阅读说明：本技术 一种义齿的一次成型制造方法 (One-step forming manufacturing method of false tooth ) 是由 不公告发明人 于 2020-08-11 设计创作，主要内容包括：本发明涉及一种义齿的一次成型制造方法,制造步骤包含：(1)用双氧水清洗基牙牙面,之后用清水冲洗；(2)用棉球对工作区域进行隔湿,用气枪吹干；(3)用磷酸液对基牙进行酸蚀处理；(4)用水冲洗,然后吹干防湿；(5)在基牙牙面涂布粘结剂,光照固化；(6)将树脂材料分层放置,分层光照固化,每层厚度不超过2mm,每次光照时间20-40 s,直到达到需要的高度和形状；(7)修整和磨光；该方案简单、易操作。(The invention relates to a one-step forming manufacturing method of a false tooth, which comprises the following manufacturing steps: (1) cleaning the tooth surface of the abutment by using hydrogen peroxide, and then washing by using clear water; (2) the working area is isolated from moisture by a cotton ball and dried by an air gun; (3) carrying out acid etching treatment on the abutment by using phosphoric acid liquid; (4) washing with water, and blow-drying for moisture prevention; (5) coating a binder on the tooth surface of the abutment, and performing light curing; (6) placing the resin materials in layers, and carrying out layered illumination curing, wherein the thickness of each layer is not more than 2mm, and the illumination time is 20-40 s each time until the required height and shape are achieved; (7) trimming and polishing; the scheme is simple and easy to operate.)

1. A one-step forming method for manufacturing false teeth comprises the following steps: (1) cleaning the tooth surface of the abutment by using hydrogen peroxide, and then washing by using clear water; (2) the working area is isolated from moisture by a cotton ball and dried by an air gun; (3) carrying out acid etching treatment on the abutment by using phosphoric acid liquid; (4) washing with water, and blow-drying for moisture prevention; (5) coating a binder on the tooth surface of the abutment, and performing light curing; (6) placing the resin materials in layers, and carrying out layered illumination curing, wherein the thickness of each layer is not more than 2mm, and the illumination time is 20-40 s each time; (7) trimming and polishing.

2. The one-shot forming method for manufacturing a denture according to claim 1, wherein: the adhesive in the step (5) comprises 90-100 parts by mass of a resin matrix and 0.5-2 parts by mass of a photoinitiator system; the resin matrix includes a urethane-containing resin monomer and a reactive diluent.

3. The one-shot forming method for manufacturing a denture according to claim 1, wherein: the resin material in the step (6) comprises 15-20 parts by mass of a resin matrix, 75-85 parts by mass of a modified filler and 1-2 parts by mass of a photoinitiator system; the resin matrix includes a urethane-containing resin monomer and a reactive diluent.

4. The one-shot manufacturing method of the denture as claimed in claim 2 or 3, wherein: the resin monomer containing the carbamate is prepared from HDI tripolymer, resorcinol dihydroxypropyl ether and hydroxyethyl methacrylate.

5. The one-shot forming method for manufacturing a denture according to claim 4, wherein: the specific synthetic method of the resin monomer containing the carbamate comprises the following steps: adding tetrahydrofuran and dibutyltin dilaurate into HDI trimer, then slowly adding resorcinol dihydroxypropyl ether, controlling the temperature at 60-80 ℃ for reaction for 4-7 hours, cooling to 40-50 ℃ after the reaction is finished, slowly adding hydroxyethyl methacrylate, and reacting for 4-6 hours to obtain the resin monomer containing carbamate.

6. The one-shot manufacturing method of the denture as claimed in claim 2 or 3, wherein: the reactive diluent is selected from one or more of triethylene glycol dimethacrylate (TEGDMA), ditrimethylolpropane acrylate (TMPTMA) and hydroxyethyl methacrylate (HEMA).

7. The one-shot manufacturing method of the denture as claimed in claim 2 or 3, wherein: the mass ratio of the resin monomer containing the carbamate to the reactive diluent is 1:1 to 3: 1.

