Plastic solid-state auxiliary material for fixing molded sheet in dental filling and preparation method of plastic solid-state auxiliary material

Abstract

The invention provides a plastic solid auxiliary material for fixing a molded sheet in dental filling and a preparation method thereof, and relates to the technical field of high polymer materials. The preparation method of the plastic solid-state auxiliary material for fixing the molded sheet in dental filling comprises the following steps: adding bisphenol A-glycidyl methacrylate, hydroxyethyl methylacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyltriethoxysilane and polycaprolactone microspheres into a reaction kettle, and uniformly stirring to obtain the plastic solid-state auxiliary material for fixing the molded sheet. Mixing dibutyl phthalate with an organic solvent to obtain a mixed material; mixing the mixed material with sodium carboxymethyl cellulose and butylated hydroxytoluene to obtain a prepolymer; and mixing the prepolymer with a photoinitiator under a dark condition to obtain the plastic solid-state auxiliary material for fixing the molded sheet. The material can be used for fixing a formed sheet during tooth filling, and is suitable for tooth gaps and tooth defects of different sizes and shapes due to plasticity and elasticity, so that the formed sheet is attached to the gingival end of a cavity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and particularly relates to a plastic solid-state auxiliary material for fixing a forming sheet in dental restoration and a preparation method thereof. BACKGROUND

[0002] In the dental restoration process, especially in the restoration of Class II cavity of posterior teeth caries, the fixation of the forming sheet is a key step to ensure the shape and function of the restoration, but it often faces various difficulties. First, the space in the posterior tooth area is limited, especially in the molar area. It is very cramped to place the forming sheet, wedge and operating instruments (such as a filling instrument, a carving knife and a light curing lamp), and they are easy to interfere with each other. The forming sheet and the tooth itself block the view of the doctor, and it is difficult to clearly observe the fit of the forming sheet and the tooth tissue, especially in the gum margin and the abutment point area. Second, it is difficult to individually select a wedge with a suitable size in the dental restoration process. If the size of the wedge is too large, it will hurt the gum, and if the size of the wedge is too small, it will lead to poor fixation. The position of the wedge and the pressure applied are also difficult to control, and improper placement will also lead to deformation of the forming sheet, poor sealing of the gum margin or compression of the gum to cause bleeding / pain. Further, the forming sheet holder is often used to fix the forming sheet in the dental restoration process, but the forming sheet holder is relatively large in size, and it is not easy to place in the posterior tooth area, and it will also affect the operation of the dentist. In addition, the forming sheet and the wedge will stimulate the gum and the gingival sulcus when placed, causing tissue fluid or gingival sulcus fluid to seep out, which affects the filling effect (the filling needs to be kept dry).

[0003] Therefore, the technical personnel in the field urgently need to develop a dental restoration auxiliary material that can replace the wedge and the forming sheet holder, control the amount and shape according to the actual situation, and firmly fix the forming sheet to avoid displacement caused by operation touch. SUMMARY

[0004] The purpose of the present application is to provide a plastic solid-state auxiliary material for fixing a forming sheet in dental restoration and a preparation method thereof, so as to solve the problems of existing wedges and forming sheet holders for fixing the forming sheet, such as blocking the view, being difficult to operate and being easy to displace.

[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical scheme:

[0006] The present application provides a preparation method of a plastic solid-state auxiliary material for fixing a forming sheet in dental restoration, characterized in that the method comprises the following steps:

[0007] 1) mixing bisphenol A-glycidyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyltriethoxysilane, polycaprolactone microspheres, dibutyl phthalate and an organic solvent to obtain a mixture;

[0008] 2) mixing the mixture with sodium carboxymethyl cellulose and butylated hydroxyl toluene to obtain a prepolymer;

[0009] 3) mixing the prepolymer with a photoinitiator under light-proof conditions to obtain a plastic solid-state auxiliary material for fixing the shaped sheet.

[0010] Preferably, the mass ratio of the bisphenol A-glycidyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyl triethoxysilane, polycaprolactone microspheres, dibutyl phthalate and the organic solvent in step 1) is 20-40:20-40:20-25:8-12:4-8:3-8:3-6:10-15.

[0011] Preferably, the temperature of the mixing in step 1) is 45-55℃, the mixing time is 30-50min, and the stirring rate of the mixing is 120-180r / min.

