.1.02,6) decane.
[0125] It has been found that the use of a curable component (A2) and, more particularly, of the components described above, can be beneficial in providing the cured composition with sufficient mechanical strength since it can function as a type of crosslinking agent useful to improve the mechanical properties of the cured dental composition.
[0126] The curable component (A2) is typically present in an amount of at least about 5 or at least about 10 or at least about 15% by weight with respect to the weight of the entire composition.
[0127] The curable component (A2) is typically present in an amount of at most about 60 or at most about 50 or at most about 45% by weight with respect to the weight of the entire composition.
[0128] Thus, the curable component (A2) is typically present in an amount of about 5 to about 60, or about 10 to about 50, or about 15 to about 45% by weight with respect to the weight of the entire composition. The dental composition described in this text comprises components or systems that initiate redox or dark curing.
[0129] A class of initiators capable of initiating the polymerization of radically free functional groups includes conventional chemical initiator systems such as a combination of an organic peroxide and an amine. These initiators, which depend on a redox reaction, are often called "self-healing catalysts". They are typically supplied as two-part systems in which the reagents (reducing and oxidizing agents) are stored separately from one another and then combined immediately before use.
[0130] In another alternative, heat can be used to initiate the hardening, or polymerization, of the radically free active groups. Examples of suitable heat sources for the dental materials of the invention include inductive, convective and radiant. Thermal sources must be capable of generating temperatures of at least 40 ° C to 150 ° C under normal conditions. This procedure is preferred to initiate the polymerization of materials that occurs outside the oral environment.
[0131] Organic peroxide compounds together with so-called activators are also suitable as initiators of the redox system. In particular, compounds, such as lauroyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide and p-methylbenzoyl peroxide, can be considered as organic peroxide compounds.
[0132] Suitable as activators are, for example, tertiary aromatic amines, such as the N, N-bis- (hydroxyalkyl) -3,5-xylidines known from US 3,541,068 as well as N, N-bis- (hydroxyalkyl) - 3,5-di-t-butylanilines, in particular N, N-bis - ([beta] - oxybutyl) -3,5-di-t-butylaniline as well as N, N-bis- (hydroxyalkyl) -3,4 , 5-trimethylaniline.
[0133] The most suitable activators are also barbituric acids and barbituric acid derivatives as described in US 2003/008967, DE 14 95 520 as well as malonyl sulfamides described in US 4,544,742 (which corresponds to EP 0 059 451 ). Preferred malonyl sulfamides are 2,6-dimethyl-4-isobutylmalonyl sulfamide, 2,6-diisobutyl-4-propylmalonyl sulfamide, 2,6-dibutyl-4-propylmalonyl sulfamide, 2,6-dimethyl-4- sulfamide ethylmalonyl and 2,6-dioctyl-4-isobutyl malonyl sulfamide. For further acceleration, polymerization is preferably carried out in the presence of heavy metal compounds and ionogenic or pseudo-halogen halogen.
[0134] Heavy metal is suitably used in the form of soluble organic compounds. Similarly, halide and pseudohalide ions are suitably used in the form of soluble salts, as examples, they can be called soluble amine hydrochlorides, as well as quaternary ammonium chloride compounds. Suitable accelerators are in particular metals from the iron or copper group, preferably copper and iron complexes, and in particular copper complexes. The heavy metal is preferably used in the form of soluble organic compounds. Suitable are, for example, iron carboxylates, copper carboxylates, iron procetonate, copper procetonate, copper naphthenate, copper acetate and iron naphthenate.
[0135] Additional suitable redox initiation systems are described in G. Misra et al., Prog.Polym.Sci. Vol. 8, p. 61-131 (1982). For life reasons, the curing components of the initiation system require separate storage of oxidizing and reducing agents. Therefore, the dental composition described in this text is typically provided as a two-part system.
[0136] Some components of the dark curing system (hereinafter called (X)) are contained in the base part or paste of a kit of parts, some components of the dark curing system (hereinafter called (Y)) are contained in the catalyst part or paste of a parts kit.
[0137] Typical examples of dark curing initiator components (X), contained in a base part, include amine hydrochlorides (eg, dibutylphenylethylamine hydrochloride) and components containing copper (eg, copper (II) bis ( 1-phenylpentan-1,3-dione)). Typical examples of scrubbing initiator components (Y), contained in a part catalyst base, include components comprising a barbituric acid moiety (eg, 1-benzyl-5-phenylbarbituric acid) and malonyl sulfamides, peroxides (eg tert - butylperoxy-3,5,5-trimethylhexanoate).
