CN110772430A - Calcium phosphate root canal filler with stable preservation - Google Patents
Calcium phosphate root canal filler with stable preservation Download PDFInfo
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Abstract
The invention discloses a calcium phosphate root canal filler with stable storage, which belongs to the field of medical materials, has strong collapsibility resistance, can be stably stored for years, and is difficult to separate solid from liquid. The technical scheme of the invention comprises the following steps: (1) uniformly mixing calcium phosphate powder with a developer to prepare solid-phase powder; (2) adding polydopamine microspheres into an organic solvent, and ultrasonically dispersing for 1-2 hours to prepare a liquid phase component; (3) and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filling slurry. The tooth root filling agent prepared by the invention is simple to operate, the sample is placed in the container and is injected or filled when in use, the solid phase and the liquid phase do not need to be mixed on site, and the operation time and the risk of introducing bacteria are reduced. The added polydopamine and organic solvent can lead the tooth root filling agent to be stored in a container in a sealing way, and the filling agent has good fluidity and injection performance, solid and liquid are not separated, the filling agent is stable paste in the container, after being filled into the root canal, the filling agent is gradually solidified by the liquid in the environment, the solidification time is greatly shortened, the feeding of patients is facilitated, and the polydopamine and organic solvent have good flexural strength, and the problem of large brittleness after calcium phosphate solidification is overcome.
Description
Technical Field
The invention belongs to the field of medical materials, relates to a calcium phosphate root canal filler, and particularly relates to a calcium phosphate root canal filler with stable storage and a preparation method thereof.
Background
Root canal filling is the most commonly used method for treating pulpitis and periapical periodontitis, and a root canal filling material is one of important factors affecting the efficacy of root canal treatment. The root canal fillers currently used clinically mainly include three types, i.e., solid, paste and liquid.
The solid root canal filling material (such as gutta-percha point, titanium-nickel alloy point, silver point, plastic point and the like) has no adhesiveness, can not be adhered with the internal structure of the root canal, can not enter the bent root canal and the side auxiliary root canal, can not form tight sealing, and the gutta-percha point must be matched with root canal paste for use. Paste root filling materials (such as zinc oxide clove oil, calcium hydroxide, iodoform, resins, glass ionomer cement and other pastes) can shrink in volume during the curing process, are dissolved in water or tissue fluid, and have micro-gaps with the root canal wall to cause micro-leakage, so that the apical foramen cannot be completely sealed. Although the paste has a certain improvement effect when used together with the gutta-percha point, the problem is difficult to solve fundamentally, and the clinical operation time is long. Liquid underfill materials (such as FR novolac) tend to penetrate into dentinal tubules and cause discoloration of teeth, affecting aesthetics, and are irritating and cytotoxic to tissue during polymerization. Although the gutta-percha point and paste root filling material is the most common root canal filling method in clinic, the biocompatibility is poor, if the gutta-percha point and the root filling material are carelessly beyond the root tip, long-term foreign body stimulation is formed, and some materials have stimulation and corrosiveness on tissues and even cause enamel development defects of inherited permanent teeth and the like.
The calcium phosphate cement is an orthopedic material and can be self-solidified under physiological condition to obtain solidified product similar to human bone tissue. The calcium phosphate bone cement has good biocompatibility and can be arbitrarily shaped according to the defect part. After being hydrated, the calcium phosphate cement is converted into hydroxyapatite which can guide bone growth. The self-curing performance and biocompatibility of the calcium hydroxide paste are obviously superior to those of calcium hydroxide paste, and the calcium hydroxide paste also has potential dentin reconstruction function. The product after solidification is hydroxyapatite which is similar to inorganic components of human hard tissues, but calcium phosphate bone cement has degradability and is easily dispersed by blood or body fluid after filling, so that the volume of the material is reduced, bacteria easily enter the root canal again for reproduction, inflammation is recurrent, and treatment fails, and the traditional calcium phosphate bone cement needs to be prepared by a doctor on site, so that the defects exist: firstly, the doctor can influence the performance of the bone cement by on-site blending; secondly, tools prepared on site need to be disinfected in advance; third, physician scheduling increases working time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a calcium phosphate root canal filler which is stable to store, has strong collapsibility resistance, can be stably stored for years and is difficult to separate solid from liquid.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a stable calcium phosphate root canal filler, which is characterized by comprising the following steps:
(1) uniformly mixing calcium phosphate powder with a developer to prepare solid-phase powder;
(2) adding polydopamine microspheres into an organic solvent, and ultrasonically dispersing for 1-2 hours to prepare a liquid phase component;
(3) and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filling slurry.
