CN112494341B - Dental restoration composition and preparation method and application thereof - Google Patents
Dental restoration composition and preparation method and application thereof Download PDFInfo
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- CN112494341B CN112494341B CN202011410455.2A CN202011410455A CN112494341B CN 112494341 B CN112494341 B CN 112494341B CN 202011410455 A CN202011410455 A CN 202011410455A CN 112494341 B CN112494341 B CN 112494341B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/16—Refractive index
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/76—Fillers comprising silicon-containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
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Abstract
The invention relates to the technical field of materials, in particular to a dental restoration composition and a preparation method and application thereof. The dental restoration composition provided by the invention comprises the following raw materials in mass ratio (5-20): (75-95) a polymerizable resin matrix and a filler, the filler comprising glass flakes, the mass ratio of the glass flakes to the resin matrix being 1: (1-5). The dental restoration composition has extremely high mechanical strength and toughness, can be used for manufacturing dental restoration at a bearing part, and has aesthetic effect similar to that of natural teeth; the dental restoration composition is pre-cured, is prepared into a dental restoration body after computer aided design and manufacturing, can be directly used for the oral cavity of a patient, and is suitable for a CAD/CAM system beside a dental chair.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a dental restoration composition and a preparation method and application thereof.
Background
Caries, a common disease of the oral cavity that is widespread worldwide, has been listed by the World Health Organization (WHO) as the third most serious disease (second only to cancer and cardiovascular disease) that severely affects human health. WHO-related studies have shown that as oral medicine develops, the caries loss index (DMFT) declines worldwide, but still affects the physical and quality of life of 60-90% of school-age children and most adults. With the improvement of living standard and the development of new materials and techniques, the demand of people on tooth restoration is higher and higher, and the requirements of beautifying appearance, mechanical property, biocompatibility, convenience for clinical operation and the like are also continuously improved.
The dental caries repairing filling method is the most common method for treating dental caries, is suitable for manufacturing teeth with fixed hole shapes after dental caries, fixes filling materials on the teeth, and recovers the defects and functions of the teeth so as to maintain the appearance of the teeth and maintain the integrity of the teeth. The dental restoration composition material has the characteristics of simple and convenient operation, vivid color and luster, developed bonding technology, capability of retaining tooth tissues to the maximum extent, less micro-leakage, similar elastic modulus to a tooth body, capability of enhancing the tooth structure and the like, is fully determined by extensive clinicians and patients, and is widely applied to the tooth restoration filling treatment.
With the development of digital dental diagnosis and treatment technology, the dental restoration composition material also generates a pre-cured polymer-based material for CAD/CAM. The pre-cured polymer has good toughness, processability, easy polishing, wear resistance and X-ray radiation resistance, and the restoration effect after cutting is close to that of natural teeth, so the pre-cured polymer is an ideal CAD/CAM material beside a dental chair. The dental digital diagnosis and treatment technology can complete the prosthesis manufacture within 30 minutes without a temporary prosthesis, reduces the number of times of patient's treatment, can obviously improve the precision and accuracy of the prosthesis, improves the success rate of the repair treatment, effectively reduces the problems of gum discoloration, edge non-fit and the like of the traditional porcelain teeth and movable false teeth, and obviously improves the satisfaction degree of the treatment effect of the patient.
Compared with the traditional light-cured dental restoration composition, the mechanical property of the pre-cured polymer-based composition material is greatly improved, the bending strength can reach more than 160MPa, the compressive strength can reach more than 400MPa, and the restoration of the tooth body defect of the non-bearing part can be met, wherein the pre-cured polymer-based composition material comprises an inlay, an onlay, a dental crown and a veneer of the non-bearing part. However, in the repair of a defect in a dental body (e.g., a posterior maxillofacial surface) at a load bearing site, since the prosthesis is to directly bear an occlusal force, an ideal repair material should satisfy the following requirements: (1) The bending strength is at least over 220MPa, so that the fracture of the restoration can be prevented; (2) Moderate hardness and good wear resistance, but can not cause abrasion to the jaw teeth. The hardness of the pre-cured dental restoration composition material in the prior art can generally meet the requirements, but the bending strength is difficult to meet the requirements of restoration of the defect of the tooth body at the clinical bearing part, and the pre-cured dental restoration composition material can not be particularly used for the restoration of a back crown bridge.
Patent application CN 201080058442.1 discloses a dental composition, a milling block and a method, wherein the composition material is prepared by a thermosetting process, can be used in cooperation with a CAD/CAM technology, but has a bending strength only reaching 194.5MPa, and still cannot meet the requirement of repairing the defect of the tooth body at a bearing part.
Disclosure of Invention
The invention aims to provide a dental restoration composition which is a pre-cured polymer-based composition material, has excellent mechanical properties and can be used for restoring teeth at a load-bearing part. It is another object of the present invention to provide a method for preparing the dental restorative composition.
Specifically, the invention provides the following technical scheme:
firstly, the invention provides a dental prosthetic composition, which comprises the following raw materials in percentage by mass (5-20): (75-95) a polymerizable resin matrix and a filler, the filler comprising glass flakes, the mass ratio of the glass flakes to the resin matrix being 1: (1-5).
In order to obtain the dental prosthetic material which has excellent mechanical properties and can be used for repairing the teeth at the bearing part, the invention researches, screens and verifies the mechanical properties of a large number of materials and combinations thereof.
The glass flakes can be one or two of medium-alkali glass flakes and alkali-free glass flakes.
The medium-alkali glass flakes and the alkali-free glass flakes can be medium-alkali glass flakes and alkali-free glass flakes commonly used in the field of materials. Preferably, medium-alkali glass flakes and alkali-free glass flakes having the chemical compositions shown in table 1 are used.
