Dental product for the formation of endodontic cement
A dental product with propylene glycol, dicalcium phosphate, tetracalcium phosphate, and zirconium oxide, combined with potassium citrate or chlorhexidine, addresses the challenges of radiopacity, bacterial prevention, and stability in endodontic cements, ensuring effective sealing and ease of use in dental canals.
Patent Information
- Authority / Receiving Office
- FR · FR
- Patent Type
- Applications
- Current Assignee / Owner
- PROD DENTAIRES PIERRE ROLLAND
- Filing Date
- 2024-11-29
- Publication Date
- 2026-06-05
AI Technical Summary
Existing endodontic cements face challenges in maintaining radiopacity, preventing bacterial proliferation, ensuring stable setting time and compressive strength, and avoiding phase separation, while being easy to process and revise, especially in the presence of moisture in dental canals.
A dental product comprising propylene glycol, a mixture of dicalcium phosphate and tetracalcium phosphate, zirconium oxide, and either potassium citrate or chlorhexidine, formulated to achieve limited viscosity, radiopacity, and bacterial prevention, with a setting time and compressive strength similar to 'Total Fill®', and packaged to prevent premature setting.
The formulation provides a stable, biocompatible cement with radiopacity, effective bacterial inhibition, and manageable viscosity, allowing easy revision and long-term stability, while maintaining compressive strength and setting time.
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Abstract
Description
Title of the invention: Dental product for the formation of endodontic cement. Technical field
[0001] The present disclosure relates to a dental product enabling the formation of an endodontic cement, or canal sealing cement, in the presence of moisture in a dental canal. Previous technique
[0002] Endodontic treatment is a delicate procedure upon which periodontal health and the longevity of the tooth depend. It consists of the prevention, diagnosis, and treatment of dental pulp and periapical infections (in the bone and around the roots) in order to transform a diseased tooth into a healthy, asymptomatic, and functional one in the dental arch.
[0003] Root canal or endodontic treatment is indicated in the context of irreversible pulpitis (inflammation, pulp infection) or necrotic pulp with or without clinical and / or radiographic signs of apical periodontitis (inflammatory lesions of the periodontium) or in the context of a living pulp if the prognosis of pulp vitality is unfavorable, if there is a root amputation or hemisection and if the probability of pulp exposure during coronal restoration not allowing direct capping is high.
[0004] Pulp inflammation and infection can be caused by multiple factors such as cavities, cracks, fractures, or dental trauma. If an infected or inflamed pulp is not treated, it can cause significant pain and even lead to an abscess. Endodontic treatment aims to prevent or eliminate infection by removing bacteria and their toxins from the root canal system, as well as any residue that could serve as nutrients and support bacterial growth. To maintain this disinfection, the pulp, or what remains of it, must be replaced in a healthy root canal system with a hermetic filling that promotes healing. This procedure eliminates and neutralizes organic and bacterial substances that irritate the periapical tissues. The result must be stable and long-lasting. Once restored, the tooth must be functional, asymptomatic, and show no clinical signs..
[0005] The use of canal sealing cements that are well tolerated and exhibit good adhesion is known. Furthermore, the sealant material marketed under the trade name "Total Fill ®" is known, which exhibits a radio- significant opacity allowing simple radiographic monitoring and control of the cement during its placement.
[0006] It is desirable to propose a new dental product with limited viscosity, designed to form an endodontic cement in a dental canal, that exhibits radiopacity similar to that of "Total Fill®", while offering satisfactory setting time and compressive strength, as well as preventing bacterial proliferation. It is also desirable that the formula be stable over time (no phase separation of the composition, or unwanted setting in the packaging before insertion into the dental canal), and that the resulting cement be relatively easy to process. Description of the invention
[0007] The present description relates, according to a first embodiment, to a dental product intended to form an endodontic cement in a dental canal, said product comprising at least: - propylene glycol in a mass content greater than or equal to 20%, - a mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content between 34% and 40%, - a binder with a mass content between 1% and 4%, - a radiopaque contrast agent of zirconium oxide in a mass content greater than or equal to 20%, and - potassium citrate in a mass content between 0.1% and 0.38%, for example between 0.2% and 0.3%.
[0008] The present description relates, according to a second embodiment, to a dental product intended to form an endodontic cement in a dental canal, said product comprising at least: - propylene glycol in a mass content greater than or equal to 20%, - a mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content between 34% and 43%, - a binder with a mass content between 0.3% and 1.3%, for example between 0.7% and 1.1%, - a radiopaque contrast agent of zirconium oxide in a mass content greater than or equal to 20%, and - an antiseptic agent comprising chlorhexidine in a mass content between 0.20% and 1.50%.