[0138] In addition to the dark curing initiator component, the dental composition described in this text may also contain, in addition, curing initiator components by the action of visible light, if desired.
[0139] Such primers may typically be able to generate free radicals for polymerization upon exposure to light energy that has a wavelength between about 400 and about 800 nm. Examples of visible light curing initiator components include, for example, systems based on an amine and an α-diketone. Suitable systems are described, for example, in US 4,071,124 and WO 2009151957. The content of these references is hereby incorporated by reference.
[0140] The dental composition may additionally comprise at least one or all of the following components: • plasticizer, • particles visible on X-rays, • additives.
[0141] The addition of a plasticizer component is optional.
[0142] Plasticizers that can be added typically include components without polymerizable portions. Examples of useful plasticizers include poly (ethylene glycol) derivatives, poly (propylene glycols), dibutyl, dioctyl, dinonyl, and diphenyl phthalates, adipinic, sebacinic and citric acid esters, phosphates such as tricresyl phosphate, paraffin oils, triacetate glycerol, bisphenol A ethoxylated and propoxylated diacetate, and silicone oils, and mixtures thereof.
[0143] The molecular weight of the plasticizer is typically in the range of about 200 to about 2,500, or about 300 to about 2,000 g / mol. If present, plasticizers are typically present in an amount of about 0.1 to about 10, or about 0.5 to about 7.5, or about 1 to about 5% by weight with respect the weight of the entire composition. The use of a plasticizer can typically facilitate the formulation of the composition, particularly if the composition is to be supplied in the form of a paste.
[0144] The addition of particles visible on the X-ray to the dental composition is beneficial in that it allows the dental professional to better identify the dental material in a patient's mouth and be able to distinguish between the dental structure of the healthy tooth and the dental material. dental restoration. Dental material becomes radiopaque.
[0145] The radiopacity of a dental material is advantageous in certain instances where X-rays are used to diagnose a dental condition. For example, a radiopaque material would allow the detection of secondary caries that could form in the dental tissue that surrounds a filling. The desired degree of radiopacity can be varied, depending on the particular application and the expectations of the professional who evaluates the film for X-rays.
[0146] Particles visible on X-rays include particles of metal oxides and metal fluorides. Heavy metal oxides or fluorides having an atomic number greater than about 28 may be preferred. The heavy metal oxide or fluoride can be chosen in such a way that shading or unwanted colors are not imparted to the tempered resin in which it is dispersed. For example, iron and cobalt would not be favored, as they impart contrasting and dark colors to the neutral tooth color of dental material. Most preferably, heavy metal oxide or fluoride is a metal oxide or fluoride that has an atomic number greater than 30. Suitable metal oxides are the oxides of elements of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanide (that is, elements that have atomic numbers in the range 57 to 71, inclusive), cerium and combinations thereof. Suitable metal fluorides are, for example, yttrium fluoride and ytterbium fluoride. Most preferably, heavy metal oxides and fluorides that have an atomic number greater than 30 but less than 72, are optionally included in the materials of the invention. Particularly, the preferred radiopacifying metal oxides include lanthanum oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, cerium oxide and combinations thereof. Other fillers suitable for increasing radiopacity are barium and strontium salts, especially strontium sulfate and barium sulfate. The surface of the heavy metal oxide or metal fluoride particles can be treated.
[0147] The average particle size of particles visible in X-rays (in non-aggregated state) is typically in a range of about 20 to about 500 or about 50 to about 300 nm. If present, X-ray visible particles are typically present in an amount of about 0.1 to about 15, or about 1 to about 10, or about 2 to about 5% by weight with respect to the weight of the entire composition.
[0148] Additional additives, which can be optionally added, include retarder (s), antimicrobial (s), pigment (s), dye (s), photobleaching color (s), stabilizer (s), and fluoride release.
[0149] Examples of pigment (s) and dye (s) that can be used include titanium dioxide or zinc sulfide (lithopones), red iron oxide 3395, Bayferrox 920 Z yellow, Neazopon blue 807 (phthalocyanine based dye copper) or Helio Fast yellow ER. These additives can be used for individual staining of dental compositions.
[0150] Examples of photodegradable dyes that may be present include cane rose, methylene violet, methylene blue, fluorescein, eosin yellow, eosin Y, ethyl eosin, eosin blue, eosin B, erythrosine B, yellowish erythrosine blend , toluidine blue, 4 ', 5'-dibromofluorescein and mixtures thereof. Additional examples of photodegradable dyes can be found in US Patent No. 6,444,725. The color of the compositions of the invention can be additionally imparted by means of a sensitizing compound.