Chemical composition of alkali glass flakes and alkali-free glass flakes in Table 1
| Component (wt%) | SiO 2 | Al 2 O 3 | CaO | MgO | B 2 O 3 | Na 2 O+K 2 O | BaO |
| Medium alkali glass | 65-70 | 2-6 | 4-9 | 0-5 | 2-7 | 9-13 | 1-6 |
| Alkali-free glass | 52-56 | 12-16 | 20-25 | 0-5 | 5-10 | ≤0.8 | - |
The invention finds that the glass flakes can better interact with resin by controlling the thickness and the length of the glass flakes, and the glass flakes are helpful for improving the mechanical strength of the dental restoration composition.
Preferably, the thickness of the glass flake is 0.5 to 5 μm, more preferably 0.5 to 3 μm. The length of the glass flakes is 1 to 30 μm, more preferably 1 to 10 μm.
Preferably, the glass flake has a refractive index ranging from 1.40 to 1.70, more preferably from 1.45 to 1.60.
The glass flakes are surface-treated in order to improve the affinity of the surface between the glass flakes and the dental restorative composition and to improve the bonding strength between the glass flakes and the dental restorative composition. The surface treatment method may be a coupling agent modification, a plasma treatment, a chemical grafting treatment, or the like.
Preferably, the glass flakes are silanized glass flakes.
The mass percentage of the silane coupling agent used for the silanization modification to the glass flake is 2-20%.
The silanization coupling agent for silanization modification of glass flake may be gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-mercaptopropyltriethoxysilane (KH-580), gamma-aminopropyltrimethoxysilane (JH-A111), etc.
In order to improve the bonding strength between the glass flake and the dental restorative composition, the glass flake may be subjected to a cleaning treatment. The cleaning method can be a heat treatment method, a solvent soaking method or an acid-base corrosion treatment. For example, acid etching treatment: putting the glass flakes into hydrofluoric acid solution with the concentration of 0.01-0.5g/L, stirring for 1-8h, and then performing centrifugal separation at the rotating speed of 2000-5000r/min for 1-20min; taking the white precipitate, adding a small amount of saturated sodium bicarbonate solution to neutralize residual hydrofluoric acid; repeatedly washing with water, centrifuging for 1-3 times until the water solution is neutral, and drying at 100-120 deg.C for 10-48 hr to obtain clean glass flake.
Preferably, the glass flakes are present in the dental restorative composition in an amount ranging from 1% to 30% by weight. More preferably 3 to 15%.
The invention also discloses that the dental restoration composition is added with chopped fibers, and the chopped fibers can be cooperated with glass flakes within a certain proportion range, so that the mechanical strength and the fracture toughness of the dental restoration composition can be greatly improved.
Based on the discovery, the filler also comprises chopped fibers, and the mass ratio of the chopped fibers to the glass flakes is 1: (1-5).
Preferably, the mass ratio of the chopped fibers to the resin matrix is 1: (2-8).
The mass percentage content range of the chopped fiber in the dental restoration composition is 1-15%. More preferably 1 to 10%.
The chopped fiber is one or more selected from glass fiber, quartz fiber, siliceous fiber, ceramic fiber and high molecular polymer fiber.
The invention finds that the interaction between the chopped fibers and the glass flakes and between the chopped fibers and the resin can be better realized by controlling the diameter and the length of the chopped fibers, and the mechanical strength and the toughness of the dental restoration composition can be improved more favorably.
Preferably, the chopped fibers have a diameter of 0.1 to 25 μm, more preferably 0.5 to 10 μm. The chopped fibers have a length in the range of 0.1 to 10mm, more preferably 0.5 to 5mm.
Preferably, the chopped fibers have a refractive index in the range of 1.40 to 1.70, more preferably 1.45 to 1.60.
The fibers are surface treated in order to improve the surface affinity between the chopped fibers and the dental restorative composition and to increase the bond strength between the fiber material and the dental restorative composition. The surface treatment method may be a coupling agent modification, a plasma treatment, a chemical grafting treatment, or the like.
Preferably, the chopped fibers are silanized and modified chopped fibers.
The mass percentage of the silane coupling agent used for the silanization modification to the chopped fiber is 2-20%.
The silane coupling agent used for the silanization modification can be gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-mercaptopropyltriethoxysilane (KH-580), gamma-aminopropyltrimethoxysilane (JH-A111) and the like.
In order to improve the bonding strength between the chopped fibers and the dental restorative composition, the chopped fibers are subjected to a cleaning treatment. The cleaning method can be a heat treatment method, a solvent soaking method or an acid-base corrosion treatment. For example, acid etching treatment: putting the fiber material into hydrofluoric acid solution with the concentration of 0.01-0.5g/L, stirring for 1-8h, and then performing centrifugal separation at the rotating speed of 2000-5000r/min for 1-20min; taking the white precipitate, and adding a small amount of saturated sodium bicarbonate solution to neutralize residual hydrofluoric acid; repeatedly washing with water, centrifuging for 1-3 times until the water solution is neutral, and drying at 100-120 deg.C for 10-48 hr to obtain clean chopped fiber.
The chopped fibers of the present invention are preferably quartz chopped fibers. The invention discovers that quartz chopped fibers and glass flakes can generate a better synergistic effect, and the mechanical strength and the fracture toughness of the dental restoration composition can be remarkably improved by matching the quartz chopped fibers and the glass flakes.
In order to enhance the aesthetic effect of the restorative material of the dental restorative composition, so that the material has a transparency close to that of natural teeth, the resin matrix according to the present invention can be used with polymerizable ethylenically unsaturated compounds with or without acid functionality, as well as other polymerizable resinated monomers, such as epoxy resins.
In the dental restorative composition described above, the resin matrix includes an ethylenically unsaturated compound, or includes an ethylenically unsaturated compound and an epoxy resin. Wherein the ethylenically unsaturated compound is one or more selected from the group consisting of acrylate, methacrylate, hydroxy-functionalized acrylate, hydroxy-functionalized methacrylate.
