A self-curing material for enhancing the holding force of an oral implant and a preparation method and application thereof

Abstract

The application discloses a self-curing material capable of enhancing the holding force of an oral implant, and a preparation method and application thereof. The self-curing material comprises the following components: a solid phase component and a liquid phase component; the solid phase component is composed of a mixture of a phosphate and a phosphosilicate bioactive glass; and the liquid phase component contains chitosan and phytic acid. The application further provides the self-curing material and application thereof as a biological medical material for oral use. The self-curing material can enhance the holding force of the oral implant, promote the formation of hydroxyapatite, a main component of bone tissue, and thus is favorable to the formation of new bone and further enhances the bone combination capacity of the implant.

Description

Technical Field

[0001] This invention belongs to the field of biomedical materials technology, specifically relating to a self-curing material that can be used to enhance the holding power of dental implants, its preparation method, and its application. Background Technology

[0002] With the continuous development of dental implant technology, the use of implant restoration in clinical practice has been increasing year by year, which indicates that dental implants have a promising future.

[0003] Although implants have a high long-term survival rate, implant failure still occurs frequently in clinical practice. Implant failure is mainly divided into early failure and late failure, with early failure primarily caused by the lack of proper osseointegration around the implant.

[0004] To address the issue of early implant failure, current research primarily focuses on improving the performance of the implant itself. This includes developing novel implant structures, such as CN213552507U and CN206603826U, or introducing new implant materials that promote bone integration and regeneration around the implant, such as CN111467572A. While these methods effectively solve the problem of early implant failure, they are costly, increasing the financial burden on users.

[0005] Therefore, this invention attempts to propose a new solution: during the implantation process of dental implants, the use of self-curing materials can improve the early retention of dental implants and promote the formation of new bone, thereby avoiding early implant failure.

[0006] Existing research indicates that self-curing materials used for human bone repair possess adhesive properties and relatively high mechanical strength, while also promoting new bone formation, such as CN107343965A and CN107303397A. These materials primarily utilize the excellent bone-repairing capabilities of bioactive glass, employing calcium sulfate as a carrier to self-cur with the liquid phase, enabling the bioactive glass solid-phase composite to self-cur within the system; or leveraging the rapid curing ability of α-cyanoacrylate, allowing the bioactive glass solid-phase composite to rapidly self-cur. Although these carriers contribute to enhancing the self-curing ability of bioactive glass, their effect on material activity is somewhat delayed; the bioactive glass only exhibits its bioactivity after exposure or contact with body fluids, following carrier degradation or swelling. However, due to the clinical problem of early implant failure in dental implants, there is a need for a material that can rapidly promote bone repair, thereby improving early implant retention. Therefore, it is necessary to provide a self-curing system that allows the bioactive components themselves to cure rapidly. Summary of the Invention

[0007] The purpose of this invention is to provide a self-curing material that can be used to enhance the holding power of dental implants, its preparation method, and its application. The self-curing material allows its bioactive components to solidify rapidly, quickly promoting bone repair and thus enhancing the holding power of dental implants. Simultaneously, it can also promote the formation of hydroxyapatite, a major component of bone tissue, thereby facilitating the formation of new bone and further enhancing the osseointegration capacity of the implant.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] In a first aspect, the self-curing material provided by the present invention comprises the following components: a solid phase component and a liquid phase component; wherein the solid phase component is composed of a mixture of phosphate and phosphosilicate bioactive glass; and the liquid phase component contains chitosan and phytic acid.

[0010] This invention selects phosphate and phosphosilicate bioactive glass as solid phase components not only because they have good mineralization ability and can promote the rapid formation of hydroxyapatite (HA), the main component of bone tissue, but also because, compared with other solid phase materials (such as silicate bioactive ceramics mentioned in CN107343965A), they can react rapidly with acidic liquid phases, reduce the acidity of the material, and improve the biocompatibility of the material.

[0011] Simultaneously, this invention selects chitosan and phytic acid as active ingredients in the liquid phase component. Chitosan is a natural polymer material with good adhesion, biodegradability, and biocompatibility, exhibiting excellent adhesion to osteoblasts. Phytic acid possesses strong acidity, antioxidant properties, and chelating ability. Compared to other acid solvents (such as acetic acid and citric acid mentioned in CN107303397A), choosing phytic acid as a solvent allows for more complete dissolution of chitosan, providing higher viscosity. Furthermore, it can chelate with calcium in the solid phase component, enabling rapid solidification after solid-liquid mixing, while simultaneously reducing the acidity of the material.

