A dental restoration material containing lubricating porcelain resin and preparation method thereof

Abstract

The present invention relates to the technical field of dental materials, and specifically to a dental restorative material containing a lubricating resin and a preparation method thereof. The lubricating resin is a mixture of inorganic materials and organic matter, wherein the inorganic material is one or more of quartz powder, barium glass powder, lanthanum glass powder, borosilicate glass powder, silicon oxide-zirconia composite powder, silicon oxide-ytterbium oxide composite powder, nano silicon oxide powder, nano zirconium oxide powder or titanium oxide powder, and the organic material is one or more of polycarbonate, polyepoxide, polymerized methacrylic resin or polymer containing propionate group; the mass fraction of inorganic material in the lubricating resin is 50-80%. Compared with the use of traditional materials, the present invention can save the silanization process by using lubricating resin, greatly improve the uniformity of the material, effectively reduce the shrinkage rate of the composite resin, and improve the optical and aesthetic effects of the composite resin.

Description

Technical Field

[0001] The present invention relates to the technical field of dental materials, and in particular to a dental restorative material containing a lubricating porcelain resin and a preparation method thereof. Background Art

[0002] Dental filling resins are intended to replace missing tooth structure and change tooth color and contour to enhance aesthetics. Many commercial resin composites are available for various applications, some optimized for aesthetics, while others are designed for areas subject to higher stress. Dental restorative compositions are basically composed of a combination of polymerizable monomers, fillers and polymerization initiators. In order to impart the ability to approach natural teeth, acrylic resin monomers, highly transparent inorganic glass fillers, visible light photoinitiators and pigments similar to teeth are mostly selected in the prior art. Fillers account for the majority of the volume or weight of the composite material. The role of the filler is to strengthen the resin matrix, provide appropriate transmittance, and control the volume shrinkage of the composite material during polymerization. Fillers are traditionally mostly inorganic powder fillers, usually obtained by grinding minerals such as quartz, glass or sol-gel derived ceramics. Most fillers contain glass powders of heavy metal oxides such as barium or zinc, so when exposed to X-rays, they can provide non-transmissive visualization effects.

[0003] However, the surface of inorganic powder fillers needs to be treated during use, otherwise the compatibility with acrylic resin monomers is poor. The surface treatment of inorganic powders generally adopts silanization treatment, and the silane coupling agent used is a silane coupling agent containing acrylic groups, and the added content is generally 5%-10%. However, the particle size of the powder is generally small, 0.5-2um, so the silanization process has the following difficulties: 1) The specific surface area of ​​inorganic powders is large, surface treatment is more difficult, and compatibility is difficult to ensure. The powder particle size is small, and granulation is required to form a relatively large powder. 2) The silanization process has large errors. The silanization process requires hydrolysis and high-speed stirring, and it takes a long time. The uniformity of the powder treated with surface silane is difficult to ensure. 3) The addition and mixing process of powder and resin monomer requires a relatively long surface infiltration process. In view of the above reasons, it is difficult to ensure the interface compatibility and particle size distribution of silanized powders, and the following defects often exist: 1) The shrinkage rate of the composite resin is difficult to compensate, and the large shrinkage gap may cause the resin to break at any time; 2) The optical and aesthetic effects of the composite resin are difficult to guarantee; 3) The mechanical strength of the composite resin is difficult to guarantee. Summary of the invention

[0004] In order to solve the above problems existing in the dental restoration materials in the prior art, the present invention provides a dental restoration material containing a lubricating resin, wherein the raw materials for preparing the dental restoration material include an acrylate monomer resin, a lubricating resin and an inorganic powder filler;

[0005] The porcelain-running resin is a mixture of inorganic materials and organic matter. The inorganic materials include but are not limited to: quartz powder, barium glass powder, lanthanum glass powder, borosilicate glass powder, silicon oxide-zirconium oxide composite powder, silicon oxide-ytterbium oxide composite powder, nano silicon oxide powder, nano zirconium oxide powder, titanium oxide powder, and the organic materials include but are not limited to polycarbonate, polyepoxide, polymerized methacrylic resin, and polymer containing propionate groups. The mass fraction of inorganic materials in the porcelain-running resin is 50-80%.

[0006] The resin material of the present invention is added with a porcelain resin, and the organic powder in the porcelain resin can increase the wettability of the polymerized monomer to the powder, thereby guiding the monomer to wet the filler powder, and the organic powder can cover the inorganic powder, and has a certain surface modification effect. Moreover, after adding the porcelain resin, the processing performance is better (no sticking to the equipment), the resin curing shrinkage rate is low, the mechanical properties of the resin are better, and the color and transparency meet the requirements.

