Dental hydraulic cement containing ultra-fine calcium silicate particles that rapidly harden and have suitable mechanical properties

Abstract

The present invention relates to the provision of dental restorative materials from dental hydraulic cements containing ultrafine calcium silicate (UCS) particles in the presence of limited amounts of water, which harden rapidly and provide materials with mechanical properties suitable for dental restorations, particularly high compressive strength.

Description

Technical Field

[0001] The present invention relates to the field of dentistry. In particular, the present invention provides a material that rapidly hardens and has mechanical properties suitable for dental restoration, particularly high compressive strength, obtained in the presence of a limited amount of water, and relates to the provision of a dental restorative material from a hydraulic cement for dentistry containing ultra-fine calcium silicate (UCS) particles. The UCS particles used in the hydraulic cement for dentistry of the present invention have finely adjusted d 10 , d 50 and d 90 sizes and specific surface areas.

Background Art

[0002] Dental restoration aims to restore the integrity and shape of teeth, including repairing the loss of calcified substances caused by caries or external trauma. Direct restoration is performed by placing a plastic filling material into the prepared tooth and then curing the material in situ.

[0003] Ideally, the restorative material should have several properties including appropriate adhesive ability, insolubility, dimensional stability, biocompatibility, bioactivity, and suitable mechanical properties. Various filling materials, particularly calcium silicate-based cements, are available.

[0004] The implementation of dental restorative materials often requires a first preparation step by the operator of the filling material and a subsequent in-situ curing period. This is particularly the case when using hydraulic dental cements, such as calcium silicate-based cements, which usually have to be exposed to water by mixing an anhydrous powder cement phase with an aqueous liquid phase to initiate curing.

[0005] The main parameters controlled when providing calcium silicate-based cements for dentistry include the handling properties of the cured material, the curing time, and the mechanical properties.

[0006] Regardless of handling characteristics, the texture of the filling material must be creamy for good handling by the practitioner. Further, the working time must be just sufficient to allow its placement when preparation and restoration of the filling material are required.

[0007] The setting time should ideally be relatively short. In fact, an overly long setting time is painful for the patient and may cause loss of the restorative material due to saliva and irritation of the oral tissues.

[0008] The hardened restorative material must have mechanical properties similar to those of the tooth. In particular, the compressive strength must be sufficient to avoid breakage of the restorative material and to guarantee its lifespan.

[0009] Mineral trioxide aggregate (MTA) is a calcium silicate-based cement for dentistry introduced over 25 years ago. Despite its good clinical effectiveness, MTA presents drawbacks that prevent its use in many cases. The main drawbacks are a very long setting time (about 3 - 4 hours) and its poor handling characteristics.

[0010] Sanaee et al. investigated the effect of the particle size of formulated MTA on the setting time (Sanaee et al., "The influence of particle size and multi-walled carbon nanotube on physical properties of mineral trioxide aggregate", Mater. Res. Express, 2019, Vol. 6(6), 065413). The setting time of the formulated MTA used in this study was about 65 minutes. They demonstrated that by reducing the particle size distribution by grinding the MTA powder before use, the setting time could be accelerated to about 12 minutes. Nevertheless, reducing the particle size distribution had a negative impact on the compressive and flexural strengths. The addition of multi-walled carbon nanotubes could increase the mechanical strength by restoring the flexural strength, but had no significant effect on the compressive strength.

[0011] The applicant has previously provided bioactive and biocompatible dental restorative materials obtained from calcium silicate-based cements and having good mechanical properties, as described in U.S. Patent No. 7,819,663 and U.S. Patent No. 8,974,586. In particular, the applicant has developed the Biodentine® restorative material, a bioactive calcium silicate-based cement that is easy to handle and has mechanical properties and mechanical behavior similar to those of human dentin and that cures in only 10 - 12 minutes.

[0012] There is still a need for the patient and the practitioner to have a restorative material that has good handling properties (such as a creamy texture, working time, etc.) for the practitioner and that cures more rapidly when placed in the patient's mouth while maintaining mechanical properties, particularly compressive strength, at least as good as those of currently available products.

[0013] The applicant has demonstrated herein that by using ultra-fine calcium silicate (UCS) particles in a calcium silicate-based cement powder composition in the presence of a limited amount of water, the curing time can be significantly shortened while maintaining the good compressive strength of the resulting restorative material. The UCS particles used in the dental hydraulic cement of the present invention have finely adjusted d 10 , d 50 and d 90 sizes and specific surface areas. By replacing all or part of the calcium silicate particles, particularly C3S particles, in the calcium silicate-based cement with the UCS particles of the present invention, it is also possible to maintain good handling properties and a satisfactory appearance.

Summary of the Invention

[0014] The present invention relates to a first container containing a powder phase, the powder phase comprising · ultra-fine calcium silicate particles in an amount of 15% to 98% by weight based on the total weight of the powder phase, having a d 10 size in the range of 0.4 μm to 0.9 μm, preferably in the range of 0.4 μm to 0.8 μm or 0.4 μm to 0.7 μm, a d 50 size in the range of 0.7 μm to 2.9 μm, preferably in the range of 0.8 μm to 2.5 μm, preferably in the range of 1 μm to 2.1 μm, and a d 90 size in the range of 1.3 μm to 7.0 μm, preferably in the range of 1.5 μm to 7 μm or 2 μm to 5 μm (the d 10 , d 50 and d 90 sizes are measured by laser diffraction), · a radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, · optionally, one or more additives selected from hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants and fillers and a first container; a second container containing an aqueous liquid phase and the weight ratio of the powder phase present in the kit to the liquid phase present in the kit is in the range of 2 to 5, preferably in the range of 2.5 to 4.0. Relates to a kit for preparing a dental restorative material.

[0015] In one embodiment, the first container containing the powder phase · Ultra-fine particles of calcium silicate in the range of 0.5 μm to 0.9 μm, preferably 0.5 μm to 0.8 μm, even more preferably 0.5 μm to 0.7 μm in terms of d 10 Size, in the range of 0.7 μm to 2.9 μm, preferably 0.8 μm to 2.5 μm, preferably 1 μm to 2.1 μm in terms of d 50 Size and in the range of 1.3 μm to 7.0 μm, preferably 1.5 μm to 7 μm or 2 μm to 5 μm in terms of d 90 Size (d 10 、d 50 And d 90 Size is measured by laser diffraction), ultra-fine particles of calcium silicate in a weight range of 15% to 98% based on the total weight of the powder phase Containing.

[0016] In one embodiment, calcium silicate is selected from tricalcium silicate (C3S), dicalcium silicate (C2S) and any combination thereof, preferably calcium silicate is tricalcium silicate.

[0017] In one embodiment, the powder phase contains Portland cement and / or mineral trioxide aggregate (MTA) as ultra-fine calcium silicate particles.

[0018] In one embodiment, the powder phase further contains non-ultra-fine particles of calcium silicate. In one embodiment, the amount of ultra-fine calcium silicate particles is in the range of 10% to 100% by weight based on the total weight of calcium silicate present in the powder phase, preferably in the range of 10% to 70% by weight, more preferably in the range of 10% to 50% by weight.

[0019] In one embodiment, the radiopaque agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof, and preferably the radiopaque agent is zirconium oxide.

[0020] In one embodiment, the powder phase contains one or more additives selected from hardening accelerators such as calcium carbonate, calcium oxide, calcium phosphate, and mixtures thereof, and pigments such as iron oxide.

[0021] In one embodiment, the powder phase is · ultrafine particles of tricalcium silicate that are 20% to 60% by weight based on the total weight of the powder phase, · having a specific surface area measured by the BET technique in the range of 3 to 11 m 2 / g, · in the range of 0.4 μm to 0.9 μm, preferably in the range of 0.4 μm to 0.82 μm, in the range of 0.4 μm to 0.8 μm or in the range of 0.4 μm to 0.7 μm for the d 10 size, · in the range of 0.7 μm to 2.9 μm, preferably in the range of 0.8 μm to 2.5 μm, preferably in the range of 1 μm to 2.1 μm or in the range of 0.8 μm to 2.1 μm for the d 50 size, and · in the range of 1.3 μm to 7.0 μm, preferably in the range of 1.4 μm to 7 μm, in the range of 1.5 μm to 7 μm or in the range of 2 μm to 5 μm for the d 90 size (d 10 , d 50 and d 90 sizes are measured by laser diffraction)), ultrafine particles of tricalcium silicate having, · non-ultrafine particles of calcium silicate that are 0% to 50% by weight based on the total weight of the powder phase, · a radiopaque agent that is 2% to 35% by weight based on the total weight of the powder phase, · one or more hardening accelerators such as calcium carbonate, calcium oxide, and mixtures thereof that are 0% to 25% by weight based on the total weight of the powder phase and contains.

[0022] In one embodiment, the powder phase is · Ultra-fine particles of tricalcium silicate that are 20% to 60% by weight based on the total weight of the powder phase, · with a specific surface area measured by the BET technique in the range of 3 to 11 m 2 / g, · with a d 10 size in the range of 0.5 μm to 0.9 μm, preferably 0.5 μm to 0.8 μm, and even more preferably 0.5 μm to 0.7 μm, · with a d 50 size in the range of 0.7 μm to 2.9 μm, preferably 0.8 μm to 2.5 μm, preferably 1 μm to 2.1 μm or 0.8 μm to 2.1 μm, and · with a d 90 size in the range of 1.3 μm to 7.0 μm, preferably 1.5 μm to 7 μm or 2 μm to 5 μm and containing ultra-fine particles of tricalcium silicate having the same are included.

[0023] In one embodiment, the aqueous liquid phase is water. In one embodiment, the aqueous liquid phase further contains one or more additives, and the additives are selected from hardening accelerators such as calcium chloride and water reducers such as modified polycarboxylates.

[0024] In one embodiment, the aqueous liquid phase is · 60% to 85% by weight of water based on the total weight of the aqueous liquid phase, and · 5% to 35% by weight of a hardening accelerator, preferably calcium chloride, based on the total weight of the aqueous liquid phase, and · 0% to 5% by weight of a water reducer, preferably modified polycarboxylate, based on the total weight of the aqueous liquid phase are included.

[0025] The present invention also relates to a dental composition obtained by mixing the entire content of the first container of the kit according to the present invention with the entire content of the second container.

[0026] In one embodiment, the composition has a curing time in the range of 1 minute to 12 minutes, preferably 4 minutes to 9 minutes.

[0027] In one embodiment, the dental composition has a compressive strength at 24 hours of greater than 100 MPa, preferably greater than 150 MPa.

[0028] The present invention further relates to a medical device comprising the kit according to the present invention, preferably the medical device is an injection system, more preferably a syringe.

[0029] Definitions In the present invention, the following terms have the following meanings.

[0030] "About" before a number means ±10% of the value of that number.

[0031] "Additive" refers to any substance that is preferably added to the composition in a small amount to improve its physicochemical properties according to its use. Additives may be selected from, for example, radiopaque agents (such as zirconium oxide), curing accelerators (such as calcium oxide, calcium carbonate, calcium chloride, etc.), pigments (such as iron oxide), water reducers (such as modified polycarboxylate), texturing agents, pH stabilizers, surfactants, fillers and mixtures thereof.

[0032] "Alcohol" refers to any compound having a hydroxyl functional group (-OH).

[0033] "Aqueous" refers to any compound or composition containing water and / or moisture.

[0034] "BET" refers to any technique based on the Brunauer-Emmett-Teller theory that describes the physical adsorption of gases on the surface of a solid. According to one embodiment, the BET technique measures the surface area (m 2It is used to determine (expressed in / g). According to one embodiment, the BET technique is performed by a particle size measuring device such as Gemini 2375 (registered trademark) or Gemini V (registered trademark) manufactured by Micromeritics.

[0035] "Calcium silicate" refers to a compound that can be produced by reacting calcium oxide and silica in various ratios. According to one embodiment, the expression "calcium silicate" preferably refers to tricalcium silicate, dicalcium silicate or any mixture thereof, more preferably tricalcium silicate C3S (formula: Ca 3 SiO 5 ), dicalcium silicate C2S (formula: Ca 2 SiO 4 ) or a compound prepared from calcium and silica selected from any mixture thereof.

[0036] According to one embodiment, "calcium silicate mixture" refers to the entire calcium silicate present in the solid phase according to the present invention, and the calcium silicate is in the form of ultrafine and / or non-ultrafine calcium silicate particles. According to one embodiment, the expression "calcium silicate mixture" refers to one or more calcium silicate compounds defined above, namely tricalcium silicate, dicalcium silicate or any mixture thereof. According to one embodiment, the expression "calcium silicate mixture" refers to a mixture of calcium silicate compounds defined above, where the calcium silicate compounds are in the form of ultrafine and / or non-ultrafine calcium silicate particles. According to one embodiment, the "calcium silicate mixture" may include calcium silicate that is part of Portland cement and / or MTA.

