WO2019062144A1 - 透光率和颜色渐变的牙科材料的制备方法及其制备的产品 - Google Patents

透光率和颜色渐变的牙科材料的制备方法及其制备的产品 Download PDF

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Publication number
WO2019062144A1
WO2019062144A1 PCT/CN2018/087109 CN2018087109W WO2019062144A1 WO 2019062144 A1 WO2019062144 A1 WO 2019062144A1 CN 2018087109 W CN2018087109 W CN 2018087109W WO 2019062144 A1 WO2019062144 A1 WO 2019062144A1
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Prior art keywords
light transmittance
layer
composite resin
powder
resin material
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PCT/CN2018/087109
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English (en)
French (fr)
Inventor
王鸿娟
石凤
吴佳航
Original Assignee
辽宁爱尔创生物材料有限公司
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Application filed by 辽宁爱尔创生物材料有限公司 filed Critical 辽宁爱尔创生物材料有限公司
Priority to KR1020207012478A priority Critical patent/KR102306376B1/ko
Priority to AU2018340731A priority patent/AU2018340731B2/en
Priority to US16/650,269 priority patent/US11517507B2/en
Priority to JP2020517809A priority patent/JP6953626B2/ja
Priority to EP18861418.4A priority patent/EP3689322B1/en
Publication of WO2019062144A1 publication Critical patent/WO2019062144A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0022—Blanks or green, unfinished dental restoration parts
    • 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
    • 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
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/65—Dyes
    • 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
    • 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
    • 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
    • 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
    • A61K6/78—Pigments
    • 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
    • A61K6/79—Initiators
    • 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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • 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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/836—Glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A61C13/082—Cosmetic aspects, e.g. inlays; Determination of the colour
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers

Definitions

  • the present application relates to the field of dental restoration technology, and in particular to a method for preparing a dental material having light transmittance and color gradation and a product thereof.
  • CAD/CAM technology has also been used in the field of dental technology.
  • the CAD/CAM technology next to the dental chair is to place the computer-aided design and computer-aided manufacturing equipment on the dental chair.
  • the doctor uses the digital technology to obtain the patient's tooth model, and the computer analyzes the data and the teeth.
  • the dental chair side diagnosis and treatment technology can complete the restoration preparation at one time, no need for temporary restoration, reduce the number of patient visits, can significantly improve the precision and accuracy of the restoration, improve the success rate of the repair treatment; effectively reduce the traditional porcelain teeth and
  • the problem of discoloration of the gums and inconsistency of the edges of the movable dentures significantly improves the satisfaction of the patient's treatment effect.
  • the development of CAD/CAM next to dental chairs has also led to the advancement of supporting materials.
  • commonly used composite materials mainly include: composite resin materials, resin-infiltrated ceramic composite materials, and polyetheretherketone (PEEK) materials.
  • PEEK polyetheretherketone
  • Natural teeth are composed of enamel and dentin. The two tissues are completely different in source and characteristics and have their own unique optical properties. Dentin constitutes the body of the tooth, has light-blocking properties, and the enamel covers the dentin. It has translucency and light transparency, which causes the light transmittance and color of the natural tooth to be gradually changed from the neck to the cut end.
  • a prosthesis made of a single aesthetically pleasing composite resin material has a disadvantage of low light transmittance and color similarity compared with natural teeth.
  • the multi-layer composite resin material comprises at least three layers of composite resin materials of different colors, that is, composite resin materials of the same kind of light transmittance, the composite resin materials of the respective layers are superposed on each other, and the composite resin materials of the respective layers are from the bottom layer.
  • the color of the top layer changes sequentially, which in turn mimics the color of natural teeth, but does not reflect the gradual change of natural tooth transmittance; in addition, the existing multi-layer composite resin material has the disadvantage of low strength.
  • the purpose of the present application is to provide a method for preparing a dental material having a light transmittance and a color gradation and a product thereof to achieve the purpose of improving the aesthetic effect and strength of the composite resin material.
  • the specific technical solutions are as follows:
  • the present application provides a method for preparing a dental material having light transmittance and color gradation, the method comprising:
  • each of the composite resin material precursor powders comprises: weighing raw materials, the raw materials including resin monomers, fillers, The initiator and the coloring agent are mixed to obtain a composite resin material precursor powder, wherein the weight ratio of the filler to the resin monomer is 10:90-90:10, preferably 70:30-85:15, and the initiator weight It is 0.1-3%, preferably 0.1-2% by weight of the resin monomer, and the colorant weight is 0.001-0.2%, preferably 0.002-0.1%, based on the total weight of the resin monomer and the filler; the resin monomer includes an olefin bond Unsaturated monomer and/or epoxy resin;
  • the first composite resin material precursor powder of the at least three different light transmittances in the composite resin material precursor powder of the at least three different light transmittances, the first composite resin material precursor powder is dry-formed under a pressure of 3-20 MPa, preferably 4-10 MPa, Obtaining a first green body; wrapping the first green body in the second composite resin material precursor powder in the at least three kinds of composite resin material precursor powders with different light transmittance, at 3-20 MPa, preferably Dry pressing molding under a pressure of 4-10 MPa to obtain a second green body; repeating the wrapping and dry pressing forming operation until the at least three composite resin material precursor powders are dry pressed to obtain light transmittance and color a gradual dental material preform preform, wherein the light transmittance of each layer of the precursor powder in the dental material preform body of the light transmittance and the color gradation is sequentially increased from the inside to the outside;
  • the curing treatment conditions are a temperature of 115 to 185 ° C, preferably 131 to 171 ° C, a pressure of more than 160 MPa, preferably 160 to 300 MPa, more preferably 200 to 250 MPa, and a holding time of 0.5 to 4 h, preferably 0.5 to 3 h.
  • the light transmittance and the color gradient of the dental material further have a multi-layer color, between the two adjacent layers of the composite resin material, the chromaticity difference based on the Lab color system is greater than or equal to 1, and less than or equal to 11;
  • the maximum difference of the chromaticity difference based on the Lab color system between the composite resin materials of the non-adjacent layers in the light transmittance and the color grading dental material is greater than or equal to 2 and less than or equal to 15;
  • a sum of chromaticity differences between all adjacent layers of the composite resin material in the light transmittance and color grading dental material, and a composite resin having the highest chromaticity among the light transmittance and color grading dental materials The difference in chromaticity between the material and the layer of composite resin material having the lowest chroma is not more than 2;
  • ⁇ E is the chromaticity difference
  • ⁇ L is the difference between the L values between the two layers
  • ⁇ a is the difference between the a values between the two layers
  • ⁇ b is the difference between the b values between the two layers.
  • the light transmittance and the color grading dental material further have a multilayer transmittance, and the difference between the transmittance between the adjacent two layers and the color gradient of the dental material is 0.5-10%.
  • the difference in light transmittance between two adjacent composite resin materials is 1-15%; and the visible light (wavelength of 550 nm) transmittance of a composite resin material having the highest light transmittance is 50-75%.
  • the light transmittance of the composite resin material having the lowest light transmittance is 30-60%, and the other composite resin material having the highest light transmittance and the other composite resin material having the lowest light transmittance are
  • the layer composite resin material has a light transmittance of 40 to 70%.
  • the weight ratio of the filler to the resin monomer is 31:69-69:31, preferably 43:57-62:38, and the initiator weight is 0.1-3%, preferably 0.1% by weight of the resin monomer. -2%, the colorant weight is 0.001-0.2%, preferably 0.002-0.1% of the total weight of the resin monomer and the filler;
  • the heat curing treatment conditions are a temperature of 115 to 169 ° C, preferably 155 to 165 ° C, a pressure of 210 to 300 MPa, preferably 240 to 290 MPa, and a holding time of 1.1 to 1.8 h, preferably 1.6 to 1.8 h.
  • the raw material is mixed to obtain a composite resin material precursor powder, including:
  • the raw material is mixed with a ball milling aid, and the composite resin material precursor powder is prepared by a ball milling method, wherein the mass ratio of the raw material: grinding ball: ball milling aid is (1:1:1)-(3:6:2), preferably For 2:4:1, the ball milling time is 0.5-2h.
  • the filler has a particle size ranging from not more than 2.5 ⁇ m, preferably not more than 2 ⁇ m, more preferably from 0.05 to 2 ⁇ m; and the filler has a refractive index of from 1.40 to 1.7, preferably from 1.45 to 1.6.
  • the raw material further comprises a polymerization inhibitor, and the polymerization inhibitor accounts for 0.1-3%, preferably 0.2-2%, of the total weight of the resin monomer.
  • the raw material further comprises an accelerator, the accelerator comprising 0.1-3%, preferably 0.2-2%, based on the total weight of the resin monomer.
  • the raw material further comprises at least one of a fluorescent-imparting agent, an indicator, an inhibitor, an accelerator, a viscosity modifier, a wetting agent, an antioxidant, a surfactant, a stabilizer, and a diluent.
  • a fluorescent-imparting agent an indicator, an inhibitor, an accelerator, a viscosity modifier, a wetting agent, an antioxidant, a surfactant, a stabilizer, and a diluent.
  • the filler may further comprise nanoparticles, wherein the nanoparticles comprise 1-25%, preferably 1-15% by weight of the filler; the nanoparticles have an average diameter of 35-100 nm, preferably It is 40-50nm.
  • the raw material further comprises reinforcing fibers, the reinforcing fibers are 1-30%, preferably 1-10% by weight of the filler; and the reinforcing fibers have a diameter of 0.1-25 ⁇ m, preferably 0.5-10 ⁇ m.
  • the reinforcing fiber has a length of 0.001 to 1 mm, preferably 0.1 to 0.5 mm; the reinforcing fiber has a refractive index of 1.4 to 1.7, preferably 1.45 to 1.6; and the reinforcing fiber comprises glass fiber, quartz fiber, and silicon.
  • the raw material is mixed to obtain a composite resin material precursor powder, including:
  • the resin monomer, the filler, the initiator and the coloring agent other than the reinforcing fiber are mixed and then ball-milled to obtain a raw material mixture, wherein the raw material: grinding ball: ball milling aid has a mass ratio of 1:1:1-3: 6:2, preferably 2:4:1, ball milling time is 0.5-2h;
  • the raw material mixture is mixed with the reinforcing fibers to obtain a composite resin material precursor powder.
  • the coloring agent comprises one or a combination of a red coloring agent, a yellow coloring agent and a black coloring agent, wherein the red coloring agent accounts for 0.001-0.06%, preferably iron oxide, of the weight of the raw material.
  • Red preferably iron oxide
  • yellow coloring agent comprises 0.001-0.04% by weight of the raw material, and comprises one or a combination of iron oxide yellow, yttrium yellow, vanadium zirconium yellow, and yttrium yellow
  • the black coloring agent occupies the raw material 0-0.03% by weight, preferably iron oxide black.
  • the present application also provides a light-transmitting and color-grading dental material prepared by the above method.
  • the light transmittance and color grading dental material prepared by the method provided by the present application have extremely high flexural strength, and the flexural strength reaches 248 MPa or more as determined experimentally.