Among the above resin matrices, the resin matrix preferably used comprises urethane dimethacrylate UDMA and triethylene glycol dimethacrylate TEGDMA, or comprises urethane dimethacrylate UDMA and triethylene glycol dimethacrylate TEGDMA and one or more selected from polyethylene glycol dimethacrylate PEGDMA, bisphenol a-glycidyl dimethacrylate Bis-GMA, ethoxylated bisphenol a dimethacrylate Bis-EMA6, hydroxyethyl methacrylate HEMA, bisphenol a epoxy resin E-44. The present invention has found that the resin matrix of the UDMA and TEGDMA combination can interact better with glass flakes and chopped fibers than other resin matrices, effectively improving the mechanical strength and toughness of the dental restorative composition. On the basis of a resin matrix combined by UDMA and TEGDMA, one or more of Bis-GMA, bisphenol A epoxy resin E-44, PEGDMA, bis-EMA6 and HEMA is further added, so that the mechanical strength and toughness of the dental restoration composition can be well ensured.
In the above-described resin matrix, the mass ratio of urethane dimethacrylate UDMA to triethylene glycol dimethacrylate TEGDMA is preferably (1.5 to 5): 1.
in the dental restorative composition of the present invention, the mass percentage of the resin matrix is 5 to 40%, preferably 5 to 20%.
Specifically, the resin matrix comprises (preferably consists of) the following components in percentage by mass:
in addition to glass flakes and chopped fibers, other fillers are added to the dental restorative composition material system of the present invention. These fillers may be inorganic fillers or else prepolymerized organic fillers which are insoluble in the resin system. Among these, inorganic fillers 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, nano titanium oxide powder or other inorganic fillers capable of realizing the effect. Organic fillers include, but are not limited to, polycarbonate, polyepoxide powder, polymerized methacrylic resin powder, and the like, with or without inorganic materials.
In the dental restorative composition of the present invention, the filler is present in an amount of 40 to 95% by mass, preferably 60 to 95% by mass.
The selection and particle size of the filler can affect the physical and chemical properties of the dental restorative composition, such as appearance, X-ray radiation resistance, mechanical properties and the like; by adjusting the content and relative refractive index of the filler, the transparency of the dental restorative composition material can be changed, thereby adjusting the aesthetic effect of the material.
The filler used in the present invention is in the form of a powder, the maximum particle size of which does not exceed 20 μm, preferably does not exceed 5 μm, more preferably does not exceed 1 μm. The particle size range of the powder filler is preferably 0.01 μm to 10 μm, more preferably 0.01 μm to 1 μm.
The refractive index of the filler is close to that of the resin matrix, so that the aesthetic effect of the dental restoration composition material can be better ensured, and the appearance is closer to that of natural teeth. Preferably, the refractive index of the filler is 1.48 to 1.60, more preferably 1.50 to 1.58.
In order to further improve the polishing property and the wear resistance of the dental restorative composition material, the filler of the invention has a certain particle size distribution; wherein, the granularity of a part of fillers (glass powder and silicon oxide composite powder) is micron-sized and/or submicron-sized (0.1-1 μm), the granularity of a part of fillers (nano-powder) is nano-sized (less than or equal to 0.1 μm), and meanwhile, the nano-powder is added into the dental restoration composition material, so that the dental restoration composition material has an opalescence effect close to that of natural teeth, and the aesthetic effect is improved.
The average particle size of the nanopowder used in the present invention is preferably 10 to 100nm, more preferably 10 to 70nm, and most preferably 15 to 50nm. The mass percentage of the nano powder in the filler is preferably 1-20%, more preferably 2-10%.
Specifically, the filler of the present invention further comprises one or more selected from quartz powder, barium glass powder, lanthanum glass powder, borosilicate glass powder, silica-zirconia composite powder, silica-ytterbium oxide composite powder, nano silica powder, nano zirconia powder, and nano titania powder.
Preferably, the filler comprises, by mass ratio, (60-90): (1-15) glass powder and nano-powder.
Specifically, the glass powder is one or more selected from barium glass powder, lanthanum glass powder and silicon oxide-zirconium oxide composite powder, and the nano powder is nano silicon oxide powder and/or nano zirconium oxide powder.
Preferably, the filler comprises (preferably consists of) the following components in percentage by mass:
in order to improve the surface affinity between the inorganic filler and the resin and to improve the bonding strength between the inorganic filler and the dental restorative composition, the surface of the filler is sufficiently silanized, that is, the surface of the filler is completely coated with the silane coupling agent.
Preferably, the glass powder and the nano powder are modified by silanization, and the mass percentage of a silane coupling agent used for silanization modification to the glass powder or the nano powder is 2-20%.
The silane coupling agent can be gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-mercaptopropyltriethoxysilane (KH-580), gamma-aminopropyltrimethoxysilane (JH-A111) and the like.
The silanization treatment method specifically comprises the following steps: adding the inorganic filler, the catalyst and the silane coupling agent into a volatile solvent, reacting at room temperature for 30-150 min, stirring at 50-80 ℃ for 30-120min, removing the solvent, and drying in a vacuum oven at 50-120 ℃ for 10-30h to obtain the silanized inorganic filler. Wherein, the catalyst can be one of ammonia water, n-propylamine, acetic acid and oxalic acid; the volatile solvent can be one of toluene, cyclohexane, ethanol and acetone.
The minimum amount of the silane coupling agent used is confirmed by the following formula:
minimum amount of silane coupling agent used = filler mass × filler specific surface area/coupling agent minimum coating area
The usage amount of the silane coupling agent is larger than the minimum usage amount and is 2-20% of the filling material by weight percentage.
The catalyst is used in an amount of adjusting the pH value of the reaction system to 9-11 or 3-6.
