Silicon dioxide modified tooth binding material as well as preparation method and application thereof

Abstract

The invention relates to a silicon dioxide modified tooth binding material which comprises zirconium oxide serving as a base material and silicon dioxide particles adsorbed on the surface of the zirconium oxide, wherein the silicon dioxide particles are generated based on in-situ pyrolysis modified PDMS. The zirconium oxide material subjected to heat treatment is non-toxic and harmless, good in biocompatibility and excellent in bonding strength and toughness, the preparation method of muffle furnace heat treatment is simple and easy to operate, the obtained zirconium oxide finished product is excellent in performance, compared with a commercial spray, the cost is greatly reduced, and wide clinical application prospects are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of tooth restoration, and in particular relates to a silicon dioxide-modified tooth bonding material and a preparation method and application thereof. Background Art

[0002] Porcelain is widely used in dentistry as a means of restoring dentition to a functional state. Porcelain is a preferred material over porcelain fused to metal restorations, the gold standard of the previous generation, due to its color closely resembling that of natural dentition. Porcelain-fused-to-metal restorations have been shown to offer long-term success rates. However, due to the presence of metal coping, porcelain-fused-to-metal restorations lack the color compatibility required for aesthetics. This situation has driven the search for all-ceramic materials that can withstand occlusal loads while providing superior aesthetics. In this regard, zirconium oxide, a high-strength ceramic material, offers an effective option for metal-free restorations. The element's high strength can be attributed to its unique phase transformation toughening. Furthermore, zirconium oxide has been shown to be highly biocompatible.

[0003] Long-term, durable resin bonding to ceramics is desirable to enhance retention, improve marginal adaptation, and increase fracture resistance of restored teeth and restorations. To achieve high bond strength and bond durability to zirconia, both mechanical and chemical zirconia surface pretreatment are necessary. Methods such as aluminum oxide air particle abrasion, ceramic coatings, selective infiltration etching, tribochemical silica coatings, and primers / adhesives have been proposed for this purpose.

[0004] Airborne particle abrasion is the most commonly used method for roughening and cleaning zirconia surfaces, although its functionality in zirconia veneer ceramic adhesion has not been demonstrated. However, a concern with air abrasion is that it induces a phase transformation on the surface, changing the crystal structure from tetragonal to monoclinic. Airborne particle abrasion using aluminum oxide particles is the most commonly used physical conditioning method to promote bond strength between zirconia and adhesives. This method cleans the surface, increasing wettability and surface area; however, airborne particle abrasion can reduce the biaxial flexural strength of zirconia. Therefore, a combination of tribochemical silica coatings and silane coupling agents has been widely recommended as a physical and chemical surface treatment for zirconia.

[0005] However, current methods for attaching silica to zirconia surfaces suffer from issues such as insufficient bonding performance, complex preparation processes, and high prices for commercial sprays. Therefore, a method for attaching silica coatings to zirconia with simple preparation methods, inexpensive raw materials, and superior performance is needed. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a silica-modified tooth bonding material to address the problems of weak adhesion, cracking and delamination of the selective layer when using zirconium oxide base for tooth bonding restoration. The material can significantly improve the bonding strength and durability of zirconium oxide and has good effects in actual tooth restoration.

[0007] To this end, the first aspect of the present invention provides a silica-modified tooth bonding material, which includes zirconium oxide as a matrix material and silica particles adsorbed on the surface of the zirconium oxide; wherein the silica particles are generated based on in-situ pyrolysis modification of PDMS.

[0008] The second aspect of the present invention provides a method for preparing the tooth bonding material according to the first aspect of the present invention, comprising:

[0009] Step A, placing a clarified PDMS solution into a spray gun and evenly spraying it onto the surface of the zirconia substrate to obtain a zirconia substrate with a PDMS coating on the surface;

[0010] Step B, heating the zirconia substrate with the PDMS coating to a reaction temperature, performing a constant temperature heat treatment, and then cooling to room temperature to obtain a crude tooth bonding material;

[0011] Step C: Clean the surface of the crude tooth bonding material with anhydrous ethanol to obtain a finished product of the silica-modified tooth bonding material.