Preferably, the solid-phase powder comprises the following components in parts by mass: 60-100 parts of calcium phosphate powder and 20-40 parts of developing agent; the liquid phase component comprises the following components in parts by mass: 30-130 parts of solvent and 10-20 parts of polydopamine microsphere.
Preferably, the solid-phase powder comprises, by mass, 8 parts of calcium phosphate powder and 40 parts of a developer, wherein the calcium phosphate powder is α -tricalcium phosphate, the developer is iodoform, the solvent in the liquid-phase component is glycerol, and the liquid-phase component comprises, by mass, 60 parts of the solvent and 15 parts of polydopamine microspheres.
Preferably, the preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 0.5-2g dopamine hydrochloride in 40-60ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 40-80ml of ethanol and 3-8ml of 28 mass percent concentrated ammonia water in 10-30ml of deionized water, performing ultrasonic treatment for 8-20min to obtain an ethanol ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol ammonia water mixed solution, fully stirring for 12-36h, centrifuging (3000 plus 10000rpm, 20-60 min), washing with acetone for 1-4 times, and drying at 50-70 ℃ to obtain the polydopamine microspheres with the particle size of 200 plus 400 nm.
Preferably, the preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain the polydopamine microspheres with the particle size of 300 nm.
Preferably, the mass ratio of the solid-phase powder to the liquid phase is 1 (0.3-0.8).
Preferably, the calcium phosphate in the solid phase powder is selected from one or more of tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, anhydrous calcium hydrophosphate, calcium hydrophosphate dihydrate, calcium biphosphate, calcium pyrophosphate, hydroxyapatite, fluorapatite, strontium apatite and carbonate-containing apatite.
In the liquid phase component, the organic solvent is glycerol or polyethylene glycol.
Preferably, the solid-phase powder further comprises the following components in parts by mass: 2-5 parts of an antibacterial agent selected from: one or more of metronidazole, tinidazole, tylon and tobramycin, and preferably 4 parts of antibacterial agent.
Preferably, the developer is selected from: at least one of iodoform, barium sulfate and zirconium dioxide, and preferably, the developing agent is iodoform.
The invention also provides the calcium phosphate root canal filler prepared by the method.
The root canal filler of the invention is not solidified under the anhydrous condition, and the solid-liquid separation can not occur in the long-term storage, probably because the hydroxyl on the poly dopamine molecule and the hydroxyl on the glycerol form the hydrogen bond effect to form a network structure in the system, thereby promoting the system to keep stable, the calcium phosphate particles of the root canal filler do not settle, the system is kept stable, and the solid-liquid separation does not occur.
The root canal filling agent is stored in a container at 4-50 ℃, the root canal filling agent can be stored at normal temperature, is convenient to store, is prepared into paste in advance, and is directly injected or filled into a tooth root. The paste can be stored in a container because the paste does not contain water, the paste can not be hydrated in the storage process, the storage time can reach more than 1 year, the commercial popularization and application of the product are facilitated, and the dental root filling agent is cured and reacts with water to generate hydroxyapatite after being extruded into a dental root canal.
The invention also provides the application of the root canal filler, which is directly injected and filled by a filling mode or a syringe.