8. The one-shot forming method for manufacturing a denture according to claim 3, wherein: the modified filler is surface modified nano silicon dioxide, and the specific preparation method comprises the following steps: adding nano silicon dioxide, n-propylamine and gamma-aminopropyltriethoxysilane into a cyclohexane solvent, reacting for 0.5-2 hours at room temperature, then reacting for 0.5-2 hours at 50-70 ℃, then adding HDI trimer, continuing to react for 2-4 hours, removing the solvent, and drying for 12-24 hours to obtain the surface modified nano silicon dioxide.

9. The one-shot forming method for manufacturing a denture according to claim 3, wherein: the preparation method of the resin material in the step (6) comprises the following steps: firstly, uniformly mixing a resin monomer containing carbamate and an active diluent to form a resin matrix; adding a photoinitiator system, and stirring uniformly; and thirdly, adding the modified filler, and fully and uniformly stirring in a vacuum stirrer to eliminate bubbles.

10. The one-shot manufacturing method of the denture as claimed in claim 2 or 3, wherein: the photoinitiator system comprises a photoinitiator and an accelerator, wherein the photoinitiator is selected from more than one of camphorquinone, benzophenone, trimethylbenzoyl, 4-dimethoxybenzil and 1-phenyl-1, 2-propanedione; the accelerator is selected from: one or more of N, N-dimethylamino ethyl methacrylate (DMAEMA), ethyl dimethylaminobenzoate and N, N-dimethylamino ethyl ester; the mass ratio of the photoinitiator to the accelerator is 1: 2-1: 4.

Technical Field

The invention relates to the field of medical oral cosmetology, in particular to a one-step forming manufacturing method of a denture, which can conveniently manufacture the denture with excellent comprehensive performances such as toughness, wear resistance, strength and the like in a short time.

Background

Decayed teeth and teeth fracture due to trauma are common dental oral problems, and with the continuous development of tooth cosmetic repair medicine, denture materials and manufacturing methods are continuously updated. The light-cured composite resin has better aesthetic property, bonding property with teeth, minimally invasive property during treatment and convenient operability, so that the light-cured composite resin has wider and wider application in the oral cavity field.

Currently, as for the manufacturing method, with the continuous development of technology, methods such as a 3D printing method, a method of making a dental impression model based on three-dimensional dental impression data obtained by a computed tomography apparatus (CT apparatus), a magnetic resonance imaging apparatus (MRI), a digital X-ray imaging apparatus (CR apparatus), and the like have emerged.

For example, CN106897574A discloses a 3D printing-based tooth implantation guide plate immediate implantation restoration method, which includes: firstly, acquiring a three-dimensional digital model of the dental implant guide plate, layering the three-dimensional digital model of the dental implant guide plate according to a preset thickness by utilizing CAD/CAM software, and manufacturing a plurality of layered images; secondly, inputting the layered image into a DLP photocuring 3D printer of the dental implant guide plate; thirdly, manufacturing the dental implant guide plate by using a DLP (digital light processing) photocuring 3D printer; and fourthly, before the dental implant guide plate is used for the implant operation, firstly, the implant position is judged according to the X-ray film, the jaw bone of the patient is simulated by using a three-dimensional modeling mode, the implant direction of the implant is positioned, and the dental implant guide plate is immediately implanted and repaired according to the preoperative surgical scheme according to the implant implantation direction planned by the dental implant guide plate and the incision direction of the surgical cutter. Also of interest is CN 106863782A.

However, the above method cannot be popularized in a large scale, and the general oral clinics and beauty hospitals do not have operation conditions at all, so that the research and the application of a simple and easy-to-operate method for manufacturing the false teeth are still needed.

The method for forming the denture by coating the adhesive on the basis of the abutment and then curing the composite resin is a convenient and easy-to-operate method, can be executed by common oral clinics and beauty hospitals, and starts from the last 90 years of research. On the other hand, there are related art disclosures, examples of which are as follows.

