A non-disintegrating injectable paste material and its preparation method and use

Abstract

The application discloses an injectable anti-disintegration paste material and a preparation method and application thereof, and belongs to the field of biomedical materials. The paste material comprises a powder component and a liquid component. The powder component comprises tricalcium silicate powder, beta-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate. The liquid component is a hydroxypropyl methylcellulose aqueous solution with a mass percentage concentration of 1-3%. The mass ratio of the powder component to the liquid component of the paste material is 1.5-2.5:1. The prepared injectable anti-disintegration paste material has excellent anti-disintegration performance and injection performance, can be self-cured quickly, is convenient to operate and easy to fill, can prevent the paste from being eroded by a water-containing environment, can induce the generation of bone-like hydroxyapatite, and can be used in the field of dental repair such as pulp capping, root tip shaping and root canal treatment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of biomedical materials, and particularly relates to an anti-disintegration injectable paste material and a preparation method and application thereof. BACKGROUND

[0002] There are various dental materials used in clinic, including silver amalgam, gutta-percha, zinc oxide eugenol cement, glass ionomer cement, and bioactive ceramic materials. Calcium silicate-based bioactive materials are promising dental materials. In 1993, Mahmoud Torabinejad successfully developed a mineral trioxide aggregate (MTA) as a calcium silicate-based bioactive ceramic material for use in the field of dentistry, and applied for a patent in 1995. The MTA was approved by the Food and Drug Administraton (FDA) in 1998 and was used for the treatment of pulp-related diseases, achieving good clinical efficacy.

[0003] The MTA has intrinsic curing properties, good biocompatibility, sealing properties, X-ray blocking properties, and certain antibacterial properties, and is widely used in the treatment of endodontic diseases such as root canal filling, apex shaping, pulp capping, pulpotomy, and perforation repair of pulp floor. The main components of the MTA are tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite, and bismuth oxide. The self-curing properties of the Portland cement gel phase in the MTA are the prerequisite for its application in the field of endodontics. In clinical use, the solid powder and the liquid are mixed in a certain proportion to form a paste, and a hydration reaction occurs, gradually forming a solidified material with mechanical strength from the flowable paste. However, the main problems of traditional MTA dental materials are insufficient curing performance (the curing time is as long as 3-4 hours), poor anti-disintegration, and poor operation performance. The newly prepared calcium silicate-based self-curing material will disintegrate when it comes into contact with a water-containing liquid phase, which not only easily causes the paste to fail to tightly fill the tooth, forming microleakage and leading to treatment failure, but also is not conducive to the development of the performance of the filling material.

[0004] Calcium chloride, calcium carbonate, and sodium carbonate have been reported to promote the curing reaction of calcium silicate-based materials and shorten the curing time. The use of konjac gum, sodium alginate, and gelatin can effectively improve the anti-disintegration and injection performance of silicate bone cement. This method mainly improves the interparticle bonding force by forming an organic film on the surface of the paste, enhances the resistance to water solution erosion, and improves the injection performance of the paste. However, the organic film will inevitably hinder the curing reaction of silicate, thus prolonging the curing time.

[0005] Chinese patent CN105999418A discloses an injectable bioactive bone cement material and its preparation method. The bone cement material includes calcium silicate-based inorganic material, glycerol and other high molecular polymers, and hydroxypropyl methyl cellulose and calcium chloride and other additives. The material contains only a single calcium silicate-based self-curing system, and a pre-mixed paste is formed by glycerol and the like. The bone cement curing reaction is slow. In addition, hydroxypropyl methyl cellulose is added as an additive to the bone cement material. The system does not contain an aqueous phase, and the hydroxypropyl methyl cellulose exists only in the form of powder particles and does not form an aqueous solution. Therefore, it cannot play a bonding role and film-forming properties. Therefore, the anti-disintegration performance of the bone cement material is poor.

