阅读说明：本技术 一种稳定的磷酸钙根管填充剂 (Stable calcium phosphate root canal filler ) 是由 车七石 单玲星 刘少辉 张俊辉 赵澎 于 2019-12-10 设计创作，主要内容包括：本发明属于医用材料领域,涉及一种牙根填充剂,具体涉及一种可稳定保存的根管填充剂及其制备方法。由固相粉末与液相成分组成,其特征在于,包括固相粉末与液相成分,所述固相粉末包括以下质量份的组分：磷酸钙粉末60-90份、β-环糊精10-20份、壳聚糖膨润土10-20份、显影剂20-40份；所述液相成分包括以下质量份的组分：有机溶剂40-120份。本发明制备的牙根填充剂操作简单,样品置于容器中,使用时注射或者填充,无需现场将固相和液相混合,减少操作时间和引入细菌的风险。加入的壳聚糖膨润土、β-环糊精和有机溶剂能够使牙根填充剂密封存放于容器中并在室温下长期稳定保存而固液不分离,牙根填充剂具有良好的流动性,注射性能,填充剂在容器中为稳定的糊剂,填入根管后,由环境中的液体逐渐固化,固化时间大大的缩短,方便患者进食。(The invention belongs to the field of medical materials, and relates to a root filling agent, in particular to a root filling agent capable of being stably stored and a preparation method thereof, wherein the root filling agent consists of solid-phase powder and liquid-phase components, and is characterized by comprising the solid-phase powder and the liquid-phase components, wherein the solid-phase powder comprises, by mass, 60-90 parts of calcium phosphate powder, 10-20 parts of β -cyclodextrin, 10-20 parts of chitosan bentonite and 20-40 parts of a developing agent, and the liquid-phase components comprise, by mass, 40-120 parts of an organic solvent.)

1. The stable calcium phosphate root canal filler consists of solid phase powder and liquid phase component, and features that the solid phase powder consists of calcium phosphate powder 60-90 weight portions, β -cyclodextrin 10-20 weight portions, chitosan bentonite 10-20 weight portions and developer 20-40 weight portions, and the liquid phase component consists of organic solvent 40-120 weight portions.

2. The calcium phosphate root canal filler according to claim 1, wherein the solid phase powder comprises 80 parts by mass of a-tricalcium phosphate powder, 15 parts by mass of β -cyclodextrin, 15 parts by mass of chitosan bentonite, and 30 parts by mass of a developing agent, the developing agent is iodoform, the solvent in the liquid phase component is glycerol, and the liquid phase component comprises 50 parts by mass of an organic solvent.

3. The calcium phosphate endodontic filler according to claim 1, wherein said chitosan bentonite is prepared by the following method:

(1) adding sodium bentonite with the granularity of 100-400 meshes into water with the mass 10-30 times of that of the bentonite, stirring and dispersing for 0.5-3 hours to obtain bentonite suspension;

(2) dissolving chitosan with the mass being 0.5-3 times of that of bentonite in an acetic acid solution with the mass concentration of 1% to prepare a chitosan solution with the mass concentration of 2-8% and the pH value of 3-6;

(3) uniformly adding the bentonite suspension into the chitosan solution within 6-12 hours at 50-100 ℃ under stirring, and continuing to react for 20-50 hours after the bentonite suspension is added to obtain a reaction completion solution;

(4) and filtering, washing and drying the reaction finished liquid to obtain the chitosan bentonite.

4. The calcium phosphate endodontic filler according to claim 3, wherein said chitosan bentonite is prepared by the following method:

(1) adding sodium bentonite with the granularity of 250 meshes into water with the mass 20 times of that of the bentonite, stirring and dispersing for 2 hours to obtain bentonite suspension;

(2) dissolving chitosan with the mass 2 times of that of bentonite in an acetic acid solution with the mass concentration of 1% to prepare a chitosan solution with the mass concentration of 5% and the pH value of 4.5;

(3) uniformly adding the bentonite suspension into the chitosan solution within 8 hours under the stirring at the temperature of 80 ℃, and continuing to react for 35 hours after the bentonite suspension is added to obtain a reaction completion solution;

(4) and filtering, washing and drying the reaction finished liquid to obtain the chitosan bentonite.

5. The calcium phosphate endodontic filler according to claim 1, wherein the mass ratio of the solid phase powder to the liquid phase is 1 (0.4-0.7).

6. The calcium phosphate root canal filler of claim 1, wherein the calcium phosphate in the solid phase powder is selected from one or more 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 carbonate-containing apatite.

7. The calcium phosphate root canal filler according to claim 1, wherein the organic solvent in the liquid-phase component is glycerin or polyethylene glycol.

8. The calcium phosphate endodontic filler according to claim 1, wherein said 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, tylenol and tobramycin, preferably, the solid phase powder further comprises the following components in parts by mass: 4 parts of antibacterial agent.

9. The calcium phosphate endodontic filler of claim 1, wherein said imaging agent is selected from the group consisting of: at least one of iodoform, barium sulfate, strontium chloride and zirconium dioxide, and preferably, the developer is iodoform.

Technical Field

The invention belongs to the field of medical materials, relates to a root canal filler, and particularly relates to a root canal filler capable of being stably stored 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 can be stably stored for more than 1 year, is not easy to separate solid from liquid, and can not be dispersed when the root canal filler is implanted into a root apex.