CN1131015C discloses a method for forming a light-cured denture for oral cavity of human body, which comprises molding a retainer and a bridge of denture by using a Gossah Durafier composite resin based on an abutment, and connecting the molded denture to the bridge at two end groups by light curing to form a whole bridge with complete fixation. The bridge body consists of a base bridge, a middle bridge and an upper bridge. Selecting a Gusha Durafiler composite resin material, and designing the force points and radians of a base bridge, a middle bridge and an upper bridge according to different jaw relations.

Similarly, CN106137442B discloses a cosmetic method of one-shot forming for fixing a loose tooth, which is to select a loose tooth and a body tooth with two sides not loose as an abutment, reset the loose tooth, select a resin matched with the color of the abutment, mold the lingual side and the labial side of all the loose teeth and the abutment into a whole, perform light curing simultaneously, and then set a color-shielding reinforcing layer and an enamel outer fixing layer: the loose teeth and the missing teeth are repaired by one-step forming.

However, the actual operation according to the above patent has problems that the three-time curing is actually insufficient, and the Gusha Durafiller resin is selected, and the properties are general, and the combination of the properties results in the desired improvement of the final denture.

The photocurable resin containing urethane repeating units has excellent properties that can provide excellent overall properties of strength, toughness, wear resistance, hardness, etc. of dentures, and thus some related studies have been conducted in the prior art. For example, CN105491976B discloses a method for producing a liquid dental photocurable resin composition, which contains at least 1 of a urethane-based di (meth) acrylate compound (a-1a) represented by the following general formula (a-1a) and a di (meth) acrylate compound (a-1b) represented by the following general formula (a-1b) as at least a part of a radically polymerizable organic compound (a).

The urethane di (meth) acrylate compound (a-1a) is obtained by a reaction between 1 mol of an organic diisocyanate compound and 2 mol of a hydroxyalkyl (meth) acrylate.

JP2019199448A discloses a photocurable resin composition containing a urethane (meth) acrylic compound (a), a polymerizable monomer (B) having an ionic group, and a photopolymerization initiator (C).

In view of the above, there is still a need in the market for a simple and easy-to-use denture form manufacturing method and an improvement in performance is desired, while CN1131015C and the like have certain drawbacks.

Disclosure of Invention

The object of the present invention is to produce a denture by using a photocurable resin containing urethane repeating units and by a simple and easy-to-handle method.

The manufacturing method is realized by the following technical scheme:

a one-step forming method for manufacturing false teeth comprises the following steps: (1) cleaning the tooth surface of the abutment by using hydrogen peroxide, and then washing by using clear water; (2) the working area is isolated from moisture by a cotton ball and dried by an air gun; (3) carrying out acid etching treatment on the abutment by using phosphoric acid liquid; (4) washing with water, and blow-drying for moisture prevention; (5) coating a binder on the tooth surface of the abutment, and performing light curing; (6) placing the resin materials in layers, and carrying out layered illumination curing, wherein the thickness of each layer is not more than 2mm, and the illumination time is 20-40 s each time until the required height and shape are achieved; (7) trimming and polishing.

Wherein, the binder in the step (5) comprises 90-100 parts by mass of resin matrix and 0.5-2 parts by mass of photoinitiator system; the resin matrix includes a urethane-containing resin monomer and a reactive diluent.

The resin monomer containing the carbamate is prepared from HDI tripolymer, resorcinol dihydroxypropyl ether and hydroxyethyl methacrylate. The specific synthesis method comprises the following steps: adding tetrahydrofuran and dibutyltin dilaurate into HDI trimer, then slowly adding resorcinol dihydroxypropyl ether, controlling the temperature at 60-80 ℃ for reaction for 4-7 hours, cooling to 40-50 ℃ after the reaction is finished, slowly adding hydroxyethyl methacrylate, and reacting for 4-6 hours to obtain the resin monomer containing carbamate.