The addition of silanized fillers may increase the percentage by weight of filler in the dental restorative composition to 85% to 90%.
Specifically, the invention provides a dental restoration composition, which comprises the following components in parts by weight: 10-20 parts of methacrylate or hydroxyl functionalized methacrylate, 0-2 parts of bisphenol A epoxy resin E-44, 2-15 parts of glass flakes, 0-10 parts of chopped fibers, 60-90 parts of glass powder and 1-15 parts of nano powder.
Preferably, the raw materials of the dental restorative composition comprise the following components in parts by weight: 5-15 parts of urethane dimethacrylate UDMA, 2-8 parts of triethylene glycol dimethacrylate TEGDMA, 0-44-3 parts of bisphenol A epoxy resin E, 0-5 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 0-70 parts of barium glass powder, 0-40 parts of lanthanum glass powder, 2-10 parts of nano silicon dioxide powder, 0-10 parts of nano zirconium dioxide powder, 2-60 parts of silicon oxide-zirconium oxide composite powder, 2-10 parts of glass flakes and 0-10 parts of chopped fibers.
More preferably, the dental restorative composition comprises the following components in parts by weight: 5-15 parts of urethane dimethacrylate UDMA, 2-8 parts of triethylene glycol dimethacrylate TEGDMA, 0-3 parts of bisphenol A epoxy resin E-44, 0-5 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 0-70 parts of barium glass powder, 0-40 parts of lanthanum glass powder, 2-10 parts of nano silicon dioxide powder, 0-10 parts of nano zirconium dioxide powder, 2-60 parts of silicon oxide-zirconium oxide composite powder, 2-10 parts of glass flakes and 2-10 parts of chopped fibers.
As a preferred embodiment of the present invention, the raw materials of the dental restorative composition comprise the following components in parts by weight: 5-10 parts of urethane dimethacrylate UDMA, 2-6 parts of triethylene glycol dimethacrylate TEGDMA, 1-2 parts of bisphenol A epoxy resin E-44, 30-40 parts of barium glass powder, 30-40 parts of lanthanum glass powder, 2-4 parts of nano silicon dioxide powder, 1-3 parts of nano zirconium dioxide powder, 3-6 parts of silicon oxide-zirconium oxide composite powder and 2-8 parts of glass flakes.
Or the raw materials of the dental restoration composition comprise the following components in parts by weight: 5-10 parts of urethane dimethacrylate UDMA, 2-6 parts of triethylene glycol dimethacrylate TEGDMA, 50-70 parts of barium glass powder, 3-7 parts of nano silicon dioxide powder, 2-5 parts of silicon oxide-zirconium oxide composite powder, 8-12 parts of glass flakes and 3-7 parts of chopped fibers.
Or the raw materials of the dental restoration composition comprise the following components in parts by weight: 5-10 parts of urethane dimethacrylate UDMA, 2-6 parts of triethylene glycol dimethacrylate TEGDMA, 2-5 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 8-12 parts of lanthanum glass powder, 5-9 parts of nano silicon dioxide powder, 50-60 parts of silicon oxide-zirconium oxide composite powder, 6-10 parts of glass flakes and 1-4 parts of chopped fibers.
The dental restorative composition of the present disclosure may also optionally include additives suitable for use in the oral environment, including, but not limited to, colorants, initiators, accelerators, inhibitors, fluorescence imparting agents, dyes, pigments, indicators, inhibitors, accelerators, viscosity modifiers, emollients, antioxidants, stabilizers, diluents, and other similar ingredients apparent to those skilled in the art.
The initiator, the accelerator and the polymerization inhibitor are required for curing the dental restorative composition material, and the mass percentage content of the initiator, the accelerator and the polymerization inhibitor in the dental restorative composition is 0.1-3%, and preferably 0.3-2%. Wherein, the initiator can be selected from one or more of dicumyl peroxide, tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxyacetate and tert-butyl peroxybenzoate. The mass percentage of the initiator in the dental restoration composition is 0.1-1%. Accelerators may be used in combination with the initiator, and accelerators useful herein include one or more combinations of N, N-dimethyl-p-toluidine (DMT), N, N-dihydroxyethyl-p-toluidine (DHET), ethyl 4-dimethylaminobenzoate (EDMAB), and N, N-dimethylamino ethyl methacrylate (DMAEMA). The mass percentage of the accelerator in the dental restoration composition is 0.1-1%. The polymerization inhibitor is one or two of 2, 6-di-tert-butyl-p-cresol (BHT) and tert-butyl hydroquinone (TBHQ). The mass percentage of the polymerization inhibitor in the dental restoration composition is 0.1-1%.
The colorant, which is used to improve the appearance of the dental restorative composition to have the aesthetic effect of natural teeth, is mainly composed of metal oxides, and is contained in the dental restorative composition in an amount ranging from 0.01% to 0.2%, preferably from 0.03% to 0.1%, by mass. Wherein the red colorant is iron oxide red, and the mass percentage content of the red colorant in the dental restoration composition is 0.002% -0.06%. The black colorant is black iron oxide, and the mass percentage of the black colorant in the dental restoration composition is 0-0.03%. The yellow colorant is one or more of iron oxide yellow, bismuth yellow, vanadium zirconium yellow and cerium praseodymium yellow in any ratio, and the mass percentage content of the yellow colorant in the dental restoration composition is 0.001-0.04%. The above colorants may be used in combination. The colorant pigment is preferably present in the polymeric material in an increasing amount from the cut end layer to the neck layer.
The additives in the dental restorative composition may also include surfactants, such as nonionic and cationic surfactants, anionic surfactants, or a combination thereof; useful surfactants include non-polymerizable and polymerizable surfactants.