[0006] Chinese patent CN111110571A discloses a high-efficiency sealing treatment composition for a tooth root canal system, a preparation method and application. The silicate in the composition is tricalcium silicate and beta-dicalcium silicate, and contains calcium hydrogen phosphate dihydrate. The composite has an accelerated curing reaction, but does not solve the problems of poor anti-disintegration performance of calcium silicate-based paste and insufficient operation performance. Excessive amount of acidic phosphate is not conducive to the development of silicate hydration performance. Chinese patent CN112843341A discloses an injectable calcium silicate-based self-curing bioceramic, a preparation method and application thereof. The patent technology is to mix tricalcium silicate, calcium chloride, strontium carbonate, zirconium oxide, amorphous calcium phosphate and polyethylene glycol liquid phase to form a pre-mixed paste. The self-curing bioceramic material is a pre-mixed paste, which has good injection performance and operation performance. However, the material curing is based on the replacement of polyethylene glycol and water molecules in the aqueous environment, so that the silicate undergoes hydration reaction, and the system has a long curing time. In addition, the amorphous calcium phosphate in the material does not have curing characteristics and cannot improve the curing reaction rate of the system.

[0007] In addition, Chinese patent CN103007340A discloses a self-curing composite bone repair material for human hard tissue repair and application. The material is composed of solid phase powder and liquid phase. The solid phase contains tricalcium silicate, fused magnesium oxide, calcium phosphate cement, potassium dihydrogen phosphate, etc. The liquid phase selects deionized water, soluble phosphate, sodium alginate, citric acid, potassium citrate, chitosan, or a mixture of one or more of the above. The composite bone repair material has a shortened curing time. However, the composite material system contains multiple curing reaction materials such as calcium phosphate and magnesium phosphate, so the material has poor operation performance and is difficult to inject. In addition, the silicate in the composite material is only a small amount of secondary phase, and the problem of poor anti-disintegration performance of silicate bone cement is not solved.

[0008] In summary, various methods have been proposed at home and abroad to solve the problems of insufficient curing performance and poor anti-disintegration performance of calcium silicate-based dental materials. However, different strategies have certain defects. It is an urgent problem in the field to develop an injectable anti-disintegration bio-ceramic self-curing material. SUMMARY

[0009] The present application aims to solve the problems of poor anti-disintegration performance and poor operation performance of the existing silicate-based materials, and overcome the deficiency of single organic anti-disintegration material damaging the curing performance of silicate materials. The present application provides an anti-disintegration injectable type cement paste material and a preparation method and application thereof by using β-tricalcium phosphate powder, anhydrous calcium dihydrogen phosphate and hydroxypropyl methyl cellulose aqueous solution.

[0010] Although the prior art involves introducing calcium phosphate or magnesium phosphate and other self-curing systems to enhance the curing performance of calcium silicate-based paste, the calcium phosphate system is tetracalcium phosphate or α-tricalcium phosphate, and potassium dihydrogen phosphate is additionally added (as mentioned in the background art). At present, there is no β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite introduced into the tricalcium silicate curing system, assisted by a hydroxypropyl methyl cellulose solution as a liquid phase, to construct an injectable anti-disintegration cement paste material. The system enhances the curing performance and anti-disintegration characteristics of tricalcium silicate material through inorganic-organic composite reinforcement.

[0011] The technical problems to be solved by the present application are solved by the following technical solutions:

[0012] An anti-disintegration injectable type cement paste material, which is composed of a powder and a liquid. The powder comprises 80-95% of tricalcium silicate powder and 5-20% of β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate powder by mass percentage, and the liquid is a hydroxypropyl methyl cellulose solution. The molar ratio of the β-tricalcium phosphate powder to the anhydrous calcium dihydrogen phosphate powder is 0.6-1.4:1.

[0013] Preferably, the mass ratio of the powder to the liquid is 1.5-2.5:1.

[0014] Preferably, the concentration of the hydroxypropyl methyl cellulose solution is 1-3 wt%.

[0015] Preferably, the particle size of the tricalcium silicate powder is 0.1-10 μm.

[0016] Preferably, the particle size of the β-tricalcium phosphate powder is 0.1-10 μm.

[0017] Preferably, the particle size of the anhydrous calcium dihydrogen phosphate powder is 0.1-50 µm.

[0018] The present application also provides a preparation method of the anti-disintegration injectable type cement paste material, which comprises the following steps:

[0019] Mixing tricalcium silicate powder, beta-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder according to a proportion to obtain a powder material; dissolving hydroxypropyl methylcellulose in water to obtain a liquid material; mixing the powder material and the liquid material according to a mass ratio of 1.5-2.5:1 to obtain an injectable anti-disintegration paste material.