The reactive diluent is selected from one or more of triethylene glycol dimethacrylate (TEGDMA), ditrimethylolpropane acrylate (TMPTMA) and hydroxyethyl methacrylate (HEMA).

Further, the mass ratio of the urethane-containing resin monomer to the reactive diluent is 1:1 to 3: 1.

The preparation of the binder in the step (5) comprises the following steps: firstly, uniformly mixing a resin monomer containing carbamate and an active diluent to form a resin matrix; ② adding the photoinitiator and the accelerant, and stirring evenly.

The resin material in the step (6) comprises 15-20 parts by mass of a resin matrix, 75-85 parts by mass of a modified filler and 1-2 parts by mass of a photoinitiator system; the resin matrix includes a urethane-containing resin monomer and a reactive diluent.

Wherein, the resin monomer containing the carbamate is prepared from HDI tripolymer, resorcinol dihydroxypropyl ether and hydroxyethyl methacrylate. The specific synthesis method comprises the following steps: adding tetrahydrofuran and dibutyltin dilaurate into HDI trimer, then slowly adding resorcinol dihydroxypropyl ether, controlling the temperature at 60-80 ℃ for reaction for 4-7 hours, cooling to 40-50 ℃ after the reaction is finished, slowly adding hydroxyethyl methacrylate, and reacting for 4-6 hours to obtain the resin monomer containing carbamate.

The reactive diluent is selected from one or more of triethylene glycol dimethacrylate (TEGDMA), ditrimethylolpropane acrylate (TMPTMA) and hydroxyethyl methacrylate (HEMA).

Further, the mass ratio of the urethane-containing resin monomer to the reactive diluent is 1:1 to 3: 1.

Further, the modified filler is surface modified nano silicon dioxide. The preparation method comprises the following steps: adding nano silicon dioxide, n-propylamine and gamma-aminopropyltriethoxysilane into a cyclohexane solvent, reacting for 0.5-2 hours at room temperature, then reacting for 0.5-2 hours at 50-70 ℃, then adding HDI trimer, continuing to react for 2-4 hours, removing the solvent, and drying for 12-24 hours to obtain the surface modified nano silicon dioxide.

The nano silicon dioxide is prepared by a conventional sol-gel method.

The preparation of the resin material in the step (6) comprises the following steps: firstly, uniformly mixing a resin monomer containing carbamate and an active diluent to form a resin matrix; adding photoinitiator and accelerator, and stirring uniformly; and thirdly, adding the surface modified nano silicon dioxide, and fully and uniformly stirring in a vacuum stirrer to eliminate bubbles.

The photoinitiator system related to the step (5) and the step (6) comprises a photoinitiator and an accelerator, wherein the photoinitiator is selected from more than one of camphorquinone, benzophenone, trimethylbenzoyl, 4-dimethoxybenzil and 1-phenyl-1, 2-propanedione.

The accelerator is selected from: one or more of N, N-dimethylamino ethyl methacrylate (DMAEMA), ethyl dimethylaminobenzoate and N, N-dimethylamino ethyl ester; the mass ratio of the photoinitiator to the accelerator is 1: 2-1: 4.

Further, the hydrogen peroxide used in the step (1) is 1-5% hydrogen peroxide, preferably 3% hydrogen peroxide.

The phosphoric acid solution used in the step (3) is 30-50% of phosphoric acid, preferably 35% of phosphoric acid.

And (5) coating the adhesive on the tooth surface of the abutment, wherein the time of light curing is 20-50 s.

Has the advantages that:

1. the invention adopts layered placement and layered illumination curing, the thickness of each layer is not more than 2mm, and the defects of three sections of a base bridge, a middle bridge and an upper bridge in the prior art are overcome.

2. The binder in step (5) and the resin matrix contained in the resin material in step (6) are the same, except that no modified filler is added to the binder, and the same resin matrix is selected so that the binder and the resin matrix can be sufficiently bonded and integrated.