[0012] Preferably, in step B, the heating rate is 10° C. / min, the reaction temperature is 650° C.; and / or the time of the constant temperature heat treatment is 2 h.

[0013] According to the present invention, the preparation method of the clarified PDMS solution comprises:

[0014] Step S1, adding vinyl silicone oil and hydroxy silicone oil to n-heptane solvent and stirring to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution;

[0015] Step S2, adding inhibitor HR-107 to the vinyl silicone oil-hydroxy silicone oil mixed solution, stirring, to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution containing inhibitor HR-107;

[0016] Step S3, adding platinum catalyst PT-3000 to the vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107, stirring, and fully reacting to obtain a clear PDMS solution.

[0017] In some embodiments of the present invention, in the vinyl silicone oil-hydroxy silicone oil mixture, the mass ratio of vinyl silicone oil to hydroxy silicone oil is 10:1, and the total concentration of the vinyl silicone oil and hydroxy silicone oil is 5wt%-40wt%; accordingly, the concentration of the clarified PDMS solution is 5wt%-40wt%; and / or, in step S1, the stirring time is 0.5h.

[0018] In some embodiments of the present invention, in the vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107, the mass ratio of the vinyl silicone oil-hydroxy silicone oil mixture to the inhibitor HR-107 is 1:0.005; and / or, in step S2, the stirring time is 0.5h.

[0019] According to the present invention, in step S3, the mass ratio of the vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107 to the platinum catalyst PT-3000 is 1:0.025; and / or, in step S3, the stirring time is 0.5 h.

[0020] The third aspect of the present invention provides use of the tooth bonding material according to the first aspect of the present invention or the tooth bonding material prepared by the preparation method according to the second aspect of the present invention in preparing a dental restoration preparation.

[0021] Compared with existing technologies, this solution uses hydroxyl silicone oil and vinyl silicone oil as raw materials and generates silica through heat treatment. The rough surface produced by silica can effectively improve the adhesion strength of zirconia materials. The silica-modified zirconia material modified by heat treatment in this invention is non-toxic and harmless, has good biocompatibility, and has excellent adhesion strength and toughness. The preparation method of muffle furnace heat treatment is simple and easy to operate. The resulting silica-modified zirconia product has excellent performance and greatly reduces costs compared to commercial sprays, which has broad clinical application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to make the present invention easier to understand, the present invention will be described in detail below with reference to the accompanying drawings.

[0023] Figure 1 The results are shown in which the silica-modified dental bonding material of the present invention is used as a dental restoration preparation and a traditional dental restoration preparation is used for dental restoration.

[0024] Figure 2 The electron micrographs of the samples sprayed with 5 wt% and 40 wt% PDMS solutions and heat-treated are compared with those of the zirconia substrate and the commercial spray.

[0025] Figure 3The energy spectrum scanning results of the sample surface after spraying PDMS solution and heat treatment are shown; among them, the left figure is the energy spectrum scanning diagram of the sample surface after spraying 40wt% PDMS solution and heat treatment, and the right figure is the element composition table of the sample surface after spraying 40wt% PDMS solution and heat treatment.

[0026] Figure 4 The shear strength comparison results of PDMS heat-treated material and commercial spray and sandblasted materials are shown. DETAILED DESCRIPTION

[0027] To facilitate understanding of the present invention, the present invention will be described in detail below with reference to the accompanying drawings. However, before describing the present invention in detail, it should be understood that the present invention is not limited to the specific embodiments described. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting.

[0028] Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, preferred methods and materials are now described.

[0029] In the present invention, the so-called range of dosage concentration, temperature or other physical or chemical properties or characteristics covers or includes the upper limit and lower limit of the range unless otherwise specified.

[0030] I. Terminology

[0031] The term “PDMS” in the present invention refers to polydimethylsiloxane, whose chemical formula is (C 2 H 6 OSi) n .

[0032] The term "bonding resin" as used herein refers to a dental restoration adhesive, for example, a sub-composite resin adhesive such as PANAVIA TM V5 (Kuraray Noritake Dental, Germany).