[0020] The application further provides application of the injectable anti-disintegration paste material in the field of dental repair such as pulp capping, root canal shaping and root canal treatment.

[0021] The application has the following advantages:

[0022] 1. The beta-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite and hydroxypropyl methylcellulose solution are used for the first time to solve the technical problems of poor anti-disintegration performance and insufficient curing performance of tricalcium silicate bioceramic paste material. By introducing the beta-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate self-curing system, the hardening rate of the composite paste is enhanced. The triclinic calcium phosphate generated by the reaction of beta-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate can react with the calcium hydroxide generated by the hydration of tricalcium silicate to form apatite, thereby further improving the curing reaction of the paste, shortening the curing time, enhancing the adhesive bonding properties between paste particles and improving the anti-disintegration performance of the paste. In addition, the hydroxypropyl methylcellulose can enhance the paste particle force and improve the water erosion resistance, so that the paste has excellent injectability and anti-disintegration performance.

[0023] 2. The beta-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite and hydroxypropyl methylcellulose are mixed to solve the drawbacks of traditional organic anti-disintegration agents weakening the hydration ability of tricalcium silicate-based paste and effectively improve the anti-disintegration performance of the paste. By the interaction between hydroxypropyl methylcellulose and the beta-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite, the flow characteristics of beta-tricalcium phosphate / anhydrous calcium dihydrogen phosphate particles are enhanced, the operation and injection performance of the system are improved, and the technical problem of the anti-disintegration performance and hardening process of bioceramic bone cement material being unable to be synergistically enhanced is solved. On the other hand, the beta-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite can compensate for the hydration hysteresis effect of hydroxypropyl methylcellulose and improve the self-curing reaction rate of the system.

[0024] 3. The paste has good operation performance, is easy to fill and can seal small and complex root canal systems to improve the sealing and filling quality.

[0025] 4. The paste has good biocompatibility and apatite formation ability, can induce bone-like apatite deposition, improve the bonding strength of the filling material and the tooth and reduce the risk of microleakage. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate embodiments consistent with the application and, together with the description, further serve to explain the principles of the application wherein:

[0027] Figure 1 Photos of the anti-dispersion performance of the water-settable paste materials prepared for Comparative Examples 1-4;

[0028] Figure 2 Photos of the anti-dispersion performance of the anti-dispersion injectable water-settable paste materials prepared for Examples 1-3 and the water-settable paste material prepared for Comparative Example 3;

[0029] Figure 3 Quantitative results of the anti-dispersion performance of the anti-dispersion injectable water-settable paste materials prepared for Examples 1-3 and the water-settable paste material prepared for Comparative Example 3;

[0030] Figure 4 Injection performance of the anti-dispersion injectable water-settable paste materials prepared for Examples 1-3 and the water-settable paste material prepared for Comparative Example 3;

[0031] Figure 5 Injection force and displacement results of the anti-dispersion injectable water-settable paste material prepared for Example 3 of the present application;

[0032] Figure 6 Curing time results of the anti-dispersion injectable water-settable paste materials prepared for Examples 1-3 and the water-settable paste material prepared for Comparative Example 3;

[0033] Figure 7 SEM image of the anti-dispersion injectable water-settable paste material prepared for Example 2 of the present application after immersion in simulated body fluid.

[0034] Figure 8 Photos of the anti-dispersion performance of the anti-dispersion injectable water-settable paste material prepared for Example 6 of the present application;

[0035] Figure 9 Photos of the anti-dispersion performance of the anti-dispersion injectable water-settable paste material prepared for Example 7 of the present application. DETAILED DESCRIPTION

[0036] The following disclosure provides many different embodiments, or examples, for implementing different structures of the present application. For purposes of explanation and ease of understanding, specific examples of the present application are set forth. Of course, the present application is not limited in scope to the particular examples described. In addition, the present application can refer to different examples using the same reference numbers and / or the same reference letters. This practice is for the purpose of simplifying and clarifying the present application, and is not intended to indicate any relationship between the various embodiments and / or features of the present application.

[0037] Example 1

[0038] The solid phase powder is weighed according to the following mass percentage: 95% tricalcium silicate powder, the rest being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate is 1:1. The three powders are uniformly mixed to form a powder;

[0039] 0.2 g of hydroxypropyl methyl cellulose is dissolved in 9.8 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 2%, which is used as a liquid agent;

[0040] The powder and the liquid agent are fully stirred and uniformly mixed according to a mass ratio of 2:1 to prepare a water-setting paste material.