  • the light transmittance and color grading dental material prepared by the method provided by the present application have extremely high compressive strength, and the compressive strength has reached 581 MPa or more as determined by experiments.
  • the light transmittance and color gradient dental material prepared by the method provided by the present application can effectively improve the aesthetic effect of the restoration, so that the color and transparency are gradually changed in the height direction, and the cut end and the neck of the natural tooth are better simulated. Aesthetic characteristics.
  • the embodiment of the present application provides a method for preparing a dental material with light transmittance and color gradation, including:
  • each of the composite resin material precursor powders comprises: weighing raw materials, the raw materials including resin monomers, fillers, The initiator and the coloring agent are mixed to obtain a composite resin material precursor powder, wherein the weight ratio of the resin monomer to the filler is 10:90-90:10, preferably 70:30-85:15, and the initiator weight It is 0.1-3%, preferably 0.1-2% by weight of the resin monomer, and the colorant weight is 0.001-0.2%, preferably 0.002-0.1%, based on the total weight of the resin monomer and the filler; the resin monomer includes an olefin bond Unsaturated monomers and / or epoxy resins.
  • the resin monomer may be selected from polymerizable ethylenically unsaturated monomers with or without acid functional groups, such as acrylates, methacrylates, hydroxy-functional acrylates, hydroxy-functionalized nails. One or a combination of acrylates.
  • the resin monomer may also use a polymerizable resinizable monomer other than methacrylate, such as an epoxy resin such as polyethylene glycol dimethacrylate (PEGDMA), bisphenol A-dimethacrylic acid. Glycidyl ester (Bis-GMA), urethane dimethacrylate (UDMA), triethylene glycol dimethacrylate (TEGDMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA6) And one or a combination of hydroxyethyl methacrylate (HEMA), bisphenol A epoxy resin (epoxy resin E-44).
  • an epoxy resin such as polyethylene glycol dimethacrylate (PEGDMA), bisphenol A-dimethacrylic acid. Glycidyl ester (Bis-GMA), urethane dimethacrylate (UDMA), triethylene glycol dimethacrylate (TEGDMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA6) And one or a combination of
  • the resin monomer may also be a mixture of an ethylenically unsaturated monomer and an epoxy resin.
  • the epoxy resin can be from 5 to 30% by weight of the ethylenically unsaturated monomer.
  • a resin monomer can be obtained according to the following formulation.
  • Bis-GMA 0-70%, preferably 0-30%;
  • UDMA 10-70%, preferably 40-60%;
  • Bis-EMA6 0-50%, preferably 0-30%;
  • Epoxy resin E-44 0-40%, preferably 0-20%;
  • TEGDMA 10-60%, preferably 20-40%;
  • HEMA 0-50%, preferably 0-20%.
  • the filler has a particle size ranging from not more than 2.5 ⁇ m, preferably not more than 2 ⁇ m, more preferably from 0.05 to 2 ⁇ m; and the filler has a refractive index of from 1.40 to 1.7, preferably 1.45. -1.6.
  • the filler may also have a certain size fraction, for example, a portion of the filler may have a particle size ranging from 0.1 to 1 ⁇ m, and another portion of the filler may have a particle size ranging from less than 0.1 ⁇ m. Having a certain particle size grading of the filler allows the light transmittance and color grading of the dental material to have better polishing and abrasion resistance.
  • the filler may be an inorganic material, including but not limited to: quartz powder, bismuth glass powder, bismuth glass powder, borosilicate glass powder, silica-zirconia composite powder, silica-yttria composite powder. , nano-silica powder, nano-zirconia powder, nano-titanium oxide powder.
  • the filler may also be an organic filler including, but not limited to, a polycarbonate powder filled with an inorganic material, a polyepoxide powder, a polymerized methacrylic resin powder, and a polycarbonate powder not filled with an inorganic material, Polyepoxide powder, polymerized methacrylic resin powder.
  • the initiator includes, but is not limited to, one of dicumyl peroxide, t-butyl peroxide, benzoyl peroxide, tert-butyl peroxyacetate, t-butyl peroxybenzoate or a combination thereof.
  • the filler in order to increase the bonding strength between the filler and the polymerized monomer, is subjected to surface modification treatment with a coupling agent before being mixed with other raw materials.
  • Coupling agents which may be used include, but are not limited to, ⁇ -methacryloxypropyltrimethoxysilane KH-570, ⁇ -mercaptopropyltriethoxysilane KH-580, ⁇ -aminopropyltrimethoxysilane JH-A111 and so on.
  • the treatment of the surface of the filler with a coupling agent enhances the bonding strength between the filler particles and the polymerized monomer, such as an ethylenically unsaturated monomer, thereby increasing the hardness of the restoration.
  • the raw material is mixed to obtain a composite resin material precursor powder, comprising: mixing the raw material with a ball milling aid, and preparing a composite resin material precursor powder by a ball milling method, wherein the raw material: Grinding ball: The mass ratio of the ball milling aid is (1:1:1)-(3:6:2), preferably 2:4:1, and the ball milling time is 0.5-2 h.
  • the process conditions of the ball mill mixture may be: using agate or zirconia grinding balls, and the ball milling aid is a volatile organic substance such as one of methanol, ethanol, acetone or a combination thereof.
  • the mixture obtained by ball milling and mixing can be subjected to a rotary evaporation and drying process to prepare a composite resin material precursor powder having a light transmittance and a color gradation, wherein the temperature during rotary evaporation is 20-100 ° C, preferably 30-80. °C is further preferably 45-58 °C.
  • the temperature at the time of drying is 20 to 100 ° C, preferably 30 to 80 ° C, and more preferably 45 to 58 ° C.
  • the preparation of the composite resin material precursor powder according to the above ball milling method can make the components in the composite resin material precursor powder more uniformly mixed, can also improve the preparation efficiency, and can also facilitate the molding of the material.
  • the ratio between the resin monomer, the filler, the initiator and the colorant in each composite resin material can be adjusted according to actual needs, thereby obtaining a composite resin material having different light transmittance.
  • composite resin material precursor powder A having a light transmittance of 50-75%; composite resin material precursor powder B having a light transmittance of 40-70%; composite resin having a light transmittance of 30-60%
  • the material precursor powder C wherein the light transmittance is measured by a light transmittance tester when the test light wavelength is 550 nm.
  • the first method for obtaining a composite resin precursor powder having a specific light transmittance is: preparing a composite resin precursor powder of a plurality of formulations, and then curing the prepared precursor powder under a predetermined condition. Then, when the test light wavelength is 550 nm, the transmittance of the plurality of composite resin material precursor powders after curing is tested by a light transmittance tester, and then the prosthesis precursor corresponding to the light transmittance is selected according to the required light transmittance.
  • the powder is formulated according to the formula to prepare a composite resin material precursor powder.
  • the second is to use the empirical formula to calculate the light transmittance of each composite resin material precursor powder according to the nature and proportion of each component in the composite resin material precursor powder, and then select and transmit according to the required light transmittance.
  • the formula of the prosthetic precursor powder corresponding to the rate is prepared, and the composite resin material precursor powder is prepared according to the formula.
  • the composite resin material precursor powder C may be added to the mold in the order of light transmittance from low to high, and the upper surface of the precursor powder is flattened to be flat; and the composite resin material is further used.
  • the precursor powder B is added to the mold, and the upper surface of the precursor powder is flattened to a flat state; the above composite resin material precursor powder A is added to the mold, and the upper surface of the precursor powder is flattened to be flat; 3-20 MPa, preferably 4-10 MPa under pressure, dry-pressed to obtain a dental material preform having a light transmittance and a color gradient;
  • the composite resin material precursor powder C is dry-formed under a pressure of 3-20 MPa, preferably 4-10 MPa, to obtain a first green body; the first green body is wrapped in the composite resin material precursor powder B in the three different transmittance composite resin material precursor powders, at 3-20 MPa, preferably 4-10 MPa Pressing and forming under pressure to obtain a second green body; repeating the wrapping and dry pressing forming operation until the three composite resin material precursor powders are dry-formed to obtain a dental material with a light transmittance and a color gradient
  • the curing treatment conditions are a temperature of 115 to 185 ° C, preferably 131 to 171 ° C, a pressure of more than 160 MPa, preferably 160 to 300 MPa, more preferably 200 to 250 MPa, and a holding time of 0.5 to 4 h, preferably 0.5 to 3 h.
  • the thermal curing initiator is dicumyl peroxide, t-butyl peroxide, benzoyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate One or a combination thereof.
  • the chromaticity difference between the adjacent two layers of the composite resin material precursor powder in the light transmittance and the color grading dental material preform body is based on the Lab color system. Greater than or equal to 1, and less than or equal to 11;
  • the maximum value of the chromaticity difference based on the Lab color system is greater than or equal to 2, and less than or equal to 15;
  • a sum of chromaticity differences between all adjacent layers of the composite resin material in the light transmittance and color grading dental material, and a composite resin having the highest chromaticity among the light transmittance and color grading dental materials The difference in chromaticity between the material and the layer of composite resin material having the lowest chroma is not more than 2;
  • ⁇ E is the chromaticity difference
  • ⁇ L is the difference between the L values between the two layers
  • ⁇ a is the difference between the a values between the two layers
  • ⁇ b is the difference between the b values between the two layers.
  • the light transmittance and color grading dental material further has a multilayer transmittance, a transmittance between adjacent two layers of light transmittance and a color gradation of the dental material.
  • the difference is 0.5-10%; the difference in light transmittance between two adjacent composite resin materials is 1-15%; and the transmittance of a composite resin material having the highest light transmittance is 50-75%
  • the light transmittance of the layer of the composite resin material having the lowest light transmittance is 30-60%, and the other layer of the composite resin material having the highest light transmittance and the layer of the composite resin material having the lowest light transmittance are the other
  • the light transmittance of each layer of the composite resin material is 40-70%.
  • a composite resin material with moderate translucency belongs to the transition layer, which can be one layer or multiple layers;
  • the light transmittance of the composite resin material precursor powder prepared by the following three kinds of composite resin material precursor powders and the color gradient of the dental material can be satisfied, and the chromaticity difference between the three composite resin material precursor powders needs to be satisfied.
  • the conditions are explained.
  • chromaticity difference is sometimes also referred to simply as “chromatic aberration.”
  • the chromaticity of the three composite resin precursor powders is based on the Lab color system and is measured by a color difference meter or a spectrophotometer.
  • the chromaticity of the first composite resin material precursor powder may be marked by L1, a1, b1; the chromaticity of the second composite resin material precursor powder may be marked by L2, a2, b2; labeled with L3, a3, b3
  • the color of the three composite resin material precursor powders may be marked by L1, a1, b1; the chromaticity of the second composite resin material precursor powder may be marked by L2, a2, b2; labeled with L3, a3, b3 The color of the three composite resin material precursor powders.
  • the inter-layer chromaticity difference ⁇ E is calculated, where ⁇ E is the chromaticity difference; ⁇ L is the difference between the L values between the two layers; ⁇ a is the difference between the a values between the two layers; and ⁇ b is the difference between the b values between the two layers.