[0037] "Calcium silicate particles" refer to an aggregate containing one or more calcium silicate compounds. The term "calcium silicate particles" also includes an aggregate consisting of one or more calcium silicate compounds.

[0038] "Coarsely crushed particles" refers to particles having a d size in the range of more than 1.7 to 5 μm, a d size in the range of more than 8 to 14 μm, and a d size in the range of more than 20 to 40 μm, as well as a specific surface area in the range of 0.3 to 1.2 m / g. 10 size, a d size in the range of more than 8 to 14 μm, 50 size and a d size in the range of more than 20 to 40 μm, 90 size and a specific surface area in the range of 0.3 to 1.2 m 2 / g.

[0039] "Crushed particles" refers to particles having a d size in the range of more than 2 to 6 μm, a d size in the range of more than 17 to 25 μm, and a d size in the range of more than 150 to 330 μm, as well as a specific surface area of about 0.5 m / g. 10 size, a d size in the range of more than 17 to 25 μm, 50 size and a d size in the range of more than 150 to 330 μm, 90 size and a specific surface area of about 0.5 m 2 / g.

[0040] "Dental cement" refers to any composition suitable for restorative dentistry that functions as an adhesive to hold a casting together against a tooth structure.

[0041] "Dental composition" refers to any formulation suitable for dental use.

[0042] "Dual syringe" refers to an injection system comprising and / or consisting of a mixing system and / or mixing chamber, two cartridges and plungers.

[0043] "d 10 size" means that 10% of the particles have an average diameter less than the value. According to one embodiment, d 10 size is measured by laser diffraction.

[0044] "d 50 size" means that 50% of the particles have an average diameter less than the value. According to one embodiment, d 50 size is measured by laser diffraction.

[0045] "d 90 size" means that 90% of the particles have an average diameter less than the value. According to one embodiment, d 90The size is measured by laser diffraction.

[0046] "Glycol" or "diol" refers to any compound having two hydroxyl groups bonded to different carbon atoms. According to one embodiment, the term "glycol" includes vicinal diols, i.e., compounds having two hydroxyl groups bonded to two adjacent carbon atoms. Examples of glycols include ethylene glycol, propylene glycol, and polyethylene glycol.

[0047] "Ethylene glycol" refers to a glycol of the formula: HO-(CH 2 ) 2 -OH.

[0048] "Rapid hardening" refers to a compound or composition that can harden in less than 12 minutes, preferably less than 9 minutes, after its hydration.

[0049] "Grinding beads" are in the form of inert particles located within a grinding device and refer to the physical elements that enable the mechanical destruction of a solid material into smaller fragments.

[0050] "Grinding chamber" refers to a part of a grinding device into which a solid sample to be broken into smaller fragments is introduced.

[0051] "Grinding time" refers to the time of implementation for breaking a solid sample into smaller fragments.

[0052] "Hardened dental material" refers to a material suitable for dental applications in solid form. According to one embodiment, the expression "hardened dental material" refers to the material obtained after the hardening of the dental composition of the present invention. In particular, "hardened dental filling material" refers to a hardened dental material suitable for filling dental restorations.

[0053] "Hydraulic cement" refers to a cement that can self-harden when contacted with water.

[0054] "Laser diffraction analysis" refers to a technique that uses the diffraction pattern of a laser beam passing through particulate matter to determine its particle size.

[0055] "Medical device" refers to any device, material or object that can be used alone or in combination for diagnostic and / or therapeutic purposes.

[0056] "Metal oxide" refers to a compound containing or consisting of metal cations and oxide anions.

[0057] "Micronized particles" refers to particles having a d 10 size in the range of greater than 0.7 to 1.7 μm, a d 50 size in the range of greater than 2.9 to 8 μm and a d 90 size as well as a specific surface area in the range of 6 to 20 μm 2 and having a specific surface area in the range of 0.8 to 3 m

[0058] "Modified polycarboxylate" refers to any polymer having repeating units and a moiety containing at least one carboxylic acid functional group, where some or all of the carboxylic acid functional groups are modified to provide another chemical function. According to one embodiment, the expression "modified polycarboxylate" refers to any polymer containing at least two carboxylic acid functional groups in its backbone, where some or all of the carboxylic acid functional groups are modified to provide another chemical function. According to one embodiment, the expression "modified polycarboxylate" refers to a polymer having a plurality of carboxylic acid functional groups, where some or all of the carboxylic acid functional groups have reacted with one functional group of a chemical component, and the functional group is selected from amine, hydroxyl, nitrile and halo.

[0059] "MTA" or "mineral trioxide aggregate" refers to a hydraulic cement containing Portland cement combined with a radiopaque agent, which may be, for example, bismuth oxide. According to one embodiment, the term "MTA" refers to a hydraulic cement containing tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite, calcium sulfate and a radiopaque agent such as bismuth oxide.

[0060] "Non-aqueous" (see also "water-free") refers to any compound or composition that does not contain water and / or moisture.

[0061] "Pigment" refers to any coloring compound, which may be a natural or synthetic inorganic or organic substance.

[0062] "Polyethylene glycol" or "polyethylene oxide" refers to a polymer that is a polyether compound of the general formula: H-[O-CH 2 -CH 2 n -OH, where n is a positive integer.

[0063] "Portland cement" refers to a hydraulic material containing, as a main component, at least two-thirds by mass of calcium silicate (3CaO·SiO 2 and 2CaO·SiO 2 ), and a further compound containing an aluminum and / or iron-containing cross-linking agent phase (for example, tricalcium aluminate and tetracalcium aluminoferrite). The expression "Portland cement" includes all Portland cement compositions well known to those skilled in the art as defined by the European EN197 standard and the international ASTM C150 standard.

[0064] "Radiopaque agent" refers to a substance added to a material to make it opaque, especially for visualization by X-ray imaging.

[0065] ​"Hardening accelerator" refers to any hardening accelerator that, when added to a material, shortens the hardening time of the material compared to the hardening time of the same material without the hardening accelerator.

[0066] As used herein, "hardening time" refers to the period required to completely harden the dental composition of the present invention after its hydration. The hardening time begins when the test composition is placed under defined temperature and humidity conditions (typically a 37°C water bath). The hardening time may be measured by several methods, such as a Gilmore apparatus (Gilmore needle) or a Vicat apparatus (Vicat needle). For example, the hardening time may be measured using a Gilmore apparatus. The test material is placed in a mold introduced into a 37°C water bath, and the hardening of the material is evaluated using a 400 g Gilmore needle. The material is considered hardened when the needle leaves no mark on the surface of the mold. The hardening time corresponds to the period from when the mold is placed in the water bath until hardening is observed.

[0067] "Particle size" refers to the average diameter of the particles.

[0068] "Specific surface area" refers to the ratio of the area of the actual surface of an object / the amount of substance of the object. The specific surface area is expressed in square meters per gram (m 2 / g). According to one embodiment, the specific surface area is measured by the BET (Brunauer-Emmett-Teller technique).

[0069] "Subject" refers to a warm-blooded animal, more preferably a human. Preferably, the subject is a patient, i.e., the subject is waiting to receive or is receiving medical care, or is currently the subject of a medical treatment or will be a subject in the future.

[0070] "Texturing agent" refers to any compound that, when added to a substance, increases the viscosity and cohesion of the substance.

[0071] "Treatment" or "treating" refers to a therapeutic treatment that can cure the subject or slow (alleviate) the progression of a targeted pathological condition or disorder. A subject or mammal is considered to have had a "successful treatment" for a disease or disorder if, after administration of the dental composition or hardened dental material of the present invention to the patient, a measurable and / or observable decrease in one or more symptoms associated with a particular disease or illness and an improvement in quality of life issues are shown. The above parameters for evaluating treatment success and disease or illness improvement are readily measurable by routine procedures with which physicians are familiar.

[0072] "Ultrafine particles" are particles having a d 10 size less than 0.7 μm, a d 50 size in the range of about 0.7 μm to 2.9 μm, and a d 90 size in the range of about 2.0 μm to 7.0 μm, 2 as well as a specific surface area measured by BET in the range of about 3 to 11 m 10 / g. According to one embodiment, d 50 and d 90 sizes are measured by laser diffraction. According to one embodiment, ultrafine particles have a d 10 size in the range of 0.4 μm to 0.9 μm, preferably in the range of 0.4 μm to 0.82 μm or 0.4 μm to 0.8 μm, a d 50 size in the range of 0.7 μm to 2.9 μm, and a d 90 size in the range of 1.3 μm to 7 μm. According to one embodiment, ultrafine particles have a d 10 size in the range of 0.4 μm to 0.8 μm, a d 50 size in the range of 0.8 μm to 2.1 μm, and a d 90 size in the range of 1.4 μm to 7 μm, 2 as well as a specific surface area measured by BET in the range of about 3 to 11 m

[0073] "Water non-containing" (see also "non-aqueous") refers to any non-aqueous or non-hydrated compound, phase or material. According to one embodiment, the term "non-hydrated" further means that the compound or material is not in contact with water molecules at all.

[0074] "Water reducing agent" refers to a substance that can enhance the rheological properties of a composition. In particular, the "water reducing agent" may be a plasticizer or a fluidizing agent.

[0075] "Working time" refers to the period during which an operator can work on a dental composition until its placement into the oral cavity of the subject in need thereof. In one embodiment, the working time corresponds to the period from the end of the mixing of the calcium silicate phase and the aqueous phase to the start of hardening when the consistency of the composition becomes too high for the operator to handle. Preferably, the working time is more than 1 minute.

[0076] Furthermore, in the present invention, when referring to a range, the "range of X to Y" means that X and Y are included in the range, the "range of more than X to Y" means that X is not included in the range but Y is included in the range, and "less than X" means that the range includes X or a lower value than it.

Embodiments for Carrying Out the Invention

[0077] Therefore, the present invention relates to the provision of a dental hydraulic cement, that is, a dental restorative material obtained from a calcium silicate-based cement, which has a short hardening time and good compressive strength when hardened.

[0078] The present invention also relates to the provision of a starting composition that enables the preparation of the dental restorative material of the present invention. Therefore, in one embodiment, a calcium silicate anhydrous phase suitable for preparing the dental restorative material of the present invention is provided.

[0079] The solution of the present invention involves using ultrafine calcium silicate particles (hereinafter referred to as "UCS particles") having a finely adjusted particle size distribution in an anhydrous phase of calcium silicate, and adjusting other components to keep the amount of water required to harden the hydraulic cement low.

[0080] First, the characteristics of suitable UCS particles will be described in detail. Next, the content of the starting composition and kits suitable for providing the expected dental restorative material will be explained. The characteristics of the resulting dental restorative material and possible uses will also be considered.

[0081] UCS particles In one embodiment, the present invention relates to ultrafine particles of calcium silicate (UCS particles).

[0082] According to one embodiment, the calcium silicate of the UCS particles of the present invention is selected from tricalcium silicate, dicalcium silicate or any mixture thereof, preferably tricalcium silicate (C3S). According to one embodiment, tricalcium silicate has the formula: Ca 3 SiO 5 (also referred to as "C3S") and the formula: Ca 3 Si 3 O 9 (also called "calcium oxosilanedioleate"). According to one embodiment, dicalcium silicate has the formula: Ca 2 SiO 4 (also referred to as "C2S").

[0083] In one embodiment, the calcium silicate of the UCS particles of the present invention may be the calcium silicate present in Portland cement. In another embodiment, the calcium silicate of the UCS particles of the present invention may be the calcium silicate present in mineral trioxide aggregate (MTA).

[0084] According to one embodiment, the UCS particles of the present invention are in powder form.

[0085] In one embodiment, the UCS particles of the present invention are characterized by their particle size distribution, particularly their d 10 , d 50 and / or d 90 size. According to one embodiment, d 10 , d 50 and d 90 size are measured by laser diffraction.