[0009] The inventors sought a dental product with radiopacity similar to that of "Total Fill®" and evaluated compositions with a significant radiopaque contrast agent content. Extensive optimization of the other constituents of the product was required to meet all the desired properties for this product with a high radiopaque agent content, namely, to ensure that the resulting cement exhibits satisfactory setting time and compressive strength, prevents bacterial growth, and maintains a limited viscosity.Stable formulas were also sought, particularly when packaged in syringes ("ready-to-use" packaging), that do not exhibit phase separation or undesired setting before insertion into the dental canal, and cements with sufficient cohesion to provide the desired hold without being so strong as to hinder easy and safe revision, for example, using an ultrasonic tip. The specific compositions referred to in the first and second embodiments described above are the result of this optimization work and exhibit these advantageous properties.
[0010] The choice of zirconium oxide for the radio-opaque contrast agent advantageously makes it possible to obtain a product with limited viscosity, and significantly lower than that obtained if, for example, barium sulfate were used as a replacement.
[0011] The presence of propylene glycol at a concentration of at least 20% by mass also contributes to giving the product a satisfactory viscosity. Furthermore, replacing propylene glycol with another carrier such as glycerol results in a product that sets too quickly and has an excessively high viscosity. Generally, the dynamic viscosity of the product is advantageously less than or equal to 240 Pa·s, for example, less than or equal to 220 Pa·s.
[0012] Bacterial proliferation is prevented in the embodiments of the invention due to the significant propylene glycol content and the presence of a preservative compound, namely: potassium citrate in the first embodiment and an antiseptic agent comprising chlorhexidine in the second embodiment. The reduced presence, or even absence, of water in the embodiments also contributes to preventing this proliferation.
[0013] It should also be noted that the first embodiment does not require chlorhexidine due to the presence of potassium citrate, thus avoiding product classification that would delay marketing for regulatory reasons. The inventors observed that removing the chlorhexidine-based antiseptic agent led to an acceleration of the cement setting time, which needed to be counteracted. The choice of potassium citrate is the result from a series of tests which also revealed that the use of different preservatives, as a replacement for chlorhexidine, negatively affected at least one of the viscosity, setting time or compressive strength.
[0014] The embodiments of the invention also have the advantage of forming a biocompatible and non-irritating cement. It is based on hydroxyapatite CaiO(PO4)6(OH)2, which is the major constituent of dentin, and it sets naturally upon contact of the product with canal moisture.
[0015] Dicalcium phosphate and tetracalcium phosphate are capable of forming hydroxyapatite in the presence of moisture. They are each in powder form. The formation of hydroxyapatite from these compounds is known per se. Dicalcium phosphate is an acidic calcium phosphate and can be anhydrous, with the formula CaHPO4, or dihydrate, with the formula CaHPO4·2H2O. Tetracalcium phosphate is a basic calcium phosphate and has the formula Ca4(PO4)2O.
[0016] According to an example relating to the first embodiment, a ratio [amount of substance of dicalcium phosphate] / [amount of substance of tetracalcium phosphate] can be between 0.99 and 1.18.
[0017] According to an example relating to the second embodiment, a ratio [amount of substance of dicalcium phosphate] / [amount of substance of tetracalcium phosphate] can be between 1.13 and 1.16.
[0018] It should be noted that the dental product having the composition according to the embodiments above corresponds to a product ready to be introduced into the dental canal for cement formation. The product may be packaged in a single composition comprising all of its constituents before use, for example in a syringe. However, it does not depart from the scope of the invention if the product is packaged in several separate parts, each in a distinct compartment, intended to be mixed only at the time of use. Unless otherwise specified, the contents of the constituents of the dental product are determined before introduction into the dental canal.
[0019] According to an example of the first embodiment, propylene glycol is present in a mass content of between 20% and 26%, for example between 22% and 24%.
[0020] According to an example of the second embodiment, propylene glycol is present in a mass content of between 24% and 34%, for example between 24% and 30%, or even between 24% and 26%.
[0021] These propylene glycol contents in the first and second embodiments contribute advantageously to optimizing the viscosity of the product.
[0022] In one embodiment, the binder comprises carboxymethylcellulose, polyvinylpyrrolidone, or a mixture of these compounds.