  • the first composite resin material precursor powder is used as the uppermost layer material
  • the second composite resin material precursor powder is used as the intermediate transition layer
  • the third composite resin material precursor powder is used as the lowermost layer material
  • L1 ⁇ L2 ⁇ L3, a1 ⁇ a2 ⁇ a3, b1 ⁇ b2 ⁇ b3; the L value of the first composite resin material precursor powder, the second composite resin material precursor powder, and the third composite resin material precursor powder are decreased
  • the trend when the a value and the b value have an increasing trend, can simulate the gradual change of the transmittance of the natural tooth.
  • the chromaticity difference between the uppermost layer and the lowermost layer should be 2 or more and 15 or less; the chromaticity difference between the uppermost layer and the intermediate transition layer is 1 or more and 11 or less; the intermediate transition layer and The chromaticity difference between the lowermost layer is 1 or more and 11 or less, and the chromaticity difference between the uppermost layer and the lowermost layer - (the chromaticity difference between the intermediate transition layer and the lowermost layer + the most The chromaticity difference between the upper layer and the intermediate transition layer)
  • the first composite resin material precursor powder L1 ranges from 62 to 80, a1 ranges from -2.2 to 2.2, and b1 ranges from 5 to 16, and the light transmittance ranges from 50 to 75%.
  • the second composite resin material precursor powder L2 ranges from 58 to 76, a2 ranges from -2.0 to 2.5, and b2 ranges from 8 to 20, and the light transmittance ranges from 40 to 70%.
  • the third composite resin material precursor powder L3 ranges from 53 to 72, a3 ranges from -1.8 to 2.8, and b3 ranges from 10 to 24, and the light transmittance ranges from 30 to 60%.
  • the light transmittance and color grading of the dental material prepared by using the above three composite resin material precursor powders the light transmittance of the first composite resin material precursor powder as the uppermost layer is higher than that of the intermediate transition layer.
  • the transmittance of the second composite resin material precursor powder; and the transmittance of the second composite resin material precursor powder as the intermediate transition layer is higher than that of the third composite resin material precursor powder as the lowermost layer Light transmittance of the body.
  • the difference in chromaticity between adjacent layers is 2 or more and 15 or less, and between adjacent layers The chromaticity difference is 1 or more and 11 or less.
  • the transmittance of each layer of the composite resin material from the lowermost layer to the uppermost layer is sequentially increased. High; or when the light transmittance of the uppermost layer of the restoration is the lowest, the light transmittance of each layer of the composite resin material from the lowermost layer to the uppermost layer is sequentially lowered.
  • the upper and lower light transmittance and the color grading dental material prepared by using the composite resin material precursor powder having the above-mentioned inter-layer chromaticity difference can simulate the characteristics of natural tooth transmittance from the cut end to the neck light transmittance and color gradation. Further, the dental restoration is more beautiful.
  • the above three composite resin material precursor powders can be used to prepare another dental material having a light transmittance and a color inside and outside gradation, and conditions for satisfying the chromaticity difference between the three composite resin material precursor powders are required. Be explained.
  • the first composite resin material precursor powder having a chromaticity value of L1, a1, b1 is used as the outermost layer material; the second composite resin material precursor powder having a chromaticity of L2, a2, b2 is used as the secondary outer layer material;
  • the third composite resin material precursor powder having a chromaticity of L3, a3, and b3 is used as the innermost layer material.
  • the chromaticity difference between the outermost layer and the innermost layer should be 2 or more and 15 or less; the chromaticity difference between the outermost layer and the secondary outer layer is 1 or more and 11 or less; The chromaticity difference from the innermost layer is 1 or more and 11 or less, and the chromaticity difference between the outermost layer and the innermost layer - (the chromaticity difference between the outermost layer and the outer outer layer + the outer The chromaticity difference between the layer and the innermost layer)
  • the light transmittance of the first composite resin material precursor powder as the outermost layer is higher than that of the second composite resin material precursor powder as the secondary outer layer;
  • the light transmittance of the second composite resin material precursor powder is higher than that of the third composite resin material precursor powder which is the innermost layer.
  • the dental material prepared by using the composite resin material precursor powder having the above-mentioned inter-layer chromaticity difference powder can simulate the gradual change of the light transmittance of the natural tooth from the inside to the outside, thereby making the dental prosthesis More beautiful.
  • the raw material further includes a polymerization inhibitor, and the polymerization inhibitor accounts for 0.1-3%, preferably 0.2-2%, of the total weight of the resin monomer.
  • the polymerization inhibitor includes, but is not limited to, one of 2,6-di-tert-butyl-p-cresol (BHT) and t-butyl hydroquinone (TBHQ) or combination.
  • BHT 2,6-di-tert-butyl-p-cresol
  • TBHQ t-butyl hydroquinone
  • the raw material further includes an accelerator, the accelerator comprising 0.1-3%, preferably 0.2-2%, based on the total weight of the resin monomer.
  • the promoter includes, but is not limited to, N,N-dimethyl-p-toluidine (DMT), N,N-dihydroxyethyl-p-toluidine (DHET), 4-dimethyl One or more combinations of ethylaminobenzoate (EDMAB) and N,N-dimethylaminoethyl methacrylate (DMAEMA).
  • DMT N,N-dimethyl-p-toluidine
  • DHET N,N-dihydroxyethyl-p-toluidine
  • EDMAB ethylaminobenzoate
  • DMAEMA N,N-dimethylaminoethyl methacrylate
  • the raw material further includes a reagent for imparting fluorescence, an indicator, an inhibitor, an accelerator, a viscosity modifier, a wetting agent, an antioxidant, a surfactant, a stabilizer, and a diluent. At least one of them.
  • the reagent for imparting fluorescence may be an azo fluorescent pigment, a tryptophan or a pyridine fluorescent pigment, etc.; the indicator may be a redox indicator or a wear indicator; the inhibitor may be a curing inhibitor or the like; the accelerator may be It is a photopolymerization accelerator or a thermal polymerization accelerator; the viscosity modifier may be paraffin wax or polyethylene wax; the wetting agent may be a silane agent; the antioxidant may be sodium ascorbate; and the surfactant may be octylphenol.
  • the filler further includes nanoparticles, wherein the nanoparticles account for 1-25%, preferably 1-15% by weight of the filler; an average diameter of the nanoparticles It is 35-100 nm, preferably 40-50 nm.
  • the dental material having a light transmittance and a color gradation can have an opalescent effect close to that of a natural tooth.
  • the raw material further includes reinforcing fibers, the reinforcing fibers being 1-30%, preferably 1-10% by weight of the filler; and the reinforcing fibers having a diameter of 0.1- 25 ⁇ m, preferably 0.5-10 ⁇ m; the reinforcing fiber has a length of 0.001 to 1 mm, preferably 0.1 to 0.5 mm; the reinforcing fiber has a refractive index of 1.4 to 1.7, preferably 1.45 to 1.6; the reinforcing fiber comprises glass One or a combination of fibers, quartz fibers, siliceous fibers, ceramic fibers, and polymer fibers, which are preferably polyethylene fibers.
  • the addition of reinforcing fibers to the raw material can improve the fracture toughness of the light-transmitting and color-grading dental materials.
  • the reinforcing fiber is subjected to a cleaning treatment and a surface modification treatment before being mixed with other raw materials
  • the cleaning method comprises: heat treatment cleaning, solvent soak cleaning or acid-base corrosion cleaning
  • the modification treatment method includes : Modification of coupling agent, modification by plasma treatment and modification by chemical grafting treatment.
  • the surface of the reinforcing fibers can be treated with a coupling agent.
  • Coupling agents which may be used include, but are not limited to, ⁇ -methacryloxypropyltrimethoxysilane KH-570, ⁇ -mercaptopropyltriethoxysilane KH-580, ⁇ -aminopropyltrimethoxysilane JH-A111 and so on.
  • the use of a coupling agent to treat the surface of the filler enhances the bonding strength between the fiber and the ethylenically unsaturated monomer, thereby increasing the hardness of the light-transmitting and color-grading dental material.
  • the surface modification treatment of the reinforcing fibers can further improve the fracture toughness of the densities and the color gradient of the dental materials.
  • the raw materials other than the reinforcing fibers may be ball-milled to obtain a raw material mixture; and the raw material mixture may be mixed with the reinforcing fibers to obtain a composite resin material precursor powder.
  • the raw material is mixed to obtain a composite resin material precursor powder, including:
  • the resin monomer, the filler, the initiator and the coloring agent other than the reinforcing fiber are mixed and then ball-milled to obtain a raw material mixture, wherein the raw material: grinding ball: ball milling aid has a mass ratio of 1:1:1-3: 6:2, preferably 2:4:1, ball milling time is 0.5-2h;
  • the raw material mixture is mixed with the reinforcing fibers to obtain a composite resin material precursor powder.
  • the coloring agent comprises one or a combination of a red coloring agent, a yellow coloring agent, and a black coloring agent, wherein the red coloring agent accounts for 0.001% of the weight of the raw material. 0.06%, preferably iron oxide red; the yellow colorant comprises 0.001-0.04% by weight of the raw material, and comprises one or a combination of iron oxide yellow, bismuth yellow, vanadium zirconium yellow and yellow enamel;
  • the black colorant comprises from 0 to 0.03% by weight of the starting material, preferably iron oxide black.
  • the colorant is generally a metal oxide such as iron oxide, zirconium oxide, vanadium oxide, and antimony oxide.
  • the ratio of the red colorant, the yellow colorant, and the black colorant can be adjusted according to different practical needs, thereby preparing dental materials of different colors of light transmittance and color gradation.
  • the embodiments of the present application also provide a light-transmitting and color-grading dental material prepared by using any of the above methods.
  • Table 1 shows the formulation and process parameters of four kinds of composite resin material precursor powders with different light transmittance.
  • the values corresponding to the resin monomer, filler, initiator and colorant in Table 1 are parts by weight, and each part by weight may be 100 g.
  • Table 2 shows the chromaticity values and light transmittance of the powders 1-4 based on the Lab color system.
  • the chromaticity values and the light transmittance corresponding to the powders 1-4 are shown in Table 2.
  • the light transmittance of the powders 1-4 is sequentially decreased, wherein the chromaticity of the powders 1-4 is Based on the Lab color system, the above powder is solidified under a preset condition and measured by a color difference meter or a spectrophotometer.
  • the light transmittance is measured by a light transmittance tester after the powder is cured under a predetermined condition and the test light wavelength is 550 nm.
  • the powder 1 is added to the mold as the first layer, after the flattening, the powder 2 is added, and the powder 2 is used as the second layer, and after flattening, the powder 4 is added, and the powder 4 is taken as the third layer.
  • the processing temperature is 115 ° C
  • the pressure is 160 MPa
  • the holding time is 0.5 h
  • the three-layer light transmittance and color gradient can be prepared.