[0033] II. Implementation Plan

[0034] As mentioned above, the actual use of zirconia substrates for tooth bonding restorations has shown problems such as weak adhesion, cracking of the selective layer and delamination. These problems are in urgent need of solution but have not been solved for a long time. In view of this, the inventors have conducted extensive research on the technology of using zirconia substrates for tooth bonding.

[0035] The inventors have discovered that a new type of silica particles can be generated based on in-situ pyrolysis modification of PDMS. The silica particles adhere to the surface of zirconia to form silica-particle-modified zirconia, which can be connected to the "adhesive resin" through chemical covalent bonds, thereby creating a rough surface on the zirconia surface and having chemical bonding force, thereby significantly improving the bonding strength and durability of zirconia. The silica-modified zirconia is effective in actual tooth restoration processes.

[0036] To achieve the present invention, the present invention provides a method for preparing a silica-modified dental bonding material. The method is based on in-situ pyrolysis of a PDMS substrate to generate silica particles, and the silica particles are adsorbed on the surface of a zirconia substrate to improve the bonding strength thereof by chemical covalent bonding. The method comprises:

[0037] (1) adding vinyl silicone oil and hydroxy silicone oil in a mass ratio of 10:1 to n-heptane solvent, adjusting the total concentration of vinyl silicone oil and hydroxy silicone oil to 5 wt%-40 wt%, and stirring for 0.5 h to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution;

[0038] (2) Inhibitor HR-107 (Shenzhen Kejunchi Technology Co., Ltd.) was added to the uniformly stirred vinyl silicone oil-hydroxy silicone oil mixture at a mass ratio of 1:0.005, and stirred for 0.5 h to obtain a vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107;

[0039] (3) Platinum catalyst PT-3000 (Shenzhen Kejunchi Technology Co., Ltd.) was added to the vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107 at a mass ratio of 1:0.025, stirred for 0.5 h, and fully reacted to obtain a clear PDMS solution; corresponding to the total concentration of vinyl silicone oil and hydroxy silicone oil in step (1), the concentration of the clear PDMS solution was 5 wt%-40 wt%;

[0040] (4) placing the clarified PDMS solution into a spray gun and spraying it onto the surface of the zirconia substrate to form a uniform and smooth surface, thereby obtaining a zirconia substrate having a PDMS coating on the surface;

[0041] (5) placing the zirconia substrate with the PDMS coating in a muffle furnace, heating it to 650°C at a rate of 10°C / min, heat treating it at this constant temperature for 2 h, and then cooling it to room temperature to obtain a crude tooth bonding material;

[0042] (6) The crude tooth bonding material is taken out, and the dust on the surface of the crude tooth bonding material is swept away using cotton soaked in anhydrous ethanol to obtain a finished product of the silica-modified tooth bonding material.

[0043] Based on the above, it's easy to understand that the silica-modified dental bonding material prepared using the above method is a silica-modified zirconia material, comprising zirconia as a base material and silica particles adsorbed on the surface of the zirconia. The silica particles are generated by in-situ pyrolysis-modified PDMS and are chemically covalently bonded to the zirconia. This material significantly improves the bond strength and durability of the zirconia.

[0044] Since the silica-modified dental adhesive material provided by the present invention contains only two components, zirconium oxide and silica, among which zirconium oxide is a dental restoration material that has been clinically used, the content of silica in this product is extremely small. The silica concentration was measured using the molybdate reduction method, and the result showed that it was lower than the toxic concentration of silica of 0.04 mg / kg. It can be seen that the silica-modified dental adhesive material product provided by the present invention is non-toxic to the human body.

[0045] The present invention also provides the use of the silicon dioxide modified tooth bonding material in preparing a dental restoration preparation.