[0086] D90 According to one embodiment, the UCS particles have a d 90 size in the range of 1.4 μm to 6.0 μm, preferably 1.4 to 5.0 μm, more preferably 1.4 to 3.5 μm. In one embodiment, the UCS particles have a d 90 size in the range of 1.4 μm to 5.9 μm, 1.4 μm to 5.8 μm, 1.4 μm to 5.7 μm, 1.4 μm to 5.6 μm, 1.4 μm to 5.5 μm, 1.4 μm to 5.4 μm, 1.4 μm to 5.3 μm, 1.4 μm to 5.2 μm, 1.4 μm to 5.1 μm, 1.4 μm to 5.0 μm, 1.4 μm to 4.9 μm, 1.4 μm to 4.8 μm, 1.4 μm to 4.7 μm, 1.4 μm to 4.6 μm, 1.4 μm to 4.5 μm, 1.4 μm to 4.4 μm, 1.4 μm to 4.3 μm, 1.4 μm to 4.2 μm, 1.4 μm to 4.1 μm, 1.4 μm to 4.0 μm, 1.4 μm to 3.9 μm, 1.4 μm to 3.8 μm, 1.4 μm to 3.7 μm, 1.4 μm to 3.6 μm, 1.4 μm to 3.5 μm, 1.4 μm to 3.4 μm, 1.4 μm to 3.3 μm, 1.4 μm to 3.2 μm, 1.4 μm to 3.1 μm, 1.4 μm to 3.0 μm, 1.4 μm to 2.9 μm, 1.4 μm to 2.8 μm, 1.4 μm to 2.7 μm, 1.4 μm to 2.6 μm, 1.4 μm to 2.5 μm, 1.4 μm to 2.4 μm, 1.4 μm to 2.3 μm, 1.4 μm to 2.2 μm, 1.4 μm to 2.1 μm, 1.4 μm to 2.0 μm, 1.4 μm to 1.9 μm, 1.4 μm to 1.8 μm, 1.4 μm to 1.7 μm, 1.4 μm to 1.6 μm, 1.4 μm to 1.5 μm. According to one embodiment, the UCS particles have a d90 has a size. According to one embodiment, the UCS particles have a d of 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 or 5 μm 90 has a size. According to one embodiment, the UCS particles have a d in the range of 1.5 μm to 6.0 μm, preferably 2 μm to 6 μm, 2.5 μm to 6 μm, 3 μm to 6 μm, 3.5 μm to 6 μm, 4 μm to 6 μm, 4.5 μm to 6 μm or 5 μm to 6 μm 90 has a size. According to one embodiment, the UCS particles have a d in the range of 2 μm to 4.6 μm, preferably 2 μm to 4.7 μm, 2 μm to 4.8 μm or 2 μm to 4.9 μm 90 has a size. According to one embodiment, the UCS particles have a d of 2.05 μm, 2.47 μm, 3.12 μm or 4.55 μm 90 has a size.

[0087] According to one embodiment, the UCS particles have a d in the range of 1.5 μm to 2 μm 90 has a size. According to one embodiment, the UCS particles have a d of 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.77, 1.78, 1.79, 1.80, 1.81, 1.82, 1.83, 1.84, 1.85, 1.86, 1.87, 1.88, 1.89, 1.90, 1.91, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, 1.99, 2.00, 2.01, 2.02, 2.03, 2.04, 2.05 μm 90 has a size. According to one embodiment, the UCS particles have a d in the range of 4 to 7 μm 90It has a size. According to one embodiment, the UCS particles have a d size of 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9 or 7.0 μm 90 It has a size.

[0088] According to one embodiment, the UCS particles have a d size in the range of 1.3 μm to 6.0 μm, preferably 1.3 to 5.0 μm, more preferably 1.3 to 3.5 μm 90 It has a size. In one embodiment, the UCS particles have a d size in the range of 1.3 μm to 5.9 μm, 1.3 μm to 5.8 μm, 1.3 μm to 5.7 μm, 1.3 μm to 5.6 μm, 1.3 μm to 5.5 μm, 1.3 μm to 5.4 μm, 1.3 μm to 5.3 μm, 1.3 μm to 5.2 μm, 1.3 μm to 5.1 μm, 1.3 μm to 5.0 μm, 1.3 μm to 4.9 μm, 1.3 μm to 4.8 μm, 1.3 μm to 4.7 μm, 1.3 μm to 4.6 μm, 1.3 μm to 4.5 μm, 1.3 μm to 4.4 μm, 1.3 μm to 4.3 μm, 1.3 μm to 4.2 μm, 1.3 μm to 4.1 μm, 1.3 μm to 4.0 μm, 1.3 μm to 3.9 μm, 1.3 μm to 3.8 μm, 1.3 μm to 3.7 μm, 1.3 μm to 3.6 μm, 1.3 μm to 3.5 μm, 1.3 μm to 3.4 μm, 1.3 μm to 3.3 μm, 1.3 μm to 3.2 μm, 1.3 μm to 3.1 μm, 1.3 μm to 3.0 μm, 1.3 μm to 2.9 μm, 1.3 μm to 2.8 μm, 1.3 μm to 2.7 μm, 1.3 μm to 2.6 μm, 1.3 μm to 2.5 μm, 1.3 μm to 2.4 μm, 1.3 μm to 2.3 μm, 1.3 μm to 2.2 μm, 1.3 μm to 2.1 μm, 1.3 μm to 2.0 μm, 1.3 μm to 1.9 μm, 1.3 μm to 1.8 μm, 1.3 μm to 1.7 μm, 1.3 μm to 1.6 μm, 1.3 μm to 1.5 μm 90 It has a size.

[0089] D50 According to one embodiment, the UCS particles have a d size in the range of 0.7 μm to 2.9 μm, preferably 0.7 μm to 2.0 μm, preferably 0.7 μm to 1.5 μm50 has a size. According to one embodiment, the UCS particles have a d in the range of 0.7 μm to 2.8 μm, 0.7 μm to 2.7 μm, 0.7 μm to 2.6 μm, 0.7 μm to 2.5 μm, 0.7 μm to 2.4 μm, 0.7 μm to 2.3 μm, 0.7 μm to 2.2 μm, 0.7 μm to 2.1 μm, 0.7 μm to 2.0 μm, 0.7 μm to 1.9 μm, 0.7 μm to 1.8 μm, 0.7 μm to 1.7 μm, 0.7 μm to 1.6 μm, 0.7 μm to 1.5 μm, 0.7 μm to 1.4 μm, 0.7 μm to 1.3 μm, 0.7 μm to 1.2 μm, 0.7 μm to 1.1 μm, 0.7 μm to 1.0 μm, 0.7 μm to 0.9 μm, 0.7 μm to 0.8 μm 50 has a size. According to one embodiment, the UCS particles have a d in the range of 0.8 μm to 2.9 μm, preferably 0.8 μm to 2.1 μm, preferably 1.5 μm to 2.1 μm, preferably 1.04 μm to 2.1 μm, more preferably 1 μm to 2.1 μm or 1.04 μm to 1.93 μm 50 has a size. According to one embodiment, the UCS particles have a d in the range of 1 μm to 2.9 μm, preferably 1 μm to 2.8 μm, 1 μm to 2.7 μm, 1 μm to 2.6 μm, 1 μm to 2.5 μm, 1 μm to 2.4 μm, 1 μm to 2.3 μm, 1 μm to 2.2 μm, 1 μm to 2.1 μm, 1 μm to 2.0 μm, 1 μm to 1.9 μm, 1 μm to 1.8 μm, 1 μm to 1.7 μm, 1 μm to 1.6 μm or 1 μm to 1.5 μm 50 has a size. According to one embodiment, the UCS particles have a d in the range of 1.1 μm to 2.9 μm, preferably 1.2 μm to 2.9 μm, 1.3 μm to 2.9 μm, 1.4 μm to 2.9 μm, 1.5 μm to 2.9 μm, 1.6 μm to 2.9 μm, 1.7 μm to 2.9 μm, 1.8 μm to 2.9 μm, 1.9 μm to 2.9 μm, 2 μm to 2.9 μm, 2.1 μm to 2.9 μm, 2.2 μm to 2.9 μm, 2.3 μm to 2.9 μm or 2.4 μm to 2.9 μm 50 has a size. According to one embodiment, the UCS particles have a d of 1.04 μm, 1.29 μm, 1.50 μm or 1.93 μm 50It has a size. According to one embodiment, the UCS particles have a d of 0.80:0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99 or 1 μm 50 It has a size.

[0090] D10 According to one embodiment, the UCS particles have a d in the range of less than 0.7 μm, preferably 0.1 μm to 0.7 μm, preferably 0.2 μm to 0.6 μm, 0.3 μm to 0.55 μm, 0.35 μm to 0.50 μm, 0.40 μm to 0.50 μm 10 It has a size.

[0091] According to one embodiment, the UCS particles have a d in the range of 0.4 μm to 0.9 μm, preferably 0.5 μm to 0.9 μm, 0.4 μm to 0.85 μm, 0.4 μm to 0.82 μm or 0.5 μm to 0.85 μm, more preferably 0.4 μm to 0.82 μm, 0.4 μm to 0.8 μm or 0.4 μm to 0.7 μm 10 It has a size. According to one embodiment, the UCS particles have a d in the range of 0.4 μm to 0.6 μm, more preferably 0.4 μm to 0.5 μm 10 It has a size. According to one embodiment, the UCS particles have a d in the range of 0.5 μm to 0.9 μm, 0.6 μm to 0.9 μm, 0.7 μm to 0.9 μm or 0.8 μm to 0.9 μm 10 It has a size. According to one embodiment, the UCS particles have a d of 0.5 μm, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, or 0.82 μm 10 It has a size.

[0092] According to one embodiment, the UCS particles are - having a d in the range of 0.7 μm to 2.9 μm 50Size, and -1.4 μm to 6.0 μm range of d 90 Size (d 50 and d 90 Size is measured by laser diffraction) Characterized by.

[0093] According to one embodiment, the UCS particles are -0.4 μm to 0.9 μm, preferably 0.4 μm to 0.82 μm or 0.4 μm to 0.8 μm, more preferably 0.5 μm to 0.8 μm range of d 50 Size, and -1.3 μm to 7.0 μm, preferably 1.4 μm to 7 μm range of d 90 Size (d 50 and d 90 Size is measured by laser diffraction) Characterized by.

[0094] According to one embodiment, the UCS particles are -1 μm to 2.9 μm, preferably 1 μm to 2.1 μm range of d 50 Size, and -1.4 μm to 6.0 μm, preferably 2 μm to 5 μm range of d 90 Size (d 50 and d 90 Size is measured by laser diffraction) Characterized by.

[0095] According to one embodiment, the UCS particles are Less than -0.7 μm of d 10 Size, -0.7 μm to 2.9 μm range of d 50 Size, and -1.4 μm to 6.0 μm range of d 90 Size (d 10 , d 50 and d 90 Size is measured by laser diffraction) characterized by

[0096] According to one embodiment, the UCS particles are d in the range of -0.1 μm to 0.7 μm 10 size, d in the range of -0.7 μm to 2.9 μm 50 size, and d in the range of -1.4 μm to 6.0 μm 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) characterized by

[0097] According to one embodiment, the UCS particles are d in the range of -0.5 μm to less than 0.7 μm 10 size, d in the range of -0.7 μm to 2.9 μm, preferably 1 μm to 2.1 μm 50 size, and d in the range of -1.4 μm to 6.0 μm, preferably 2 μm to 5 μm 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) characterized by

[0098] According to one embodiment, the UCS particles are d in the range of less than -0.7 μm to 0.9 μm, preferably 0.7 μm to 0.9 μm 10 size, d in the range of -0.7 μm to 2.9 μm, preferably 1 μm to 2.1 μm 50 size, and d in the range of -1.4 μm to 6.0 μm, preferably 2 μm to 5 μm 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) characterized by

[0099] According to one embodiment, the UCS particles are -0.5 μm to 0.9 μm in d 10 size, -1 μm to 2.1 μm in d 50 size, and -2.0 μm to 5.0 μm in d 90 size (d 10 , d 50 and d 90 size are measured by laser diffraction) characterized by

[0100] The UCS particles can also be characterized by specific surface area. According to one embodiment, the UCS particles have a specific surface area measured by BET (Brunauer-Emmett-Teller technique) in the range of 3 to 11 m 2 / g, preferably 3 to 9 m 2 / g, preferably 4 to 8 m 2 / g, more preferably 5 to 7 m 2 / g. According to one embodiment, the UCS particles have a specific surface area measured by BET in the range of 4 to 11 m 2 / g, 5 to 11 m 2 / g, 6 to 11 m 2 / g, 7 to 11 m 2 / g, 8 to 11 m 2 / g, 9 to 11 m 2 / g, 10 to 11 m 2 / g. According to one embodiment, the UCS particles have a specific surface area measured by BET in the range of 3 to 9 m 2 / g, preferably 3 to 8 m 2 / g, 3 to 7 m 2 / g, 3 to 6 m 2 / g, 3 to 5 m 2 / g or 3 to 4 m 2 / g. According to one embodiment, the UCS particles have a specific surface area measured by BET of about 3, 4, 5, 6, 7, 8, 9, 10 or 11 m 2 / g. According to one embodiment, the UCS particles have a specific surface area of 5 m 2 / g to 9 m2 / g, preferably 5.17 m 2 / g to 8.72 m 2 / g and has a specific surface area measured by BET in the range of

[0101] According to one embodiment, the UCS particles are -3 to 11 m 2 / g and has a specific surface area measured by BET in the range of, and -d as defined above in this specification 10 , d 50 and d 90 and is characterized by

[0102] According to one embodiment, the UCS particles are -3 to 11 m 2 / g and has a specific surface area measured by BET in the range of -d size less than 0.7 μm 10 , -d size in the range of 0.7 μm to 2.9 μm 50 , and -d size in the range of 1.4 μm to 6.0 μm 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) and is characterized by

[0103] According to one embodiment, the UCS particles are -3 to 11 m 2 / g and has a specific surface area measured by BET in the range of -d size in the range of 0.1 μm to 0.7 μm 10 , -d size in the range of 0.7 μm to 1.5 μm 50 , and -d size in the range of 1.4 μm to 3.5 μm 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) and is characterized by

[0104] According to one embodiment, the UCS particles are -3 to 11 m 2 / g, preferably 5 to 9 m 2 / g of specific surface area measured by BET, -0.5 μm to 0.9 μm in d 10 size, -0.7 μm to 2.9 μm in d 50 of size, and -1.4 μm to 6.0 μm in d 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) characterized by.