  • the chromaticity difference between the first layer and the third layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The chromaticity difference between 1 is 1 or more and 11 or less, and the chromaticity difference between the first layer and the third layer - (the chromaticity difference between the first layer and the second layer + the second layer and the third layer The difference in chromaticity)
  • the light transmittance and the color gradient of the dental material prepared by using the above three powders have a light transmittance of the first layer greater than that of the second layer; the light transmittance of the second layer is greater than the transmittance of the third layer
  • the color from the first layer to the third layer is deepened in turn.
  • the powder 3 and the powder 4 in Table 1 three kinds of composite resin material precursor powders were prepared. Then, the powder 4 is added to the mold as the first layer, after the flattening, the powder 3 is added, and the powder 3 is used as the second layer, and after flattening, the powder 1 is added, and the powder 1 is taken as the third layer. a layer in which the thickness of the powder 1 is 3 mm, the thickness of the powder 3 is 7 mm, and the thickness of the powder 4 is 4 mm, and then dry-pressed under a pressure of 10 MPa to obtain a dental material preform having a light transmittance and a color gradient. Blank body.
  • the dental material preform body with light transmittance and color gradation is subjected to heat curing treatment, and the treatment temperature is 131 ° C, the pressure is 250 MPa, and the heat preservation time is 3 hours, thereby preparing a dental having three layers of light transmittance and color gradation. material.
  • the chromaticity difference between the first layer and the third layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The chromaticity difference between 1 is 1 or more and 11 or less, and the chromaticity difference between the first layer and the third layer - (the chromaticity difference between the first layer and the second layer + the second layer and the third layer The difference in chromaticity)
  • the light transmittance and the color gradient of the dental material prepared by using the above three powders have a light transmittance of the third layer greater than that of the second layer; the light transmittance of the second layer is greater than the transmittance of the first layer
  • the color from the third layer to the first layer is deepened in turn.
  • the third layer corresponds to the portion of the cut end of the tooth, and the first layer corresponds to the neck of the tooth.
  • the powder 4 is added, and the powder 4 is used as the fourth layer, wherein the thickness of the powder 1 is 4 mm, the thickness of the powder 2 is 4 mm, the thickness of the powder 3 is 3 mm, and the powder 4
  • the thickness of the film is 3 mm, and then dry-pressed under a pressure of 20 MPa to obtain a dental material preform having a light transmittance and a color gradient.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 185 ° C, a pressure of 300 MPa, and a holding time of 4 hours, thereby preparing a four-layer light transmittance and a color gradation.
  • Dental materials are subjected to heat curing treatment at a treatment temperature of 185 ° C, a pressure of 300 MPa, and a holding time of 4 hours, thereby preparing a four-layer light transmittance and a color gradation.
  • the chromaticity difference between the first layer and the third layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The difference in chromaticity is 1 or more and 11 or less, and the chromaticity difference between the third layer and the fourth layer is 1 or more and 11 or less; and
  • the light transmittance and color grading dental material prepared by the above four kinds of powders have a light transmittance of the first layer greater than that of the second layer; the light transmittance of the second layer is greater than the light transmittance of the third layer; The light transmittance of the third layer is greater than the light transmittance of the fourth layer, and the color from the first layer to the fourth layer is sequentially deepened.
  • the first layer corresponds to the cut end of the tooth and the fourth layer corresponds to the neck of the tooth.
  • dental materials having light transmittance and color gradation can also be obtained by the method as shown in Examples 4-6.
  • the four molds of 1#-4# are used, the four molds have the same shape, and the 4# mold volume>3# mold volume>2# mold volume>1# mold volume .
  • the powder 4 is placed in a 1# mold, and dry pressing is performed under a pressure of 4 MPa to obtain a first green body; then the powder 2 is placed in a 2# mold, and the first green body is placed in 2#.
  • the powder 2 is wrapped with the first body while the first body is located in the middle of the powder 2, and is dry-formed under a pressure of 4 MPa to obtain a second body; then the powder 1 is placed in 4
  • the second blank is placed in the 4# mold, so that the powder 1 wraps the second green body while the second green body is located in the middle of the powder 1, and is dry-formed under a pressure of 4 MPa.
  • Dental material preforms with light transmittance and color gradation.
  • the dental material preform of the light transmittance and the color gradation is thermally cured at a treatment temperature of 115 ° C, a pressure of 160 MPa, and a holding time of 0.5 h, thereby preparing a three-layer light transmittance and a color gradient.
  • Dental materials are thermally cured at a treatment temperature of 115 ° C, a pressure of 160 MPa, and a holding time of 0.5 h, thereby preparing a three-layer light transmittance and a color gradient.
  • the powder 1 is the outermost layer
  • the powder 2 is the outer layer
  • the powder 4 is the innermost layer, wherein the outermost layer and the innermost layer.
  • the chromaticity difference between the layers is 2 or more and 15 or less; the chromaticity difference between the outermost layer and the second outer layer is 1 or more and 11 or less; the chromaticity difference between the sub-outer layer and the innermost layer is 1 or more And 11 or less, and the chromaticity difference between the outermost layer and the innermost layer - (the difference in chromaticity between the outermost layer and the outer layer + the difference in chromaticity between the outer layer and the innermost layer)
  • the light transmittance and the color-graded dental material prepared in Example 4 of the present application have a light transmittance decreasing from the outermost layer to the innermost layer in turn; the color is sequentially deepened from the outermost layer to the innermost layer.
  • the powder 3 and the powder 4 in Table 1 three kinds of composite resin material precursor powders were prepared.
  • the powder 4 is placed in a 1# mold, and dry pressing is performed under a pressure of 10 MPa to obtain a first green body; then the powder 3 is placed in a 3# mold, and the first green body is placed in a 3# mold.
  • the powder 3 is wrapped in the first body while the first body is located in the middle of the powder 3, and is dry-formed under a pressure of 10 MPa to obtain a second body, and then the powder 1 is placed in 4#.
  • the second blank is placed in the 4# mold, so that the powder 1 wraps the second blank while the second blank is located in the middle of the powder 1, and is dry-formed under a pressure of 10 MPa.
  • Dental material preforms with light rate and color gradients.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 131 ° C, a pressure of 250 MPa, and a holding time of 3 h, thereby preparing a three-layer light transmittance and a color gradation.
  • Dental materials are subjected to heat curing treatment at a treatment temperature of 131 ° C, a pressure of 250 MPa, and a holding time of 3 h, thereby preparing a three-layer light transmittance and a color gradation.
  • the powder 1 serves as the outermost layer
  • the powder 3 serves as the outer layer
  • the powder 4 serves as the innermost layer
  • the outermost layer and the innermost layer
  • the chromaticity difference between the layers is 2 or more and 15 or less
  • the chromaticity difference between the outermost layer and the second outer layer is 1 or more and 11 or less
  • the chromaticity difference between the sub-outer layer and the innermost layer is 1 or more And 11 or less
  • the light transmittance is sequentially decreased from the outermost layer to the innermost layer; the color is sequentially deepened from the outermost layer to the innermost layer.
  • the powder 3 is wrapped in the first body while the first body is located in the middle of the powder 3, and is dry-formed under a pressure of 20 MPa to obtain a second body; then the powder 2 is placed in the 3# In the mold, the second blank is placed in the 3# mold, so that the powder 2 wraps the second blank while the second blank is located in the middle of the powder 2, and is dry-formed under a pressure of 20 MPa to obtain the first Three blanks, then the powder 1 is placed in the 4# mold, and the third blank is placed in the 4# mold, so that the powder 1 wraps the third blank while the third blank is located in the middle of the powder 1. Dry press molding was carried out under a pressure of 20 MPa to obtain a dental material preform body having a light transmittance and a color gradient.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 185 ° C, a pressure of 300 MPa, and a holding time of 4 h, thereby preparing a four-layer light transmittance and a color gradient.
  • Dental materials are subjected to heat curing treatment at a treatment temperature of 185 ° C, a pressure of 300 MPa, and a holding time of 4 h, thereby preparing a four-layer light transmittance and a color gradient.
  • the material after curing of the powder 1 can be referred to as a first layer, and similarly, the material obtained by curing the powder 2 is referred to as a second layer; the material obtained by curing the powder 3 is referred to as a third layer; The cured material is called the fourth layer.
  • the chromaticity difference between the first layer and the fourth layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The difference in chromaticity is 1 or more and 11 or less; the chromaticity difference between the third layer and the fourth layer is 1 or more and 11 or less, and
  • the light transmittance and color grading dental material prepared in Embodiment 6 of the present application have a light transmittance decreasing from the outermost layer to the innermost layer, that is, the light transmittance of the first layer is greater than the light transmittance of the second layer;
  • the light transmittance of the second layer is greater than the light transmittance of the third layer; and
  • the light transmittance of the third layer is greater than the light transmittance of the fourth layer, and the color thereof is sequentially deepened from the outermost layer to the innermost layer.
  • Comparative Example 7 differs from Example 1 in that the heat curing pressure was 13 MPa, and the formulation of Comparative Example 7 and various process parameters were identical to those of Example 1.
  • Comparative Example 8 differs from Example 2 in that the heat curing pressure was 16 MPa, and the formulation of Comparative Example 8 and various process parameters were identical to those of Example 2.
  • Comparative Example 9 differs from Example 3 in that the heat curing pressure was 20 MPa, and the formulation of Comparative Example 9 and various process parameters were identical to those of Example 3.
  • Comparative Example 10 differs from Example 4 in that the heat curing pressure was 130 MPa, and the formulation of Comparative Example 10 and various process parameters were identical to those of Example 4.
  • Comparative Example 11 differs from Example 5 in that the heat curing pressure was 150 MPa, and the formulation of Comparative Example 11 and various process parameters were identical to those of Example 5.
  • test method for flexural strength refers to the standard YY/T 0710-2009/ISO 10477-2004; the test method for compressive strength refers to the ISO 4049:2009 standard; the test method for fracture toughness refers to the ISO6872-2015 standard.
  • Table 3 shows the properties of the dental materials prepared in Examples 1-6 and Comparative Examples 7-12.
  • the flexural strength of Examples 1-3 with respect to Comparative Examples 7-9 increased from less than 213 MPa to more than 248 MPa; the compressive strength increased from 557 MPa to over 581 MPa; the fracture toughness increased from 1.3 MPa to 1.67. More than MPa.
  • the flexural strength, compressive strength and fracture toughness of the light transmittance and color grading dental materials prepared by using the examples of the present application are greatly improved, thereby improving the wear resistance of the material.
  • the flexural strength of Examples 4-6 with respect to Comparative Examples 10-11 was increased from less than 223 MPa to more than 252 MPa; the compressive strength was increased from 566 MPa to over 593 MPa; and the fracture toughness was increased from 1.58 MPa to 1.76 MPa or more.
  • the flexural strength, compressive strength and fracture toughness of the light transmittance and color grading dental materials prepared by using the examples of the present application are greatly improved, thereby improving the wear resistance of the material.