Specifically, the dental restoration composition comprises the following additives in percentage by mass:
benzoyl peroxide: 0.1% -0.3%;
2, 6-di-t-butyl-p-cresol: 0.2 to 0.4 percent;
n, N-dihydroxyethyl p-toluidine: 0.1% -0.3%;
and colored oxides including red iron oxide, yellow iron oxide, black iron oxide, yellow bismuth oxide, and the like.
The invention also provides the use of the dental restorative composition in the preparation of a pre-cured polymer-based material for dental restorations.
The invention also provides a preparation method of the dental restorative composition, which comprises the following steps of:
(1) Preparing precursor powder: mixing the raw materials with a ball milling auxiliary agent, then carrying out ball milling mixing, and drying to obtain precursor powder, wherein the ball milling auxiliary agent is a volatile organic matter;
(2) Dry pressing and preforming: pressing and molding the precursor powder prepared in the step (1) under the molding pressure of 3-20MPa to obtain a blank;
(3) Heating and pressurizing treatment: heating and pressurizing the blank obtained by dry pressing preforming for 0.5-3h at the temperature of 100-200 ℃ and under the pressure of 20-200 MPa;
preferably, the ball milling auxiliary agent is one or more of methanol, ethanol and acetone; the mass ratio of the raw materials to the ball-milling auxiliary agent is (1-3): 1.
in order to improve the production efficiency of the dental restoration composition material and ensure the content of the inorganic filler in the material, the invention adopts a powder method to prepare the material, uses volatile organic matters with strong dispersibility (methanol, ethanol and acetone) as ball milling aids to mix the high molecular monomer and the inorganic filler, so that the mixing is more uniform, and the efficiency is effectively improved; and then drying to obtain a powdery precursor, which is beneficial to the molding of products. Furthermore, the dental restoration composition material is cured by adopting a hot-pressing technology, so that the strength of the dental restoration composition material is effectively improved, the monomer residue is greatly reduced, and the biocompatibility of the dental restoration composition material is improved.
In the step (1), the method further comprises a step of treating the surface of the filler with a coupling agent, wherein the step of treating with the coupling agent comprises: adding a filler, a catalyst and a silane coupling agent (one or more of gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-mercaptopropyltriethoxysilane (KH-580) and gamma-aminopropyltrimethoxysilane (JH-A111)) into a volatile solvent, reacting at room temperature for 30-150 min, stirring at 50-80 ℃ for 30-120min, removing the solvent, and drying in a vacuum oven at 50-120 ℃ for 10-30h to obtain the silanized filler. Wherein, the catalyst can be one of ammonia water, n-propylamine, acetic acid and oxalic acid; the volatile solvent can be one of toluene, cyclohexane, ethanol and acetone.
In the treatment of the coupling agent, the using amount of the silane coupling agent is more than the minimum using amount, and the mass of the silane coupling agent accounts for 2-20% of the mass of the filler.
The minimum amount of the silane coupling agent used is confirmed by the following formula: the minimum amount of silane coupling agent used = filler mass × filler specific surface area/coupling agent minimum coating area.
The catalyst is used in an amount of adjusting the pH value of the reaction system to 9-11 or 3-6.
The specific conditions of ball milling and mixing are as follows: the ball stone is made of agate or zirconia. The mass ratio of the raw materials to the ball stones to the ball milling aids is preferably 2:4:1; the mixing time is 0.5-2h.
The specific conditions for drying the slurry are: firstly, rotary evaporation is used, and then drying is carried out to obtain the dental polymer material precursor powder, wherein the temperature during the rotary evaporation is 20-100 ℃, preferably 30-80 ℃, and more preferably 40-60 ℃. The drying temperature is 20 ℃ to 100 ℃, preferably 30 ℃ to 80 ℃, and more preferably 40 ℃ to 60 ℃.
In the step (2), the dental polymer material precursor powder is added into a mold, and is pressed and molded by a dry press, wherein the molding pressure is preferably 4-10MPa.
In the step (3), the polymer material blank after dry pressing preforming is processed by a heating and pressurizing device to obtain the dental polymer material. The temperature of the heating and pressurizing curing treatment is preferably 120-180 ℃, and more preferably 130-160 ℃. The pressurizing mode can be dry pressure, air pressure or hydraulic pressure. The pressure is preferably from 100 to 180MPa, more preferably from 120 to 170MPa. The holding time is preferably 1 to 2 hours.
The invention has the beneficial effects that: the invention provides a dental restoration composition for restoring a load-bearing part of a dental crown, which has at least the following advantages:
(1) Has extremely high mechanical strength (bending strength of over 280MPa and compressive strength of over 570 MPa) and toughness (fracture toughness of 1.2 MPa-m) 1/2 ) Can be used for manufacturing dental restorations of load-bearing parts (such as a two-unit dental bridge, a load-bearing crown and the like);
(2) The dental restoration composition is pre-cured, is prepared into a dental restoration body after computer aided design and manufacture, can be directly used for the oral cavity of a patient, is suitable for a CAD/CAM system beside a dental chair, and can be used for manufacturing veneers, inlays, crowns, bridges and upper structures of dental implants;
(3) Dental restorative compositions have an aesthetic effect close to that of natural teeth.
The preparation method of the dental restoration composition provided by the invention has at least the following advantages:
(1) The dental restoration composition material is prepared by a powder method, and volatile organic matters are used as ball milling aids for mixing, so that the mixing is more uniform, the production efficiency of the material can be improved, the content of fillers in the material can be ensured, and the molding of the product is facilitated;
(2) The dental restoration composition material is cured by adopting a pressure heating curing technology, monomer residues (without cytotoxicity) are not detected in the material, and the biological safety and compatibility of the material are high.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The glass flakes used in the following examples were alkali-free glass flakes having a thickness of 0.8 μm, a length of 3 μm, and a refractive index of 1.53. The chopped fibers used were quartz chopped fibers having a diameter of 0.7 μm, a length of 2mm and a refractive index of 1.50. The glass powder has a particle size of 0.7 μm, and the nano powder has an average particle size of 0.04 μm.