[0012] Preferably, the mass ratio of the mixture, sodium carboxymethyl cellulose and butylated hydroxyl toluene in step 2) is 100:12-15:1-3.

[0013] Preferably, the temperature of the mixing in step 2) is 45-55℃, the mixing time is 25-35min, and the stirring rate of the mixing is 160-220r / min.

[0014] Preferably, the mixing ratio of the prepolymer and the photoinitiator in step 3) is 100:0.5-1.5;

[0015] The temperature of the mixing of the prepolymer and the photoinitiator is ≤20℃, the stirring rate of the mixing is 60-80r / min, and the mixing time is 12-18min;

[0016] The photoinitiator includes one or more of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and ethyl(2,4,6-trimethylbenzoyl) phenyl phosphinate.

[0017] Preferably, the degree of substitution DS of the sodium carboxymethyl cellulose is ≥0.8;

[0018] The average molecular weight of the polyethylene glycol diacrylate is 400-450.

[0019] The application also provides a plastic solid-state auxiliary material for fixing the shaped sheet in dental filling, which is prepared by the above preparation method.

[0020] The application has at least the following beneficial effects:

[0021] The application adopts bisphenol A-glycidyl methacrylate and hydroxyethyl methacrylate to construct a double crosslinking system, and adds carboxymethyl cellulose sodium, polyvinyl butyral, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyl triethoxysilane, butyl hydroxytoluene and a photoinitiator to make the material have elasticity, moisture absorption, plasticity and peelability, so that it can be fixed and shaped in tooth filling. The carboxymethyl cellulose sodium and polyethylene glycol diacrylate in the raw material endow the material with the characteristics of moisture absorption and expansion, and can automatically absorb water after being placed in the tooth gap, which is beneficial to maintaining the dryness of the tooth filling environment. The polyethylene glycol microspheres in the material can also store the absorbed water in the matrix, maintaining the dryness of the material surface. The pentaerythritol tetra-3-mercaptopropionate can make the material have a certain elasticity and compressibility after curing, which can adapt to different sizes of interdental gaps and various shapes of tooth defects. The elasticity and compressibility can make the shaped piece fit the cavity gingival end, preventing the filling body from appearing overhanging. The butyl hydroxytoluene (BHT) can inhibit the slow crosslinking of the prepolymer, so that it still has good plasticity after being stored in the dark for 12 months. The perfluorooctyl triethoxysilane can make the material form a low surface energy layer after curing, which can be easily removed without applying a large force after the tooth filling is completed, avoiding secondary damage to the teeth. DETAILED DESCRIPTION

[0022] The application provides a preparation method of a plastic solid auxiliary material for fixing a shaped piece in dental filling, and has the characteristics that the method comprises the following steps:

[0023] 1) Bisphenol A-glycidyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyl triethoxysilane, polycaprolactone microspheres, dibutyl phthalate and an organic solvent are mixed to obtain a mixture;

[0024] 2) The mixture is mixed with carboxymethyl cellulose sodium and butyl hydroxytoluene to obtain a prepolymer;

[0025] 3) The prepolymer is mixed with a photoinitiator under light-proof conditions to obtain a plastic solid auxiliary material for fixing a shaped piece.

[0026] In the present application, the mass ratio of the bisphenol A-glycidyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyl triethoxysilane, polycaprolactone microspheres, dibutyl phthalate and the organic solvent in step 1) is 20-40:20-40:20-25:8-12:4-8:3-8:3-6:10-15, preferably 23-38:23-38:21-24:9-11:4.5-7.5:3.5-7.5:3.5-5.5:11-14, further preferably 25-35:25-35:22-23:9.5-10.5:5-7:4-7:4-5:12-13.

[0027] In the present application, the temperature of the mixing in step 1) is 45-55℃, preferably 47-53℃, further preferably 49-51℃, more preferably 50℃; the mixing time is 30-50min, preferably 33-48min, further preferably 35-45min, more preferably 38-42min; the stirring rate of the mixing is 120-180r / min, preferably 130-170r / min, further preferably 140-160r / min, more preferably 150r / min.

[0028] In the present application, the mass ratio of the mixed materials, sodium carboxymethyl cellulose and butyl hydroxytoluene in step 2) is 100:12-15:1-3, preferably 100:12-15:1-3, further preferably 100:12-15:1-3, more preferably 100:12-15:1-3.