  • the weight ratio of the filler to the resin monomer is 31:69-69:31, preferably 43:57-62:38, and the weight of the initiator is a resin single. 0.1 to 3% by weight, preferably 0.1 to 2% by weight, the weight of the colorant is 0.001 to 0.2% by weight based on the total weight of the resin monomer and the filler, preferably 0.002 to 0.1%; and the pressure for dry compression molding is 11 to 19 MPa, preferably
  • the heat curing treatment condition is a temperature of 151-169 ° C, preferably 155-165 ° C, a pressure of 210-300 MPa, preferably 240-290 MPa, and a holding time of 1.1-1.8 h, preferably 1.6. -1.8h.
  • Table 4 shows the formulation and process parameters of four kinds of composite resin material precursor powders with different light transmittance.
  • the values corresponding to the resin monomer, filler, initiator and colorant in Table 4 are parts by weight, and each part by weight may be 100 g.
  • Table 5 shows the chromaticity values and light transmittance of the powders 5-8 based on the Lab color system.
  • the chromaticity values and the light transmittances of the powders 5-8 are shown in Table 5.
  • the light transmittance of the powders 5-8 is sequentially decreased, wherein the chromaticity of the powders 5-8 is Based on the Lab color system, the above powder is solidified under a preset condition and measured by a color difference meter or a spectrophotometer.
  • the light transmittance is measured by a light transmittance tester after the powder is cured under a predetermined condition and the test light wavelength is 550 nm.
  • three different colors of powder 5, powder 6 and powder 8 can be prepared by mixing the raw materials. Then, the powder 5 is added to the mold as the first layer, after the flattening, the powder 6 is added, and the powder 6 is used as the second layer, and after flattening, the powder 8 is added, and the powder 8 is taken as the third layer. a layer in which the thickness of the powder 5 is 4 mm, the thickness of the powder 6 is 6 mm, and the thickness of the powder 8 is 4 mm, and then dry-pressed under a pressure of 11 MPa to obtain a dental material preform having a light transmittance and a color gradient.
  • the treatment temperature is 155 ° C
  • the pressure is 210 MPa
  • the holding time is 1.1 h, which can be prepared with three layers of light transmittance and color.
  • Gradient dental material
  • the chromaticity difference between the first layer and the third layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The chromaticity difference between 1 is 1 or more and 11 or less, and the chromaticity difference between the first layer and the third layer - (the chromaticity difference between the first layer and the second layer + the second layer and the third layer The difference in chromaticity)
  • the light transmittance and the color gradient of the dental material prepared by using the above three powders have a light transmittance of the first layer greater than that of the second layer; the light transmittance of the second layer is greater than the transmittance of the third layer The color gradually deepens from the first layer to the third layer.
  • the first layer corresponds to the portion of the cut end of the tooth
  • the third layer corresponds to the neck of the tooth.
  • the powder 7 and the powder 8 in Table 4 three kinds of composite resin material precursor powders were prepared. Then, the powder 8 is added to the mold as the first layer, after the flattening, the powder 7 is added, and the powder 7 is used as the second layer, and after flattening, the powder 5 is added, and the powder 5 is taken as the third layer. a layer in which the thickness of the powder 5 is 3 mm, the thickness of the powder 7 is 7 mm, and the thickness of the powder 8 is 4 mm, and then dry-pressed under a pressure of 16 MPa to obtain a dental material preform having a light transmittance and a color gradient. Blank body.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 165 ° C, a pressure of 240 MPa, and a holding time of 1.6 h, thereby preparing a three-layer light transmittance and a color gradient.
  • Dental materials are subjected to heat curing treatment at a treatment temperature of 165 ° C, a pressure of 240 MPa, and a holding time of 1.6 h, thereby preparing a three-layer light transmittance and a color gradient.
  • the chromaticity difference between the first layer and the third layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The chromaticity difference between 1 is 1 or more and 11 or less, and the chromaticity difference between the first layer and the third layer - (the chromaticity difference between the first layer and the second layer + the second layer and the third layer The difference in chromaticity)
  • the light transmittance and the color gradient of the dental material prepared by using the above three powders have a transmittance of the third layer greater than that of the second layer; the transmittance of the second layer is greater than the transmittance of the first layer From the third layer to the first layer, the color gradually deepens.
  • the third layer corresponds to the portion of the cut end of the tooth, and the first layer corresponds to the neck of the tooth.
  • Powder 5 is added to the mold as the first layer, after the flattening, powder 6 is added, and powder 6 is used as the second layer, after flattening, powder 7 is added, and powder 7 is used as the third layer.
  • the powder 8 is added, and the powder 8 is used as the fourth layer, wherein the thickness of the powder 5 is 4 mm, the thickness of the powder 6 is 4 mm, the thickness of the powder 7 is 3 mm, and the powder 8 is The thickness was 3 mm and then dry-pressed under a pressure of 19 MPa to obtain a dental material preform having a light transmittance and a color gradient.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 169 ° C, a pressure of 290 MPa, and a holding time of 1.8 h, thereby preparing a four-layer translucent transmittance and Dental material with a gradient of color.
  • the chromaticity difference between the first layer and the third layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The difference in chromaticity is 1 or more and 11 or less, and the chromaticity difference between the third layer and the fourth layer is 1 or more and 11 or less; and
  • the light transmittance and the color gradient of the dental material prepared by using the above four powders the light transmittance of the first layer is greater than the light transmittance of the second layer; the light transmittance of the second layer is greater than the light transmittance of the third layer; The transmittance of the third layer is greater than the transmittance of the fourth layer, and the color from the first layer to the fourth layer is gradually deepened.
  • the first layer corresponds to the portion of the cut end of the tooth and the fourth layer corresponds to the neck of the tooth.
  • dental materials having light transmittance and color gradation can also be obtained by the method as shown in Examples 15-17.
  • the powder 6 and the powder 8 in Table 4 three kinds of composite resin material precursor powders were prepared.
  • the powder 8 is placed in a 1# mold, and dry pressing is performed under a pressure of 11 MPa to obtain a first green body; then the powder 6 is placed in a 2# mold, and the first green body is placed in 2#.
  • the powder 6 is wrapped around the first body while the first body is located in the middle of the powder 6, and is dry-formed under a pressure of 11 MPa to obtain a second body; then the powder 5 is placed in 4
  • the second blank is placed in the 4# mold, and the powder 5 is wrapped around the second green body while the second green body is placed in the middle of the powder 5, and dry pressing is performed under a pressure of 11 MPa.
  • Dental material preforms with light transmittance and color gradation.
  • the dental material preform of the light transmittance and the color gradation is thermally cured at a treatment temperature of 155 ° C, a pressure of 210 MPa, and a holding time of 1.1 h, thereby preparing a three-layer light transmittance and a color gradient.
  • Dental materials are thermally cured at a treatment temperature of 155 ° C, a pressure of 210 MPa, and a holding time of 1.1 h, thereby preparing a three-layer light transmittance and a color gradient.
  • the powder 5 serves as the outermost layer
  • the powder 6 serves as the outer layer
  • the powder 8 serves as the innermost layer, wherein the outermost layer and the innermost layer
  • the chromaticity difference between the layers is 2 or more and 15 or less
  • the chromaticity difference between the outermost layer and the second outer layer is 1 or more and 11 or less
  • the chromaticity difference between the sub-outer layer and the innermost layer is 1 or more And 11 or less
  • the chromaticity difference between the outermost layer and the innermost layer - (the difference in chromaticity between the outermost layer and the outer layer + the difference in chromaticity between the outer layer and the innermost layer)
  • the light transmittance and color grading dental materials prepared in Example 15 of the present application the light transmittance is sequentially decreased from the outermost layer to the innermost layer; the color is sequentially deepened from the outermost layer to the innermost layer.
  • the powder 7 and the powder 8 in Table 4 three kinds of composite resin material precursor powders were prepared.
  • the powder 8 is placed in a 1# mold, and dry press molding is performed under a pressure of 11 MPa to obtain a first green body; then the powder 7 is placed in a 3# mold, and the first green body is placed in a 3# mold.
  • the powder 7 is wrapped in the first body while the first body is located in the middle of the powder 7, and is dry-formed under a pressure of 11 MPa to obtain a second body, and then the powder 5 is placed in 4#.
  • the second blank is placed in the 4# mold, so that the powder 5 wraps the second blank while the second blank is located in the middle of the powder 5, and is dry-formed under a pressure of 11 MPa.
  • Dental material preforms with light rate and color gradients.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 165 ° C, a pressure of 240 MPa, and a holding time of 1.6 h, thereby preparing a three-layer light transmittance and a color gradient.
  • Dental materials are subjected to heat curing treatment at a treatment temperature of 165 ° C, a pressure of 240 MPa, and a holding time of 1.6 h, thereby preparing a three-layer light transmittance and a color gradient.
  • the powder 5 serves as the outermost layer
  • the powder 7 serves as the outer layer
  • the powder 8 serves as the innermost layer
  • the outermost layer and the innermost layer The chromaticity difference between the layers is 2 or more and 15 or less; the chromaticity difference between the outermost layer and the second outer layer is 1 or more and 11 or less; the chromaticity difference between the sub-outer layer and the innermost layer is 1 or more And 11 or less, and the chromaticity difference between the outermost layer and the innermost layer - (the difference in chromaticity between the outermost layer and the outer layer + the difference in chromaticity between the outer layer and the innermost layer)
  • the light transmittance is sequentially decreased from the outermost layer to the innermost layer; the color is sequentially deepened from the outermost layer to the innermost layer.
  • the powder 8 is dry-formed in a 1# mold under a pressure of 11 MPa to obtain a first green body; then the powder 7 is placed in a 2# mold, and the first green body is placed in a 2# mold. , the powder 7 is wrapped in the first body while the first body is located in the middle of the powder 7, and is dry-formed under a pressure of 11 MPa to obtain a second body; then the powder 6 is placed in the 3# mold.
  • the second blank is placed in the 3# mold, so that the powder 6 wraps the second blank while the second blank is located in the middle of the powder 6, and is dry-formed under a pressure of 11 MPa to obtain a third
  • the green body, the powder 5 is placed in the 4# mold, and the third blank is placed in the 4# mold, so that the powder 5 wraps the third blank while the third blank is located in the middle of the powder 5.
  • Dry press molding was carried out under a pressure of 11 MPa to obtain a dental material preform having a light transmittance and a color gradation.
  • the dental material preform body having the light transmittance and the color gradation is subjected to heat curing treatment at a treatment temperature of 169 ° C, a pressure of 290 MPa, and a holding time of 1.8 h, thereby preparing four layers of light transmittance and color. Gradient dental material.
  • the material after the powder 5 is solidified may be referred to as a first layer, and similarly, the material obtained by curing the powder 6 is referred to as a second layer; the material obtained by curing the powder 7 is referred to as a third layer; The cured material is called the fourth layer.