[0007] The porcelain-running resin of the present invention generally includes other additives such as a colorimetric regulator in addition to inorganic materials and organic substances. Before use, the inorganic materials, organic substances and other additives need to be uniformly mixed by stirring and kneading.

[0008] As a preferred solution, the organic matter in the porcelain-running resin is a mixture of bisphenol A propylene glycol dimethacrylate and triethylene glycol dimethacrylate, and the inorganic powder is barium glass powder and nano-silicon dioxide.

[0009] Further preferably, the porcelain-running resin includes 6-9 parts of bisphenol A propylene glycol dimethacrylate, 1-4 parts of triethylene glycol dimethacrylate, 28-32 parts of barium glass powder, and 4-6 parts of nano-silicon dioxide.

[0010] Preferably, the acrylic monomer resin includes bisphenol A glycerol dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA), methyl methacrylate (MMA), hydroxyethyl methacrylate (HEMA), urethane dimethacrylate (UDMA), ethoxylated bisphenol A glycerol dimethacrylate (BisEMA), polyethylene glycol acrylate (PEGDMA), camphorquinone (EGDMA), methyl α-cyanoacrylate, butyl α-cyanoacrylate or butyl α-cyanoacrylate, or a combination of two thereof.

[0011] Further preference is given to BisGMA, UDMA, TEGDMA or HEMA.

[0012] Preferably, the inorganic powder filler is one or more of quartz powder, barium glass powder, lanthanum glass powder, borosilicate glass powder, silicon oxide-zirconium oxide composite powder, silicon oxide-ytterbium oxide composite powder, nano silicon oxide powder, nano zirconium oxide powder, and nano titanium oxide powder.

[0013] More preferably, one or more of barium glass powder, lanthanum glass powder, and silicon oxide-zirconium oxide composite powder are used.

[0014] Preferably, the particle size of the inorganic powder is 0.5-50 um.

[0015] More preferably, the particle size of the inorganic powder is 0.5-2 um.

[0016] Preferably, the mass of the acrylic ester monomer resin, the porcelain resin and the inorganic powder filler is 5-40 parts of acrylic resin monomer, 5-40 parts of porcelain resin powder, and 30-80 parts of inorganic powder.

[0017] Preferably, the raw materials for preparing the dental restorative material further include an auxiliary agent, which is one or more of a fluorescent agent, an indicator, an inhibitor, an accelerator, a viscosity regulator, a wetting agent, an antioxidant, a surfactant, a stabilizer and a diluent.

[0018] Preferably, the raw materials for preparing the dental restorative material further include an initiator, and the initiator is camphorquinone, TPO or a mixture of the two.

[0019] The present invention also provides a method for preparing the dental restorative material of the present invention, comprising the following steps:

[0020] 1) ball milling the porcelain-wetting resin to obtain a porcelain-wetting resin powder;

[0021] 2) mixing the ball-milled porcelain-running resin with other raw materials except the inorganic powder filler, and fully stirring them by a double planetary stirring device;

[0022] 3) Mixing the inorganic powder filler with the above-mentioned fully stirred material, and processing it by using a screw kneader.

[0023] Preferably, the ball milling process may be dry ball milling or wet ball milling; and / or,

[0024] The ball milling aid for wet ball milling is a volatile organic compound, preferably one or a combination of methanol, ethanol, and isopropanol; and / or,

[0025] The mass ratio of the porcelain-wetting resin, the grinding balls and the ball-milling aid is 1:1-2:0.5-1, and the ball-milling time is 2-4 hours; and / or,

[0026] After the wet ball milling is completed, the ball-milled mixture is dried by rotary evaporation, and the temperature of the rotary evaporation is 20-100° C., preferably 30-80° C.; and / or,

[0027] The ball mill uses agate or zirconium oxide grinding balls.

[0028] Preferably, the double planetary stirring speed is 5-20 rpm; the stirring temperature is 10-60°C, preferably 60°C, and the stirring time is 1-4 hr; and / or,

[0029] During the kneading process, the screw length-diameter ratio of the kneading machine is 5-50, and the rotation speed is 5-200 rpm.

[0030] The present invention has the following beneficial effects:

[0031] Compared with traditional materials, the present invention can save the silanization process by using the porcelain resin, greatly improve the uniformity of the material, effectively reduce the shrinkage rate of the composite resin, improve the optical and aesthetic effects of the composite resin, and improve the mechanical strength of the composite resin. DETAILED DESCRIPTION

[0032] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0033] The run porcelain resins involved in the examples were all purchased from Liaoning Aierchuang Biomaterials Co., Ltd.