[0012] This invention, through the selection and combination of solid and liquid phase components, produces a self-curing material whose initial and final curing times meet the clinical needs of dental implants. Its mechanical strength meets or even exceeds that of cancellous bone, thereby enhancing the holding power of dental implants. At the same time, it promotes the formation of hydroxyapatite, the main component of bone tissue, which is beneficial to the formation of new bone and further enhances the osseointegration capacity of implants.

[0013] The mass-to-volume ratio (solid-liquid ratio) of the solid phase component to the liquid phase component is (0.5-3):1; preferably (2-3):1 (g / mL).

[0014] The phosphate is tetracalcium phosphate (TTCP, Ca / P = 2, mol%), which has the advantage of promoting the rapid formation of hydroxyapatite compared to other phosphates.

[0015] The bioactive phosphosilicate glass is a calcium phosphosilicate glass with P2O5 9-15 mol%, SiO2 50-60 mol%, and CaO 30-40 mol%; preferably, it is a calcium phosphosilicate glass with P2O5-10.8 mol%, SiO2-54.2 mol%, and CaO-35 mol%. Compared with other bioactive phosphosilicate glasses, this specific ratio of calcium phosphosilicate glass has the advantages of a stable physiological pH value and promoting the rapid formation of hydroxyapatite.

[0016] The mass ratio of the phosphate to the phosphosilicate bioactive glass is 1:2 to 2:1, preferably (0.8-1.2):1.

[0017] The liquid phase component is preferably an aqueous solution containing chitosan and phytic acid.

[0018] The mass ratio of phytic acid to chitosan is (5-10):1, preferably (8-10):1.

[0019] In the liquid phase component, the mass concentration of phytic acid is 10%-50%, preferably 30-50%, and the mass concentration of chitosan is 1-10%, preferably 4-6%.

[0020] Secondly, the present invention provides a method for preparing the self-curing material, comprising the following steps:

[0021] S1. Mix and grind the phosphate and phosphosilicate bioactive glass evenly to obtain a solid phase component;

[0022] S2. Chitosan is added to a solution containing phytic acid to obtain a liquid phase component;

[0023] S3. Mix the solid phase component and the liquid phase component to obtain a self-curing material.

[0024] The preferred mass concentration of the phytic acid solution is 50%.

[0025] Thirdly, the present invention provides the application of the self-curing material as a biomedical material for oral use.

[0026] Preferably, the self-curing material is used as a material to enhance the holding power of dental implants.

[0027] The beneficial effects achieved by this invention are as follows:

[0028] 1. The selected solid components TTCP and PSC have good mineralization ability and can promote the rapid formation of hydroxyapatite (HA), the main component of bone tissue.

[0029] 2. Phytic acid in the liquid phase has strong acidity, antioxidant properties and chelating properties. As a solvent, it can dissolve chitosan and provide high viscosity. On the other hand, it can chelate with calcium in the solid phase, so that the solid and liquid can be quickly solidified after mixing, while reducing the acidity of the material.

[0030] 3. The self-curing material obtained after mixing solid and liquid components has good biological properties, which can improve the early retention of implants and promote the formation of new bone tissue. Attached Figure Description

[0031] Figure 1 This is an optical photograph of the self-curing material obtained in Example 1 after curing.

[0032] Figure 2 The image shows the XRD patterns of different self-curing materials in Test Example 3 after they have been cured and deposited in SBF solution for one week.

[0033] Figure 3 The image shows SEM images of different self-curing materials in Test Example 3 after they have been cured and deposited in SBF solution for one week. Detailed Implementation

[0034] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0035] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0036] Example 1

[0037] 1) Weigh out TTCP (6g) and PSC (3g) respectively, mix and grind them evenly, and use them as the solid phase component;

[0038] The quality ratio of TTCP to PSC is 2:1;

[0039] 2) Weigh 8g of 50% phytic acid solution, add 2g of water to dilute it to obtain 40% phytic acid solution; then add 0.4g of chitosan to obtain phytic acid solution containing 4% chitosan, as the liquid phase component;

[0040] In the liquid phase component: the mass ratio of phytic acid to chitosan is 10:1; the mass concentration of phytic acid is 40%, and the mass concentration of chitosan is 4%.