[0105] According to one embodiment, the UCS particles are -3 to 11 m 2 / g, preferably 5 to 9 m 2 / g of specific surface area measured by BET, -0.5 μm to 0.9 μm in d 10 size, -1 μm to 2.1 μm in d 50 size, and -2.0 μm to 5.0 μm in d 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) characterized by.

[0106] The ultrafine UCS particles defined above may be obtained by various production processes.

[0107] According to the first embodiment, the UCS particles may be produced by a mechanical grinding process. According to one embodiment, the mechanical grinding process of the present invention is (i) A step of mixing calcium silicate particles crushed and / or roughly crushed in a crushing chamber with a non-aqueous solvent such as alcohol, and (ii) A step of crushing the mixture obtained in step (i) with crushing beads preferably having a diameter in the range of 0.4 mm to 3 mm is included.

[0108] According to one embodiment, the calcium silicate particles crushed and / or roughly crushed used for producing the UCS particles of the present invention are selected from tricalcium silicate crushed and / or roughly crushed, dicalcium silicate or any mixture thereof, and preferably tricalcium silicate (C3S) crushed and / or roughly crushed. In one embodiment, the calcium silicate particles crushed and / or roughly crushed used for producing the UCS particles of the present invention are the calcium silicate present in Portland cement. In such a case, the crushed and / or roughly crushed Portland cement is crushed so that the calcium silicate particles contained therein have the specifications of the UCS particles of the present invention. In one embodiment, the calcium silicate particles crushed and / or roughly crushed used for producing the UCS particles of the present invention are the calcium silicate present in mineral trioxide aggregate (MTA). In such a case, the crushed and / or roughly crushed MTA is crushed so that the calcium silicate particles contained therein have the specifications of the UCS particles of the present invention.

[0109] According to one embodiment, the non-aqueous solvent is alcohol. In one embodiment, the alcohol is selected from primary, secondary or tertiary alcohols. According to one embodiment, the alcohol is isopropanol.

[0110] According to one embodiment, in order to avoid blackening the powder due to the presence of a small amount of stainless steel and to prevent contamination of the powder, the grinding chamber is not made of stainless steel. According to one embodiment, the grinding chamber is made and / or coated with a metal oxide such as zirconium oxide, tungsten carbide and / or silicon carbide.

[0111] According to one embodiment, the grinding chamber is filled with 33% by volume of calcium silicate particles and 66% by volume of alcohol for grinding. According to one embodiment, the grinding chamber is filled with 50% by volume of calcium silicate particles and 50% by volume of alcohol for grinding.

[0112] According to one embodiment, step (i) is preferably carried out by mixing the crushed or roughly ground C3S particles in the grinding chamber of the grinding device with isopropanol.

[0113] According to one embodiment, the grinding step (ii) is mechanical grinding. According to one embodiment, the grinding is carried out by a grinding device well known to those skilled in the art, such as, for example, EMAX (registered trademark) of RETSCH.

[0114] According to one embodiment, the grinding beads are not made of stainless steel for the same reasons detailed above. According to one embodiment, the grinding beads are made and / or coated with a metal oxide such as zirconium oxide, tungsten carbide and / or silicon carbide.

[0115] According to one embodiment, the average diameter of the grinding beads ranges from 0.4 mm to 3 mm, preferably from 0.5 to 2.5 mm, 0.5 to 2 mm, 0.5 to 1.5 mm, 0.5 to 1 mm or 0.4 mm to 0.8 mm.

[0116] According to one embodiment, the grinding is carried out for a time ranging from 1 minute to 60 minutes, preferably from 10 minutes to 40 minutes, more preferably from 20 minutes to 30 minutes. Such a short grinding time avoids contamination of the UCS particle powder by the inorganic or metallic elements of the grinding means.

[0117] According to one embodiment, the grinding is carried out at a grinding speed in the range of more than 0 rpm to 5000 rpm, preferably 1000 rpm to 3000 rpm, more preferably about 1900 rpm. According to one embodiment, the grinding is carried out at a grinding speed in the range of 9 to 15 m / s.

[0118] According to one embodiment, the process of the present invention is carried out using 45 g of coarsely ground C3S particles, 30 mL of isopropanol and 90 g of grinding beads. According to one embodiment, the process of the present invention is carried out using an EMAX (registered trademark) apparatus at a grinding speed of about 1900 rpm for 20 minutes.

[0119] According to one embodiment, the process for producing UCS particles further includes a drying step. According to one embodiment, the drying step is carried out after step (ii). According to one embodiment, the drying step enables the removal of an alcohol such as isopropanol from the grinding mixture. According to one embodiment, the drying step is carried out at a temperature in the range of 30°C to 300°C, preferably 40°C to 100°C, more preferably about 50°C. According to one embodiment, the drying step is carried out at a temperature of about 90°C.

[0120] According to one embodiment, the process of the present invention further includes a sieving step. According to one embodiment, the sieving step is carried out by sorting the grinding mixture through a sieve after step (ii).

[0121] The UCS particles defined above may be used as a curing accelerator, preferably as a curing accelerator for dental compositions such as hydraulic dental cements. In one embodiment, when used in a hydraulic dental cement, the UCS particles of the present invention shorten the curing time of the cement by 10% to 70%, preferably 30% to 65%, more preferably 40% to 65% compared to the same hydraulic dental cement containing only non-ultrafine calcium silicate particles. According to one embodiment, when used in a hydraulic dental cement, the UCS particles of the present invention shorten the curing time of the cement by about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60% or even 65% compared to the same hydraulic dental cement containing only non-ultrafine calcium silicate particles.

[0122] Powder phase and aqueous liquid phase Accordingly, the present invention relates to the provision of a starting composition that enables the preparation of the dental restorative material of the present invention, and in particular, a calcium silicate anhydrous phase containing UCS particles is provided.

[0123] In one embodiment, a powder phase containing UCS particles, preferably an anhydrous powder phase containing UCS particles, more preferably an anhydrous calcium silicate cement powder phase containing UCS particles is provided. In this embodiment, an aqueous phase, preferably an aqueous liquid phase, is also required so that the dental restorative material of the present invention can be obtained when mixed with the powder phase containing UCS particles.

[0124] Powder phase In one embodiment, the powder phase of the present invention contains the UCS particles defined above.

[0125] In a preferred embodiment, the powder phase is anhydrous or water-free. In fact, calcium silicate starts to cure in the presence of water. Therefore, it is important that the powder phase remains free of water during storage to avoid its undesirable curing at this stage.

[0126] According to one embodiment, the powder phase is a calcium silicate phase, preferably a calcium silicate-based cement phase. According to one embodiment, the powder phase contains ultra-fine and non-ultra-fine calcium silicate particles. According to one embodiment, the powder phase does not contain any aluminates such as calcium aluminate. According to one embodiment, the powder phase does not contain any halogens or halogenated compounds such as fluorides. According to one embodiment, the powder phase does not contain any phosphates such as calcium phosphate. According to one embodiment, the powder phase does not contain any porous compounds. According to one embodiment, the powder phase does not contain any porous fillers and / or porous fibers.

[0127] According to one embodiment, the powder phase contains the ultra-fine calcium silicate particles defined above and other components in the form of particles that are not in the ultra-fine particle form but are crushed, coarsely pulverized, and / or micronized. The "other components" of the powder phase may be additives and / or non-ultra-fine calcium silicate particles as detailed below.

[0128] According to one embodiment, the powder phase contains a calcium silicate mixture, where the calcium silicate mixture contains (i) the UCS particles of the present invention and optionally (ii) non-ultra-fine calcium silicate particles.

[0129] In the present invention, the expression "non-ultra-fine calcium silicate particles" does not have the particle size distribution characteristics of the UCS particles defined above, particularly the defined d 10 , d 50 and / or d 90 refers to calcium silicate particles that do not have the size and specific surface area. According to one embodiment, the non-ultra-fine calcium silicate particles may be in the form of crushed, coarsely pulverized, and / or micronized calcium silicate particles. With respect to the UCS particles, the non-ultra-fine calcium silicate particles are selected from tricalcium silicate particles, dicalcium silicate particles, or any mixture thereof.

[0130] According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size in the range of more than 1.7 to 5 μm, preferably more than 1.7 to 3 μm, more preferably about 2.1 μm. 10 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size in the range of more than 8 to 14 μm, preferably more than 8 to 13 μm, more preferably about 9.8 μm. 50 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size in the range of more than 20 μm to 40 μm, preferably 25 to 35 μm, more preferably about 28.0 μm. 90 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size of about 2.1 μm. 10 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size of about 2.1 μm, a d size of about 9.8 μm, 50 and a d size of about 28.0 μm. 90 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size of 2.1 μm, 10 a d size of 9.8 μm, 50 and a d size of 28.0 μm. 90 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a specific surface area measured by BET (Brunauer-Emmett-Teller technique) in the range of 0.3 to 1.2 m / g, preferably 0.5 to 1.5 m / g, more preferably about 0.78 m / g. 2 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size of 2.1 μm, 2 a d size of 9.8 μm, 2 and a d size of 28.0 μm, 10 as well as a specific surface area measured by BET of about 0.78 m / g. 50 According to one embodiment, the coarsely pulverized calcium silicate particles are characterized by a d size of 2.1 μm, 90 a d size of 9.8 μm, 2 and a d size of 28.0 μm,

[0131] According to one embodiment, the micronized calcium silicate particles are characterized by a d size in the range of more than 0.7 to 1.7 μm, preferably more than 0.7 to 1.0 μm, more preferably about 0.8 μm. 10Characterized by size. According to one embodiment, the micronized calcium silicate particles are in the range of more than 2.9 to 8 μm, preferably more than 3.0 to 5 μm, more preferably about 3.4 μm of d 50 Characterized by size. According to one embodiment, the micronized calcium silicate particles are in the range of more than 6.0 to 20 μm, preferably more than 6.0 to 10 μm, more preferably about 7.2 μm of d 90 Characterized by size. According to one embodiment, the micronized calcium silicate particles are about 0.8 μm of d 10 Size, about 3.4 μm of d 50 And about 7.2 μm of d 90 Characterized by. According to one embodiment, the micronized calcium silicate particles are 0.8 μm of d 10 Size, 3.4 μm of d 50 And 7.2 μm of d 90 Characterized by. According to one embodiment, the micronized calcium silicate particles are 0.8 to 3 m 2 / g, preferably 0.8 to 2 m 2 / g, more preferably about 1.56 m 2 / g of the specific surface area measured by BET (Brunauer - Emmett - Teller technique). According to one embodiment, the micronized calcium silicate particles are 0.8 μm of d 10 Size, 3.4 μm of d 50 And 7.2 μm of d 90 As well as about 1.56 m 2 / g of the specific surface area measured by BET.

[0132] In one embodiment, the powder phase of the present invention consists of UCS particles according to the present invention.

[0133] In one embodiment, the powder phase of the present invention comprises or consists of a mixture of UCS particles according to the present invention and non - ultra - fine calcium silicate particles such as crushed, coarsely pulverized and / or micronized calcium silicate particles.

[0134] In one embodiment, the powder phase of the present invention contains UCS particles according to the present invention as a calcium silicate source.

[0135] In one embodiment, the powder phase of the present invention contains a mixture of UCS particles according to the present invention and non-ultrafine calcium silicate particles such as crushed, coarsely pulverized and / or micronized calcium silicate particles.

[0136] According to one embodiment, the powder phase contains UCS particles in an amount in the range of 10% to 100% by weight, preferably 10% to 98% by weight, preferably 15% to 60% by weight, more preferably 20 to 55% by weight, based on the total weight of the powder phase.

[0137] According to one embodiment, the powder phase contains a calcium silicate mixture in an amount in the range of 10% to 100% by weight, preferably 40% to 100% by weight, 50% to 95% by weight, 50% to 85% by weight, based on the total weight of the powder phase. This amount of the calcium silicate mixture corresponds to the total amount of calcium silicate present in the powder phase regardless of the particle size distribution.