The barium glass powder, the nano powder, the chopped fiber and the glass flake used in the following examples are all subjected to silanization treatment, and the silanization treatment method is as follows:
silanization treatment of glass powder: 10g of a glass powder (specific surface area 7 m) 2 Per g) and 1.2g of gamma-methacryloxypropyltrimethoxysilane (KH-570, 316m minimum coating area) 2 /g) adding into acetone, adding ammonia water to adjust the pH value to 9, reacting at room temperature for 60min, stirring at 50 ℃ for 60min, removing the acetone, and drying in a vacuum oven at 100 ℃ for 10h to obtain the barium glass powder filler.
Silanization treatment of nano powder: 10g of nano powder (the specific surface area is about 28 m) 2 G) and 1.7g of gamma-methacryloxypropyltrimethoxysilane (KH-570, minimum cladding area 316 m) 2 And/g) adding into cyclohexane, adding glacial acetic acid to adjust the pH value to 5.5, reacting at room temperature for 60min, stirring at 50 ℃ for 60min, removing cyclohexane, and drying in a vacuum oven at 100 ℃ for 10h to obtain the barium glass powder filler.
Silanization treatment of chopped fibers: 10g of chopped quartz fibers (specific surface area 0.5 m) 2 Per g) and 0.2g of gamma-mercaptopropyltriethoxysilane (KH-580) (KH-580, minimum coating area 380m 2 /g) adding into acetone, adding n-propylamine to adjust the pH value to 10, and adjusting the temperature to room temperatureReacting for 50min, stirring for 100min at 60 ℃, removing acetone, and drying in a vacuum oven at 120 ℃ for 15h to obtain the chopped quartz fiber filler.
Silanization treatment of glass flakes: 10g of glass flake (specific surface area 1.5 m) 2 Per g) and 0.4g of gamma-methacryloxypropyltrimethoxysilane (KH-570, minimum cladding area 316 m) 2 /g) adding into toluene, adding acetic acid to adjust the pH value to 3.5, reacting at room temperature for 120min, stirring at 80 ℃ for 120min, removing the toluene, and drying in a vacuum oven at 120 ℃ for 20h to obtain the glass flake filler.
Example 1
This example provides a dental restorative composition, which has the following raw material formulation: 10 parts of urethane dimethacrylate UDMA, 4 parts of triethylene glycol dimethacrylate, 1 part of bisphenol A epoxy resin E-44, 34 parts of barium glass powder, 36 parts of lanthanum glass powder, 3 parts of nano silicon dioxide powder, 2 parts of nano zirconium dioxide powder, 5 parts of silicon oxide-zirconium oxide composite powder, 5 parts of glass flakes, 0.25 part of benzoyl peroxide, 0.2 part of 2, 6-di-tert-butyl-p-cresol, 0.1 part of N, N-dihydroxyethyl-p-toluidine, 0.010 part of iron oxide red and 0.015 part of iron oxide yellow.
This example also provides a method of making the above dental restorative composition, including the steps of:
(1) Preparing precursor powder: all the raw materials, the ball stone and the ball-milling assistant acetone are mixed according to the mass ratio of 2:4:1, mixing, performing ball milling and mixing for 1.5h, performing rotary evaporation at 50 ℃ for 1.5h, and drying at 55 ℃ for 3.5h to obtain precursor powder;
(2) Dry pressing and preforming: adding the precursor powder prepared in the step (1) into a steel die, and preparing a dental polymer material preformed block by adopting a dry pressing process, wherein the forming pressure is 6MPa;
(3) Heating and pressurizing treatment: and then heating and pressurizing the preformed block, wherein the treatment temperature is 150 ℃, the pressure is 160MPa, and the heat preservation time is 2h to obtain the final dental polymeric material.
Example 2
This example provides a dental restorative composition, which has the following raw material formulation: 6 parts of urethane dimethacrylate UDMA, 4 parts of triethylene glycol dimethacrylate TEGDMA, 68 parts of barium glass powder, 4 parts of nano silicon dioxide powder, 3 parts of silicon oxide-zirconium oxide composite powder, 10 parts of glass flakes, 5 parts of chopped fibers, 0.3 part of benzoyl peroxide, 0.2 part of 2, 6-di-tert-butyl-p-cresol, 0.2 part of N, N-dihydroxyethyl-p-toluidine, 0.022 part of iron oxide red, 0.018 part of cerium praseodymium yellow and 0.001 part of iron oxide black.
This example also provides a method of making the above dental restorative composition, including the steps of:
(1) Preparing precursor powder: all the raw materials, the ball stone and the ball milling auxiliary agent ethanol are mixed according to the mass ratio of 1:1:1, ball milling and mixing materials after mixing, wherein the mixing time is 1h, rotary evaporation is carried out at 45 ℃ for 2h, and then drying is carried out at 55 ℃ for 4h to obtain precursor powder;
(2) Dry pressing and preforming: adding the precursor powder prepared in the step (1) into a steel die, and preparing a dental polymer material preformed block by adopting a dry pressing process, wherein the forming pressure is 6MPa;
(3) Heating and pressurizing treatment: and then heating and pressurizing the preformed block, wherein the treatment temperature is 150 ℃, the pressure is 150MPa, and the heat preservation time is 2h to obtain the final dental polymeric material.
Example 3
This example provides a dental restorative composition, which has the following raw material formulation: 6 parts of urethane dimethacrylate UDMA, 4 parts of triethylene glycol dimethacrylate TEGDMA, 3 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 10 parts of lanthanum glass powder, 7 parts of nano silicon dioxide powder, 60 parts of silicon oxide-zirconium oxide composite powder, 8 parts of glass flakes, 2 parts of chopped fibers, 0.2 part of benzoyl peroxide, 0.3 part of 2, 6-di-tert-butyl-p-cresol, 0.01 part of iron oxide red and 0.005 part of cerium praseodymium yellow.