[0041] 3) Mix the solid component from step 1) and the liquid component from step 2) at a solid-liquid ratio of 2:1 (g / mL), stir thoroughly, and place in a mold to obtain a self-curing material. The optical photograph of the cured material is shown below. Figure 1 As shown.

[0042] Example 2

[0043] 1) Weigh out 3g of TTCP and 3g of PSC respectively, mix and grind them evenly, and use them as the solid phase component;

[0044] The quality ratio of TTCP to PSC is 1:1;

[0045] 2) Weigh 10g of 50% phytic acid solution and add 0.5g of chitosan to obtain a phytic acid solution containing 5% chitosan, which is used as the liquid phase component.

[0046] In the liquid phase component: the mass ratio of phytic acid to chitosan is 10:1; the mass concentration of phytic acid is 50%, and the mass concentration of chitosan is 5%.

[0047] 3) Mix the solid phase component from step 1) and the liquid phase component from step 2) at a solid-liquid ratio of 2:1 (g / mL) until homogeneous to obtain a self-curing material.

[0048] Example 3

[0049] 1) Weigh out TTCP (3g) and PSC (6g) respectively, mix and grind them evenly, and use them as the solid phase component;

[0050] The quality ratio of TTCP to PSC is 1:2;

[0051] 2) Weigh 6g of 50% phytic acid solution, add 4g of water to dilute it to obtain 30% phytic acid solution; then add 0.6g of chitosan to obtain phytic acid solution containing 6% chitosan, as the liquid phase component;

[0052] In the liquid phase component: the mass ratio of phytic acid to chitosan is 5:1; the mass concentration of phytic acid is 30%, and the mass concentration of chitosan is 6%.

[0053] 3) Mix the solid phase component from step 1) and the liquid phase component from step 2) at a solid-liquid ratio of 2:1 (g / mL) until homogeneous to obtain a self-curing material.

[0054] Comparative Example 1

[0055] The difference from Example 1 is that TTCP is replaced with tricalcium phosphate;

[0056] The results showed that, compared with tetracalcium phosphate, the self-curing material prepared from tricalcium phosphate had a slower mineralization rate, and hydroxyapatite only began to form after 2 days.

[0057] Comparative Example 2

[0058] The difference from Example 1 is that the PSC is replaced with 45S5 bioglass.

[0059] The results showed that, compared with PSC, the self-curing material prepared from 45S5 bioglass had a slower mineralization rate, and hydroxyapatite only began to form after 3 days.

[0060] Comparative Example 3

[0061] The difference from Example 1 is that phytic acid is replaced with citric acid;

[0062] The results showed that, compared with phytic acid, the initial setting time and final setting time of the self-curing material prepared from citric acid were increased.

[0063] Comparative Example 4

[0064] The difference from Example 1 is that chitosan is replaced with gelatin;

[0065] The results showed that, compared with chitosan, the initial setting time and final setting time of the self-curing material prepared from gelatin were increased.

[0066] Test Example 1

[0067] According to the international standard ISO 9597:2008(E), the curing time of each group of self-curing materials was determined using a Vicat apparatus, as shown in Table 1.

[0068] Table 1. Curing time of self-curing materials obtained in each embodiment.

[0069] Example 1 15±1.2 35±3.1 Example 2 13±0.9 30±2.4 Example 3 20±1.5 40±3.5 Comparative Example 3 26±1.7 51±3.9 Comparative Example 4 29±1.8 62±4.5

[0070] The following conclusions can be drawn from the experimental results in Table 1:

[0071] The initial coagulation time required for clinical procedures of dental implants is 10-20 minutes, and the final coagulation time is 30-40 minutes.

[0072] The initial and final setting times of the self-curing materials obtained in Examples 1-3 all meet the clinical requirements for dental implant procedures. However, due to the differences in the PSC and TTCP ratios, liquid phase components, and solid-liquid ratios in the formulations of Examples 1-3, the initial and final setting times of the self-curing materials obtained also show significant differences. Among them, the self-curing material obtained in Example 2 has the earliest initial and final setting times, and the interval between the initial and final setting times is also the shortest, thus exhibiting better applicability in clinical implementation.

[0073] In contrast, in Comparative Examples 3-4, due to the mismatch between the solid and liquid phase components, the initial and final setting times of the resulting self-curing materials could not simultaneously meet the clinical operational needs of dental implants.

[0074] Test Example 2

[0075] Each group of self-curing materials was placed in a mold, and after curing, a uniaxial compression test was performed on them using a universal tensile testing machine. The results are shown in Table 2.