[0138] According to one embodiment, the calcium silicate mixture contains UCS particles according to the present invention and optionally non-ultrafine calcium silicate particles. According to one embodiment, the calcium silicate mixture contains UCS particles in an amount in the range of 10% to 100% by weight, preferably 10% to 100% by weight, 10% to 70% by weight, 30% to 70% by weight, 30% to 60% by weight, 30% to 50% by weight, based on the total weight of the calcium silicate mixture. In a particular embodiment, the amount of UCS particles is about 50% by weight based on the total weight of calcium silicate present in the powder phase.

[0139] According to one embodiment, the powder phase contains non-ultrafine calcium silicate particles in an amount in the range of 0% to 70% by weight based on the total weight of the powder phase. In one embodiment, the powder phase does not contain non-ultrafine calcium silicate particles. In another embodiment, the powder phase contains non-ultrafine calcium silicate particles in an amount in the range of 10% to 60% by weight, preferably 20% to 50% by weight, more preferably 25 to 45% by weight.

[0140] According to one embodiment, the calcium silicate mixture present in the powder phase is - 10% to 100% of the ultra-fine calcium silicate particles according to the present invention, and - 0% to 90% by weight, based on the total weight of the calcium silicate mixture, of crushed, coarsely pulverized and / or micronized calcium silicate particles including.

[0141] According to one embodiment, the calcium silicate mixture includes 50% by weight of UCS particles and 50% by weight of coarsely pulverized calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture consists of or includes 50% by weight of UCS particles and 50% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture consists of or includes 50% by weight of ultra-fine tricalcium silicate (C3S) and 50% by weight of coarsely pulverized calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture consists of or includes 50% by weight of ultra-fine tricalcium silicate particles (C3S) and 50% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture.

[0142] According to one embodiment, the calcium silicate mixture consists of or includes 30% by weight of UCS particles and 70% by weight of coarsely pulverized calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture consists of or includes 30% by weight of UCS particles and 70% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture consists of or includes 30% by weight of ultra-fine tricalcium silicate particles (C3S) and 70% by weight of coarsely pulverized calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture consists of or includes 30% by weight of ultra-fine tricalcium silicate particles (C3S) and 70% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture.

[0143] According to one embodiment, the calcium silicate mixture comprises or consists of 70% by weight of UCS particles and 30% by weight of coarsely ground calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture comprises or consists of 70% by weight of UCS particles and 30% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture comprises or consists of 70% by weight of ultra-fine tricalcium silicate particles (C3S) and 30% by weight of coarsely ground calcium silicate particles, based on the total weight of the calcium silicate mixture.

[0144] According to one embodiment, the calcium silicate mixture comprises or consists of 70% by weight of ultra-fine tricalcium silicate particles (C3S) and 30% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture.

[0145] According to one embodiment, the calcium silicate mixture comprises or consists of 20% by weight of UCS particles and 80% by weight of coarsely ground calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture comprises or consists of 20% by weight of UCS particles and 80% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture comprises or consists of 20% by weight of ultra-fine tricalcium silicate particles (C3S) and 80% by weight of coarsely ground calcium silicate particles, based on the total weight of the calcium silicate mixture. According to one embodiment, the calcium silicate mixture comprises or consists of 20% by weight of ultra-fine tricalcium silicate particles (C3S) and 80% by weight of crushed calcium silicate particles, based on the total weight of the calcium silicate mixture.

[0146] According to one embodiment, the calcium silicate mixture does not contain crushed calcium silicate particles. According to one embodiment, the calcium silicate mixture does not contain crushed C3S particles.

[0147] According to one embodiment, the powder phase comprises Portland cement and / or mineral trioxide aggregate (MTA). According to one embodiment, the powder phase comprises Portland cement and / or mineral trioxide aggregate (MTA) in which the calcium silicate particles are the ultra-fine calcium silicate as defined in the present invention. According to one embodiment, the calcium silicate particles contained therein are d 10 , d 50 , d 90 and S spe and Portland cement and / or mineral trioxide aggregate (MTA) that are ground to have. According to one embodiment, the calcium silicate mixture of the powder phase comprises or consists of calcium silicate and / or mineral trioxide aggregate (MTA) present in Portland cement.

[0148] According to one embodiment, the powder phase further comprises additives such as, for example, radiopaque agents, hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants, fillers and mixtures thereof.

[0149] According to one embodiment, the radiopaque agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof. In a particular embodiment, the radiopaque agent is zirconium oxide. According to one embodiment, the hardening accelerator is calcium carbonate, calcium oxide, calcium phosphate, sodium bicarbonate, calcium lactate, calcium chloride, or mixtures thereof. According to one embodiment, the hardening accelerator is calcium carbonate, calcium oxide, or mixtures thereof. According to one embodiment, the hardening accelerator is calcium chloride. According to one embodiment, the pigment may be iron oxide. According to one embodiment, the water reducing agent is selected from gluconic acid, polynaphthalene sulfonate, and modified polycarboxylate. According to one embodiment, the texturing agent may be selected from, for example, silica, povidone (also referred to as polyvinylpyrrolidone), cellulose or its derivatives such as methylcellulose, hydroxypropylcellulose, and hydroxyethylcellulose, polymers such as acrylamide / acryloyldimethyltaurine sodium copolymer / isohexadecane and hydroxyethyl acrylate / acryloyldimethyltaurine sodium copolymer, inorganic fillers, fumed silica (hydrophilic and / or hydrophobic), xanthan gum, or mixtures thereof. According to one embodiment, the pH stabilizer is an inorganic acid or an organic acid. According to one embodiment, the surfactant is polysorbate.

[0150] According to one embodiment, the powder phase contains at least one additive, which is preferably selected from a radiopaque agent, a curing accelerator, a pigment, and a texturing agent. According to one embodiment, the powder phase contains one or more additives selected from a radiopaque agent (such as zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, or a mixture thereof), a curing accelerator (such as calcium carbonate, calcium oxide, calcium phosphate, or a mixture thereof), a pigment (such as iron oxide), and a mixture thereof. According to one embodiment, the powder phase contains at least one additive in an amount ranging from 0% to 60% by weight, preferably from 2% to 50% by weight, more preferably from 2% to 35% by weight, based on the total weight of the powder phase.

[0151] According to one embodiment, the powder phase contains at least one radiopaque agent such as zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and a mixture thereof. In a particular embodiment, the powder phase contains zirconium oxide.

[0152] According to one embodiment, the powder phase contains a radiopaque agent in an amount ranging from 0 to 40% by weight, preferably from 2 to 35% by weight, 5 to 35% by weight, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35% by weight, based on the total weight of the powder phase.

[0153] According to one embodiment, the powder phase contains at least one curing accelerator such as calcium carbonate, calcium oxide, calcium phosphate, and a mixture thereof. In a particular embodiment, the powder phase contains calcium carbonate. In a particular embodiment, the powder phase contains calcium carbonate and calcium oxide.

[0154] According to one embodiment, the powder phase contains a curing accelerator, preferably calcium carbonate, and the d of the UCS particles 50 d of the curing accelerator particles of size50 The ratio to the size is less than 10, preferably in the range of 0.1 to 9, preferably 0.2 to 5, more preferably 0.5 to 2.

[0155] According to one embodiment, the powder phase contains a curing accelerator in an amount of 0 to 25% by weight, preferably 4 to 20% by weight, preferably 4 to 15% by weight, preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20% by weight based on the total weight of the powder phase.

[0156] According to one embodiment, the powder phase contains at least one pigment or a mixture of pigments such as iron oxide. Those skilled in the art can select a suitable mixture of pigments so that the composition has the expected color.

[0157] According to one embodiment, the powder phase · having a d size in the range of 0.7 μm to 2.9 μm 50 and a d size in the range of 1.4 μm to 6.0 μm 90 (the d size 50 and d size 90 being measured by laser diffraction), and ultrafine particles of calcium silicate in an amount of 15% to 98% by weight based on the total weight of the powder phase, · a radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, · optionally, one or more additives selected from a curing accelerator, a pigment, a water reducing agent, a texturing agent, a pH stabilizer, a surfactant and a filler and containing.

[0158] According to one embodiment, the powder phase · having a d size in the range of 1 μm to 2.1 μm 50 and a d size in the range of 2 μm to 5.0 μm 90 (the d size 50 and d size 90 being measured by laser diffraction), and ultrafine particles of calcium silicate in an amount of 15% to 98% by weight based on the total weight of the powder phase, · a radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, · Optionally, one or more additives selected from hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants, and fillers, and comprises.

[0159] According to one embodiment, the powder phase is · having a d size in the range of 0.5 μm to 0.9 μm, preferably 0.5 μm to 0.82 μm or 0.5 μm to 0.8 μm, and even more preferably 0.5 μm to 0.7 μm, a d size in the range of 0.7 μm to 2.9 μm, preferably 0.8 μm to 2.5 μm, preferably 1 μm to 2.1 μm, and a d size in the range of 1.3 μm to 7.0 μm, preferably 1.5 μm to 7 μm or 2 μm to 5 μm (the d size, d size, and d size are measured by laser diffraction), and 15% to 98% by weight of ultrafine particles of calcium silicate based on the total weight of the powder phase, 10 · 2% to 35% by weight of a radiopaque agent based on the total weight of the powder phase, 50 · Optionally, one or more additives selected from hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants, and fillers, and 90 comprises. 10 50 90 and · 2% to 35% by weight of a radiopaque agent based on the total weight of the powder phase, · Optionally, one or more additives selected from hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants, and fillers, and comprises.

[0160] According to one embodiment, the powder phase is · having a d size in the range of 0.7 μm to 2.9 μm, preferably 1 μm to 2.1 μm, a d size in the range of 1.4 μm to 6.0 μm, preferably 2 μm to 5 μm (the d size and d size are measured by laser diffraction), and 15% to 98% by weight of ultrafine particles of tricalcium silicate (C3S) based on the total weight of the powder phase, 50 · 2% to 35% by weight of a radiopaque agent, preferably zirconium oxide, based on the total weight of the powder phase, 50 90 90 and 50 90 and · 2% to 35% by weight of a radiopaque agent, preferably zirconium oxide, based on the total weight of the powder phase, · Optionally, one or more additives selected from a curing accelerator, a pigment, a water reducing agent, a texturing agent, a pH stabilizer, a surfactant, and a filler, and are included.

[0161] According to one embodiment, the powder phase is · Ultra-fine calcium silicate particles that are 15% to 98% by weight based on the total weight of the powder phase, · Specific surface area measured by the BET technique in the range of 3 to 11 m 2 / g, · d less than 0.7 μm 10 size, · d in the range of 0.7 μm to 2.9 μm 50 size, and · d in the range of 1.4 μm to 6.0 μm 90 size, (d 10 , d 50 and d 90 sizes are measured by laser diffraction) and ultra-fine calcium silicate particles having, · A radiopaque agent that is 2% to 35% by weight based on the total weight of the powder phase, preferably zirconium oxide, · Optionally, one or more additives selected from a curing accelerator, a pigment, a water reducing agent, a texturing agent, a pH stabilizer, a surfactant, and a filler, and are included.

[0162] According to one embodiment, the powder phase is · Ultra-fine calcium silicate particles that are 15% to 98% by weight based on the total weight of the powder phase, · Specific surface area measured by the BET technique in the range of 3 to 11 m 2 / g, · d in the range of 0.5 μm to 0.9 μm 10 size, · d in the range of 1 μm to 2.1 μm 50 size, and · d in the range of 2 μm to 5 μm 90 size, (d 10 , d 50 and d 90The size is measured by laser diffraction) ultrafine particles of calcium silicate having, · a radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, preferably zirconium oxide, · optionally, one or more additives selected from hardening accelerators, pigments, water reducing agents, texturing agents, pH stabilizers, surfactants and fillers and containing.

[0163] According to one embodiment, the powder phase is, · ultrafine particles of tricalcium silicate in an amount of 20% to 60% by weight based on the total weight of the powder phase, · having a specific surface area measured by the BET technique in the range of 3 to 11 m 2 / g, · a d 10 size of less than 0.7 μm, preferably a d 10 size in the range of 0.5 μm to 0.9 μm, · a d 50 size in the range of 0.7 μm to 2.9 μm, preferably a d 50 size, and · a d 90 size in the range of 1.4 μm to 6.0 μm, preferably a d 90 size in the range of 2 μm to 5 μm, (d 10 , d 50 and d 90 The size is measured by laser diffraction) ultrafine particles of tricalcium silicate having, · non-ultrafine particles of calcium silicate in an amount of 0% to 50% by weight based on the total weight of the powder phase, · a radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, · one or more hardening accelerators such as calcium carbonate, calcium oxide and mixtures thereof in an amount of 0% to 25% by weight based on the total weight of the powder phase and containing.