  • the chromaticity difference between the first layer and the fourth layer is 2 or more and 15 or less; the chromaticity difference between the first layer and the second layer is 1 or more and 11 or less; the second layer and the third layer The difference in chromaticity is 1 or more and 11 or less; the chromaticity difference between the third layer and the fourth layer is 1 or more and 11 or less, and
  • the light transmittance and color grading dental material prepared in the embodiment 17 of the present application is sequentially decreased from the outermost layer to the innermost layer, that is, the light transmittance of the first layer is greater than the light transmittance of the second layer;
  • the light transmittance of the second layer is greater than the light transmittance of the third layer;
  • the light transmittance of the third layer is greater than the light transmittance of the fourth layer; the color is sequentially deepened from the outermost layer to the innermost layer.
  • Comparative Example 18 differs from Example 12 in that the heat curing pressure was 13 MPa, and the formulation of Comparative Example 18 and various process parameters were identical to those of Example 12.
  • Comparative Example 19 differs from Example 13 in that the heat curing pressure was 16 MPa, and the formulation of Comparative Example 19 and various process parameters were identical to those of Example 13.
  • Comparative Example 20 differs from Example 14 in that the heat curing pressure was 20 MPa, and the formulation of Comparative Example 20 and various process parameters were identical to those of Example 14.
  • Comparative Example 21 differs from Example 15 in that the heat curing pressure was 130 MPa, and the formulation of Comparative Example 21 and various process parameters were identical to those of Example 15.
  • Comparative Example 22 differs from Example 16 in that the heat curing pressure was 150 MPa, and the formulation of Comparative Example 22 and various process parameters were identical to those of Example 16.
  • test method for flexural strength refers to the standard YY/T 0710-2009/ISO 10477-2004; the test method for compressive strength refers to the ISO 4049:2009 standard; the test method for fracture toughness refers to the ISO6872-2015 standard.
  • Table 6 shows the properties of light transmittance and color graded dental materials prepared in Examples 12-17 and Comparative Examples 18-22.
  • the flexural strength of Examples 12-14 relative to Comparative Examples 18-20 increased from less than 218 MPa to more than 250 MPa; the compressive strength increased from 549 MPa to over 591 MPa; and the fracture toughness increased from 1.28 MPa to 1.72. More than MPa.
  • the flexural strength, compressive strength and fracture toughness of the light transmittance and color grading dental materials prepared by using the examples of the present application are greatly improved, thereby improving the wear resistance of the material.
  • the flexural strength of Examples 15-17 relative to Comparative Examples 21-22 increased from less than 220 MPa to more than 257 MPa; the compressive strength increased from 553 MPa to over 596 MPa; and the fracture toughness increased from 1.35 MPa to 1.78 MPa or more.
  • the flexural strength, compressive strength and fracture toughness of the light transmittance and color grading dental materials prepared by using the examples of the present application are greatly improved, thereby improving the wear resistance of the material.

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Abstract

一种透光率和颜色渐变的牙科材料的制备方法及其制备的产品，方法包括：(1)、制备至少三种不同透光率的复合树脂材料前驱粉体(2)、按照透光率从低到高的顺序，或从高到低的顺序，依次将前驱粉体加入到模具中，干压成型得到预成型坯体；或(2')，将第一种前驱粉体干压成型为第一坯体；将第一坯体包裹于第二前驱粉体中，干压成型得到第二坯体；重复进行包裹、干压成型操作，直至将所有前驱粉体干压成型后，得到预成型坯体；(3)、将步骤(2)或者步骤(2')所制备的预成型坯体进行热压固化处理，得到透光率和颜色渐变的牙科材料。应用本申请可以提高修复体的挠曲强度，还可以更好模拟天然牙切端和颈部的美学特征。

Description

透光率和颜色渐变的牙科材料的制备方法及其制备的产品
本申请要求于2017年9月30日提交中国专利局、申请号为201710923133.X发明名称为“透光率和颜色渐变的牙科材料的制备方法及其制备的产品”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及牙科修复技术领域，特别是涉及一种透光率和颜色渐变的牙科材料的制备方法及其制备的产品。
背景技术
随着牙科技术的进步，CAD/CAM技术也被用到了牙科技术领域。牙科椅旁CAD/CAM技术，就是将计算机辅助设计和计算机辅助制作设备放在牙科椅旁，医生在完成牙体预备等治疗之后，采用数码技术获取病人的牙齿模型，由计算机进行数据分析、牙齿设计、假牙(修复体)制造的技术。采用牙科椅旁诊疗技术可一次完成修复体制作，无需临时修复体，减少了病人就诊次数，可以明显提高修复体的精密度和准确性，提高修复治疗的成功率；有效降低传统烤瓷牙和活动假牙的牙龈变色、边缘不密合等问题，显著提高病人的治疗效果满意度。牙科椅旁CAD/CAM的发展也带动了配套材料的进步，目前，常用的复合材料主要包括：复合树脂材料、树脂渗透陶瓷复合材料、聚醚醚酮(PEEK)材料等。通过CAD/CAM技术，利用复合树脂材料制作的修复体能够满足牙科领域对修复体精密制造以及效率的要求。但是，由于现有的复合树脂材料都是单色且单透光率的材料，因此，制作出来的修复体整体的颜色和透光率是一样的。而对于天然牙齿的美学效果来说，这显然是不够的。天然牙齿由牙釉质和牙本质组成，两种组织的来源和特征完全不同，具有各自独特的光学特性。牙本质构成牙的本体，具有光阻射性，牙釉质覆盖牙本质之上，具有半透明性和光透视性，这就导致天然牙齿的透光率和颜色由牙齿颈部至切端是渐变的。由单一美学效果的复合树脂材料制作的修复体与天然牙齿相比，存在透光率和颜色相似度不高的缺点。
目前，深圳爱尔创口腔技术有限公司在中国境内申请了CAD/CAM用聚合物材料相关专利(申请号:CN105362084A：一种牙科用多层色复合材料及其制备方法)，该专利可以制备多层色复合树脂材料。多层复合树脂材料包含有至少三层的不同颜色的复合树脂材料，即相同种类透光率的复合树脂材料，各层的复合树脂材料相互叠加后，且各层复合树脂材料从最下一层到最上一层的颜色依次变化，进而模仿天然牙齿的颜色，但是未能体现出天然牙透光率渐变的特点；此外，现有的多层色复合树脂材料存在强度较低的缺点。
发明内容
有鉴于此，本申请的目的在于提供一种透光率和颜色渐变的牙科材料的制备方法及其制备的产品，以实现提高复合树脂材料的美学效果和强度的目的。具体技术方案如下：
本申请提供了一种透光率和颜色渐变的牙科材料的制备方法，所述方法包括：