[0023] In particular, the binder may be an aqueous gel of carboxymethylcellulose and may be present in a mass content of between 2% and 5%, for example between 3% and 4%, the mass content of carboxymethylcellulose in the dental product being for example between 0.15% and 0.20%.
[0024] Such a characteristic contributes advantageously to optimizing the stability of the product. The binder can be an aqueous gel of sodium carmellose.
[0025] In one embodiment, the radio-opaque zirconium oxide contrast agent is present in a mass content of between 25% and 35%, for example between 28% and 32%.
[0026] In one embodiment, the dental product further comprises hydroxyapatite present in a mass content of between 3% and 10%, for example between 3% and 7%.
[0027] Hydroxyapatite is a setting accelerator and contributes advantageously to optimizing the setting time of cement.
[0028] In one embodiment, the dental product further comprises a suspending agent.
[0029] The suspending agent contributes advantageously to optimizing the stability of the dental product.
[0030] The suspending agent may contain silica. For example, the product marketed under the reference Aerosil® 200 by Evonik may be used. The suspending agent may be present in the dental product at a mass concentration of 1.5% or less, for example, 1% or less. This concentration may be between 0.25% and 1.5%, for example, between 0.25% and 1%, or between 0.5% and 1.5%, for example, between 0.5% and 1%.
[0031] According to an example relating to the second embodiment, the antiseptic agent may be selected from chlorhexidine hydrochloride, chlorhexidine dihydrochloride, chlorhexidine gluconate, chlorhexidine digluconate, or mixtures thereof. The antiseptic agent may in particular comprise chlorhexidine gluconate or chlorhexidine digluconate; in particular, it may be chlorhexidine digluconate.
[0032] According to an example relating to the first embodiment, the dental product comprises, for example essentially comprises, or even consists of: - propylene glycol in a mass content of between 20% and 26%, for example between 22% and 24%, - the mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content of between 35% and 37%, - the binder, which is an aqueous gel of carboxymethylcellulose and is present in a mass content of between 2% and 5%, for example between 3% and 4%, the mass content of carboxymethylcellulose in the dental product being, for example, between 0.15% and 0.20%, - a suspending agent in a mass concentration between 0.5% and 1.5%, - the radiopaque contrast agent zirconium oxide in a mass content between 28% and 32%, - hydroxyapatite in a mass content of between 5% and 7%, and - potassium citrate in a mass content between 0.1% and 0.38%, for example between 0.2% and 0.3%.
[0033] According to an example relating to the second embodiment, the dental product comprises, for example, essentially comprises, or even consists of: - propylene glycol in a mass content of between 24% and 30%, for example between 24% and 26%, - the mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content of between 35% and 40%, - the binder which includes polyvinylpyrrolidone and is present in a mass content of between 0.5% and 1%, - a suspending agent with a mass concentration between 0.25% and 0.75%, - the radiopaque contrast agent zirconium oxide in a mass content between 28% and 32%, - hydroxyapatite in a mass content of between 3% and 5%, and - the antiseptic agent comprising chlorhexidine in a mass content of between 0.20% and 1.50%, for example between 0.50% and 1.50% or between 0.75% and 1.25%.
[0034] In one embodiment, the total mass water content in the dental product may be less than or equal to 4%, and the product may, in particular, be water-free. This total water content includes water in all its forms, and therefore, in particular, any water that may be present in the aforementioned constituents.
[0035] The reduced water content contributes advantageously to reducing the risk of bacterial proliferation.
[0036] In general, the product may be free of calcium carbonate, calcium hydroxide or tricalcium silicate.
[0037] The invention also relates to an assembly for obturating and sealing a dental canal, comprising at least one product as described above in an introduction device suitable for introducing the product into the dental canal.
[0038] The delivery device may be a single or double-compartment syringe with specific tips for filling the channel. Such a device The introduction method is well-established, and as an example of a usable introduction device, one can cite the tool marketed under the reference Colibri™ by Sulzer Mixpac™ (a dual-compartment example). Once introduced into the root canal, the dental product hardens upon contact with the moisture in the canal to form hydroxyapatite, thus obturating and sealing the root canal.
[0039] The cement has a moderate hardness that allows it to be easily removed, for example, for a dental cement restoration. The cement can be removed, in whole or in part, from the canal by contact with a vibrating tool at an ultrasonic frequency, for example, an ultrasonic tip. The vibration frequency of the tool can be between 26 kHz and 36 kHz. The ultrasonic vibrating tool is known per se, and as an example of a usable tool, insert No. ET25S, marketed by SATELEC, can be cited.