[0041] Example 2

[0042] The solid phase powder is weighed according to the following mass percentage: 90% tricalcium silicate powder, the rest being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate is 1:1. The three powders are uniformly mixed to form a powder;

[0043] 0.2 g of hydroxypropyl methyl cellulose is dissolved in 9.8 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 2%, which is used as a liquid agent;

[0044] The powder and the liquid agent are fully stirred and uniformly mixed according to a mass ratio of 2:1 to prepare a water-setting paste material.

[0045] Example 3

[0046] The solid phase powder is weighed according to the following mass percentage: 80% tricalcium silicate powder, the rest being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate is 1:1. The three powders are uniformly mixed to form a powder;

[0047] 0.2 g of hydroxypropyl methyl cellulose is dissolved in 9.8 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 2%, which is used as a liquid agent;

[0048] The powder and the liquid agent are fully stirred and uniformly mixed according to a mass ratio of 2:1 to prepare a water-setting paste material.

[0049] Example 4

[0050] The solid phase powder is weighed according to the following mass percentage: 90% tricalcium silicate powder, the rest being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate is 1:1. The three powders are uniformly mixed to form a powder;

[0051] 0.1 g of hydroxypropyl methyl cellulose was dissolved in 9.9 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 1% as a liquid agent;

[0052] The powder and the liquid were fully stirred and mixed in a mass ratio of 2.5:1 to prepare a cementitious paste material.

[0053] Example 5

[0054] Solid phase powder was weighed in the following mass percentages: 95% tricalcium silicate powder, the remaining 5% being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate being 1:1, and the three powders were uniformly mixed to form a powder;

[0055] 0.3 g of hydroxypropyl methyl cellulose was dissolved in 9.7 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 3% as a liquid agent;

[0056] The powder and the liquid were fully stirred and mixed in a mass ratio of 1.5:1 to prepare a cementitious paste material.

[0057] Example 6

[0058] Solid phase powder was weighed in the following mass percentages: 95% tricalcium silicate powder, the remaining 5% being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate being 0.6:1, and the three powders were uniformly mixed to form a powder;

[0059] 0.2 g of hydroxypropyl methyl cellulose was dissolved in 9.8 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 2% as a liquid agent;

[0060] The powder and the liquid were fully stirred and mixed in a mass ratio of 2:1 to prepare a cementitious paste material.

[0061] Example 7

[0062] Solid phase powder was weighed in the following mass percentages: 90% tricalcium silicate powder, the remaining 10% being a mixture of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder, and the molar ratio of β-tricalcium phosphate powder to anhydrous calcium dihydrogen phosphate being 1.4:1, and the three powders were uniformly mixed to form a powder;

[0063] 0.2 g of hydroxypropyl methyl cellulose was dissolved in 9.8 g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 2% as a liquid agent;

[0064] The powder and the liquid were fully stirred and mixed in a mass ratio of 1.5:1 to prepare a cementitious paste material.

[0065] Comparative Example 1

[0066] The single tricalcium silicate powder is used as the powder;

[0067] The deionized water is used as the liquid;

[0068] The powder and the liquid are fully stirred according to the mass ratio of 2:1, and a water-setting paste material is prepared.

[0069] Comparative Example 2

[0070] The tricalcium silicate powder with the mass percentage of 100% is used as the powder;

[0071] 0.1g of hydroxypropyl methyl cellulose is dissolved in 9.9g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 1%, which is used as the liquid;

[0072] The powder and the liquid are fully stirred according to the mass ratio of 2:1, and a water-setting paste material is prepared.

[0073] Comparative Example 3

[0074] The single tricalcium silicate powder is used as the powder;

[0075] 0.2g of hydroxypropyl methyl cellulose is dissolved in 9.8g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 2%, which is used as the liquid;

[0076] The powder and the liquid are fully stirred according to the mass ratio of 2:1, and a water-setting paste material is prepared.