The present embodiment also provides a method for preparing the above dental restorative composition, which includes the steps of:
(1) Preparing precursor powder: all the raw materials, the ball stone and the ball-milling auxiliary agent methanol are mixed according to the mass ratio of 3:5:1, ball-milling and mixing the materials after mixing, wherein the mixing time is 1h, rotary evaporation is carried out at 50 ℃ for 2h, and then drying is carried out at 45 ℃ for 5h to obtain precursor powder;
(2) Dry pressing and preforming: adding the precursor powder prepared in the step (1) into a steel die, and preparing a dental polymer material preformed block by adopting a dry pressing process, wherein the forming pressure is 5MPa;
(3) Heating and pressurizing treatment: and then heating and pressurizing the preformed block, wherein the treatment temperature is 140 ℃, the pressure is 170MPa, and the heat preservation time is 1h, so that the final dental polymeric material is obtained.
Comparative example 1
This comparative example provides a dental restorative composition that differs from example 1 only in that the raw material does not contain glass flakes, and the amount of barium glass powder was adjusted to 39 parts.
Comparative example 2
This comparative example provides a dental restorative composition that differs from example 2 only in that the raw materials do not contain chopped fibers and the amount of barium glass frit is adjusted to 73 parts.
Comparative example 3
The present comparative example provides a dental restorative composition having the following raw material formulation: 5 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 8 parts of urethane dimethacrylate UDMA, 2 parts of triethylene glycol dimethacrylate TEGDMA, 6 parts of ethoxybisphenol A dimethacrylate Bis-EMA, 1 part of hydroxyethyl methacrylate HEMA, 74 parts of barium glass powder, 7 parts of nano silicon dioxide powder, 0.15 part of benzoyl peroxide, 0.25 part of 2, 6-di-tert-butyl-p-cresol, 0.1 part of N, N-dihydroxyethyl-p-toluidine, 0.006 part of iron oxide red and 0.004 part of iron oxide yellow.
This comparative example also provides a method of preparing the above dental restorative composition, comprising the steps of:
(1) Preparing precursor powder: mixing all the raw materials with ball stone and ball milling auxiliary agent acetone according to the mass ratio of 2:4:1, ball milling and mixing the materials after mixing, wherein the mixing time is 1h, rotary evaporation is carried out at 50 ℃ for 1.5h, and then drying is carried out at 50 ℃ for 4h to obtain precursor powder;
(2) Dry pressing and preforming: adding the precursor powder prepared in the step (1) into a steel die, and preparing a dental polymer material preformed block by adopting a dry pressing process, wherein the forming pressure is 6MPa;
(3) Heating and pressurizing treatment: and then heating and pressurizing the preformed block, wherein the treatment temperature is 150 ℃, the pressure is 150MPa, and the heat preservation time is 2h, so that the final dental polymeric material is obtained.
Comparative example 4
The present comparative example provides a dental restorative composition, which comprises the following raw material formula: 2 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 13 parts of urethane dimethacrylate UDMA, 3 parts of triethylene glycol dimethacrylate TEGDMA, 2 parts of hydroxyethyl methacrylate HEMA, 72 parts of lanthanum glass powder, 8 parts of nano zirconium dioxide powder, 0.2 part of benzoyl peroxide, 0.3 part of 2, 6-di-tert-butyl-p-cresol, 0.011 part of iron oxide red and 0.018 part of bismuth yellow.
This comparative example also provides a method of preparing the above dental restorative composition, comprising the steps of:
(1) Preparing precursor powder: all the raw materials, the ball stone and the ball-milling auxiliary agent methanol are mixed according to the mass ratio of 3:5:1, mixing, performing ball milling and mixing for 1.5h, performing rotary evaporation at 55 ℃ for 3h, and drying at 45 ℃ for 5h to obtain precursor powder;
(2) Performing dry pressing preforming: adding the precursor powder prepared in the step (1) into a steel die, and preparing a dental polymer material preformed block by adopting a dry pressing process, wherein the forming pressure is 5MPa;
(3) Heating and pressurizing treatment: and then heating and pressurizing the preformed block, wherein the treatment temperature is 140 ℃, the pressure is 170MPa, and the heat preservation time is 1h to obtain the final dental polymeric material.
The dental restoration composition materials of the examples and the comparative examples are tested for mechanical strength, toughness and light transmittance, wherein the flexural strength is tested by the flexural strength testing method in YY/T1042-2011 dental science polymer-based restoration material; the detection of the compression strength is referred to as YY/T0271.1-2016 department 1 of dental water-based cement: a method for detecting the compression strength in powder/liquid acid-base cement; the detection of fracture toughness refers to GB/T23806-2009 Fine ceramic fracture toughness test method unilateral pre-crack Beam (SEPB) method; the detection of the light transmittance refers to GB/T5433-2008 daily glass light transmittance determination method.
The detection results are shown in table 2, and the results show that the dental restoration composition materials of the examples have both mechanical strength and fracture toughness obviously superior to those of each proportion, and have good light transmittance.
Table 2 dental restorative composition performance test results
Although the invention has been described in detail with respect to the general description and the specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (19)
1. A dental restoration composition is characterized in that raw materials thereof comprise the following components in mass ratio (5-20): (75-95) a polymerizable resin matrix and a filler, the filler comprising glass flakes and chopped fibers, the mass ratio of the glass flakes to the resin matrix being 1: (1-5), wherein the mass ratio of the chopped fibers to the glass flakes is 1: (1-5), wherein the mass ratio of the chopped fibers to the resin matrix is 1: (2-8);
the glass flakes are medium-alkali glass flakes and/or alkali-free glass flakes;
the thickness of the glass flake is 0.5-5 μm;
the length of the glass flake is 1-30 μm;
the glass flakes are silanized and modified;
the chopped fibers are one or more selected from glass fibers, quartz fibers and ceramic fibers;
the diameter of the chopped fiber is 0.1-25 μm;
the length of the chopped fiber is 0.1-10mm;
the chopped fibers are silanized and modified.