[0046] The silica-modified tooth bonding material was used as a dental restoration preparation for tooth restoration and compared with the traditional bonding method. Figure 1 As shown, the limitations of traditional bonding methods are that the interface between the zirconia surface and the bonding resin is smooth and has poor locking ability; there is no chemical bonding force, and the interface is easily destroyed by hydrolysis; the bonding strength is weak, and the restoration is easy to fall off; while the present invention adopts a chemical covalent bonding method, and the SiO2 layer on the surface of the zirconia pores provides active silanol groups, which covalently bridge the zirconia and the resin through a silane coupling agent. Its advantages are that the roughness of the interface between the zirconia surface and the bonding resin is increased, and the locking ability is strong; it has chemical bonding force, and the interface is not easily destroyed by hydrolysis; the bonding strength is high, and the restoration is stable, indicating that the tooth bonding material provided by the present invention is effective in the process of tooth restoration.

[0047] III. Examples

[0048] To make the present invention easier to understand, the present invention will be further described in detail below with reference to the following examples. These examples are merely illustrative and are not intended to limit the scope of application of the present invention. The raw materials or components used in the present invention can be obtained by commercial routes or conventional methods unless otherwise specified.

[0049] Example 1:

[0050] (1) 0.2273 g of vinyl silicone oil, 0.0227 g of hydroxy silicone oil, and 4.7500 g of n-heptane were added to a cillin bottle to a solid content of 5 wt %. The mixture was magnetically stirred for 0.5 h to allow the vinyl silicone oil and hydroxy silicone oil to be fully mixed and dissolved in n-heptane to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution.

[0051] (2) Add 0.0250 g of HR-107 inhibitor into the vial and stir for 0.5 h to fully react to obtain a vinyl silicone oil-hydroxy silicone oil mixture containing the inhibitor HR-107.

[0052] (3) Add 0.1250 g of PT-3000 platinum catalyst into the vial and stir for 0.5 h to fully react to obtain a clear PDMS solution.

[0053] The clarified PDMS solution prepared in steps (1) to (3) above was used to modify the zirconia substrate. The specific preparation process is as follows:

[0054] (1) The prepared clarified PDMS solution is placed in a spray gun and evenly sprayed onto the surface of the zirconia to obtain a zirconia substrate with a PDMS coating on the surface.

[0055] (2) The sprayed zirconia sample was placed in a muffle furnace, heated to 650°C at 10°C / min, subjected to constant temperature heat treatment for 2 hours, and cooled to room temperature to obtain a crude tooth bonding material.

[0056] (3) The heat-treated sample is taken out from the muffle furnace, and the surface of the sample is cleaned with anhydrous ethanol to remove the powdered floating sample to obtain a finished product of the silica-modified tooth bonding material.

[0057] Example 2:

[0058] (1) 1.8182 g of vinyl silicone oil, 0.1818 g of hydroxy silicone oil, and 3.0000 g of n-heptane were added to a vial to a solid content of 40 wt %. The mixture was magnetically stirred for 0.5 h to allow the vinyl silicone oil and hydroxy silicone oil to be fully mixed and dissolved in n-heptane to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution.

[0059] (2) Add 0.0250 g of HR-107 inhibitor into the vial and stir for 0.5 h to fully react to obtain a vinyl silicone oil-hydroxy silicone oil mixture containing the inhibitor HR-107.

[0060] (3) Add 0.1250 g of PT-3000 platinum catalyst into the vial and stir for 0.5 h to fully react to obtain a clear PDMS solution.

[0061] The clarified PDMS solution prepared in steps (1) to (3) above was used to modify the zirconia substrate. The specific preparation process is as follows:

[0062] (1) The prepared clear solution is placed in a spray gun and sprayed evenly onto the surface of the zirconia to obtain a zirconia substrate with a PDMS coating on the surface.

[0063] (2) The sprayed zirconia sample was placed in a muffle furnace, heated to 650°C at 10°C / min, subjected to constant temperature heat treatment for 2 hours, and cooled to room temperature to obtain a crude tooth bonding material.

[0064] (3) The heat-treated sample is taken out from the muffle furnace, and the surface of the sample is cleaned with anhydrous ethanol to remove the powdered floating sample to obtain a finished product of the silica-modified tooth bonding material.