[0151] Examples of fluoride releasing agents that may be present include naturally occurring minerals or synthetic fluoride. These fluoride sources can optionally be treated with surface treatment agents. Additional additives that can be added include stabilizers, especially free radical scavengers such as substituted and / or unsubstituted hydroxy aromatics (eg, butylated hydroxytoluene (BHT), hydroquinone, hydroquinone monomethyl ether (MEHQ), 3,5-di- tert-butyl-4-hydroxyanisole (2,6-di-tert-butyl-4-ethoxyphenol), 2,6-di-tert-butyl-4- (dimethylamino) methylphenol or 2,5-di-tert-butyl- hydroquinone, 2- (2'-hydroxy-5'-methylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzophenone (UV- 9), 2- (2'-hydroxy-4 ', 6'-di-tert-pentylphenyl) -2H-benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'-hydroxy-5'- methacryloxyethylphenyl) ) -2H-benzotriazole, phenothiazine and HALS (hindered amine light stabilizers), such auxiliary compounds may optionally comprise reactive moieties, so that they will be copolymerized with the resin.
[0152] A suitable retarder is, for example, 1,2-diphenylethylene. Additional additives, which can be added, include absorbents, emulsifiers, antioxidants, and wetting agents. There is no need for these auxiliary compounds or additives to be present, so auxiliary compounds or additives may not be present in any form. However, if present, they are typically present in an amount that is not detrimental to the intended purpose.
[0153] Useful amounts of additives include: • at least about 0.1% by weight, or at least about 0.5% by weight, or at least about 1% by weight, and / or • up to about 15% by weight or up to about 10% by weight or up to about 5% by weight.
[0154] Typical ranges include from about 0.1% to about 15% by weight, or from about 0.5% to about 10% by weight, or from about 1% by weight, to about 5% by weight.
[0155] All components used in the dental composition described in this text must be sufficiently biocompatible, that is, the composition must not produce a toxic, harmful or immunological response in living tissue. The composition described in this text typically does not comprise components selected from the polymerizable component comprising an acidic group, for example, in an amount above about 5% by weight, monofunctional (meth) acrylates, for example, in an amount above about 5% by weight, the solvent, for example in an amount above about 5% by weight, the acid reactive filler, for example in an amount above about 5% by weight, the filler particles having a size particle average of about 1 to about 100 pm, for example, in an amount above about 10% by weight or above about 5% by weight, the non-agglomerated, nanodimensioned fillers, for example, in an amount above about 10% by weight or above about 5% by weight, and mixtures thereof.
[0156] That is, these components are not typically intentionally added and therefore are not present in an amount above about 10 or above about 8 or above about 5 or above about 2% by weight with respect to the weight of the entire composition.
[0157] However, depending on the raw materials chosen, it can sometimes be inevitable that the composition contains traces of any of the above components.
[0158] Examples of acid reactive fillers that typically are not present include fluoroaluminassilicate glasses (sometimes also called GIZ glasses), hydroxides, oxides and carbonates of alkaline earth metals such as Ca (OH) 2, Mg (OH) 2, CaO, MgO, CaCO3, MgCO3.
[0159] The addition of filler having an average particle size in the range mentioned above in an amount above about 10% by weight can negatively influence properties such as polishability and gloss retention.
[0160] Examples of such types of fillers include fluoroaluminosilicate glasses, quartz, ground glass, non-water-soluble fluorides, such as CaF2, cristobalite, calcium silicate, zeolites, including molecular sieves, metal oxide powders, such as aluminum or zirconia or mixtures of its oxides, barium sulfate, calcium carbonate. The addition of such a filler in a high amount can negatively influence the aesthetic properties of the hardened dental composition.
[0161] Examples of solvents that are typically not present include saturated or unsaturated, linear, branched or cyclic alcohols, ketones, esters or mixtures of two or more of said types of solvents with 2 to 10 atoms, such as methanol, ethanol, iso- propanol, n-propanol, THF, acetone, methyl and ethyl ketone, cyclohexanol, toluene, alkanes and alkyl esters of acetic acid.