[0029] In the present application, the temperature of the mixing in step 2) is 45-55℃, preferably 47-53℃, further preferably 49-51℃, more preferably 50℃; the mixing time is 25-35min, preferably 27-33min, further preferably 29-31min, more preferably 30min; the stirring rate of the mixing is 160-220r / min, preferably 170-210r / min, further preferably 180-200r / min, more preferably 190r / min.

[0030] In the present application, the mixing ratio of the prepolymer and the photoinitiator in step 3) is 100:0.5-1.5, preferably 100:0.7-1.3, further preferably 100:0.9-1.1, more preferably 100:1.

[0031] In the present application, the temperature for mixing the prepolymer with the photoinitiator is ≤20℃, preferably 0-18℃, further preferably 5-15℃, more preferably 8-10℃; the stirring rate for mixing is 60-80r / min, preferably 65-75r / min, further preferably 70r / min; the mixing time is 12-18min, preferably 13-17min, further preferably 14-16min, more preferably 15min.

[0032] In the present application, the photoinitiator comprises one or several of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and ethyl(2,4,6-trimethylbenzoyl) phenyl phosphinate.

[0033] In the present application, the degree of substitution DS of the sodium carboxymethyl cellulose is ≥0.8, preferably 0.8≤DS≤1.0, further preferably 0.85≤DS≤0.95, more preferably 0.88≤DS≤0.92.

[0034] In the present application, the average molecular weight of the polyethylene glycol diacrylate is 400-450, preferably 410-440, further preferably 420-430.

[0035] The present application also provides a plastic solid auxiliary material for fixing the shaped sheet in dental filling, which is prepared by the above preparation method.

[0036] The technical solutions provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0037] Example 1

[0038] (1) 25g of bisphenol A-glycidyl methacrylate, 25g of hydroxyethyl methacrylate, 22g of polyethylene glycol diacrylate, 9.5g of pentaerythritol tetra-3-mercaptopropionate, 5g of perfluorooctyl triethoxysilane, 4g of polycaprolactone microspheres (Wuhan Haisan Technology Co., Ltd., C100 polycaprolactone 0.5-1.04-10.6, flocculent), 4g of dibutyl phthalate and 12g of organic solvent (glycerol) are mixed at 50℃ for 40min at a stirring rate of 150r / min to obtain a mixture.

[0039] (2) The above 100g of mixture and 12g of sodium carboxymethyl cellulose (degree of substitution DS=0.88), 1g of butyl hydroxytoluene are mixed at 50℃ for 30min at a stirring rate of 190r / min to obtain a prepolymer.

[0040] (3) 100 g of the prepolymer was mixed with 1 g of phenyl bis(2,4,6- trimethylbenzoyl) phosphine oxide under light shielding condition at 8°C for 15 min at a stirring speed of 70 r / min to obtain a plastic solid-state auxiliary material for fixing the shaped sheet.

[0041] Example 2

[0042] (1) 35 g of bisphenol A-glycidyl methacrylate, 35 g of hydroxyethyl methacrylate, 23 g of polyethylene glycol diacrylate (average molecular weight 425), 10.5 g of pentaerythritol tetra-3-mercaptopropionate, 7 g of perfluorooctyl triethoxysilane, 7 g of polycaprolactone microspheres (Wuhan Haisan Technology Co., Ltd., C100 polycaprolactone 0.5-1.04-10.6, flocculent), 5 g of dibutyl phthalate and 13 g of an organic solvent (ethanol) were stirred at 49°C for 42 min at a stirring speed of 140 r / min to prepare a mixture.

[0043] (2) 100 g of the mixture was mixed with 15 g of sodium carboxymethyl cellulose (DS = 0.92), 3 g of butyl hydroxytoluene at 51°C for 29 min at a stirring speed of 180 r / min to obtain a prepolymer.

[0044] (3) 100 g of the prepolymer was mixed with 0.9 g of 2,4,6-trimethylbenzoyl- diphenyl phosphine oxide under light shielding condition at 10°C for 15 min at a stirring speed of 70 r / min to obtain a plastic solid-state auxiliary material.