[0077] Comparative Example 4

[0078] The tricalcium silicate powder with the mass percentage of 100% is used as the powder;

[0079] 0.3g of hydroxypropyl methyl cellulose is dissolved in 9.7g of deionized water to prepare a hydroxypropyl methyl cellulose solution with a concentration of 3%, which is used as the liquid;

[0080] The powder and the liquid are fully stirred according to the mass ratio of 2:1, and a water-setting paste material is prepared.

[0081] In order to reflect the superiority of the material of the present application, the water-setting paste materials prepared in Examples 1-7 and Comparative Examples 1-4 are tested for anti-disintegration resistance, curing time, injection performance, and apatite mineralization performance.

[0082] The method for performance characterization of the above-mentioned anti-disintegration-resistant injectable water-setting paste material is as follows:

[0083] The dynamic anti-disintegration performance includes qualitative testing and quantitative testing:

[0084] The freshly prepared paste material was transferred into a syringe and injected into a glass dish containing water, and the glass dish was placed in a vibrator (100 r / min or 150 r / min) for different time, and the paste slurry was observed for the phenomenon of collapse and free dispersion; in addition, the freshly prepared paste material was molded into a spherical shape, placed in a glass dish containing water, and vibrated at 150 r / min for 15 min in a vibrator, and the slurry was weighed before and after the test to calculate the anti-collapse rate.

[0085] Examples 1-7 and Comparative Examples 1-4 were subjected to dynamic anti-collapse qualitative testing, and part of the test results are shown in Table 1. Figure 1 As shown in Table 1, the paste in Comparative Example 1 can cause powder particles to separate and disperse when injected into water, and the injection process is relatively difficult, and the injection performance is poor. After being vibrated at 100 r / min for 10 min, the entire paste slurry collapses and does not form a shape, and scatters throughout the glass dish. In contrast, the hydraulically setting paste in Comparative Examples 2, 3 and 4 does not have obvious particle separation and collapse phenomenon after being vibrated under the same conditions, and maintains the original injection shape, and is easy to inject. These pastes exhibit enhanced anti-collapse performance. In addition, Examples 1-7 show similar good anti-collapse ability, and can maintain the overall shape in the aqueous phase without paste collapse. From the above results, it can be seen that hydroxypropyl methyl cellulose can effectively improve the anti-collapse performance of tricalcium silicate paste material, and proves the anti-collapse effect of hydroxypropyl methyl cellulose.

[0086] To further verify the effect of β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate complex on the anti-collapse performance of tricalcium silicate paste, Comparative Example 3 and Examples 1-3 were subjected to anti-collapse performance testing for a longer time and at a higher vibration speed, and the results are shown in Table 2. Figure 2 As shown in Table 2, all the pastes can be easily injected, and do not have particle separation phenomenon when injected into water. After being vibrated at 150 r / min for 15 min, the tricalcium silicate paste without the introduction of β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate complex (Comparative Example 3) has obvious collapse phenomenon, and the particles separate and escape, while the hydraulically setting pastes in Examples 1-3 can maintain good shape and do not have obvious powder collapse phenomenon. From the above results, it can be seen that the prepared hydraulically setting paste is easy to inject, and has good anti-collapse performance and can maintain good shape in water. Figure 8 Figure 9 In addition, the dynamic anti-collapse performance quantitative results of Comparative Example 3 and Examples 1-3 are shown in Table 3. Figure 3 As shown in Table 3, the anti-collapse performance of the paste in Examples 1-3 is continuously improved compared to Comparative Example 3, and the maximum anti-collapse rate is greater than 95%. The above results show that the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate complex can further significantly improve the anti-collapse ability of the tricalcium silicate paste, and can synergistically exert the anti-collapse characteristics with hydroxypropyl methyl cellulose.

[0087] ​Injectability:

[0088] The freshly prepared paste material was loaded into a 2.5 mL syringe, and after 10 min, the paste was injected by applying pressure using a universal testing machine at a crosshead moving speed of 15 mm / min and a maximum load of 100 N. The injectability was expressed as the percentage of the weight of the paste after extrusion to the total weight of the original paste.