[0162] The dental composition described in this text may contain the components in the following amounts: • filler (F1): from about 30 to about 70% by weight, or from about 35 to about 60% by weight, • filler (F2): from about 1 to about 20% by weight or from about 3 to about 15% by weight, • hardenable component (A1): from about 1 to about 20% by weight, or about 3 to about 15% by weight, or from about 4.5 to about 10% by weight, • hardenable component (A2): from about 5 to about 60% by weight, or about 10 to about 50% by weight, or from about 15 to about 45% by weight, • dark curing initiator components: from about 0.1 to about 5% by weight, or about 0.3 to about 4% by weight, or from about 0.5 to about 3% by weight, • plasticizer: from about 0.1 to about 10% by weight, or from about 0.5 to about 7.5% by weight, or from about 1 to about 5% by weight, • X-ray visible particles: from about 0.1 to about 15% by weight, or about 1 to about 10% by weight, or from about 2 to about 5% by weight, • additives: from about 0.1 to about 15% by weight, or from about 0.5 to about 10 % by weight, or from about 1 to about 5% by weight, percentage by weight with respect to the weight of the entire composition.
[0163] The composition described in this text is typically provided as a two-part system.
[0164] One part is typically called the base part, while the other part is typically called the catalyst part. After combining the two parts, a curing composition is obtained.
[0165] If the individual parts are supplied in the form of paste, the viscosity of the individual pastes is typically in a range of about 1 to about 100 Pa.s or about 10 to about 75 Pa (measured at 23 ° C, shear rate of 30 1 / s using a Physica rheometer).
[0166] Thus, according to an additional modality, the dental composition is provided as a kit of parts comprising a base part (A) and a catalyst part (B), the base part (A) comprising: -fill ( F1) in an amount of about 30 to about 70% by weight, -filling (F2) in an amount of about 1 to about 20% by weight, -hardener component (A1), -hardener component (A2) , -dark curing initiator component (s) (X), weight percentage with respect to the weight of the base part, the catalyst part (B) comprising: -filling (F2), -initiator component (s) ( dark cure (Y), dark cure initiator component (s) (X) and dark cure initiator component (s) (Y) forming a redox initiator system.
[0167] According to an additional embodiment, the dental composition described in this text is described as a kit of parts comprising a base part (A) and a catalyst part (B), the base part (A) comprising: -filling (F1) in an amount of about 30 to about 70% by weight, -filling (F2) in an amount of about 1 to about 20% by weight, -hardenable component (A1) in an amount of about 1 to about 20% by weight, - curable component (A2) in an amount of about 5 to about 60% by weight, - dark curing initiator component (s) (X), percentage by weight with respect to the weight of the base part, and a catalyst part (B) comprising: -filling (F2 of about 1 to about 20% by weight) -dark curing initiator component (s) (Y) , percentage by weight with respect to the weight of the catalyst part, the dark curing initiator component (s) (X) and the dark curing initiator component (s) (Y) forming a redox initiator system .
[0168] According to an additional embodiment, the dental composition is provided as a kit of parts comprising a base part (A) and a catalyst part (B), -base part (A) comprising: -fill in (F1) in an amount of about 30 to about 70% by weight, -fill (F2) in an amount of about 1 to about 20% by weight, -hardener component (A1), -hardener component (A2), -component dark curing initiator (s) (X), percentage by weight relative to the weight of the base part, the catalyst part (B) comprising: -filling (F1) in an amount of about 30 to about 70 % by weight, -fill (F2) in an amount of about 1 to about 20% by weight, -durable component (A1), -durable component (A2), - curing initiator component (s) in the dark (Y), weight percentage with respect to the weight of the catalyst part, the dark curing initiator component (s) (X) and the dark curing initiator component (s) (Y) forming an early system redox cooler, base part A or catalyst part B do not comprise any of the following components: -polymerizable component comprising an acid group above about 5% by weight, - monofunctional (meth) acrylates above 5% by weight, -solvent an amount above about 5% by weight, - acid reactive filler above about 5% by weight, - filler particles having an average particle size of about 1 to about 100 pm, in an amount above about 10% by weight.
[0169] In addition to filler and dark curing initiator component, the catalyst part (B) optionally contains a plasticizer to facilitate the production of a paste. The plasticizers that can be used are described above.
[0170] In certain embodiments, the curable composition of redox reaction or curable in the dark satisfies at least one or more, sometimes all of the following parameters: • working time: from about 30 sec to about 1.5 min, or about 45 sec to about 1 min, • hardening time: about 2.5 to about 6 min, or about 3 to about 5 min, • flexural strength after curing: about 50 to about 200 MPa (measured according to ISO 4049), • fracture work after curing: from about 5 to about 15 KJ / m2, • impact resistance after curing: from about 5 to 15 KJ / m2 (measured according to ISO 179-1), • abrasion after curing: less than about 20 or less than about 15 or less than about 10 mm3 (measured as described in the Examples section) .