3. The resin monomer containing the urethane is prepared from HDI tripolymer, resorcinol dihydroxypropyl ether and hydroxyethyl methacrylate, the HDI tripolymer and the resorcinol dihydroxypropyl ether can be introduced into a rigid structure, the existence of a urethane bond is favorable for lower viscosity, and the HDI tripolymer is trifunctional and is favorable for forming a branched structure.

4. The nano silicon dioxide is firstly treated by the silane coupling agent and then reacts with HDI tripolymer, and after the treatment step, the mixing of the nano silicon dioxide and the resin matrix is facilitated.

Detailed Description

The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the general principles, major features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.

Surface-modified nano-silica:

adding 10 parts by mass of nano-silica, 0.5 part by mass of n-propylamine and 2 parts by mass of gamma-aminopropyltriethoxysilane into a cyclohexane solvent, reacting for 1 hour at room temperature, then reacting for 1 hour at 60 ℃, adding 2 parts by mass of HDI trimer, continuing to react for 3 hours, removing the solvent, and drying for 24 hours to obtain the surface modified nano-silica.

Urethane-containing resin monomer:

adding tetrahydrofuran and dibutyltin dilaurate into HDI tripolymer, then slowly adding resorcinol dihydroxypropyl ether (the molar ratio of the HDI tripolymer to the resorcinol dihydroxypropyl ether is controlled to be 4: 3), controlling the temperature to be about 70 ℃ for reaction for 5 hours, cooling to 45 ℃ after the reaction is finished, slowly adding hydroxyethyl methacrylate (the molar ratio of the HDI tripolymer to the hydroxyethyl methacrylate is 2: 3), and reacting for 6 hours to obtain the resin monomer containing the carbamate.

Adhesive:

uniformly mixing 70 parts by mass of the prepared urethane-containing resin monomer and 30 parts by mass of triethylene glycol dimethacrylate to form a resin matrix; (2) adding 0.5 part by mass of camphorquinone and 1 part by mass of ethyl dimethylaminobenzoate, and uniformly stirring.

Resin material 1:

uniformly mixing 10 parts by mass of the prepared urethane-containing resin monomer and 5 parts by mass of triethylene glycol dimethacrylate to form a resin matrix; (2) adding 0.5 part by mass of camphorquinone and 1 part by mass of ethyl dimethylaminobenzoate, and uniformly stirring; (3) adding 80 parts by mass of surface modified nano silicon dioxide (obtained from preparation examples), and fully and uniformly stirring in a vacuum stirrer to eliminate bubbles.

Resin material 2:

uniformly mixing 15 parts by mass of the prepared urethane-containing resin monomer and 5 parts by mass of triethylene glycol dimethacrylate to form a resin matrix; (2) adding 0.5 part by mass of camphorquinone and 1 part by mass of ethyl dimethylaminobenzoate, and uniformly stirring; (3) adding 75 parts by mass of surface modified nano silicon dioxide (obtained from preparation examples), and fully and uniformly stirring in a vacuum stirrer to eliminate bubbles.

The false tooth one-time forming manufacturing method comprises the following steps:

the manufacturing steps comprise: (1) cleaning the tooth surface of the abutment by using 3 percent hydrogen peroxide, and then washing by using clear water; (2) the working area is isolated from moisture by a cotton ball and dried by an air gun; (3) carrying out acid etching treatment on the abutment for 1.5min by using 35% phosphoric acid liquid; (4) washing with water, and blow-drying for moisture prevention; (5) coating a layer of adhesive on the tooth surface of the abutment, and performing light curing for 40 s; (6) placing the resin materials (the resin material 1 or the resin material 2) in layers, and carrying out layered illumination curing, wherein the thickness of each layer is not more than 2mm, and the illumination time is 30 s each time until the required height and shape are achieved; (7) removing excess filler from the surface, and finishing and polishing.

The present invention has been described in detail, and the embodiments are only used for understanding the method and the core idea of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.