[0034] Example

[0035] The embodiment relates to a dental restorative material, comprising the following raw materials in parts by weight:

[0036] Table 1

[0037]

[0038]

[0039] The specific components of the porcelain-running resin in the above embodiment are shown in Table 2:

[0040] Table 2 (unit: g)

[0041] A1 color A2 color B1 color Tr color BisGMA 7 7 8 8 TEGDMA 3 3 2 2 Barium glass powder 30 30 30 30 Nano Silica 5 5 5 5 Iron oxide red 0.02 0.04 0.02 - Iron oxide yellow 0.01 0.02 0.04 - Titanium dioxide 0.01 0.01 0.01 -

[0042] The preparation method of the dental restoration material described in Example 1 is as follows:

[0043] (1) Select A1 color porcelain resin;

[0044] (2) dry grinding the Run porcelain block with a ball mill for 4 hr;

[0045] (3) The monomer resin and the porcelain resin were stirred using a double planetary stirrer at a stirring speed of 20 rpm and a temperature of 60° C. for 4 hours;

[0046] (4) The above materials are mixed with fillers using a screw kneader with a screw length-to-diameter ratio of 50 and a rotation speed of 200 rpm.

[0047] The preparation method of the dental restoration material described in Examples 2 to 4 is as follows:

[0048] (1) Selecting porcelain resin

[0049] (2) Wet-milling the run porcelain block with ball milling balls for 4 hours, wherein the mass ratio of resin raw material: grinding balls: ball milling aid is 1:2:1, and the ball milling time is 4 hours, and the ball milling aid is ethanol.

[0050] (3) Use a double planetary stirrer to mix and stir the monomer resin (see the table below) and the porcelain resin at a stirring speed of 20 rpm and a temperature of 60° C. for 4 hours;

[0051] (4) The above materials are mixed with fillers and a screw kneader is used with a screw length-diameter ratio of 50 and a rotation speed of 200 rpm.

[0052] The preparation method of the dental restoration material described in Comparative Example 1 is:

[0053] 1) The monomer resin and the additive were mixed, and double planetary stirring was adopted, the stirring speed was 20 rpm, the temperature was 60°C, and the stirring was carried out for 4 hours.

[0054] 2) The above materials are mixed with fillers and a screw kneader is used with a screw length-diameter ratio of 50 and a rotation speed of 200 rpm.

[0055] The preparation method of the dental restoration material described in Comparative Example 2 is:

[0056] 1) The monomer resin and the additive were mixed, and a double planetary stirring was adopted, with a stirring speed of 20 rpm and a temperature of 60° C. for 4 hours.

[0057] 2) The above materials are mixed with fillers and a screw kneader is used with a screw length-diameter ratio of 50 and a rotation speed of 200 rpm.

[0058] The preparation method of the dental restoration material described in Comparative Example 3 is:

[0059] 1) The monomer resin and the additive were mixed using a double planetary stirrer at a stirring speed of 20 rpm and a temperature of 60° C. for 4 hours.

[0060] 2) The above materials are mixed with fillers and a screw kneader is used with a screw length-diameter ratio of 50 and a rotation speed of 200 rpm.

[0061] Comparative Example 4

[0062] Compared with Examples 1 to 4, the preparation method of the dental material in this comparative example is different, and screw kneading is not used, and the method includes the following steps:

[0063] 1) Mix the monomer resin, the porcelain resin and the additives, use a double planetary stirrer, stir at a speed of 20 rpm, at a temperature of 60° C., and stir for 4 hours.

[0064] 2) The above materials are mixed with fillers using a double planetary mixer at a rotation speed of 50 rpm.

[0065] Experimental example

[0066] This experimental example involves testing the shrinkage, mechanical properties, light transmittance and color change of the tree material of the present invention:

[0067] The shrinkage rate was measured by the volume change 14 days after the reaction;

[0068] The mechanical properties testing method is as follows: Flexural strength is tested according to the method specified in 7.11 of YY 1042-2011, and the results meet the requirements of 2.4. Compression performance is tested according to GB / T 1041-2008 Determination of compression properties of plastics, and the size of the sample is a cylinder with a diameter of 4mm and a height of 6-10mm.

[0069] The transmittance and color change are the color differences of the composite materials in the dental material over time, and the maximum value of the difference in chromaticity based on the L*a*b* color system is greater than or equal to 2 and less than or equal to 15; L is brightness data, a is red-blue phase data, and b is yellow-green phase data.

[0070] The test results are shown in Table 3 and Table 4:

[0071] Table 3

[0072]

[0073] From the above data, it can be seen that the mechanical properties and shrinkage rate of the material are improved to a certain extent after adding porcelain resin.

[0074] Table 4

[0075]

[0076] It can be seen from the embodiments and comparative examples that after adding the porcelain-running resin, the brightness of the transparent resin is improved, the red and yellow hue values ​​in the hue are low, and the color interference is weak. However, the colors of A1, A2, and B1 are normal and the brightness (L) is improved.