[0171] In certain modalities, the combination of the following characteristics is desirable: high flexural strength, high fracture work, and low abrasion. If desired, the characteristics above can be determined as described in the Examples section above.
[0172] The composition described in this text can be produced by mixing its respective components. Mixing is typically done using mechanical equipment, which includes a speed mixer or dissolver available from, for example, Hauschild + Co KG, Germany. The filler components are usually incorporated as powders or particles. If desired, the filler component (s) can be dispersed in a liquid component of the first composition.
[0173] In a further aspect, the invention relates to a kit of parts comprising the dental composition described in this text, supplied in a paste or paste form and filled in the chambers of a double chamber cartridge or two individual syringes, and at least one or all of the following parts: • dental impression material, • dental cement, • adhesive.
[0174] During use, the dual chamber cartridge is typically equipped with a static mixing tip and acts as a medium for mixing and application. The volume ratio between the chamber (I) and the chamber (II) is typically in the range of about 1: 1 to about 20: 1, specifically preferred 1: 1 to about 10: 1. Useful cartridges are described in 2007/0090079 or US 5,918,772, their disclosure is hereby incorporated by reference. The cartridges that can be used are commercially available from SulzerMixpac AG (Switzerland). Useful static mixing tips are described in 2006 / 0187752 or US 5,944,419, the disclosure of which is hereby incorporated by reference. Mixing tips that can be used are commercially available from SulzerMixpac AG (Switzerland).
[0175] Due to the chosen formulation, the dental composition described in this text can be easily mixed and released from a double chamber cartridge known in the art using a manually operated gear. Alternatively, but less preferably, the paste / paste composition described in this text can be supplied in two individual syringes and the individual pastes can be mixed manually before use. If desired, to determine whether the extrusion forces that need to be applied are in an acceptable range, the following test can be performed:
[0176] A double chamber cartridge having a volume of 50 ml (volume ratio from 1: 1 to 10: 1) containing the catalyst and the base paste is equipped with a mixing tip (Sulzer Mixpac) in a plunger and then placed on a support of a universal testing machine (Zwick Z 010) equipped with a 10 kN load cell. A propellant is placed in such a way that it exerts a force on the propeller drive plate in order to extrude the dental composition. The speed of the propellant is set at 25 mm / min. If a force of> 2 N (textXpert V 8.1 software) is registered, data recording begins. The measurement is completed when the drive / propeller plate has moved a total of 20 mm forward in the cartridge. An extrusion force below about 1000 N or below about 800 N or below about 600 N is considered acceptable. If the extrusion forces extend over a certain volume, the composition cannot be expressed properly or mixed using a manually operated self-mixing system.
[0177] Examples of dental impression materials that can be used include alginate (s) based materials, polyether technology, add-curable silicone materials (eg VPS materials) and condensation-curable silicone materials.
[0178] Addition-curable silicone materials and add-curable polyether materials are sometimes preferred due to their better performance and greater accuracy.
[0179] Dental impression material is typically characterized by at least one, more or all of the following characteristics: • Consistency (according to ISO 4823): 0,1,2,3, • Hardening time: in about 15 min after mixing under ambient conditions (eg 23 ° C), • Shore A hardness (according to ISO 4823; 24h): at least about 20 or at least about 40, • Flexural strength (according to DIN 53504): at least about 0.2 MPa or at least about 3.0 MPa, • Elongation at break (according to ISO 53504): at least about 30% or at at least about 150% or at least about 200%, • Recovery from deformation (according to ISO 4823): at least about 90% or at least about 95% or at least about 98%.
[0180] Materials for dental impression are also described in EP 2,072,029 B1, US 6,677,393, EP1 512 724 B1, US 6,127,449, WO 2008/014224 and US 5,569,691. The content of these references is hereby incorporated by reference. Dental impression materials are available for sale from, for example, 3M ESPE under the trademarks Impregum ™ or Imprint ™. The fixation of the hardened dental composition to the surface of a dental structure to be restored is typically done with the use of a dental adhesive / or cement.
[0181] The nature and properties of the adhesive and / or dental cement are not particularly limited, unless the desired result cannot be achieved. Especially preferred are self-adhesive dental resin adhesives and cements. The adhesive or self-adhesive dental resin cement systems typically include a polymerizable monomer, an acidic component that optionally comprises a polymerizable portion, a filler, optionally a basic filler and a redox initiator system.