[0076] Table 2. Mechanical strength of the self-curing materials obtained in each embodiment (unit: MPa)

[0077] Compressive strength 5.4±1.3 15.4±2.3 7.9±0.8 4.3±1.1 5.3±1.4 4.9±0.7 4.7±0.9 2-12 Young's modulus 449±58 939±98 561±73 437±37 442±41 419±33 425±46 100-500

[0078] The following conclusions can be drawn from the experimental results in Table 2:

[0079] The compressive strength and Young's modulus of the self-curing materials obtained in Examples 1-3 meet the current industry standards and can simultaneously meet the requirements of cancellous bone. Among them, the compressive strength and Young's modulus of the self-curing material obtained in Example 2 are relatively the highest, and therefore have the advantage of being able to better fix the implant material in clinical implementation.

[0080] Test Example 3

[0081] Each group of self-curing materials was placed in a mold, and after curing, it was placed in SBF solution (simulated body fluid) for activity testing. The time when it began to form hydroxyapatite is shown in Table 3.

[0082] Table 3 shows the time it takes for the self-curing materials obtained in each example to begin forming hydroxyapatite (HA) in SBF solution.

[0083] HA formation time 1d 1d 1d 2d 3d 1d 1d

[0084] As shown in Table 3, the hydroxyapatite formation rate in Comparative Examples 1-2 was relatively slow, which was not conducive to the rapid fixation of the implant in the early stages. However, Examples 1-3 and Comparative Examples 3-4 were able to promote hydroxyapatite formation within 1 day, which was beneficial to the fixation of the implant in the early stages.

[0085] One week later, Examples 1-3 showed a more pronounced formation of hydroxyapatite, as indicated by the XRD results. Figure 2 As shown, the corresponding SEM characterization results are as follows: Figure 3 As shown.

[0086] according to Figure 2 It can be seen that the self-curing material obtained in Example 1 has been basically converted into hydroxyapatite, but there are still a small amount of TTCP peaks. The self-curing material obtained in Example 2 has been basically completely converted into hydroxyapatite, with only a trace amount of TTCP peaks. The self-curing material obtained in Example 3 has been completely converted into hydroxyapatite.

[0087] according to Figure 3 It can be seen that the surface of the self-curing material obtained in Example 1 has obvious needle-like hydroxyapatite formation, the surface of the self-curing material obtained in Example 2 has more needle-like hydroxyapatite formation, and the surface of the self-curing material obtained in Example 3 mainly exhibits typical dense hemispherical hydroxyapatite.

[0088] The test results above show that the solid components TTCP and PSC described in this invention have a better synergistic effect, which can significantly promote the rapid formation of hydroxyapatite (HA), the main component of bone tissue. Phytic acid and chitosan have a better synergistic effect, thereby giving the self-curing material better adhesion, a relatively faster curing speed, and reducing the acidity of the material.

[0089] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A self-curing material for enhancing the holding power of dental implants, comprising the following components: a solid phase component and a liquid phase component; The solid phase component is composed of a mixture of phosphate and phosphosilicate bioactive glass; The phosphate is tetracalcium phosphate; The phosphosilicate bioactive glass is a calcium phosphosilicate glass with P2O5 9-15 mol%, SiO2 50-60 mol%, and CaO 30-40 mol%. The mass ratio of the phosphate to the phosphosilicate bioactive glass is (0.8-1.2):1; The liquid phase component contains chitosan and phytic acid; The mass ratio of phytic acid to chitosan is (8-10):1; The mass-to-volume ratio of the solid phase component to the liquid phase component is (2-3):1; The self-curing material is obtained by mixing the solid phase component and the liquid phase component.

2. The method for preparing the self-curing material according to claim 1, comprising the following steps: S1. Mix and grind the phosphate and phosphosilicate bioactive glass evenly to obtain a solid phase component; S2. Chitosan is added to a solution containing phytic acid to obtain a liquid phase component; S3. Mix the solid phase component and the liquid phase component to obtain a self-curing material.

3. The method for preparing the self-curing material according to claim 2, characterized in that: The calculation is based on the mass of the phytic acid-containing solution described in step S2, wherein the mass concentration of the phytic acid is 10%-50% and the mass concentration of the chitosan is 1-10%.

4. The use of the self-curing material of claim 1 as a biomedical material for oral use.

5. The use of the self-curing material of claim 1 as a material for enhancing the holding power of dental implants.

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