(1)、制备至少三种不同透光率的复合树脂材料前驱粉体，其中，每一种复合树脂材料前驱粉体的制备过程包括：称取原料，所述原料包括树脂单体、填料、引发剂及着色剂，将原料混合后得到复合树脂材料前驱粉体，其中，填料与树脂单体的重量比为10:90-90:10，优选为70:30-85:15，引发剂重量为树脂单体重量的0.1-3％，优选为0.1-2％，着色剂重量为树脂单体和填料总重量的0.001-0.2％，优选为0.002-0.1％；所述树脂单体包括烯键式不饱和单体和\或环氧树脂；
(2)、按照透光率从低到高的顺序，或从高到低的顺序，依次将所述至少三种不同透光率的复合树脂材料前驱粉体加入到模具中，在3-20MPa，优选为4-10MPa的压力下，干压成型，得到透光率和颜色渐变的牙科材料预成型坯体；其中，在将每一种复合树脂材料前驱粉体加入到模具中后，将该前驱粉体的上表面平整至平坦；
或
(2′)，将所述至少三种不同透光率的复合树脂材料前驱粉体中，第一种复合树脂材料前驱粉体在3-20MPa，优选为4-10MPa的压力下干压成型，得 到第一坯体；将所述第一坯体包裹于所述至少三种不同透光率的复合树脂材料前驱粉体中的第二种复合树脂材料前驱粉体中，在3-20MPa，优选为4-10MPa的压力下干压成型，得到第二坯体；重复进行包裹、干压成型操作，直至将所述至少三种复合树脂材料前驱粉体干压成型后，得到透光率和颜色渐变的牙科材料预成型坯体，其中，所述透光率和颜色渐变的牙科材料预成型坯体中各层前驱粉体从内到外的透光率依次升高；
(3)、将步骤(2)或者步骤(2′)所制备的透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，得到透光率和颜色渐变的牙科材料，其中，热固化处理条件为，温度为115-185℃，优选为131-171℃，压力大于160MPa，优选为160-300MPa，更优选为200-250MPa，保温时间为0.5-4h，优选为0.5-3h。
可选的，所述透光率和颜色渐变的牙科材料还具有多层色，相邻两层的复合树脂材料之间，基于Lab表色系的色度差大于等于1，且小于等于11；
所述透光率和颜色渐变的牙科材料中不相邻各层的复合树脂材料之间，基于Lab表色系的色度差的最大值大于等于2，且小于等于15；
所述透光率和颜色渐变的牙科材料中所有相邻各层复合树脂材料之间的色度差的和，与所述透光率和颜色渐变的牙科材料中色度最高的一层复合树脂材料与色度最低的一层复合树脂材料之间的色度差之差不大于2；
其中，
基于Lab表色系的色度差的计算公式为，
Figure PCTCN2018087109-appb-000001
且，ΔE为色度差；ΔL为两层间的L值之差；Δa为两层间的a值之差；Δb为两层间的b值之差。
可选的，所述透光率和颜色渐变的牙科材料还具有多层透光率，相邻两层的透光率和颜色渐变的牙科材料之间的透光率的差为0.5-10％；不相邻两层复合树脂材料之间的透光率的差为1-15％；且透光率最高的一层复合树脂材料的可见光(波长为550nm)透光率为50-75％，透光率最低的一层复合树脂材料的透光率为30-60％，所述透光率最高的一层复合树脂材料与所述透光率最低的一层复合树脂材料之间的其他各层复合树脂材料的透光率为40-70％。
可选的，所述填料与树脂单体的重量比为31:69-69:31，优选为43:57-62:38， 引发剂重量为树脂单体重量的0.1-3％，优选为0.1-2％，着色剂重量为树脂单体和填料总重量的0.001-0.2％，优选为0.002-0.1％；
所述热固化处理条件为，温度为115-169℃，优选为155-165℃，压力为210-300MPa，优选为240-290MPa，保温时间为1.1-1.8h，优选为1.6-1.8h。
可选的，所述将原料混合后得到复合树脂材料前驱粉体，包括：
将原料与球磨助剂混合，利用球磨法制备复合树脂材料前驱粉体，其中，原料:研磨球:球磨助剂的质量比为(1:1:1)-(3:6:2)，优选为2:4:1，球磨时间为0.5-2h。
可选的，所述填料的粒度范围为不大于2.5μm，优选为不大于2μm，更优选为0.05-2μm；所述填料的折射率为1.40-1.7，优选为1.45-1.6。
可选的，所述原料还包括阻聚剂，所述阻聚剂占所述树脂单体总重量的0.1-3％，优选为0.2-2％。
可选的，所述原料还包括促进剂，所述促进剂占所述树脂单体总重量的0.1-3％，优选为0.2-2％。
可选的，所述原料还包括赋予荧光的试剂、指示剂、抑制剂、加速剂、粘度调节剂、润湿剂、抗氧化剂、表面活性剂、稳定剂及稀释剂中的至少一种。
可选的，所述填料还可以包括纳米粒子，其中，所述纳米粒子占所述填料重量的1-25％，优选为1-15％；所述纳米粒子的平均直径为35-100nm，优选为40-50nm。
可选的，所述原料还包括增强纤维，所述增强纤维为所述填料重量的1-30％，优选为1-10％；所述增强纤维的直径为0.1-25μm，优选为0.5-10μm；所述增强纤维的长度为0.001-1mm，优选为0.1-0.5mm；所述增强纤维的折射率为1.4-1.7，优选为1.45-1.6；所述增强纤维包含玻璃纤维、石英纤维、硅质纤维、陶瓷纤维及聚合物纤维中的一种或其组合，所述聚合物纤维优选为聚乙烯纤维。
可选的，所述将原料混合后得到复合树脂材料前驱粉体，包括：
将除增强纤维以外的树脂单体、填料、引发剂及着色剂混合后进行球磨混料，得到原料混合物，其中，原料:研磨球:球磨助剂的质量比为1:1:1-3:6:2，优选为2:4:1，球磨时间为0.5-2h；
将所述原料混合物与所述增强纤维混合，得到复合树脂材料前驱粉体。
可选的，所述着色剂包含红色着色剂、黄色着色剂及黑色着色剂中的一种或其组合，其中，所述红色着色剂占所述原料重量的0.001-0.06％，优选为氧化铁红；所述黄色着色剂占所述原料重量的0.001-0.04％，包含氧化铁黄、铋黄、钒锆黄及铈镨黄中的一种或其组合；所述黑色着色剂占所述原料重量的0-0.03％，优选为氧化铁黑。
本申请还提供了一种由上述方法制备的透光率和颜色渐变的牙科材料。
应用本申请提供的方法制备的透光率和颜色渐变的牙科材料，可以具有以下有益效果：
(1)、本申请提供的方法制备的透光率和颜色渐变的牙科材料，具有极高的挠曲强度，经实验测定，挠曲强度达到了248MPa以上。
(2)、本申请提供的方法制备的透光率和颜色渐变的牙科材料，具有极高的压缩强度，经实验测定，压缩强度达到了581MPa以上。
(3)、本申请提供的方法制备的透光率和颜色渐变的牙科材料，可以有效提高修复体的美学效果，使得在高度方向上颜色和透明度渐变，更好模拟天然牙的切端和颈部的美学特征。
当然，实施本申请的任一产品或方法必不一定需要同时达到以上所述的所有优点。
具体实施方式
本申请实施例提供了一种透光率和颜色渐变的牙科材料的制备方法，包括：
(1)、制备至少三种不同透光率的复合树脂材料前驱粉体，其中，每一种复合树脂材料前驱粉体的制备过程包括：称取原料，所述原料包括树脂单体、填料、引发剂及着色剂，将原料混合后得到复合树脂材料前驱粉体，其 中，树脂单体与填料的重量比为10:90-90:10，优选为70:30-85:15，引发剂重量为树脂单体重量的0.1-3％，优选为0.1-2％，着色剂重量为树脂单体和填料总重量的0.001-0.2％，优选为0.002-0.1％；所述树脂单体包括烯键式不饱和单体和\或环氧树脂。
在实际应用中，树脂单体可以选用可聚合的、具有或不具有酸官能团的烯键式不饱和单体，如丙烯酸酯、甲基丙烯酸酯、羟基官能化的丙烯酸酯、羟基官能化的甲基丙烯酸酯中的一种或其组合。
树脂单体也可以使用包含除甲基丙烯酸酯之外的可聚合树脂化的单体，如环氧树脂，如聚乙二醇二甲基丙烯酸酯(PEGDMA)、双酚A-二甲基丙烯酸缩水甘油酯(Bis-GMA)、氨基甲酸酯二甲基丙烯酸酯(UDMA)、三乙二醇二甲基丙烯酸酯(TEGDMA)、乙氧基双酚A二甲基丙烯酸酯(Bis-EMA6)、甲基丙烯酸羟乙酯(HEMA)、双酚A环氧树脂(环氧树脂E-44)中的一种或其组合。在本申请实施例中使用的上述材料的折射率接近天然牙齿，可以提高制备的牙科材料的美学效果。
需要说明的是，树脂单体还可以为烯键式不饱和单体和环氧树脂的混合物。通常情况下，环氧树脂可以为烯键式不饱和单体重量的5-30％。
例如，可以按照以下配方获得树脂单体，
Bis-GMA:0-70％，优选为0-30％；
UDMA:10-70％，优选为40-60％；
Bis-EMA6:0-50％，优选为0-30％；
环氧树脂E-44：0-40％，优选为0-20％；
TEGDMA:10-60％，优选为20-40％；
HEMA：0-50％，优选为0-20％。
在本申请的一种具体实施方式中，所述填料的粒度范围为不大于2.5μm，优选为不大于2μm，更优选为0.05-2μm；所述填料的折射率为1.40-1.7，优选为1.45-1.6。
在实际应用中，填料还可以具有一定的粒度级配，例如填料中的一部分的粒度范围为0.1-1μm，另一部分填料的粒度范围为小于0.1μm。使填料具有一定的粒度级配可以使透光率和颜色渐变的牙科材料具有更好的抛光性和耐磨性。
可以理解的是，不同粒度范围的填料之间的比例可以根据实际情况进行确定，本申请实施例在此不对其进行限定。填料可以是无机材料，包含但不限于：石英粉体、钡玻璃粉体、镧玻璃粉体、硼硅酸盐玻璃粉体、氧化硅-氧化锆复合粉体、氧化硅-氧化镱复合粉体、纳米氧化硅粉体、纳米氧化锆粉体、纳米氧化钛粉体。填料还可以为有机填料，包括但不限于填充无机材料的聚碳酸酯粉体、聚环氧化物粉体、聚合的甲基丙烯酸类树脂粉体；和未填充无机材料的聚碳酸酯粉体、聚环氧化物粉体、聚合的甲基丙烯酸类树脂粉体。
引发剂包括但不仅限于二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧乙酸叔丁酯、过氧化苯甲酸叔丁酯中的一种或它们的组合。
在本申请的具体实施方式中，为了提高填料与聚合单体之间的结合强度，在与其他原料混合之前，采用偶联剂对所述填料进行表面改性处理。可以使用的偶联剂包括但不仅限于γ-甲基丙烯酰氧丙基三甲氧基硅烷KH-570，γ-巯丙基三乙氧基硅烷KH-580，γ-氨丙基三甲氧基硅烷JH-A111等。使用偶联剂对填料的表面进行处理，可以增强填料颗粒与聚合单体，例如烯键式不饱和单体之间的键合强度，进而提高了修复体的硬度。
在本申请的一种具体实施方式中，所述将原料混合后得到复合树脂材料前驱粉体，包括：将原料与球磨助剂混合，利用球磨法制备复合树脂材料前驱粉体，其中，原料:研磨球:球磨助剂的质量的比为(1:1:1)-(3:6:2)，优选为2:4:1，球磨时间为0.5-2h。
具体的，球磨混料的工艺条件可以为：采用玛瑙或氧化锆研磨球，球磨助剂为易挥发有机物，如甲醇、乙醇、丙酮中的一种或其组合。再将经球磨混料后得到的混合物经旋转蒸发、干燥工序，可以制备出透光率和颜色渐变的复合树脂材料前驱粉体，其中，旋转蒸发时温度为20-100℃，优选30-80℃，进一步优选为45-58℃。干燥时温度为20-100℃，优选30-80℃，进一步优选为45-58℃。
按照上述球磨法制备复合树脂材料前驱粉体，可以使复合树脂材料前驱粉体中的各成份混合的更加均匀，还可以提高制备效率，还可以利于材料的成型。
可以理解的是，可以根据实际需求调节各个复合树脂材料中树脂单体、填料、引发剂及着色剂之间的比例，进而得到不同透光率的复合树脂材料。
(2)、按照透光率从低到高的顺序，或从高到低的顺序，依次将所述至少三种不同透光率的复合树脂材料前驱粉体加入到模具中，在3-20MPa，优选为4-10MPa的压力下，干压成型，得到透光率和颜色渐变的牙科材料预成型坯体；其中，在将一种复合树脂材料前驱粉体加入到模具中后，将该前驱粉体的上表面平整至平坦。
示例性的，有透光率为50-75％的复合树脂材料前驱粉体A；透光率为40-70％的复合树脂材料前驱粉体B；透光率为30-60％的复合树脂材料前驱粉体C，其中，透光率是在测试光线波长为550nm时，利用透光率测试仪测试出来的。