[0089] The injectability of the paste was tested for Examples 1-3 and Comparative Examples 1 and 3, and part of the test results are shown in Figure 4 The paste in Comparative Example 1 was difficult to inject and was prone to filter pressing, and particles were easily separated from the aqueous phase during injection. The injectability of the paste in Comparative Example 3 was 91.68%, and the injectability of the pastes in Examples 1-3 was 94.81%, 94.62%, and 88.55%, respectively. The above pastes all had excellent injectability. When the content of the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite was 5% and 10%, the injectability of the composite paste slightly increased, and when the content of the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite was increased to 20%, the injectability of the composite paste slightly decreased. The above results showed that the hydroxypropyl methylcellulose could effectively improve the injectability of the tricalcium silicate paste, and when the content of the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite was in the range of 5-20%, the water-setting paste of the present application still had excellent injectability. Figure 5 The change in injection force and displacement of the water-setting paste in Example 3 after 5 min of mixing was shown in the figure. The injection force of the paste was less than 30 N, and the paste was easy to inject and had good injection performance.

[0090] Setting time:

[0091] The freshly prepared paste slurry was quickly placed in a polytetrafluoroethylene mold (8 mm in diameter and 2 mm in height), and then placed in a water bath at 37°C, and the setting time was determined by a Vicat apparatus.

[0092] The setting time of the pastes in Examples 1-3 and Comparative Example 3 was tested, and the results are shown in Figure 6 As can be seen from the figure, the setting time of the water-setting pastes in Examples 1-3 was significantly lower than that of the tricalcium silicate paste material in Comparative Example 3. Compared with Comparative Example 3, 5%-20% of the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite was introduced into the water-setting pastes in Examples 1-3. This result showed that the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite significantly accelerated the setting reaction of the paste of the present application and shortened the setting time, thereby confirming the effectiveness of the β-tricalcium phosphate powder / anhydrous calcium dihydrogen phosphate composite in promoting the hardening process of the tricalcium silicate paste.

[0093] Apatite mineralization experiment:

[0094] The newly prepared paste material is filled into a mold for curing, then soaked in simulated body fluid (SBF), and then the surface of the sample is characterized by using a scanning electron microscope (SEM).

[0095] Figure 7 For the SEM photograph of the surface of the water-setting paste in Example 2 after soaking in SBF solution, it can be seen from the figure that spherical bone-like apatite is formed on the surface of the hardened paste, which shows that the water-setting paste has excellent apatite mineralization ability and can enhance the bonding and sealing performance between the paste and the tooth.

[0096] Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the application being indicated by the following claims.

[0097] It should be understood that the application is not limited to the precise construction that has been described above and shown in the accompanying drawings, and that various modifications and changes can be made by those skilled in the art without departing from the scope of the application. The scope of the application is indicated only by the appended claims.

Claims

1. A non-disintegrating injectable cement material, characterized by comprising, The water-setting paste material is composed of a powder and a liquid; the powder is composed of 80-95% of tricalcium silicate powder, 5-20% of a composite of β-tricalcium phosphate powder and anhydrous calcium dihydrogen phosphate powder; the molar ratio of the β-tricalcium phosphate powder to the anhydrous calcium dihydrogen phosphate powder is 0.6-1.4:1; the liquid is a hydroxypropyl methylcellulose solution; the mass ratio of the powder to the liquid is 1.5-2.5:

1.

2. The anti-disintegration injectable cement material according to claim 1, wherein The concentration of the hydroxypropyl methylcellulose solution is 1-3 wt%.

3. The anti-disintegration injectable cement material according to claim 1, wherein The particle size of the tricalcium silicate powder is 0.1-10 μm.

4. The anti-disintegration injectable cement material according to claim 1, wherein The particle size of the β-tricalcium phosphate powder is 0.1-10 μm.

5. The anti-disintegration injectable cement material according to claim 1, wherein The particle size of the anhydrous calcium dihydrogen phosphate powder is 0.1-50 μm.

6. The method of claim 1 wherein the injectable, non-disintegrating, water- setting paste material is prepared by the steps of: The method comprises the following steps: The tricalcium silicate powder, the β-tricalcium phosphate powder and the anhydrous calcium dihydrogen phosphate powder are mixed in proportion to obtain the powder material; hydroxypropyl methylcellulose is dissolved in water to obtain the liquid material; the powder material and the liquid material are mixed in a mass ratio of 1.5-2.5:1 to obtain the anti-dispersion injectable water-setting paste material.

7. Use of the anti-dispersion injectable water-setting paste material of any one of claims 1-5 in the preparation of a dental repair material for pulp capping, apexification and root canal treatment. ​

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