[0182] Suitable cements are also described in WO 2007/140440 (A2), US 2010/0016466, US 2004/0110864. The content of these references is hereby incorporated by reference. The adhesive and self-adhesive dental resin cements are available for sale, for example, from 3M ESPE under the trademarks RelyXM Unicem, or RelyX ™ Ultimate.
[0183] The dental compositions described in this text are particularly useful as long-lasting or permanent crown or bridge materials. The material for long-lasting crowns and bridges can be placed directly in the mouth and cured (hardened) locally, or alternatively, it can be manufactured in a prosthesis outside the mouth and subsequently placed in the mouth.
[0184] Dental compositions can also be used to produce inlays, onlays, veneers or as bulk material. In another aspect, the invention relates to a method of producing a long-lasting or permanent bridge or crown, the method comprising the steps of placing the composition as described in the present text in the molds of a hardened dental impression material. The dental impression material can be an alginate, a silicone (VPA) or a polyether dental impression material.
[0185] Alginate dental impression materials available for sale include Palgat ™ (3M ESPE). Silicone dental impression materials available for sale include Express ™, Imprint ™ and Position ™ (3M ESPE). Polyether dental impression materials available for commercialization include Impregum ™ (3M ESPE).
[0186] A typical process in dental practice comprises one or more steps of: 1. making an impression of the rigid dental structure to be restored using a dental impression material, thereby obtaining a negative impression of the dental structure, 2. waiting until the dental impression material hardens, 3.remove the hardened dental impression material from the rigid dental structure, 4.put the curable composition described in this text into the negative impression of the dental impression material, 5.reposition the filled negative impression in the dental structure to be restored, 6. wait until the curable composition is at least partially cured, so that the composition can be removed from the dental structure to be restored without leaving residues of the composition in the prepared or formatted dental structure, 7.remove the cured composition of the hardened impression material, 8. adhesively fix the removed composition to the dental structure to be restored using a dental cement.
[0187] The full description of the patents, patent documents and publications cited in the present disclosure are hereby incorporated, in their entirety, as a reference as if each were individually incorporated.
[0188] The following examples are intended to illustrate the invention. Examples
[0189] Except where otherwise noted, all parts and percentages are weight based, all water is deionized water and all molecular weights are weight average molecular weights. In addition, except where otherwise indicated, all experiments were conducted under ambient conditions (23 ° C; 101.3 kPa (1013 mbar). Measurements Flexural strength and fracture work
[0190] Flexural strength was determined by performing a three-point flexural strength test, according to ISO 4049 using test samples having a size of 2 * 2 * 25 mm. Based on the data obtained, the fracture work can be calculated. The fracture work is given in [kJ / m2]. The flexural strength is given in MPa. Abrasion
[0191] Abrasion [mm3] was measured as follows:
[0192] Abrasion tests were carried out on specific samples with a slope of 30 °. For that purpose, the materials were filled in the depression of inbus screws (with hexagonal head) M12 and cured according to the manufacturer's instructions.
[0193] The samples were ground using a 75 pm diamond saw and stored in distilled water for 4 days at 36 ° C. Then, the chewing simulation started under the following conditions:
[0194] Chewing force: 80 N; Lateral movement: 4 mm; Sliding movement: 10 mm; Antagonist: soapstone ball; Number of chewing cycles: 1,200,000; Thermocycles (5/55 ° C): 5,000.
[0195] After the mastication simulation, the abrasion was determined by measuring the volume loss with the use of VK-X200 laser scanning microscopy (Keyence Company).