Compared with the prior art, the invention has the beneficial effects that:
the tooth root filling agent prepared by the invention is simple to operate, the sample is placed in the container and is injected or filled when in use, the solid phase and the liquid phase do not need to be mixed on site, and the operation time and the risk of introducing bacteria are reduced. The added polydopamine and organic solvent can lead the tooth root filling agent to be stored in a container in a sealing way, and the filling agent has good fluidity and injection performance, solid and liquid are not separated, the filling agent is stable paste in the container, after being filled into the root canal, the filling agent is gradually solidified by the liquid in the environment, the solidification time is greatly shortened, the feeding of patients is facilitated, and the polydopamine and organic solvent have good flexural strength, and the problem of large brittleness after calcium phosphate solidification is overcome.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
In one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
the solid-phase powder comprises 60 parts of calcium phosphate powder and 20 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the liquid-phase component comprises 30 parts of solvent and 10 parts of polydopamine microspheres, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microsphere solution into glycerol, and ultrasonically dispersing for 1h to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain polydopamine microspheres with the particle size of 300 nm;
example 2
In one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
in one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
the solid-phase powder comprises 80 parts of calcium phosphate powder and 30 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the liquid-phase component comprises 60 parts of solvent and 15 parts of polydopamine microspheres, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microspheres into glycerol, and ultrasonically dispersing for 1.5 hours to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain polydopamine microspheres with the particle size of 300 nm;
example 3
In one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
in one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
the solid-phase powder comprises 100 parts of calcium phosphate powder and 40 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the liquid-phase component comprises 130 parts of solvent and 20 parts of polydopamine microspheres, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microspheres into glycerol, and ultrasonically dispersing for 2 hours to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain polydopamine microspheres with the particle size of 300 nm;
example 4
The solid-phase powder comprises 60 parts of calcium phosphate powder and 20 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the liquid-phase component comprises 60 parts of solvent and 20 parts of polydopamine microsphere, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microspheres into glycerol, and ultrasonically dispersing for 1h to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain polydopamine microspheres with the particle size of 300 nm;
example 5
In one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
in one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
the solid-phase powder comprises 100 parts of calcium phosphate powder and 40 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the liquid-phase component comprises 60 parts of solvent and 20 parts of polydopamine microspheres, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microspheres into glycerol, and ultrasonically dispersing for 2 hours to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain polydopamine microspheres with the particle size of 300 nm;
comparative example 1
A root canal filler comprises a solid phase powder and a liquid phase component;
the solid-phase powder comprises 80 parts by mass of calcium phosphate powder and 30 parts by mass of developer, the calcium phosphate powder is α -tricalcium phosphate, the developer is iodoform, and the liquid-phase component comprises 60 parts by mass of solvent, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing the calcium phosphate and the developer to prepare solid-phase powder, mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
Comparative example 2
A root canal filler comprises a solid phase powder and a liquid phase component;
the solid-phase powder comprises 80 parts of calcium phosphate powder and 30 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, and the liquid-phase component comprises 30 parts of solvent and 15 parts of dopamine microsphere, wherein the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding dopamine powder into glycerol, and ultrasonically dispersing for 1.5 hours to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
This comparative example is substantially the same as example 2 except that the polydopamine microspheres of example 2 are replaced with dopamine powder in comparative example 2.
Comparative example 3
In one embodiment of the calcium phosphate root canal filler of the present invention, the root canal filler comprises a solid-phase powder and a liquid-phase component;
the solid-phase powder comprises 80 parts by mass of calcium phosphate powder and 30 parts by mass of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, and the liquid-phase component comprises 60 parts by mass of solvent and 50 parts by mass of polydopamine microspheres, wherein the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microspheres into glycerol, and ultrasonically dispersing for 1.5 hours to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain the polydopamine microspheres with the particle size of 300 nm.
Comparative example 4
A root canal filler comprises a solid phase powder and a liquid phase component;
the solid-phase powder comprises 80 parts of calcium phosphate powder and 30 parts of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the liquid-phase component comprises 60 parts of solvent and 5 parts of polydopamine microspheres, and the solvent is glycerol.
The preparation method of the root canal filler comprises the steps of uniformly mixing calcium phosphate and a developer to prepare solid-phase powder, adding polydopamine microspheres into glycerol, and ultrasonically dispersing for 1.5 hours to prepare a liquid-phase component; and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filler.
The preparation method of the polydopamine microsphere comprises the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging (5000 rpm, 30 min), washing with acetone for 2 times, and drying at 60 ℃ to obtain the polydopamine microspheres with the particle size of 300 nm.
The following performance tests were performed on the fillers prepared in examples 1-5 and comparative examples 1-4.
1. Fluidity of the resin
According to the 7.2 test in the standard YY0717-2009 of the people's republic of china medical practice, a graduated syringe was used to deliver 0.05ml of the filler, which was placed in the center of one glass plate, and 180s after tempering, the second glass plate was placed in the middle of the top of the filler, followed by the weight block, giving a total applied mass of 120 g. The weight was removed in 10min and the maximum and minimum diameters of the filler were measured.