[0164] According to one embodiment, the powder phase is, · Ultra-fine particles of tricalcium silicate that are 20% to 60% by weight based on the total weight of the powder phase, · With a specific surface area measured by the BET technique in the range of 3 to 11 m 2 / g, · With a d 10 size in the range of 0.5 μm to 0.9 μm, preferably 0.5 μm to 0.82 μm, and even more preferably 0.5 μm to 0.7 μm, · With a d 50 size in the range of 0.7 μm to 2.9 μm, preferably 0.8 μm to 2.5 μm, and preferably 1 μm to 2.1 μm, and · With a d 90 size in the range of 1.3 μm to 7.0 μm, preferably 1.5 μm to 7 μm or 2 μm to 5 μm (d 10 , d 50 and d 90 sizes are measured by laser diffraction) Ultra-fine particles of tricalcium silicate having the above, and · Non-ultra-fine particles of calcium silicate that are 0% to 50% by weight based on the total weight of the powder phase, · A radiopaque agent that is 2% to 35% by weight based on the total weight of the powder phase, · One or more hardening accelerators such as calcium carbonate, calcium oxide, and mixtures thereof that are 0% to 25% by weight based on the total weight of the powder phase are included.

[0165] Liquid phase As described above, the dental restorative material of the present invention may be obtained from a mixture of the above calcium silicate powder phase and an aqueous liquid phase.

[0166] According to one embodiment, the aqueous liquid phase contains water, preferably purified water.

[0167] According to one embodiment, the aqueous liquid phase consists of water. In another embodiment, the aqueous liquid phase is an aqueous solution.

[0168] According to one embodiment, the aqueous liquid phase contains water in an amount of 10 to 100% by weight, preferably 20% to 90%, preferably 30% to 90%, preferably 35% to 85% based on the total weight of the aqueous liquid phase. According to one embodiment, the liquid phase contains water in an amount of 50% to 90% by weight, preferably 60% to 90%, more preferably 60% to 85%, more preferably 65% to 85% based on the total weight of the liquid phase.

[0169] According to one embodiment, the aqueous liquid phase further contains additives such as, for example, a curing accelerator, a water reducing agent, a texturing agent, a pH stabilizer, a surfactant, a filler, and mixtures thereof. Examples of such additives are provided above with respect to the powder phase and are also applicable to the additives of the liquid phase.

[0170] According to one embodiment, the aqueous liquid phase contains at least one additive, which is preferably selected from a curing accelerator and a water reducing agent. According to one embodiment, the aqueous liquid phase contains one or more additives selected from a curing accelerator (such as calcium chloride), a water reducing agent (such as a modified polycarboxylate, gluconate, polynaphthalene sulfonate, or mixtures thereof), and mixtures thereof.

[0171] According to one embodiment, the liquid phase contains at least one additive in an amount in the range of 0% to 40% by weight, preferably 10% to 35%, more preferably 15% to 35% based on the total weight of the liquid phase.

[0172] According to one embodiment, the liquid phase contains at least one curing accelerator, preferably calcium chloride. According to one embodiment, the liquid phase contains or consists of water and calcium chloride. According to one embodiment, the liquid phase contains calcium chloride in an amount of 1% to 40% by weight, preferably 5% to 35% based on the total weight of the liquid phase. In certain embodiments, the liquid phase contains calcium chloride in an amount of 15% to 35% by weight, preferably 20% to 30% based on the total weight of the liquid phase. In another embodiment, the liquid phase does not contain a curing accelerator, and in particular, the liquid phase does not contain calcium chloride.

[0173] According to one embodiment, the liquid phase contains at least one water reducing agent such as, for example, gluconium, polynaphthalenesulfonate or modified polycarboxylate. According to one embodiment, the liquid phase consists of or contains water and a water reducing agent (preferably a modified polycarboxylate). According to one embodiment, the liquid phase contains the water reducing agent in an amount of 0% to 40% by weight, preferably 0.5% to 35% by weight, based on the total weight of the liquid phase. In a particular embodiment, the liquid phase contains the water reducing agent in an amount of 0% to 5% by weight, preferably 0% to 2% by weight, based on the total weight of the liquid phase.

[0174] According to one embodiment, the liquid phase contains at least one curing accelerator and at least one water reducing agent. According to one embodiment, the liquid phase consists of or contains water, a curing accelerator and a water reducing agent, preferably the liquid phase consists of or contains water, calcium chloride and a modified polycarboxylate.

[0175] According to one embodiment, the aqueous liquid phase - water in an amount of 60% to 85% by weight based on the total weight of the aqueous liquid phase, and - a curing accelerator, preferably calcium chloride, in an amount of 5% to 35% by weight based on the total weight of the aqueous liquid phase, and - a reducing agent, preferably a modified polycarboxylate, in an amount of 0% to 5% by weight based on the total weight of the aqueous liquid phase and contains.

[0176] According to one embodiment, the aqueous liquid phase further includes a non-aqueous liquid. In one embodiment, the non-aqueous liquid is selected from glycerol, glycol, silicone, or a mixture thereof, and preferably the non-aqueous liquid is a glycol such as propylene glycol or polyethylene glycol. According to one embodiment, the glycol compound is selected from ethylene glycol, propylene glycol (or propane-1,2-diol), trimethylene glycol (or propane-1,3-diol), butylene glycol (or butane-1,3-diol), butane-1,2-diol, butane-1,4-diol, pentylene glycol (or pentane-1,5-diol), pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, dipropylene glycol, or polyethylene glycol, and preferably the glycol compound is ethylene glycol, propylene glycol, dipropylene glycol, or polyethylene glycol. According to one embodiment, the polyethylene glycol has an average molecular weight M in the range of 100 g / mol to 10,000 g / mol, preferably 200 g / mol to 5000 g / mol, more preferably about 300 g / mol or about 4000 g / mol. According to one embodiment, the silicone is selected from alkyl silicones, and more preferably is selected from methicone, dimethylmethicone, caprylyl methicone, their copolymers, or mixtures thereof. According to one embodiment, the silicone is selected from methicone, dimethylmethicone, and caprylyl methicone.

[0177] According to one embodiment, the mass ratio of water / non-aqueous liquid in the liquid phase is in the range of 50 / 50 to 80 / 20. According to one embodiment, the liquid phase comprises a mixture of 50 wt% water / 50 wt% non-aqueous liquid. According to one embodiment, the liquid phase comprises a mixture of 70% water / 30% non-aqueous liquid. According to one embodiment, the liquid phase comprises a mixture of 80% water / 20% non-aqueous liquid. According to one embodiment, the mixture of water / non-aqueous liquid in the liquid phase contains at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% water. According to one embodiment, the liquid phase contains, by weight, 10 to 100%, preferably 50 to 90%, preferably 65 to 85%, preferably 65 to 75% of a mixture of non-aqueous liquids, based on the total weight of the liquid phase. According to one embodiment, the aqueous liquid phase contains, by weight, 0 to 50%, preferably 0 to 45%, preferably 10 to 45%, preferably 10 to 20% of a non-aqueous liquid, based on the total weight of the liquid phase.

[0178] According to another embodiment, the liquid phase consists of or contains water, a non-aqueous liquid, a curing accelerator and a water reducing agent, and preferably the liquid phase consists of or contains (i) water, ethylene glycol, calcium chloride and a modified polycarboxylate, or (ii) water, polyethylene glycol, calcium chloride and a modified polycarboxylate.

[0179] According to one embodiment, the liquid phase is - 35% to 85% water, and - 0 to 45% non-aqueous liquid, and - 5% to 35% curing accelerator, and - other additives such as 0% to 35% water reducing agent by weight based on the total weight of the liquid phase and contains.

[0180] Kit The present invention also relates to a kit suitable for preparing the dental restorative material of the present invention, comprising a powder phase containing the UCS particles described above and an aqueous liquid phase.

[0181] In one embodiment, the kit of the present invention includes a first container and a second container. In one embodiment, the first container contains a solid phase, preferably a powder phase, more preferably a powder phase containing UCS particles, and even more preferably a powder phase containing the UCS particles described above. In one embodiment, the second container contains a liquid phase, preferably an aqueous liquid phase, and more preferably an aqueous liquid phase as described above.

[0182] Therefore, according to one embodiment, the kit of the present invention - a first container containing a solid phase, preferably a powder phase, containing the UCS particles defined above, - a second container containing a liquid phase, preferably an aqueous liquid phase, and more preferably an aqueous liquid phase as described above including.

[0183] All of the above embodiments regarding the powder phase and the aqueous liquid phase also apply to the powder phase and the liquid phase present in the kit of the present invention. Specific embodiments will be described in more detail below.

[0184] According to one embodiment, the present invention is a first container containing a powder phase, · d in the range of 0.7 μm to 2.9 μm, preferably 0.8 μm to 2.5 μm, and even more preferably 0.8 μm to 2.1 μm 50 size and d in the range of 1.3 μm to 7.0 μm, preferably 1.4 μm to 7 μm, 1.4 μm to 6 μm or 2 μm to 5 μm 90 size (d 50 and d 90 size measured by laser diffraction), ultra-fine calcium silicate particles of 15% to 98% by weight based on the total weight of the powder phase, · a radiopaque agent of 2% to 35% by weight based on the total weight of the powder phase, and · Optionally, one or more additives selected from hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants and fillers including a first container, a second container containing an aqueous liquid phase A kit for preparing a dental restorative material, comprising: The weight ratio of the powder phase present in the kit to the liquid phase present in the kit is in the range of 1.9 to 5.5, preferably 2 to 5, and more preferably 2.5 to 4.0. A kit is provided.

[0185] According to one embodiment, the calcium silicate present in the powder phase of the present kit is selected from tricalcium silicate (C3S), dicalcium silicate (C2S), and any combination thereof, and preferably the calcium silicate is tricalcium silicate.

[0186] According to one embodiment, the powder phase of the present kit contains Portland cement and / or mineral trioxide aggregate (MTA).

[0187] According to one embodiment, the powder phase of the present kit further contains non-ultrafine particles of calcium silicate.

[0188] According to one embodiment, the amount of ultrafine calcium silicate particles present in the powder phase of the present kit is in the range of 10% to 100% by weight, preferably 10% to 70% by weight, and more preferably 10% to 50% by weight based on the total weight of the calcium silicate present in the powder phase.

[0189] According to one embodiment, the radiopaque agent present in the powder phase of the present kit is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof, and preferably the radiopaque agent is zirconium oxide.

[0190] According to one embodiment, the powder phase of the present kit contains one or more additives, and the additives are selected from hardening accelerators such as calcium carbonate, calcium oxide, calcium phosphate, and mixtures thereof, and pigments such as iron oxide.

[0191] According to one embodiment, the powder phase of the present kit is · Tricalcium silicate ultrafine particles that are 20% to 60% by weight based on the total weight of the powder phase, · 3 to 11 m 2 / g specific surface area measured by the BET technique in the range of, · d less than 0.7 μm 10 size, · d in the range of 0.7 μm to 2.9 μm 50 size, and · d in the range of 1.4 μm to 6.0 μm 90 size (d 10 , d 50 and d 90 size is measured by laser diffraction) Tricalcium silicate ultrafine particles having, · Calcium silicate non-ultrafine particles that are 0% to 50% by weight based on the total weight of the powder phase, · A radiopaque agent that is 2% to 35% by weight based on the total weight of the powder phase, · One or more hardening accelerators selected from calcium carbonate, calcium oxide, and mixtures thereof that are 0% to 25% by weight based on the total weight of the powder phase including.

[0192] According to one embodiment, the powder phase of the kit is, · Tricalcium silicate ultrafine particles that are 20% to 60% by weight based on the total weight of the powder phase, · 3 to 11 m 2 / g specific surface area measured by the BET technique in the range of, · d in the range of 0.5 μm to 0.9 μm, preferably 0.5 μm to 0.82 μm 10 size, · In the range of 0.7 μm to 2.9 μm, preferably in the range of 1 μm to 2.1 μm 50 size, and · In the range of 1.4 μm to 6.0 μm, preferably in the range of 2 μm to 5 μm 90 size, (d 10 , d 50 and d 90 size is measured by laser diffraction) Ultra-fine particles of tricalcium silicate having · Non-ultra-fine particles of calcium silicate in an amount of 0% to 50% by weight based on the total weight of the powder phase, · A radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, · One or more hardening accelerators selected from calcium carbonate, calcium oxide and mixtures thereof in an amount of 0% to 25% by weight based on the total weight of the powder phase and containing.

[0193] According to one embodiment, the aqueous liquid phase present in the kit is water.

[0194] According to one embodiment, the aqueous liquid phase present in the kit further contains one or more additives, and the additives are selected from hardening accelerators such as calcium chloride and water reducing agents such as modified polycarboxylates.