In order to achieve the purpose, the invention adopts the technical scheme that:

the stable calcium phosphate root canal filler consists of solid phase powder and liquid phase component, and features that the solid phase powder consists of calcium phosphate powder 60-90 weight portions, β -cyclodextrin 10-20 weight portions, chitosan bentonite 10-20 weight portions and developer 20-40 weight portions, and the liquid phase component consists of organic solvent 20-90 weight portions.

Further, the solid phase powder comprises, by mass, 80 parts of a-tricalcium phosphate powder, 15 parts of β -cyclodextrin, 15 parts of chitosan bentonite and 30 parts of a developer, wherein the developer is iodoform, a solvent in the liquid phase component is glycerol, and the liquid phase component comprises, by mass, 50 parts of an organic solvent.

Further, the preparation method of the chitosan bentonite comprises the following steps:

(1) adding sodium bentonite with the granularity of 100-400 meshes into water with the mass 10-30 times of that of the bentonite, stirring and dispersing for 0.5-3 hours to obtain bentonite suspension;

(2) dissolving chitosan with the mass being 0.5-3 times of that of bentonite in an acetic acid solution with the mass concentration of 1% to prepare a chitosan solution with the mass concentration of 2-8% and the pH value of 3-6;

(3) uniformly adding the bentonite suspension into the chitosan solution within 6-12 hours at 50-100 ℃ under stirring, and continuing to react for 20-50 hours after the bentonite suspension is added to obtain a reaction completion solution;

(4) and filtering, washing and drying the reaction finished liquid to obtain the chitosan bentonite.

Still further, the preparation method of the chitosan bentonite comprises the following steps:

(1) adding sodium bentonite with the granularity of 250 meshes into water with the mass 20 times of that of the bentonite, stirring and dispersing for 2 hours to obtain bentonite suspension;

(2) dissolving chitosan with the mass 2 times of that of bentonite in an acetic acid solution with the mass concentration of 1% to prepare a chitosan solution with the mass concentration of 5% and the pH value of 4.5;

(3) uniformly adding the bentonite suspension into the chitosan solution within 8 hours under the stirring at the temperature of 80 ℃, and continuing to react for 35 hours after the bentonite suspension is added to obtain a reaction completion solution;

(4) and filtering, washing and drying the reaction finished liquid to obtain the chitosan bentonite.

Still further, the mass ratio of the solid-phase powder to the liquid phase is 1 (0.4-0.7).

Still further, 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, monocalcium phosphate, calcium pyrophosphate, hydroxyapatite, fluorapatite, strontium apatite and apatite carbonate.

Still further, in the liquid phase component, the organic solvent is glycerol or polyethylene glycol.

Still further, the solid phase powder also comprises the following components in parts by mass: 2-5 parts of an antibacterial agent selected from: one or more of metronidazole, tinidazole, tylenol and tobramycin, preferably, the solid phase powder further comprises the following components in parts by mass: 4 parts of antibacterial agent.

Still further, the developer is selected from: at least one of iodoform, barium sulfate, strontium chloride and zirconium dioxide, and preferably, the developer is iodoform.

The properties of bentonite are strongly related to the kind of exchangeable cations between the layers. Bentonite is generally classified into calcium bentonite and sodium bentonite according to the kind of cation mainly exchangeable between layers.

The bentonite has adsorbability and cation exchange performance, and can be used for removing edible oil toxin, purifying gasoline and kerosene, and treating wastewater; the fire-retardant coating has good water swelling property, dispersion, suspension and slurry making property, so that the fire-retardant coating is used for drilling mud and flame retardance (suspension fire extinguishing); can also be used as filler in paper industry to optimize the properties of coating, such as adhesion, covering power, water resistance, washing resistance, etc

And performing cation exchange on the chitosan and the bentonite to form chitosan bentonite.

β -cyclodextrin is widely used for separating organic compounds and organic synthesis, and also used as pharmaceutical adjuvant, food additive, etc. at present, people prepare natural cyclodextrin and modified cyclodextrin with some drug molecules without biocompatibility to prepare inclusion compound.

The root canal filler of the invention is not solidified under the anhydrous condition, and the solid-liquid separation can not occur after long-term storage, probably because the chitosan bentonite and β -cyclodextrin are added into the solid phase powder, the chitosan bentonite, β -cyclodextrin and organic solvent are wrapped around the calcium phosphate powder through the cross-linking reaction or the van der Waals force winding effect, 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.

Although the calcium phosphate solid phase powder can delay the time of the solidification reaction by adding the organic solvent, CPC particles in the solid phase powder can be settled to cause solid-liquid separation, and after various methods are tried by the inventor of the application, chitosan bentonite and β -cyclodextrin are added into the solid phase powder, and the chitosan bentonite and β -cyclodextrin surround the calcium phosphate powder by a cross-linking reaction or van der Waals force winding action with the organic solvent, so that the stability of the system is improved.

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:

1) 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.

2) The added chitosan bentonite, β -cyclodextrin and organic solvent can lead the root filling agent to be stored in a container in a sealing way and be stored stably for a long time at room temperature without solid-liquid separation, the root filling agent has good fluidity and injection performance, 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, and the patient can conveniently eat.

3) The root filling agent does not contain water and is stored in the container, and the root filling agent is cured when meeting water after being added into the root canal, can resist the washing of body fluid, is not dispersed in the initial filling stage, can ensure that the filling material is tightly combined with the root canal, and prevents the generation of gaps.

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.

250 mesh sodium bentonite (Changtai bentonite Co., Ltd.)