[0040] Generally, the dental product is in fluid form, and may be in the form of a suspension of solid particles in a liquid medium. The dental product is intended to be introduced into a dental canal to form an endodontic cement for filling and sealing that canal.
[0041] The invention also relates to a method for applying endodontic cement comprising at least: - the introduction of a dental product as described above into a dental canal, and - the taking of the dental product thus introduced in contact with the moisture present in the dental canal in order to form the endodontic cement.
[0042] The invention also relates to a method of treating an endodontic cement obtained from the dental product as described above and present in a dental canal in which said endodontic cement is brought into contact with a vibrating tool at an ultrasonic frequency. Brief description of the drawings [Fig.1] The [Fig.1] is an X-ray of a dental canal filled with cement according to the invention. [Fig.2] The [Fig.2] is an X-ray of a dental canal filled with cement obtained from the commercial product "Total Fill ®". [Fig.3] Fig.3 provides a photograph of an ultrasonic tip reprocessing test of a cement according to the invention. [Fig.4] Fig.4 provides a photograph of an ultrasonic tip reprocessing test of a cement according to the invention. [Fig.5] Fig.5 provides a photograph of an ultrasonic tip reprocessing test of cement obtained from the commercial product "Total Fill ®". [Fig. 6] Figure 6 provides a photograph of an ultrasonic tip reprocessing test of cement obtained from the commercial product "Total Fill®". Description of embodiments
[0043] The experimental section below demonstrates the advantages of the dental products according to the invention. It is preceded by a detailed description of the measurement protocols implemented for the various relevant parameters.
[0044] Viscosity measurement protocol
[0045] Generally, viscosity is evaluated using a planar-planar aluminum rheometer with a diameter of 20 mm, for example marketed under the reference "Discovery HR-2" from the company TA instruments, at 20°C. A "flow ramp" method from 0.01 to 10 s 1 can be used to measure viscosity.
[0046] Protocol for measuring the pH of unset cement
[0047] Generally, the measurement is carried out with a pH meter 827 marketed by the company Metrohm in a solution obtained by dissolving about 0.5 g of cement in 20 mL of distilled water, after magnetic stirring for a few minutes.
[0048] Setting time measurement protocol
[0049] Generally, the setting time of cements is evaluated by depositing the product in a plaster of Paris mold hollowed out with an impression of 10 mm in diameter and 1 mm in height, the product is leveled and then placed in the oven at 40°C and high humidity.
[0050] At regular time intervals, the mold is placed under a penetrometer equipped with a 4 mm diameter pin with a flat end. The pin is positioned so that it is flush with the surface of the cement, and the rod is released for 10 seconds. The impression is then observed. The cement setting time is determined when no impression is visible after measurement.
[0051] Protocol for measuring compressive strength
[0052] The compression force is measured using the AGS-X universal testing machine, marketed by SHIMADZU, equipped with a 500 N force cell and a P / 25 mobile.
[0053] A first step in preparing the cement test specimens is necessary. The product is incorporated into slotted Teflon molds, 6 mm in diameter and 12 mm high, using a syringe fitted with a cannula, and then leveled. The molds are then placed in an oven at 40 °C and high humidity until the cement has completely set. The test specimens are then carefully removed from the molds to avoid breakage.
[0054] Compression measurements are then carried out using a compression test at a rate of 0.75 mm / min. The maximum force applied at the moment of rupture is measured, and the stress, or compressive strength, is determined using the following formula: [Math. 1] 4 x Maximum Force Stress —.................................................................-.......................................:............................................................ Axle Diameter4
[0055] Example 1: Dental product Al according to the invention without chlorhexidine, comprising potassium citrate
[0056] The table below provides the formulation of the dental product Al according to the invention that has been prepared. In the tables provided below, DCPD denotes dicalcium phosphate dihydrate, and TTCP tetracalcium phosphate. In this formula, potassium citrate is incorporated as a 2M aqueous solution; the mass content of potassium citrate (excluding water) in this composition is approximately 0.24%.
[0057] [Tables 1] A1 Propylene glycosyl 23.00% Potassium citrate 2M 0.50% Aqueous glycine of sodium chloride 5% 3.50% Aerosol 200 1.00% Zirconium oxide 30.00% DCPD 11.50% TTCP 24.50% Hydroxyapatite 6.00%
[0058] The following characterizations were obtained for the AL product. The Al product exhibits limited viscosity and the resulting cement has satisfactory setting time and compressive strength.