[0065] Comparative Example 1:

[0066] A commercial spray (custom denture porcelain powder, Edith Technology Co., Ltd.) was sprayed on the modified zirconia base. The specific preparation process is as follows:

[0067] (1) Spray the commercial spray evenly onto the surface of zirconia.

[0068] (2) The sprayed zirconia sample was placed in a muffle furnace, heated to 650°C at 10°C / min, heat treated at constant temperature for 2 h, and cooled to room temperature.

[0069] (3) Take the heat-treated sample out of the muffle furnace and clean the sample surface with anhydrous ethanol.

[0070] The zirconia substrates treated in Examples 1 and 2 and the comparative example were observed using a SEM (ZEISS field emission scanning electron microscope Sigma 360, Germany). The test results are shown in FIG. Figure 2 and Figure 3 .

[0071] The zirconium oxide samples treated in Examples 1, 2 and Comparative Example 1 were subjected to shear force tests (Zwick Roell universal mechanical testing machine Z101, Germany). The test results are shown in Tables 1 and Figure 4 .

[0072] Table 1 Shear test results

[0073]

[0074] The shear force test data results show that compared with samples treated with commercial sprays and sandblasting, samples treated with PDMS can withstand higher shear pressure and greater shear strength, which corresponds to the fact that dental restoration materials can adhere longer in reality and have better clinical application effects.

[0075] It should be noted that the embodiments described above are only preferred embodiments of the present invention and are used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A silica-modified tooth bonding material comprising zirconium oxide as a matrix material and silica particles adsorbed on the surface of the zirconium oxide; wherein: The silica particles are generated based on in-situ pyrolysis-modified PDMS.

2. The method for preparing a tooth bonding material according to claim 1, comprising: Step A, placing a clarified PDMS solution into a spray gun and evenly spraying it onto the surface of the zirconia substrate to obtain a zirconia substrate with a PDMS coating on the surface; Step B, heating the zirconia substrate with the PDMS coating to a reaction temperature, performing a constant temperature heat treatment, and then cooling to room temperature to obtain a crude tooth bonding material; Step C: Clean the surface of the crude tooth bonding material with anhydrous ethanol to obtain a finished product of the silica-modified tooth bonding material.

3. The preparation method according to claim 2, characterized in that In step B, the heating rate is 10° C. / min, the reaction temperature is 650° C.; and / or the time of the constant temperature heat treatment is 2 h.

4. The preparation method according to claim 2 or 3, characterized in that The preparation method of the clarified PDMS solution comprises: Step S1, adding vinyl silicone oil and hydroxy silicone oil to n-heptane solvent and stirring to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution; Step S2, adding inhibitor HR-107 to the vinyl silicone oil-hydroxy silicone oil mixed solution, stirring, to obtain a vinyl silicone oil-hydroxy silicone oil mixed solution containing inhibitor HR-107; Step S3, adding platinum catalyst PT-3000 to the vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107, stirring, and fully reacting to obtain a clear PDMS solution.

5. The preparation method according to claim 4, characterized in that In the vinyl silicone oil-hydroxy silicone oil mixture, the mass ratio of vinyl silicone oil to hydroxy silicone oil is 10:1, and the total concentration of the vinyl silicone oil and hydroxy silicone oil is 5wt%-40wt%; accordingly, the concentration of the clarified PDMS solution is 5wt%-40wt%; and / or, in step S1, the stirring time is 0.5h.

6. The preparation method according to claim 4, characterized in that In the vinyl silicone oil-hydroxy silicone oil mixture containing inhibitor HR-107, the mass ratio of the vinyl silicone oil-hydroxy silicone oil mixture to the inhibitor HR-107 is 1:0.005; and / or, in step S2, the stirring time is 0.5 h.

7. The preparation method according to claim 4, characterized in that In step S3, the mass ratio of the vinyl silicone oil-hydroxy silicone oil mixed solution containing inhibitor HR-107 to the platinum catalyst PT-3000 is 1:0.025; and / or, in step S3, the stirring time is 0.5 h.

8. Use of the tooth bonding material according to claim 1 or the tooth bonding material prepared by the preparation method according to any one of claims 2 to 7 in preparing a dental restorative preparation.

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