[0196] Additional information on the abrasion test can be found in M. Rosentritt et al., Materialprüfung 39 (1997), p. 77-80. Compositions AbbreviationsTable 1
Typical syntheses of aggregate fillings (F1):
[0197] The nano-aggregated Zr / Si filling was produced as described in 6,730,156 B1, column 25, preparatory example A. The surface of the filler particles was treated according to a process as described in preparatory example B US 6,730,156 B1. General process for producing dental composition
[0198] The respective components were mixed using a speed mixer (Hasschild). The base paste and the catalyst paste were placed in a double chamber cartridge (SulzerMixpac). In the cartridge, an ecstatic mixing tip (SulzerMixpac) was assembled and the composition dispensed with the use of a manually driven gear. The mixing ratio between the base paste and the catalyst paste was 10: 1 for Examples 1 and 2 and Comparative Examples 1 to 3 and 1: 1 for Example 3. The properties of the cured pastes were analyzed. The results are given in Table 8. Example 1: Table 2
Comparative example 1: (Use of non-agglomerated nano-fillers) Table3

Comparative example 2: (Use of non-agglomerated nanoparticles in a larger amount compared to Comparative Example 1) Table4:
Example 2: Table 5

Comparative example 3: (Urethane (meth) acrylate free formulation) Table 6
Example 3: (formulation 1: 1) Table7
Table 8
Results:
[0199] Examples 1 to 3 showed high values of flexural strength and fracture work combined with low abrasion. The use of non-agglomerated nano-fillers in Comparative Example 1 also resulted in high fracture work but poor abrasion performance. The increase in non-agglomerated nano-fillers in Comparative Example 2 resulted in a formulation that, in contrast to Examples 1 to 3, could no longer be dispensed and mixed with a static mixer. Comparative Example 3 without urethane (meth) acrylate showed low mechanical properties and a low fracture work value that indicated a certain fragility.

权利要求:
Claims (13)
[0001]
1. Dental composition CHARACTERIZED by the fact that it comprises: filler (F1) comprising nanodimensioned aggregate particles in an amount of 30 to 70% by weight, filler (F2) comprising agglomerated particles nanodimensioned in an amount from 1 to 20% by weight, component hardenable (A1) which is a urethane (meth) acrylate with a functionality of at least 2 and which has a molecular weight of 400 to 3,000 g / mol, hardenable component (A2) which is a polymerizable (meth) acrylate via radical with functionality of at least 2 that is different from component (A1), redox curing initiator system, the dental composition not comprising nanodimensioned non-agglomerated filler in an amount above 10% by weight, weight percentage with respect to the weight of the entire composition; the hardenable component (A1) being selected from: compounds having structure A - (- S1-U-S2-MA) n A being a connector element comprising at least one unit, S1 being a spacer group comprising at least 4 units connected to each other, S2 being a spacer group comprising at least 4 units connected to each other, U being a urethane group that connects spacer groups S1 and S2, MA being an acrylate or methacrylate group, n being 3 to 6, the units of A, S1 and S2 being independently selected from CH3-, -CH2-, -O-, -S-, -NR1-, -CO-, -CR1 =,
[0002]
2. Dental composition, according to claim 1, CHARACTERIZED by the fact that the filling (F1) has at least one or all of the following characteristics: Specific surface: from 50 to 400 m2 / g, comprising particles selected from SiO2, ZrO2 and its mixtures.
[0003]
3. Dental composition, according to claim 1, CHARACTERIZED by the fact that the filling (F2) has at least one or all of the following characteristics: Specific surface: from 30 to 400 m2 / g, comprising particles selected from SiO2, ZrO2, Al2O3 and their mixtures.
[0004]
4. Dental composition according to claim 1, CHARACTERIZED by the fact that the hardenable component (A2) is selected from glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, diacrylate 1, diacrylate 3-propanediol, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanotriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tetramethacrylate, tetramethacrylate sorbitol hexacrylate, bis [1- (2-acryloxy)] - p-ethoxyphenyl-dimethylmethane, bis [1- (3-acryloxy-2-hydroxy)] - p-propoxyphenyldimethylmethane, bis-acrylates and di (meth) acrylates ethylene glycol, poly (ethylene glycol) and poly (propylene glycol) with molecular weight 200 to 500, bisphenol A di (meth) acrylates, ethoxylated 2,2'-bis (4- (meth) acryloxytetraethoxyphenyl) propanes, bis [ 3 [4] -methacryl-oxymethyl-8 (9) - tricycle [5.2.1.02,6] decylmethyl, 2,2-bis- 4 (3-methacryloxypropoxy) phenylpropane, bis-hydroxymethyltricyclo (5.2.1.02,6) decane di (meth) acrylates and mixtures thereof.
[0005]
5. Dental composition, according to claim 1, CHARACTERIZED by the fact that the redox curing initiator system comprises components selected from peroxide (s), components comprising a portion of barbituric acid, malonyl sulfamide (s) and mixtures thereof.
[0006]
6. Dental composition according to claim 1, CHARACTERIZED by the fact that it additionally comprises at least one or all of the following components: plasticizer, particles visible in X-rays, pigments, additives selected from retarder (s), antimicrobial (s) ), stabilizer (s), fluoride release material (s), absorbent (s), emulsifier (s), antioxidant (s) and wetting agent (s) and mixtures thereof.