[0045] Example 3

[0046] (1) 28 g of bisphenol A-glycidyl methacrylate, 28 g of hydroxyethyl methacrylate, 22.5 g of polyethylene glycol diacrylate, 10 g of pentaerythritol tetra-3- mercaptopropionate, 6 g of perfluorooctyl triethoxysilane, 5.5 g of polycaprolactone microspheres (Wuhan Haisan Technology Co., Ltd., C100 polycaprolactone 0.5-1.04-10.6, flocculent), 4.5 g of dibutyl phthalate and 12.5 g of an organic solvent (ethanol) were mixed at 50°C for 40 min at a stirring speed of 150 r / min to obtain a mixture.

[0047] (2) 100 g of the mixture was mixed with 13 g of sodium carboxymethyl cellulose (DS = 0.9), 2 g of butyl hydroxytoluene at 50°C for 30 min at a stirring speed of 190 r / min to obtain a prepolymer.

[0048] (3) 100 g of the prepolymer was mixed with 1 g of ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate under light shielding condition at 9°C for 15 min at a stirring speed of 70 r / min to obtain a plastic solid-state auxiliary material.

[0049] Comparative Example 1

[0050] (1) 25 g of bisphenol A-glycidyl methacrylate, 25 g of hydroxyethyl methacrylate, 22 g of polyethylene glycol diacrylate, 9.5 g of pentaerythritol tetra-3-mercaptopropionate, 5 g of perfluorooctyl triethoxysilane, 4 g of polycaprolactone microspheres (Wuhan Haisan Technology Co., Ltd., C100 polycaprolactone 0.5-1.04-10.6, flocculent), 4 g of dibutyl phthalate, and 12 g of an organic solvent (glycerol) were mixed at 50°C at a stirring rate of 150 r / min for 40 min to obtain a mixture.

[0051] (2) The above 100 g of the mixture was mixed with 12 g of sodium carboxymethyl cellulose (degree of substitution DS = 0.88) at 50°C at a stirring rate of 190 r / min for 30 min to obtain a prepolymer.

[0052] (3) 100 g of the prepolymer was mixed with 1 g of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide under light shielding conditions at 8°C at a stirring rate of 70 r / min for 15 min to obtain a plastic solid-state auxiliary material for fixing a shaped sheet.

[0053] Comparative Example 2

[0054] (1) 50 g of methyl methacrylate, 22 g of polyethylene glycol diacrylate, 9.5 g of pentaerythritol tetra-3-mercaptopropionate, 5 g of perfluorooctyl triethoxysilane, 4 g of polycaprolactone microspheres (Wuhan Haisan Technology Co., Ltd., C100 polycaprolactone 0.5-1.04-10.6, flocculent), 4 g of dibutyl phthalate, and 12 g of an organic solvent (glycerol) were mixed at 50°C at a stirring rate of 150 r / min for 40 min to obtain a mixture.

[0055] (2) The above 100 g of the mixture was mixed with 12 g of sodium carboxymethyl cellulose (degree of substitution DS = 0.88), 1 g of butyl hydroxytoluene at 50°C at a stirring rate of 190 r / min for 30 min to obtain a prepolymer.

[0056] (3) 100 g of the prepolymer was mixed with 1 g of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide under light shielding conditions at 8°C at a stirring rate of 70 r / min for 15 min to obtain a plastic solid-state auxiliary material for fixing a shaped sheet.

[0057] The properties of the plastic solid-state auxiliary materials for fixing a shaped sheet prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were tested, and the test method was as follows:

[0058] 1. The plastic solid-state auxiliary material is prepared by light curing to form dumbbell-shaped sample (GB / T 1040.3-2006 standard), and then stretched on a universal material testing machine at a rate of 50 mm / min to measure tensile strength, elongation at break and elastic modulus.

[0059] 2. The toxicity of the material extract to cells is evaluated according to standard ISO 10993-5 to verify the biocompatibility of the material (more than 70% of cell survival is considered non-cytotoxic according to cell survival rate).

[0060] 3. The adhesion strength between the cured material and the metal forming sheet is tested (reference GB / T 2790 peeling test).

[0061] 4. The hardness of the plastic solid-state auxiliary material is tested after it is stored in the dark at room temperature (25°C) for 3 months.

[0062] The test results are shown in Table 1.