As shown in Table 1, the products of examples 1 to 5 had good fluidity, and the maximum diameter of the disks in the fluidity test of the samples of examples 1 to 5 was 26mm and the minimum diameter was 24mm, and the fluidity was remarkably improved by adding the thickener in conformity with the specification of iso6876, and the diameters of the samples were all larger than 20 mm. The filler can reach the root canal apex, so when the filler of examples 1-5 is used for filling the tooth, the gutta percha apex is not needed, and the problem that the gutta percha apex root filling material exceeds the root apex to form foreign body stimulation can be avoided.
2. Curing time
According to the test of 7.4 in the national medical and pharmaceutical industry standard YY0717-2009, a stainless steel mold is placed on a flat glass sheet, the blended sealing material is filled in the stainless steel mold, after the blending is finished for 120s, the materials of examples 1-5 and comparative examples 1-4 are placed on a metal block in a constant temperature and humidity box, a pressure head of a penetrometer is lightly placed on the horizontal plane of the sealing material every 60s, the operation is repeated until no indentation appears by naked eyes, and the curing time is recorded.
The results are shown in Table 1, the polydopamine addition does not affect the curing time, which should not be too fast due to the time it takes for the physician to manipulate the root filling material, considering that the working time is within 30min, the curing time should exceed 30min, and too long a curing time may affect the patient's food intake.
3. Dimensional change after curing
The mold was placed on a polyethylene film-coated glass plate according to 7.6 test in the national institutes of health YY0717-2009, the solid phase powders of examples 1-5 and comparative examples 1-4 were blended with a liquid phase, respectively, and the blended material was slightly overfilled in the mold. Another glass sheet coated with a polyethylene film was placed on top of the filler. The mold is secured to the C-clamp along with the glass sheet. 5min after the blending is started, the material and the C-shaped clamp are placed into an environment with the relative humidity of 95-100% and the temperature of 37 ℃. The mold was rubbed back and forth on a wet sandpaper of P600 to flatten both ends of the sample, the sample was taken out of the mold, the height of the sample was measured, and the sample was stored in distilled water at 37 ℃ for 30 days to measure the height of the sample again. The change in specimen length and the percent of original length were calculated and the results are shown in table 1, with the sample size remaining unchanged in the examples of the invention.
TABLE 1 product Performance test results
4. Dissolution rate
According to the 7.7 test in the standard YY0717-2009 of the people's republic of China, a mold was placed on a glass plate, the solid phase powder in examples 1-5 and comparative examples 1-4 were blended with a liquid phase, and the blend was slightly overfilled in the mold. The top of the filler was covered with a polyethylene film coated glass plate. The above materials were placed in a constant temperature and humidity cabinet for 24 hours, the specimens were removed from the molds, and the quality was measured after carefully trimming the burrs.
The method comprises the following steps:
the 9 samples were placed in a tray and were not allowed to touch and interfere with each other. Adding 50ml of water, covering the tray cover and putting the tray cover into a constant temperature and humidity box for 24 hours, then taking out the sample, washing the sample in a shallow tray by using 2ml-3ml of clean water, checking the washing in the tray, and indicating that the material is decomposed if particles appear. The sample was removed, the water in the tray was evaporated, the water did not boil, and the tray was then oven dried in an oven at 110 ℃ until the tray had a constant weight. The trays were cooled to room temperature in a desiccator before each weighing. The difference of the mass of the final tray from the initial tray mass was calculated, dissolution = difference of mass of final tray from initial tray mass/initial mass of sample. The results are shown in Table 2. As can be seen from Table 2, the dissolution rate of example 2 is the lowest, and the degradation rate can be reduced by adding polydopamine microspheres to the liquid phase components of examples 1-5.
5. Compressive strength
Compressive strength the samples of examples 1-6, comparative examples 1-3 were prepared according to classical mechanical evaluation in iso 9917:1991 using a cylindrical polytetrafluoroethylene abrasive tool with a 4mm diameter and a 6mm length to remove air bubbles. The samples were stored at 37 ℃ in an incubator at 100% relative humidity for 15 minutes, then removed from the moulds and stored in distilled water at 37 ℃ for the remainder of the time.