[0059] [Tables2] AI Characterization: Viscosity at 1 s⁻¹: 211.5 Pa·s; pH of unset cement: ~8; Setting time: 3 hours; Compressive strength: 1.8 MPa
[0060] In addition, the inventors have not observed any sedimentation (phase separation) or syringe collection phenomenon for this product.
[0061] Example 2 (comparative): dental product A21 outside the invention without chlorhexidine, including calcium hydroxide
[0062] Calcium hydroxide has antibacterial activity, and its use has been evaluated with a view to developing a chlorhexidine-free product. The table below provides the formulation of the comparative dental product A21 based on calcium hydroxide that was prepared.
[0063] [Tables3] A21 Propylene glycol 26.00% DCPD 13.50% TTCP 25.20% KolMon 90F 0.80% Aerosol H 200 0.50% Zirconium oxide 28.50% Calcium hydroxide 1.50% Hydroxyapatite 4.00%
[0064] Product A21 has an insufficient compressive strength of 0.7 MPa. The setting reaction of the cement is an acid-base reaction; since calcium hydroxide is a strong base, the reaction is disrupted.
[0065] Example 3 (comparative): dental product A22 outside the invention without chlorhexidine, comprising glycerol
[0066] Glycerol acts as a preservative, and its use has been evaluated as a replacement for propylene glycol, with the aim of providing a chlorhexidine-free product. The table below provides the formulation of the comparative glycerol-based dental product A22 that was prepared.
[0067] [Tables4] A22 Glycerol 25.80% DCPD 13.50% TTCP 25.10% Kollidon 90F 0.80% AerosN 200 0.50% Zirconium Oxide 30.20% Hydroxyapatite 4.10%
[0068] The A22 product exhibits a very rapid setting time, less than 1h30, and a very high viscosity of 648 Pa.s.
[0069] In order to slow the setting of the cement and reduce the viscosity of the mixture, the inventors carried out further tests, removing hydroxyapatite from the formula and increasing either the amount of zirconium oxide or the amounts of TTCP / DCPD, which did not give a satisfactory result. Further tests were also conducted by modifying the Kollidon 90F content and increasing the glycerol content, but the cements exhibited excessive viscosity and set in the syringe at 40 °C in less than 7 days.
[0070] Example 4 (comparative): dental products A23-1 and A23-2 outside the invention without chlorhexidine, comprising sodium citrate
[0071] Sodium citrate acts as a preservative, and its use has been evaluated with a view to developing a chlorhexidine-free product. The table below provides the formulation of the sodium citrate-based dental products A23-1 and A23-2 that have been prepared.
[0072] [Tables5] A23-1 A23-2 Propylene glycine 25.00% 23.00% Sodium citrate IM 1.00% 3.00% DCPD 13.80% 13.80% TTCP 24.90% 24.90% Kollidon 90F 0.80% 0.80% AerosH 200; 0.50% 0.50% Zirconium oxide 30.00% 30.00% Hydroxyapatite 4.00% 4.00%
[0073] The two cements set in an oven at 40 °C in 2 days for the 3% cement and in 7 days for the 1% cement. The combined products are therefore not sufficiently stable over time.
[0074] Example 5 (comparative): dental product A24 outside the invention without chlorhexidine, comprising citric acid
[0075] Citric acid acts as a preservative, and its use has been evaluated with a view to developing a chlorhexidine-free product. The table below provides the formulation of the citric acid-based dental product A24 that was prepared.
[0076] [Tableauxô] A24 Propylene Glycol 25.00% Citric Acid 0 JM 1.00% Kollidon 90F 0.80% Aerosii 200 0.50% DCPD 13.80% TTCP 24.90% Zirconium Oxide 30.00% Hydroxyapatite 4.00%
[0077] Formula A24, packaged in a syringe and placed in an oven at 40°C, set in 6 days. The product is therefore not sufficiently stable over time. Example 6: Dental product B according to the invention with chlorhexidine
[0078] The table below provides the formulation of dental product B according to the invention which has been prepared.
[0079] [Tables7] B Propylene glycol 25.00% Chlorhexidine diglucate 1.00% Kollidon 90F 0.80% Aercsil 200 0.50% Zirconium oxide 30.00% DCPD 13.50% TTCP 25.20% Hydroxyapatite 4.00%
[0080] The following characterizations were obtained for product B. Product B exhibits limited viscosity and the resulting cement has satisfactory setting time and compressive strength.