[0063] Table 1 Performance test results of the plastic solid-state auxiliary material for fixing the forming sheet prepared in Examples 1-3 and Comparative Examples 1-2

[0064]

[0065] In Comparative Example 1, butylated hydroxytoluene is not added, resulting in crosslinking of the monomers in the material after long-term storage, reducing plasticity. In Comparative Example 2, methyl methacrylate, a commonly used monomer, is used as the matrix, and after modification, its elasticity, plasticity, and tensile properties are not as good as those of the double crosslinking system composed of bisphenol A-glycidyl methacrylate and hydroxyethyl methacrylate, making it unsuitable as a material for fixing the forming sheet in dental restoration.

[0066] The adhesion strength between the forming sheet is moderate, which can ensure that the touch during dental restoration will not cause the forming sheet to shift, and can also be peeled off after the dental restoration is completed without damaging the stability of the tooth.

[0067] The use method of the above-mentioned plastic solid-state auxiliary material for fixing the forming sheet is as follows:

[0068] (1) The plastic solid-state auxiliary material is molded into the shape of a dental wedge and then cured to replace the existing wedge, which has hygroscopicity and can absorb tissue fluid, gingival crevicular fluid, or a small amount of blood compared to the existing wedge, thereby effectively preventing liquid leakage at the gum end and maintaining a dry environment in the cavity.

[0069] (2) After the bean pellet (or shaped piece or celluloid strip) is placed, the pliable solid auxiliary material is filled according to the actual tooth filling position between the bean pellet / shaped piece / celluloid strip and the buccal (labial) lingual (palatal) side of the tooth, so that it is tightly attached to and fixed with the buccal (labial) lingual (palatal) side hole margin; for those with larger tooth defects, the convexity of the buccal (labial) lingual (palatal) side filling and restoration can be determined individually.

[0070] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A method for the preparation of a plastic solid auxiliary material for the fixation of a shaped sheet in dental restorations, characterized in that, The method comprises the following steps: 1) mixing bisphenol A-glycidyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyl triethoxysilane, polycaprolactone microspheres, dibutyl phthalate and an organic solvent to obtain a mixture; 2) mixing the mixture with sodium carboxymethyl cellulose and butylated hydroxyl toluene to obtain a prepolymer; 3) mixing the prepolymer with a photoinitiator under light-proof conditions to obtain a plastic solid-state auxiliary material for fixing a shaped sheet.

2. A method of preparing a plastic solid auxiliary material for use in fixing a shaped sheet in dental filling according to claim 1, characterized in that, The mass ratio of the bisphenol A-glycidyl methacrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate, pentaerythritol tetra-3-mercaptopropionate, perfluorooctyl triethoxysilane, polycaprolactone microspheres, dibutyl phthalate and the organic solvent in step 1) is 20-40:20-40:20-25:8-12:4-8:3-8:3-6:10-15.

3. A method of preparing a plastic solid auxiliary material for use in fixing a shaped sheet in dental filling according to claim 2, characterized in that, The mixing temperature in step 1) is 45-55°C, the mixing time is 30-50 min, and the mixing stirring rate is 120-180 r / min.

4. A method of preparing a plastic solid auxiliary material for use in fixing a shaped sheet in a dental filling according to claim 3, characterized in that, The mass ratio of the mixture to sodium carboxymethyl cellulose and butylated hydroxyl toluene in step 2) is 100:12-15:1-3.

5. A method of preparing a plastic solid auxiliary material for use in fixing a shaped sheet in a dental filling according to claim 4, characterized in that, The mixing temperature in step 2) is 45-55°C, the mixing time is 25-35 min, and the mixing stirring rate is 160-220 r / min.

6. A method for preparing a plastic solid auxiliary material for fixing a shaped sheet in dental filling according to any one of claims 1 to 5, characterized in that, The mixing ratio of the prepolymer to the photoinitiator in step 3) is 100:0.5-1.5; The mixing temperature of the prepolymer and the photoinitiator is ≤20°C, the mixing stirring rate is 60-80 r / min, and the mixing time is 12-18 min; The photoinitiator comprises one or more of phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and ethyl(2,4,6-trimethylbenzoyl) phenyl phosphinate.

7. A method of preparing a plastic solid auxiliary material for use in fixing a shaped sheet in dental fillings according to claim 6, characterized in that, The degree of substitution DS of the sodium carboxymethyl cellulose is ≥0.8; The average molecular weight of the polyethylene glycol diacrylate is 400-450.

8. The plastic solid-state auxiliary material for fixing a shaped sheet in dental filling prepared by the preparation method of any one of claims 1-7.

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