2. Dental restorative composition according to claim 1, wherein the glass flakes have a thickness of 0.5-3 μ ι η;
and/or the length of the glass flake is 1-10 μm;
and/or the diameter of the chopped fiber is 0.5-10 μm;
and/or the length of the chopped fiber is 0.5-5mm.
3. The dental restorative composition of claim 1, wherein the glass flakes have a refractive index of 1.40-1.70.
4. Dental restorative composition according to claim 2, characterized in that the glass flakes have a refractive index of 1.45-1.60.
5. Dental restorative composition according to claim 1, wherein the chopped fibres have a refractive index of 1.40-1.70.
6. Dental restorative composition according to claim 5, wherein the chopped fibres have a refractive index of 1.45-1.60.
7. The dental restorative composition as defined in claim 1, wherein the silane coupling agent used for the silanization modification is present in an amount of 2-20% by mass with respect to the glass flakes.
8. The dental restorative composition as claimed in claim 1, wherein the silane coupling agent used for the silanization modification is present in an amount of 2-20% by mass of the chopped fiber.
9. Dental restorative composition according to any of claims 1 to 8, wherein the resin matrix comprises an ethylenically unsaturated compound or comprises an ethylenically unsaturated compound and an epoxy resin, wherein the ethylenically unsaturated compound is one or more selected from the group consisting of acrylates, methacrylates, hydroxy-functionalized acrylates, and hydroxy-functionalized methacrylates.
10. Dental restorative composition according to claim 1, wherein the resin matrix comprises Urethane Dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA),
alternatively, the resin matrix comprises urethane dimethacrylate UDMA and triethylene glycol dimethacrylate TEGDMA and one or more selected from polyethylene glycol dimethacrylate PEGDMA, bisphenol a-glycidyl dimethacrylate Bis-GMA, ethoxylated bisphenol a dimethacrylate Bis-EMA6, hydroxyethyl methacrylate HEMA, bisphenol a epoxy resin E-44.
11. Dental restorative composition according to claim 10, characterized in that the resin matrix has a mass ratio of urethane dimethacrylate UDMA and triethylene glycol dimethacrylate TEGDMA of (1.5-5): 1.
12. the dental restorative composition of any of claims 1-8, 10, and 11, wherein the filler further comprises one or more selected from quartz powder, barium glass powder, lanthanum glass powder, borosilicate glass powder, silica-zirconia composite powder, silica-ytterbium oxide composite powder, nano silica powder, nano zirconia powder, and nano titania powder.
13. Dental restorative composition according to claim 12, characterized in that the filler comprises, in a mass ratio of (60-90): (1-15) glass powder and nano powder;
the glass powder is one or more selected from barium glass powder, lanthanum glass powder and silicon oxide-zirconium oxide composite powder, and the nano powder is nano silicon oxide powder and/or nano zirconium oxide powder.
14. The dental restorative composition as defined by claim 13, wherein the glass powder and the nano-powder are silanized, and the mass percentage of a silane coupling agent used in silanized modification to the glass powder or the nano-powder is 2-20%.
15. The dental restorative composition as defined in any of claims 1 to 8, 10, 11, 13 and 14, wherein the dental restorative composition comprises the following raw materials in parts by weight: 10-20 parts of methacrylate or hydroxyl functionalized methacrylate, 0-2 parts of bisphenol A epoxy resin E-44, 2-15 parts of glass flakes, 0-10 parts of chopped fibers, 60-90 parts of glass powder and 1-15 parts of nano powder.
16. Dental restorative composition according to claim 15, characterized in that the raw materials of the dental restorative composition comprise the following components in parts by weight: 5-15 parts of urethane dimethacrylate UDMA, 2-8 parts of triethylene glycol dimethacrylate TEGDMA, 0-3 parts of bisphenol A epoxy resin E-44, 0-5 parts of bisphenol A-glycidyl dimethacrylate Bis-GMA, 0-70 parts of barium glass powder, 0-40 parts of lanthanum glass powder, 2-10 parts of nano silicon dioxide powder, 0-10 parts of nano zirconium dioxide powder, 2-60 parts of silicon oxide-zirconium oxide composite powder, 2-10 parts of glass flakes and 0-10 parts of chopped fibers.
17. Use of a dental restorative composition according to any of claims 1 to 16 in the preparation of a pre-cured polymer-based material for dental restorations.
18. A method for preparing a dental restorative composition as defined in any of claims 1 to 16, comprising the steps of:
(1) Preparing precursor powder: mixing the raw materials with a ball milling auxiliary agent, then carrying out ball milling mixing, and drying to obtain precursor powder, wherein the ball milling auxiliary agent is a volatile organic matter;
(2) Performing dry pressing preforming: pressing and molding the precursor powder prepared in the step (1) under the molding pressure of 3-20MPa to obtain a blank;
(3) Heating and pressurizing treatment: and (3) heating and pressurizing the blank obtained by dry pressing and preforming for 0.5-3h at the temperature of 100-200 ℃ and under the pressure of 20-200 MPa.
19. The method of preparing a dental restorative composition as defined by claim 18, wherein the ball milling aid is one or more of methanol, ethanol, acetone; the mass ratio of the raw materials to the ball-milling auxiliary agent is (1-3): 1.
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| FI20065465A0 (en) * | 2006-06-30 | 2006-06-30 | Stichtech Oy | Fiber-reinforced composites and processes for their production |
| KR101257628B1 (en) * | 2011-03-24 | 2013-04-29 | (주)아모레퍼시픽 | Cosmetics comprising cosmetic composition impregnated in urethane foam |
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