[0077] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A dental restorative material containing a lubricating porcelain resin, characterized in that: The raw materials for preparing the dental restoration material include acrylic ester monomer resin, porcelain resin and inorganic powder filler; The porcelain-running resin is a mixture of inorganic materials and organic materials, wherein the inorganic materials are barium glass powder and nano-silicon dioxide, and the organic materials are a mixture of bisphenol A propylene glycol dimethacrylate and triethylene glycol dimethacrylate; the mass fraction of the inorganic materials in the porcelain-running resin is 50-80%; The porcelain-running resin comprises 6-9 parts of bisphenol A propylene glycol dimethacrylate, 1-4 parts of triethylene glycol dimethacrylate, 28-32 parts of barium glass powder, and 4-6 parts of nano-silicon dioxide; The method for preparing the dental restorative material comprises: 1) ball milling the porcelain-wetting resin to obtain a porcelain-wetting resin powder; 2) mixing the ball-milled porcelain-running resin with other raw materials except the inorganic powder filler, and fully stirring them by a double planetary stirring device; 3) mixing the inorganic powder filler with the above-mentioned fully stirred material, and processing it by using a screw kneader; The mass of the acrylic ester monomer resin, the porcelain-lubricating resin powder and the inorganic powder filler is 5 to 40 parts of acrylic ester monomer, 5 to 40 parts of porcelain-lubricating resin powder and 30 to 80 parts of inorganic powder filler.

2. The dental restorative material according to claim 1, characterized in that: The acrylic acid ester monomer resin includes one or a combination of two of bisphenol A propylene glycol dimethacrylate, triethylene glycol dimethacrylate, methacrylate, hydroxyethyl methacrylate, urethane dimethacrylate, ethoxylated bisphenol A propylene glycol dimethacrylate, polyethylene glycol acrylate, ethylene glycol dimethacrylate, camphorquinone, methyl α-cyanoacrylate, butyl α-cyanoacrylate or butyl α-cyanoacrylate.

3. The dental restorative material according to claim 1, characterized in that: The acrylic acid ester monomer resin is one or more of bisphenol A propylene glycol dimethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate or hydroxyethyl methacrylate.

4. The dental restorative material according to any one of claims 1 to 3, characterized in that: The inorganic powder filler is one or more of quartz powder, barium glass powder, lanthanum glass powder, borosilicate glass powder, silicon oxide-zirconium oxide composite powder, silicon oxide-ytterbium oxide composite powder, nano silicon oxide powder, nano zirconium oxide powder, and nano titanium oxide powder.

5. The dental restorative material according to any one of claims 1 to 3, characterized in that: The particle size of the inorganic powder filler is 0.5-50um.

6. The dental restorative material according to any one of claims 1 to 3, characterized in that: The particle size of the inorganic powder filler is 0.5-2um.

7. The dental restorative material according to any one of claims 1 to 3, characterized in that: The raw materials for preparing the dental restoration material also include auxiliary agents, which are one or more of fluorescent reagents, indicators, inhibitors, accelerators, viscosity regulators, wetting agents, antioxidants, surfactants, stabilizers and diluents.

8. The dental restorative material according to any one of claims 1 to 3, characterized in that: The raw materials for preparing the dental restoration material also include an initiator, and the initiator is camphorquinone, TPO or a mixture of the two.

9. The dental restorative material according to claim 1, characterized in that: The ball milling process is dry ball milling or wet ball milling; and / or, The ball milling aid in the wet ball milling is a volatile organic compound; and / or, The mass ratio of the porcelain-wetting resin, the grinding balls and the ball-milling aid is 1:1-2:0.5-1, and the ball-milling time is 2-4 hours; and / or, After wet ball milling, the ball-milled mixture is dried by rotary evaporation at a temperature of 20-100° C.; and / or, The ball mill uses agate or zirconium oxide grinding balls.

10. The dental restorative material according to claim 9, characterized in that: The ball milling aid for wet ball milling is one or a combination of methanol, ethanol, and isopropanol; and / or, After the wet ball milling is completed, the ball-milled mixture is dried by rotary evaporation at a temperature of 30-80°C.

11. The dental restorative material according to claim 1, characterized in that: The double planetary stirring speed is 5-20rpm; the stirring temperature is 10-60°C, and the stirring time is 1-4hr; and / or, during the kneading process, the screw aspect ratio of the kneader is 5-50, and the rotation speed is 5-200rpm.

12. The dental restorative material according to claim 11, characterized in that: The stirring temperature of the double planetary stirring speed is 60°C.

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