[0195] According to one embodiment, the aqueous liquid phase present in the kit is · 60% to 85% by weight of water based on the total weight of the aqueous liquid phase, · A hardening accelerator, preferably calcium chloride, in an amount of 5% to 35% by weight based on the total weight of the aqueous liquid phase, · A reducing agent, preferably a modified polycarboxylate, in an amount of 0% to 5% by weight based on the total weight of the aqueous liquid phase and containing.

[0196] Mixing composition According to one embodiment, the repair material of the present invention is produced by the hardening of a composition obtained by mixing the described powder phase and the aqueous liquid phase.

[0197] According to one embodiment, the composition resulting from the mixing of the powder and the aqueous liquid phase defined above is creamy (i.e., a paste in which the components are uniformly mixed together without any agglomerates). According to one embodiment, the creamy texture may be determined visually. According to one embodiment, the composition of the present invention is colored, preferably white.

[0198] According to one embodiment, the composition of the present invention does not contain any aluminate such as calcium aluminate. According to one embodiment, the composition of the present invention does not contain any halogen or halogenated compound such as fluoride. According to one embodiment, the composition of the present invention does not contain any phosphate such as calcium phosphate. According to one embodiment, the composition of the present invention does not contain any porous compound. According to one embodiment, the composition of the present invention does not contain any porous filler and / or porous fiber.

[0199] According to one embodiment, the weight ratio of the powder phase / aqueous liquid phase is in the range of 1.9 to 5.5, preferably 2 to 5, preferably 2.5 to 4.0. The weight ratio of the powder phase / aqueous liquid phase is adjusted so as to obtain a suitable creamy form for the resulting composition. The weight ratio of the powder phase / aqueous liquid phase can also control the compressive strength of the cured repair material. According to one embodiment, the weight ratio of the powder phase / aqueous liquid phase is in the range of 2.4 to 4.0, preferably 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.

[0200] According to one embodiment, the curing time of the composition resulting from the mixing of the powder and the aqueous liquid phase is more than 0 minutes to 1 hour, preferably less than 1 minute to 15 minutes, more preferably less than 1 minute to 12 minutes, more preferably less than 1 minute to 9 minutes, more preferably less than 1 minute to 8 minutes, even more preferably less than 1 minute to 7 minutes. According to one embodiment, the curing time of the composition of the present invention is in the range of 1 minute to 12 minutes, preferably 4 minutes to 9 minutes.

[0201] According to one embodiment, the working time of the composition resulting from the mixing of the powder and the aqueous liquid phase is more than 0 minutes to 10 minutes, preferably less than 1 minute to 5 minutes, more preferably in the range of 1 minute to 3 minutes.

[0202] According to one embodiment, the present composition results from the mixing of a powder phase comprising or consisting of a calcium silicate mixture containing 10% to 100% of ultra-fine calcium trisilicate particles and 0% to 90% of micronized, coarsely ground or crushed calcium silicate particles, preferably 10% to 60% of ultra-fine calcium trisilicate particles and 40% to 90% of micronized, coarsely ground or crushed calcium silicate particles, and an aqueous liquid phase containing water and calcium chloride. According to one embodiment, the composition of the present invention resulting from the mixing of a powder phase comprising a calcium silicate mixture containing 10% to 100% of ultra-fine calcium trisilicate particles and 0% to 90% of micronized, coarsely ground or crushed calcium silicate particles, preferably 10% to 60% of ultra-fine calcium trisilicate particles and 40% to 90% of micronized, coarsely ground or crushed calcium silicate particles, and an aqueous liquid phase containing water and calcium chloride has a setting time of more than 0 minutes to 12 minutes, preferably 1 minute to 9 minutes, more preferably less than 1 minute to 8 minutes, and even more preferably less than 1 minute to 7 minutes.

[0203] Pre-mixed water-free composition The present invention also provides a pre-mixed water-free composition as a starting composition enabling the preparation of the dental restorative material of the present invention. Thus, in one embodiment, the present invention provides a pre-mixed water-free calcium silicate composition containing UCS particles.

[0204] In one embodiment, the pre-mixed water-free composition is - a powder phase as defined above containing ultra-fine calcium silicate particles, the powder phase being anhydrous, and - a water-free liquid phase containing a non-aqueous liquid and not containing water resulting from the mixing of.

[0205] The pre-mixed water-free paste can be used directly for dental restoration, and thus hardens in situ when placed in the patient's oral cavity by contact with physiological fluids, thereby obtaining a hardened material. Alternatively, the pre-mixed water-free paste can be mixed later with an aqueous liquid phase or an aqueous paste. In such a case, the mixing of the pre-mixed water-free calcium silicate paste with an aqueous phase (in either liquid or paste form) causes the hardening of the present composition and a hardened material is obtained. In one embodiment, the aqueous phase mixed with the pre-mixed water-free paste contains water and optionally additives such as a hardening accelerator or a water reducing agent.

[0206] All of the above embodiments regarding the powder phase also apply to the powder present in the pre-mixed water-free composition.

[0207] According to one embodiment, the non-aqueous liquid is selected from glycerol, glycols, silicones or mixtures thereof.

[0208] According to one embodiment, the glycol is selected from ethylene glycol, propylene glycol (or propane-1,2-diol), trimethylene glycol (or propane-1,3-diol), butylene glycol (or butane-1,3-diol), butane-1,2-diol, butane-1,4-diol, pentylene glycol (or pentane-1,5-diol), pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, dipropylene glycol or polyethylene glycol, preferably the glycol compound is ethylene glycol, propylene glycol, dipropylene glycol or polyethylene glycol. According to one embodiment, the polyethylene glycol has an average molecular weight M in the range of 100 g / mol to 10,000 g / mol, preferably 200 g / mol to 5000 g / mol, more preferably about 300 g / mol or about 4000 g / mol. Preferably, the non-aqueous liquid is a glycol such as propylene glycol or polyethylene glycol.

[0209] According to one embodiment, the silicone is selected from alkyl silicones, more preferably selected from methicone, dimethylmethicone, caprylyl methicone, their copolymers or mixtures thereof. According to one embodiment, the silicone is selected from methicone, dimethylmethicone and caprylyl methicone.

[0210] According to one embodiment, the pre-mixed water-free paste contains 10 to 50%, preferably 20 to 50%, preferably 30 to 50%, preferably 40 to 50%, preferably 10, 15, 20, 25, 30, 35, 40, 45 or 50% by weight of a non-aqueous liquid based on the total weight of the paste. According to one embodiment, the pre-mixed water-free paste contains 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50% by weight of a non-aqueous liquid based on the total weight of the paste.

[0211] Hardened calcium silicate-based restorative The present invention also relates to a hardened restorative, preferably a dental restorative obtained by the hydraulic hardening of a composition containing the ultra-fine calcium silicate particles defined above. The hardening occurs by the hydration of the calcium silicate present in the composition. The composition may be a composition resulting from the mixing of a powder phase containing the ultra-fine calcium silicate particles described above and an aqueous liquid phase or alternatively a pre-mixed water-free composition described above.

[0212] According to one embodiment, the cured repair material has a compressive strength of more than 10 MPa, preferably more than 50 MPa, more than 100 MPa, more than 120 MPa, more than 130 MPa, more than 140 MPa, and even more preferably more than 150 MPa. Preferably, the compressive strength is measured by applying a force of preferably 10 kN using a compression bench device. According to one embodiment, the cured repair material has a compressive strength of more than 10 MPa, preferably more than 50 MPa, more than 100 MPa, more than 120 MPa, more than 130 MPa, more than 140 MPa, and even more preferably more than 150 MPa at 24 hours. According to one embodiment, the cured repair material has a compressive strength in the range of 160 MPa to 260 MPa. According to one embodiment, the cured repair material has a compressive strength of about 161 MPa, 174 MPa, 175 MPa, 181 MPa, 194 MPa, 243 MPa or 250 MPa.

[0213] According to one embodiment, the cured repair material has radiopacity in the range of 1 to 15 mm, preferably 3 to 10 mm, preferably 4 to 9.5 mm of aluminum. In the present invention, the radiopacity of the cured material meets the dental material standard specifications, particularly the NF EN ISO 6876 standard.

[0214] Use According to one embodiment, the compositions and kits of the present invention can be used in the dental field. According to one embodiment, the compositions and kits of the present invention can also be used in orthopedics, bone repair, craniofacial and / or maxillofacial surgery.

[0215] In one embodiment, the compositions and kits of the present invention can be used to provide materials for the treatment of dental crowns, such as temporary enamel restoration, permanent dentin restoration, deep or large carious lesion restoration, deep cervical or root lesion restoration, pulp capping or pulpotomy.

[0216] In one embodiment, the compositions and kits of the present invention can also be used to provide materials for treating tooth roots, such as root and furcation perforation, internal / external tooth resorption, apexification or retrograde root filling.

[0217] In one embodiment, the present invention relates to the use of the compositions and kits of the present invention for the treatment of dental crowns, such as temporary enamel restoration, permanent dentin restoration, restoration of deep or large carious lesions, restoration of deep cervical or root lesions, pulp capping or pulpotomy, and / or treatment of dental roots, such as root and furcation perforations, internal / external tooth resorption, apexification or retrograde root filling. In one embodiment, the present invention relates to a method for treating dental crowns in a subject in need thereof, including the use of the compositions and kits of the present invention, such as temporary enamel restoration, permanent dentin restoration, restoration of deep or large carious lesions, restoration of deep cervical or root lesions, pulp capping or pulpotomy, and / or treatment of dental roots, such as root and furcation perforations, internal / external tooth resorption, apexification or retrograde root filling.

[0218] According to one embodiment, the compositions and kits of the present invention can be used in treating bone and / or dental disorders or diseases in a subject in need thereof. According to one embodiment, the present invention refers to the compositions and kits of the present invention for treating bone and / or dental disorders or diseases in a subject in need thereof. According to one embodiment, the present invention refers to a method for treating bone and / or dental disorders or diseases in a subject in need thereof by using the compositions and kits of the present invention.

[0219] According to one embodiment, the compositions and kits of the present invention can be used for bone repair or bone regeneration. According to one embodiment, the present invention refers to the use of the compositions and kits of the present invention for bone repair or bone regeneration. According to one embodiment, the present invention refers to a method for bone repair or bone regeneration by using the compositions and kits of the present invention.

[0220] Medical device The present invention also relates to a medical device comprising a composition containing the ultra-fine calcium silicate particles defined above.

[0221] In one embodiment, the medical device is an injection system, preferably a syringe, containing a composition obtained by mixing the powder phase and the aqueous liquid phase described above. In one embodiment, the medical device is an injection system, preferably a syringe, containing the powder-liquid kit described above.

[0222] In another embodiment, the medical device is an injection system, preferably a syringe, containing the pre-mixed water-free composition described above. In a particular embodiment, the syringe is a dual syringe in which one compartment contains the pre-mixed water-free composition described above and the second compartment contains the aqueous phase.

Brief Description of the Drawings

[0223]

Figure 1

Figure 2

Figure 3

Figure 4

Examples

[0224] The present invention is further illustrated by the following examples.

[0225] Abbreviations C3S: Tricalcium silicate CS: Calcium silicate g: gram MTA: Mineral Trioxide Aggregate m 2 / g: square meters per gram min: minute mL: milliliter mm: millimeter μm: micrometer p / l ratio: mass ratio of powder phase / liquid phase rpm: revolutions per minute UCS: Ultra-fine Calcium Silicate UTCS: Ultra-fine Tricalcium Silicate (tricalcium silicate particles consisting of 100% ultra-fine C3S particles)

[0226] Materials and Methods Microscopy The morphology of calcium silicate particles such as C3S particles was observed with a Keyence (registered trademark) microscope before and after the grinding process. To avoid clot formation during analysis, the sample to be analyzed was placed on a glass slide together with a drop of ethanol.

[0227] Particle Size Distribution Using a Malvern (registered trademark) particle size measuring device based on laser diffraction particle size analysis technology, the particle size distribution of ultra-fine calcium silicate such as C3S particles was determined. The powder sample to be analyzed was dispersed in ethanol and sonicated to separate powder agglomerates. Then, several drops of the suspension were introduced into the tank of the particle size measuring device so that the measurement cell had a filling of 2% - 10%. This tank was stirred at approximately 2000 rpm.

[0228] Specific Surface Area: BET Technique Specific surface area analysis was performed by the nitrogen adsorption method using a GEMINI VII Micromeritics (registered trademark) device. This analysis was performed using 1 g of powder. The sample had been degassed at 250 °C for 3 hours before analysis by nitrogen adsorption.

[0229] Setting Time The curing time was measured using a Gilmore apparatus. The test material was placed in a mold with a diameter of 10 mm and a thickness of 2 mm, and then placed in a water bath at 37 °C. The curing of the material was evaluated using a 400 g Gilmore needle. The material is considered cured when the needle leaves no mark on the surface of the mold. The curing time corresponds to the period from when the mold is placed in the water bath until curing is observed.