The results are shown in Table 2.
6. Flexural Strength
Tested according to appendix C of the Chinese people's republic of China medical industry Standard YY 0271.2-2016.
The method comprises the following steps:
the filler was filled into the c.2.1 mold during the working time of the filler, after curing, the sample was removed from the mold, after 24h storage in water at 37 ℃, the samples of examples 1-5 and comparative examples 1-4 were removed from the water bath, the test was transferred to the flexural strength test equipment operating according to the procedure C3, the sample was placed in the center of the test fixture perpendicular to the three cylinders, the sample was removed from the water bath for 10s, the sample was loaded at a crosshead speed of 0.75mm/min until rupture of the itching, and the maximum load applied to the sample was recorded.
The flexural strength, σ, was calculated as follows: MPa;
σ=3FL/2bh
2
in the formula:
f-maximum load applied to the specimen in cattle (N);
l-distance of two supporting point components, unit is millimeter (mm), and accurate to 0.01 mm;
b-the width in millimeters of the middle of the sample measured before testing;
h-height in millimeters measured in the middle of the specimen before testing.
The results are shown in Table 2.
TABLE 2 product Performance test results
| Group of | Dissolution rate (%) | Compressive strength (MPa) | Flexural Strength (MPa) |
| Example 1 | 1.9 | 25.4 | 9.6 |
| Example 2 | 1.1 | 34.2 | 14.2 |
| Example 3 | 1.8 | 27.2 | 9.7 |
| Example 4 | 1.6 | 28.3 | 12.2 |
| Example 5 | 1.8 | 29.5 | 13.4 |
| Comparative example 1 | 4.2 | 14.3 | 6.1 |
| Comparative example 2 | 3.4 | 14.9 | 7.3 |
| Comparative example 3 | 2.5 | 18.9 | 8.2 |
| Comparative example 4 | 2.7 | 17.3 | 8.6 |
5. X-ray opacity
According to the test of 7.8 in the Chinese people's republic of China medical industry standard YY0717-2009, YY0717-2009 specifies that the X-ray radiation resistance of the sealing material is not lower than the equivalent radiation resistance of an aluminum plate with the thickness of 3 mm. Filling the mixed filler into a die, and covering cover plates on the top and the bottom of the die to enable the filler to be molded to reach the thickness of 1 mm. The mold is placed in the center of the dental X-ray occlusal splint, a wedge-shaped stepped aluminum plate is placed beside the dental X-ray occlusal splint, and a same cover plate is placed below the wedge-shaped stepped aluminum plate. The sample, wedge-shaped stepped aluminum plate and film were irradiated using 65kV X-rays at a distance of about 300mm from the film for a time sufficient to provide an optical density value of between 0.5 and 2.5 for the 1mm thick aluminum wedge and the film beneath it. After film development, fixing and drying, the optical densities of the samples and the images of the wedge-shaped stepped aluminum plate were compared using a densitometer. The X-ray opacity of the sample is expressed in millimeters of equivalent aluminum plate thickness. The results show that the formulated fillers of examples 1-5 have a radiopacity equivalent to a 7.1mm thick aluminum plate, and are satisfactory for clinical use.
6. Storage time:
the samples of examples 1 to 5 and comparative examples 1 to 4 were placed in a sealed container and stored at room temperature for 30 days, 2 months, 6 months, and 12 months, and the phases of the samples were observed. The products of examples 1-5 can be stored for 12 months, the product performance is the same as that of the product just prepared, and the products of comparative examples 1-4 can cause solid-liquid separation after being placed for more than 2 months.