[0007]
7. Dental composition, according to claim 1, CHARACTERIZED by the fact that it comprises a plasticizer selected from component (s) containing a portion of poly (ethylene glycol), poly (propylene glycol), dibutyl phthalate (s), dioctyl, dinonyl , and diphenyl, adipinic, sebacinic and citric acid ester (s), paraffin oil (s), glycerol triacetate, ethoxylated and propoxylated bisphenol A diacetate, and silicone oil (s) and mixtures thereof.
[0008]
8. Dental composition, according to claim 1, CHARACTERIZED by the fact that the composition has at least one or all of the following parameters: working time: from 30 sec to 1.5 min, fixation time: from 2, 5 sec to 6 min, flexural strength after curing: 50 to 200 MPa, measured according to ISO 4049, fracture work after curing: 5 to 15 KJ / m2, impact resistance after curing: from 5 to 15 KJ / m2, measured according to ISO 179-1, abrasion after curing: less than 20 mm3.
[0009]
9. Dental composition according to claim 1, CHARACTERIZED by the fact that it does not comprise at least one or all of the following components: polymerizable component comprising an acid group in an amount above 5% by weight, monofunctional (meth) acrylates in an amount above 5% by weight, solvent in an amount above 5% by weight, acid reactive filler in an amount above 5% by weight, filler particles having an average particle size of 1 to 100 pm in one amount above 10% by weight.
[0010]
10. Dental composition, according to claim 1, CHARACTERIZED by the fact that: amount of filler (F1): from 30 to 70% by weight, amount of filler (F2): from 1 to 20% by weight, amount of hardenable component (A1): from 1 to 20% by weight, amount of hardenable component (A2): from 5 to 60% by weight, weight percentage with respect to the weight of the entire composition.
[0011]
11. Dental composition according to claim 1, CHARACTERIZED by the fact that it is supplied as a kit of parts comprising a base part (A) and a catalyst part (B), the base part (A) comprising : filler (F1) in an amount of 30 to 70% by weight, filler (F2) in an amount of 1 to 20% by weight, hardenable component (A1), hardenable component (A2), initiator component (s) ) dark curing (s) (X), weight percentage with respect to the weight of the base part, the catalyst part (B) comprising: filler (F2), dark curing initiator component (s) (Y), the dark curing initiator component (s) (X) and the dark curing initiator component (s) (Y) form a system redox initiator.
[0012]
12. Dental composition according to claim 1, CHARACTERIZED by the fact that it is supplied as a kit of parts comprising a base part (A) and a catalyst part (B), the base part (A) comprising : filler (F1) in an amount of 30 to 70% by weight, filler (F2) in an amount of 1 to 20% by weight, hardenable component (A1) in an amount of 1 to 20% by weight, hardenable component ( A2) in an amount of 5 to 60% by weight, dark curing initiator component (s) (X), weight percentage with respect to the weight of the base part, the catalyst part (B) comprising : filler (F1) in an amount of 30 to 70% by weight, filler (F2) in an amount of 1 to 20% by weight, dark curing initiator component (s) (Y), percentage by weight with respect to the weight of the catalyst part, the dark curing initiator component (s) (X) and the dark curing initiator component (s) ) (Y) forming a redox initiator system, the part of ba if (A) or the catalyst part (B) not comprising any of the following components: polymerizable component comprising an acid group above 5% by weight, monofunctional (meth) acrylates above 5% by weight, solvent in an amount above 5% by weight, acid reactive filler above 5% by weight, filler particles having an average particle size of 1 to 100 pm in an amount above 10% by weight, non-agglomerated nanodimensioned fillers in an amount above 10% in weight.
[0013]
13. Dental composition according to claim 1, CHARACTERIZED by the fact that R1 and R2 are each independently selected from the group consisting of alkyl, cycloalkyl, aryl, ester, urethane and amide groups.

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法律状态:
2018-01-23| B07D| Technical examination (opinion) related to article 229 of industrial property law|

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2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-05-15| B07B| Technical examination (opinion): publication cancelled|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-05-05| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-08-11| B09A| Decision: intention to grant|

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2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13175512|2013-07-08|

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EP13175512.6|2013-07-08|

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PCT/US2014/044985|WO2015006087A1|2013-07-08|2014-07-01|Hardenable dental composition containing a mixture of agglomerated and aggregated nano-particles, kit of parts and use thereof|

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