[0230] Compressive strength The compressive strength was measured using a compression bench apparatus manufactured by MTS. Cement was slowly introduced into a mold with a height of 6 mm / diameter of 4 mm, and it was confirmed that there were no air bubbles. This mold was placed in a water bath at 37 °C for 15 minutes. Then the sample was taken out of the mold and placed in a test tube containing purified water and left in the water bath for 24 hours. After 24 hours, each side of the sample was polished and compressed using an MTS compression bench applying a force of 10 kN.

[0231] Part I: Preparation of ultra-fine tricalcium silicate particles

[0232] The following properties: - 3 to 11 m 2 / g range of specific surface area, - 0.4 μm to 0.82 μm, preferably 0.4 μm to 0.8 μm range of d 10 size, - 0.8 μm to 2.1 μm range of d 50 size, and - 1.4 μm to 7.0 μm range of d 90 size In order to obtain ultra-fine C3S particles having the following properties, C3S particles having a coarse particle size were pulverized.

[0233] In the following herein, separate processes are performed, which are illustrative and not limiting, depending on the apparatus.

[0234] Example 1: Process for producing ultra-fine tricalcium silicate (UTCS) particles by mechanical pulverization

[0235] In the following description, the preparation of UTCS particles was carried out by a general procedure using an EMAX (registered trademark) device manufactured by RETSCH.

[0236] Materials The crushed C3S particles used in the following examples were obtained by crushing coarse C3S using a crusher manufactured by Retch. The coarsely crushed C3S particles used in the following examples were obtained by further crushing the C3S particles crushed using a crusher roller (Crusher Faure).

[0237] General procedure In the first step, the crushed or coarsely crushed C3S particles mixed with isopropanol are added to the grinding chamber of the device. Next, grinding beads are added to the previous mixture. In the process of the present invention, the grinding beads may be, for example, zirconium oxide beads having a diameter in the range of 0.4 mm to 0.8 mm. Next, grinding is carried out for 20 to 30 minutes. According to the present invention, the grinding may be carried out for a longer period until ultrafine particles having the particle size defined above are achieved. Finally, the ground mixture is dried to remove isopropanol. After sieving, ultrafine powder of C3S particles is obtained.

[0238] Regardless of the device used, the process of the present invention requires that the grinding beads and the grinding chamber are not made of stainless steel. Preferably, the process includes the use of grinding beads and a grinding chamber made and / or coated with zirconium oxide, tungsten carbide and / or silicon carbide.

[0239] Example 1a: A general procedure was carried out using 45 g of coarsely crushed C3S particles, 30 mL of isopropanol and 90 g of grinding beads. Grinding by an EMAX (registered trademark) device was carried out for 20 minutes at a grinding speed of about 1900 rpm. Drying was carried out at about 50 °C.

[0240] Part II: Characterization of Ultrafine C3S Particles

[0241] Example 2: Characterization of the properties of the ultrafine C3S (UTCS) particles obtained in Example 1a

[0242] Microscopy The final powder of the C3S particles after pulverization into ultrafine powder according to the process described in Example 1a was compared with the size of the initial C3S particles (coarsely pulverized C3S) by optical microscopy.

[0243] Figure 1 is characterized by a significant decrease in the particle size of the ultrafine C3S particles.

[0244] Particle size The particle size distribution of the C3S particles after pulverization into ultrafine powder according to the process described in Example 1a was compared with that of the micronized C3S particles, coarsely pulverized C3S particles, and crushed C3S particles (Table 1). [Table 1]

[0245] These results indicate that the process of the present invention significantly reduces the particle size distribution. In particular, the ultrafine C3S particles are superior in d 10 , d 50 and d 90 size compared to the crushed, coarsely pulverized, and micronized C3S particles.

[0246] Specific surface area S spe The specific surface area of the C3S particles after pulverization into ultrafine powder according to the process described in Example 1a was compared with that of the micronized C3S particles and coarsely pulverized C3S particles (Table 2). The specific surface area was measured by the BET technique described above. [Table 2]

[0247] These results indicate that the specific surface area of the ultrafine C3S particles is higher than that of the coarsely pulverized and micronized C3S particles.

[0248] Part III: Compositions of the Invention

[0249] Example 3: Preparation of Dental Compositions with Different Calcium Silicate Particle Sizes

[0250] The powder phase A according to the invention and the comparative powder phase C (i.e., not containing ultra-fine calcium silicate particles) having the compositions shown in Table 3 were prepared by mixing the powder components.

[0251] By mixing the said components with water, the liquid phase B according to the invention having the compositions shown in Table 4 was prepared.

[0252] Subsequently, a mixed composition was prepared by mixing the powder phase A with the liquid phase B at a powder phase / liquid phase ratio (w / w) in the range of 1.5 to 6. [Table 3] JPEG0007684273000004.jpg77158JPEG0007684273000005.jpg77158JPEG0007684273000006.jpg77158JPEG0007684273000007.jpg71158JPEG0007684273000008.jpg71158JPEG0007684273000009.jpg72158JPEG0007684273000010.jpg72158 [Table 4]

[0253] Part IV: Characteristics of the Compositions of the Invention

[0254] Example 4: Comparison of the Setting Times of a Dental Composition Containing Ultra-Fine C3S Particles and a Composition Containing Non-Ultra-Fine C3S Particles

[0255] This experiment aims to evaluate the improvement in the setting time of a self-curing dental composition containing ultra-fine C3S particles, compared to a composition containing micronized C3S particles instead of ultra-fine C3S particles, while maintaining good handling properties such as appearance and working time.

[0256] Several compositions according to the present invention were prepared by mixing one of the powder phases A1, A2, A5, A6, A7 or A10 listed in Table 3 with one of the liquid phases B1 bis, B4 or B4 bis listed in Table 4.

[0257] For comparison, a composition equivalent to the above composition but containing only micronized C3S particles was prepared by mixing one of the powder phases C1-3, C5, C6, C7 or C10 listed in Table 3 with one of the liquid phases B1 bis, B4 or B4 bis listed in Table 4.

[0258] p / l ratio First, experiments were conducted to determine the suitable mass ratio (p / l ratio) of the powder phase to the liquid phase for each of the present compositions in order to provide a uniform creamy appearance when the powder phase was mixed with the liquid phase. In particular, various ratios of the powder phase and the liquid phase were tested until the expected creamy appearance was obtained.

[0259] The ratios reported in Table 5 were determined to be suitable for providing the expected appearance and processability for the present compositions.

Table 5

[0260] Therefore, by adapting the p / l ratio, a suitable texture can be imparted according to the composition of the powder and liquid phases used for the mixture.

[0261] Setting time The curing time of the composition obtained by mixing the powder phase A and the liquid phase B in the determined ratio was measured. The results are provided in Table 6 and are also shown in FIGS. 2 and 3.

Table 6

[0262] As demonstrated by the above results and clearly shown in FIGS. 2 and 3, the use of the ultrafine calcium silicate particles of the present invention can significantly shorten the curing time of the present composition as compared to the use of only micronized calcium silicate particles.

[0263] Particularly in FIG. 2, by using the liquid phase B1 bis together with various powder phases (A1, A2, A5, A6, A7 and A10) of the present invention, the curing time can be reduced by at least 44% (A6 vs. C6) to 65% (A5 vs. C5) (the average in these compositions is about 56%) compared to their equivalent phases containing only micronized calcium silicate particles (C1-3, C5, C6, C7 and C10).

[0264] FIG. 3 shows that regardless of which liquid phase (B1 bis, B4 or B4 bis) is used, by using the powder phase (A5) of the present invention, a reduction in the curing time can be obtained compared to the equivalent phase containing only micronized calcium silicate particles (C5).

[0265] Compressive strength

[0266] Example 5: Comparison of the compressive strength of a dental composition containing ultrafine C3S particles and a composition containing non-ultrafine C3S particles

[0267] This experiment aims to evaluate the compression retention of a self-curing dental composition containing ultrafine C3S particles compared to a composition containing micronized C3S particles instead of ultrafine C3S particles.

[0268] Several compositions were prepared by mixing the powder phases A2 or A7 bis described in Table 3 with the liquid phase B1 bis described in Table 4. Powder phases C1 - 3 containing micronized C3S particles instead of ultrafine C3S particles were used for comparison.

[0269] Different batches of C3S particles were used for the ultrafine C3S particles. The particle size distribution of the C3S particles used in the compositions of this example is detailed in Table 7.

Table 7

[0270] The compressive strength of the hardened materials was measured and these results are reported in Table 8 and also shown in Figure 4.

Table 8

[0271] As demonstrated by the above results and clearly shown in Figure 4, the use of the ultrafine calcium silicate particles of the present invention can maintain or even increase the compressive strength of the hardened repair material compared to the materials obtained using micronized calcium silicate particles.

Claims

1. A first container containing a powder phase, wherein the powder phase comprises: ・ d in the range of 0.4 μm to 0.8 μm １０ size, d in the range of 0.7 μm to 2.9 μm ５０ size and d in the range of 1.3 μm to 7 μm ９０ size (d １０ , d ５０ and d ９０ size is measured by laser diffraction), and ultrafine particles of calcium silicate that are 15% to 98% by weight based on the total weight of the powder phase - A radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase; and - Optionally, one or more additives selected from hardening accelerators, pigments, water reducers, texturing agents, pH stabilizers, surfactants, and fillers A first container; and A second container containing an aqueous liquid phase A kit for preparing a dental restorative material, comprising: A kit in which the weight ratio of the powder phase present in the kit to the liquid phase present in the kit is in the range of 2 to 5.

2. The kit according to claim 1, wherein the calcium silicate is selected from tricalcium silicate (C3S), dicalcium silicate (C2S), and any combination thereof.

3. The kit according to claim 1 or claim 2, wherein the powder phase comprises Portland cement and / or mineral trioxide aggregate (MTA) as ultra-fine calcium silicate particles.

4. The kit according to any one of claims 1 to 3, wherein the powder phase further comprises non-ultra-fine particles of calcium silicate.

5. The kit according to any one of claims 1 to 4, wherein the amount of the ultra-fine calcium silicate particles is in the range of 10% to 100% by weight based on the total weight of the calcium silicate present in the powder phase.

6. The kit according to any one of claims 1 to 5, wherein the radiopaque agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof.

7. The kit according to any one of claims 1 to 6, wherein the powder phase contains one or more additives, and the additives are selected from hardening accelerators and pigments.

8. The powder phase comprises: - Ultra-fine particles of tricalcium silicate in an amount of 20% to 60% by weight based on the total weight of the powder phase, having ・ 3 to 11 m ２ Specific surface area measured by the BET technique in the range of / g, ・d in the range of 0.4 μm to 0.8 μm １０ size ・d in the range of 0.7 μm to 2.9 μm ５０ size, and ・d in the range of 1.3 μm to 7 μm ９０ Size (d １０ , d ５０ and d ９０ sizes are measured by laser diffraction) Ultra-fine particles of tricalcium silicate; - Non-ultra-fine particles of calcium silicate in an amount of 0% to 50% by weight based on the total weight of the powder phase; - A radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase; and - One or more hardening accelerators in an amount of 0% to 25% by weight based on the total weight of the powder phase The kit according to any one of claims 1 to 7.

9. The kit according to any one of claims 1 to 8, wherein the aqueous liquid phase is water.

10. The kit according to claim 9, wherein the aqueous liquid phase further comprises one or more additives selected from a curing accelerator and a water reducing agent.

11. The aqueous liquid phase - water in an amount of 60% to 85% by weight based on the total weight of the aqueous liquid phase, - a curing accelerator in an amount of 5% to 35% by weight based on the total weight of the aqueous liquid phase, - a water reducing agent in an amount of 0% to 5% by weight based on the total weight of the aqueous liquid phase The kit according to claim 10, comprising

12. A dental composition comprising a powder phase and an aqueous liquid phase, wherein the powder phase ultrafine calcium silicate particles having a d10 size in the range of 0.4 μm to 0.8 μm, a d50 size in the range of 0.7 μm to 2.9 μm, and a d90 size of 1.3 μm to 7 μm as measured by laser diffraction, in an amount of 15% to 98% by weight based on the total weight of the powder phase, a radiopaque agent in an amount of 2% to 35% by weight based on the total weight of the powder phase, optionally one or more additives selected from a curing accelerator, a pigment, a water reducing agent, a texturing agent, a pH stabilizer, a surfactant, and a filler, comprising wherein the weight ratio of the powder phase / the aqueous liquid phase is in the range of 2 to 5, a dental composition.

13. A medical device comprising the kit according to any one of claims 1 to 11.

14. The medical device according to claim 13, wherein the medical device is an injection system.

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