TABLE 2 product Performance test results
| Group of Clip for fixing | 30 days | 2 month | 6 month | 12 month |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 1 | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 2 | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 3 | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 4 | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent |
| Fruit of Chinese wolfberry Applying (a) to Example (b) 5 | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent | The product does not solidify and flow Sex, operational time and the product is consistent |
| To pair Ratio of Example (b) 1 | The product does not solidify and flow Sex, operational time and the product is consistent | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of |
| To pair Ratio of Example (b) 2 | The product does not solidify and flow Sex, operational time and the product is consistent | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of |
| To pair Ratio of Example (b) 3 | The product does not solidify and flow Sex, operational time and the product is consistent | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of |
| To pair Ratio of Example (b) 4 | The product does not solidify and flow Sex, operational time and the product is consistent | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of | The product is not solidified and solid-liquid Separation of |
In conclusion, the root canal filler prepared by the invention is simple to operate, the added dopamine and the solvent can enable the root canal filler to be hermetically stored in the container, the root canal filler prepared by the invention has good fluidity and injection performance, solid and liquid are not separated, the filler is stable paste in the container, after being filled into a root canal, the filler is gradually solidified by the liquid in the environment, the solidification time is greatly shortened, a patient can eat after being filled for 2 hours, and the root canal filler has good flexural strength, and the problem of high brittleness after calcium phosphate solidification is solved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a calcium phosphate root canal filler with stable preservation is characterized by comprising the following steps:
(1) uniformly mixing calcium phosphate powder with a developer to prepare solid-phase powder;
(2) adding polydopamine microspheres into an organic solvent, and ultrasonically dispersing for 1-2 hours to prepare a liquid phase component;
(3) and mixing the solid-phase powder and the liquid-phase component, and uniformly stirring to obtain the calcium phosphate root canal filling slurry.
2. The method according to claim 1, wherein the solid phase powder comprises the following components in parts by mass: 60-100 parts of calcium phosphate powder and 20-40 parts of developing agent; the liquid phase component comprises the following components in parts by mass: 30-130 parts of solvent and 10-20 parts of polydopamine microsphere.
3. The preparation method of claim 2, wherein the solid phase powder comprises 80 parts by mass of calcium phosphate powder and 40 parts by mass of developing agent, the calcium phosphate powder is α -tricalcium phosphate, the developing agent is iodoform, the solvent in the liquid phase component is glycerol, and the liquid phase component comprises 60 parts by mass of solvent and 15 parts by mass of polydopamine microspheres.
4. The method of claim 1, wherein the polydopamine microsphere is prepared by a method comprising the steps of:
(1) dissolving 0.5-2g dopamine hydrochloride in 40-60ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 40-80ml of ethanol and 3-8ml of 28 mass percent concentrated ammonia water in 10-30ml of deionized water, performing ultrasonic treatment for 8-20min to obtain an ethanol ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol ammonia water mixed solution, fully stirring for 12-36h, centrifuging for 20-60min at 3000 plus 10000rpm, washing for 1-4 times with acetone, and drying at 50-70 ℃ to obtain the polydopamine microspheres with the particle size of 200 plus 400 nm.
5. The method of claim 4, wherein the polydopamine microsphere is prepared by the following steps:
(1) dissolving 1g dopamine hydrochloride in 40ml deionized water to obtain dopamine hydrochloride aqueous solution;
(2) dissolving 60ml of ethanol and 5ml of 28% concentrated ammonia water in mass percent in 20ml of deionized water, performing ultrasonic treatment for 10min to obtain an ethanol-ammonia water mixed solution, adding the dopamine hydrochloride aqueous solution prepared in the step (1) into the ethanol-ammonia water mixed solution, fully stirring for 24h, centrifuging at 5000rpm for 30min, washing with acetone for 2 times, and drying at 60 ℃ to obtain the polydopamine microspheres with the particle size of 300 nm.
6. The preparation method according to claim 1, wherein the mass ratio of the solid-phase powder to the liquid phase is 1 (0.3-0.8).
7. The method according to claim 1, wherein the calcium phosphate in the solid phase powder is one or more selected from the group consisting of tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, calcium hydrogen phosphate anhydrous, calcium hydrogen phosphate dihydrate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, fluorapatite, strontium apatite, and apatite carbonate, and the organic solvent in the liquid phase component is glycerol or polyethylene glycol.
8. The method according to claim 1, wherein the solid phase powder further comprises the following components in parts by mass: 2-5 parts of an antibacterial agent selected from: one or more of metronidazole, tinidazole, tylon and tobramycin, and preferably 4 parts of antibacterial agent.
9. The method of claim 1, wherein the developer is selected from the group consisting of: at least one of iodoform, barium sulfate and zirconium dioxide, and preferably, the developing agent is iodoform.
10. A calcium phosphate root canal filler prepared by the method of any one of claims 1 to 9.
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Application publication date: 20200211 |