[0081] [Tables8] Characterization B Viscosity at 1 s⁻¹ 217.2 Pa.s Setting time 4h30 Compressive strength 1.8 MPa
[0082] In addition, the inventors have not observed any sedimentation (phase separation) or syringe collection phenomenon for this product.
[0083] Furthermore, [Fig. 1] shows the radiopacity obtained with product B due to the high zirconium oxide content used; this radiopacity is comparable to that obtained with the commercial product "Total Fill®" provided in [Fig. 2]. The ultrasonic tip reprocessing test was conclusive for product B (Figures 3 and 4), whereas the "Total Fill®" product is more difficult to reprocess (Figures 5 and 6).
[0084] Furthermore, for comparison purposes, replacing zirconium oxide in formula B above with barium sulfate resulted in a product exhibiting a much higher viscosity of 703.6 Pa.s.
[0085] Although the present invention has been described with reference to specific embodiments, it is evident that modifications and changes can be made to these examples without departing from the general scope of the invention as defined by the claims. In particular, individual features of the various embodiments illustrated / mentioned can be combined in additional embodiments. Therefore, the description and drawings should be considered in an illustrative rather than a restrictive sense.
[0086] The expression "between ... and ..." should be understood as including the boundaries.
Claims
Demands
1. Dental product intended to form an endodontic cement in a dental canal, said product comprising at least: - propylene glycol in a mass content greater than or equal to 20%, - a mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content of between 34% and 40%, - a binder in a mass content of between 1% and 4%, - a radio-opaque contrast agent of zirconium oxide in a mass content greater than or equal to 20%, and - potassium citrate in a mass content of between 0.1% and 0.38%.
2. Dental product intended to form an endodontic cement in a dental canal, said product comprising at least: - propylene glycol in a mass content greater than or equal to 20%, - a mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content of between 34% and 43%, - a binder in a mass content of between 0.3% and 1.3%, - a radio-opaque contrast agent of zirconium oxide in a mass content greater than or equal to 20%, and - an antiseptic agent comprising chlorhexidine in a mass content of between 0.20% and 1.50%.
3. Dental product according to claim 1, wherein propylene glycol is present in a mass content of between 20% and 26%.
4. Dental product according to claim 2, wherein propylene glycol is present in a mass content of between 24% and 34%.
5. Dental product according to any one of claims 1 to 4, wherein the binder comprises carboxymethylcellulose, polyvinylpyrrolidone, or a mixture of these compounds.
6. Dental product according to claim 5, wherein the binder is an aqueous gel of carboxymethylcellulose and is present in a mass content of between 2% and 5%.
7. Dental product according to any one of claims 1 to 6, wherein the radio-opaque contrast agent zirconium oxide is present in a mass content of between 25% and 35%.
8. Dental product according to any one of claims 1 to 7, wherein the dental product further comprises hydroxyapatite present in a mass content of between 3% and 10%.
9. Dental product according to any one of claims 1 to 8, wherein the dental product further comprises a suspending agent.
10. A dental product according to any one of claims 1, 3, and 5 to 9 related to claim 1, wherein the dental product comprises: - propylene glycol in a mass content of between 20% and 26%, - a mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content of between 35% and 37%, - a binder, which is an aqueous carboxymethylcellulose gel, and is present in a mass content of between 2% and 5%, - a suspending agent in a mass content of between 0.5% and 1.5%, - the radiopaque contrast agent zirconium oxide in a mass content of between 28% and 32%, - hydroxyapatite in a mass content of between 5% and 7%, and - potassium citrate in a mass content mass fraction between 0.1% and 0.38%.
11. Dental product according to any one of claims 2, 4 and 5 to 9 related to claim 2, wherein the dental product comprises: - propylene glycol in a mass content of between 24% and 34%, - the mixture of dicalcium phosphate and tetracalcium phosphate capable of forming hydroxyapatite in the presence of moisture, this mixture being present in a mass content of between 35% and 40%, - the binder which includes polyvinylpyrrolidone and is present in a mass content of between 0.5% and 1%, - a suspending agent in a mass content of between 0.25% and 0.75%, - the radio-opaque contrast agent of zirconium oxide in a mass content of between 28% and 32%, - hydroxyapatite in a mass content of between 3% and 5%, and - the antiseptic agent including chlorhexidine in a mass content of between 0.20% and 1.50%.
12. Assembly for obturating and sealing a dental canal, comprising at least one product according to any one of claims 1 to 11 in an introduction device suitable for introducing the product into the dental canal.