在实际应用中，第一种获得特定透光率的复合树脂材料前驱粉体的方法为：制备多个配方的复合树脂材料前驱粉体，然后将制备的前驱粉体在预设条件下固化，再在测试光线波长为550nm时，利用透光率测试仪测试固化后的多个复合树脂材料前驱粉体的透光率，然后根据需要的透光率选择与该透光率对应的修复体前驱粉体的配方，再根据该配方制备复合树脂材料前驱粉体。第二种是利用经验公式，根据复合树脂材料前驱粉体中各成份的性质和比例，计算出各个复合树脂材料前驱粉体对应的透光率，然后根据需要的透光率选择与该透光率对应的修复体前驱粉体的配方，再根据该配方制备复合树脂材料前驱粉体。上述两种获得特定透光率的复合树脂材料前驱粉体的方法均为现有技术，这里不再赘述。
在具体实施过程中，按照透光率从低到高的顺序，可以将上述复合树脂材料前驱粉体C加入到模具中，将该前驱粉体的上表面平整至平坦；再将上述复合树脂材料前驱粉体B加入到模具中，将该前驱粉体的上表面平整至平坦；再将上述种复合树脂材料前驱粉体A加入到模具中，将该前驱粉体的上表面平整至平坦；在3-20MPa，优选为4-10MPa的压力下，干压成型，得到透光率和 颜色渐变的牙科材料预成型坯体；
或
(2′)，将所述三种不同透光率的单色复合树脂材料前驱粉体中，复合树脂材料前驱粉体C在3-20MPa，优选为4-10MPa的压力下干压成型，得到第一坯体；将所述第一坯体包裹于所述三种不同透光率的复合树脂材料前驱粉体中的复合树脂材料前驱粉体B中，在3-20MPa，优选为4-10MPa的压力下干压成型，得到第二坯体；重复进行包裹、干压成型操作，直至将所述三种复合树脂材料前驱粉体干压成型后，得到透光率和颜色渐变的牙科材料预成型坯体，其中，所述透光率和颜色渐变的牙科材料预成型坯体中各层前驱粉体从内到外的透光率依次升高。
(3)、将步骤(2)或者步骤(2′)所制备的透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，得到透光率和颜色渐变的牙科材料，其中，热固化处理条件为，温度为115-185℃，优选为131-171℃，压力为大于160MPa，优选为160-300MPa，更优选为200-250MPa，保温时间为0.5-4h，优选为0.5-3h。
在本申请的一种具体实施方式中，热固化引发剂为二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧乙酸叔丁酯、过氧化苯甲酸叔丁酯中的一种或其组合。
在本申请的一种具体实施方式中，所述透光率和颜色渐变的牙科材料预成型坯体中相邻两层的复合树脂材料前驱粉体之间，基于Lab表色系的色度差大于等于1，且小于等于11；
所述透光率和颜色渐变的牙科材料预成型坯体中不相邻各层的复合树脂材料之间，基于Lab表色系的色度差的最大值大于等于2，且小于等于15；
所述透光率和颜色渐变的牙科材料中所有相邻各层复合树脂材料之间的色度差的和，与所述透光率和颜色渐变的牙科材料中色度最高的一层复合树脂材料与色度最低的一层复合树脂材料之间的色度差之差不大于2；
其中，
基于Lab表色系的色度差的计算公式为，
Figure PCTCN2018087109-appb-000002
且，ΔE 为色度差；ΔL为两层间的L值之差；Δa为两层间的a值之差；Δb为两层间的b值之差。
在本申请的一种具体实施方式中，所述透光率和颜色渐变的牙科材料还具有多层透光率，相邻两层的透光率和颜色渐变的牙科材料之间的透光率的差为0.5-10％；不相邻两层复合树脂材料之间的透光率的差为1-15％；且透光率最高的一层复合树脂材料的透光率为50-75％，透光率最低的一层复合树脂材料的透光率为30-60％，所述透光率最高的一层复合树脂材料与所述透光率最低的一层复合树脂材料之间的其他各层复合树脂材料的透光率为40-70％。
在实际应用中，具有高半透明性复合树脂材料，可模拟牙齿切端效果；具有中度半透明性的复合树脂材料，属于过渡层，可以是一层，也可以是多层；具有低半透明性的复合树脂材料，可模拟牙齿颈部效果。
具体的，可以如下三种复合树脂材料前驱粉体制备的透光率上下渐变的透光率和颜色渐变的牙科材料为例，对三种复合树脂材料前驱粉体的之间色度差需要满足的条件进行说明。
在本文中，术语“色度差”有时也简称为“色差”。
三种复合树脂材料前驱粉体的色度是基于Lab表色系，利用色差仪或者分光测色仪测量出来的。例如，可以L1，a1，b1标记第一种复合树脂材料前驱粉体的色度；以L2，a2，b2标记第二种复合树脂材料前驱粉体的色度；以L3，a3，b3标记第三种复合树脂材料前驱粉体的色度。
根据上述各种前驱粉体的色度，可以利用公式
Figure PCTCN2018087109-appb-000003
计算出层间色度差ΔE，其中，ΔE为色度差；ΔL为两层间的L值之差；Δa为两层间的a值之差；Δb为两层间的b值之差。
如果将第一种复合树脂材料前驱粉体作为最上层材料，第二种复合树脂材料前驱粉体作为中间过渡层，第三种复合树脂材料前驱粉体作为最下一层材料，且L1≥L2≥L3，a1＜a2＜a3，b1＜b2＜b3；在第一种复合树脂材料前驱粉体、第二种复合树脂材料前驱粉体以及第三种复合树脂材料前驱粉体的L值有下降的趋势，a值和b值有上升的趋势的情况下，可以模拟出自然牙的透光率渐变的特点。
在实际应用中，应将最上层与最下一层之间的色度差为2以上且15以下；最上层与中间过渡层之间的色度差为1以上且11以下；中间过渡层与最下一层之间的色度差为1以上且11以下，且|最上层与最下一层之间的色度差-(中间过渡层与最下一层之间的色度差+最上层与中间过渡层之间的色度差)|≤1。
经过实验发现，第一种复合树脂材料前驱粉体L1的范围为62-80，a1的范围为-2.2-2.2，b1的范围为5-16时，透光率的范围为50-75％。第二种复合树脂材料前驱粉体L2的范围为58-76，a2的范围为-2.0-2.5，b2的范围为8-20时，透光率的范围为40-70％。第三种复合树脂材料前驱粉体L3的范围为53-72，a3的范围为-1.8-2.8，b3的范围为10-24时，透光率的范围为30-60％。
可以理解的是，利用上述三种复合树脂材料前驱粉体制备的透光率和颜色渐变的牙科材料，作为最上层的第一种复合树脂材料前驱粉体的透光率高于作为中间过渡层的第二种复合树脂材料前驱粉体的透光率；且作为中间过渡层的第二种复合树脂材料前驱粉体的透光率高于作为最下一层的第三种复合树脂材料前驱粉体的透光率。
如果制备的修复体是由四种或者四种以上的复合树脂材料前驱粉体制备的，其不相邻各层的之间的色度差为2以上且15以下，且相邻两层之间的色度差为1以上且11以下，同时还需要在修复体的最下一层的透光率最低时，使各层复合树脂材料从最下一层到最上一层的透光率依次升高；或者在修复体的最上一层的透光率最低时，使各层复合树脂材料从最下一层到最上一层的透光率依次降低。
利用具有上述层间色度差的复合树脂材料前驱粉体制备的上下透光率和颜色渐变的牙科材料，可以模拟自然牙的透光率从切端到颈部透光率和颜色渐变的特点，进而使牙科用修复体更加美观。
具体的，还可以上述三种复合树脂材料前驱粉体制备另一种透光率和颜色内外渐变的牙科材料为例，对三种复合树脂材料前驱粉体的之间色度差需要满足的条件进行说明。
以色度值为L1，a1，b1的第一种复合树脂材料前驱粉体作为最外层材料；以色度为L2，a2，b2的第二种复合树脂材料前驱粉体作为次外层材料；以色 度为L3，a3，b3的第三种复合树脂材料前驱粉体作为最内层材料。
在实际应用中，应将最外层与最内层之间的色度差为2以上且15以下；最外层与次外层之间的色度差为1以上且11以下；次外层与最内层之间的色度差为1以上且11以下，且|最外层与最内层之间的色度差-(最外层与次外层之间的色度差+次外层与最内层之间的色度差)|≤1。
可以理解的是，作为最外层的第一种复合树脂材料前驱粉体的透光率高于作为次外层的第二种复合树脂材料前驱粉体的透光率；且作为次外层的第二种复合树脂材料前驱粉体的透光率高于作为最内层的第三种复合树脂材料前驱粉体的透光率。
利用具有上述层间色度差的复合树脂材料前驱粉体制备的内外透光率和颜色渐变的牙科材料，可以模拟自然牙从内到外的透光率渐变的特点，进而使牙科用修复体更加美观。
在本申请的一种具体实施方式中，所述原料还包括阻聚剂，所述阻聚剂占所述树脂单体总重量的0.1-3％，优选为0.2-2％。
在本申请的一种具体实施方式中，阻聚剂包括但不仅限于2,6—二叔丁基对甲苯酚(BHT)和叔丁基对苯二酚(TBHQ)中的一种或它们的组合。
在本申请的一种具体实施方式中，所述原料还包括促进剂，所述促进剂占所述树脂单体总重量的0.1-3％，优选为0.2-2％。
在本申请的一种具体实施方式中，促进剂包括但不仅限于N,N-二甲基对甲苯胺(DMT)，N,N—二羟乙基对甲苯胺(DHET)，4-二甲基氨基苯甲酸乙酯(EDMAB)和N,N-二甲氨基甲基丙烯酸乙酯(DMAEMA)中的一种或多种组合。
在本申请的一种具体实施方式中，所述原料还包括赋予荧光的试剂、指示剂、抑制剂、加速剂、粘度调节剂、润湿剂、抗氧化剂、表面活性剂、稳定剂及稀释剂中的至少一种。例如，赋予荧光的试剂可以为偶氮类荧光颜料、色氨酸或者吡啶类荧光颜料等；指示剂可以为氧化还原指示剂或者磨损指示剂等；抑制剂可以为固化抑制剂等；加速剂可以为光聚合加速剂或者热聚合加速剂等；粘度调节剂可以为石蜡或者聚乙烯蜡等；润湿剂可以为硅烷剂等；抗氧化剂可以为抗坏血酸钠等；表面活性剂可以为辛基酚聚氧乙烯醚、壬基 酚聚氧乙烯醚、高碳脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯或者聚氧乙烯胺等；稳定剂可以为环氧化合物或者季四戊醇等；稀释剂可以为甲基丙烯酸酯等。可以理解的是，上述添加剂仅仅是为了对添加剂的种类加以说明的举例，在实际应用中，可以使用上述举例的种类之外的种类的添加剂，还可以根据实际需求对添加剂的种类进行调整。
在本申请的一种具体实施方式中，所述填料还包括纳米粒子，其中，所述纳米粒子占所述填料重量的1-25％，优选为1-15％；所述纳米粒子的平均直径为35-100nm，优选为40-50nm。
在原料中加入纳米粒子，可以使透光率和颜色渐变的牙科材料具有与天然牙接近的乳光效果。
在本申请的一种具体实施方式中，所述原料还包括增强纤维，所述增强纤维为所述填料重量的1-30％，优选为1-10％；所述增强纤维的直径为0.1-25μm，优选为0.5-10μm；所述增强纤维的长度为0.001-1mm，优选为0.1-0.5mm；所述增强纤维的折射率为1.4-1.7，优选为1.45-1.6；所述增强纤维包含玻璃纤维、石英纤维、硅质纤维、陶瓷纤维及聚合物纤维中的一种或其组合，所述聚合物纤维优选为聚乙烯纤维。
在原料中加入增强纤维，可以提高透光率和颜色渐变的牙科材料的断裂韧性。
在实际应用中，在与其他原料混合之前，对所述增强纤维进行清洗处理和表面改性处理，其中，清洗的方法包括：热处理清洗、溶剂浸泡清洗或酸碱腐蚀清洗；改性处理方法包括：偶联剂改性、等离子体处理改性及化学接枝处理改性。
可以使用偶联剂对增强纤维的表面进行处理。可以使用的偶联剂包括但不仅限于γ-甲基丙烯酰氧丙基三甲氧基硅烷KH-570，γ-巯丙基三乙氧基硅烷KH-580，γ-氨丙基三甲氧基硅烷JH-A111等。使用偶联剂对填料的表面进行处理，可以增增强纤维与烯键式不饱和单体之间的键合强度，进而提高了透光率和颜色渐变的牙科材料的硬度。
对增强纤维进行表面改性处理，可以进一步提高透光率和颜色渐变的牙 科材料的断裂韧性。
对于原料中加入增强纤维的实施方式中，可以先将除增强纤维以外的原料进行球磨混料，得到原料混合物；再将所述原料混合物与所述增强纤维混合，得到复合树脂材料前驱粉体。具体地，在本申请的一种具体实施方式中，所述将原料混合后得到复合树脂材料前驱粉体，包括：
将除增强纤维以外的树脂单体、填料、引发剂及着色剂混合后进行球磨混料，得到原料混合物，其中，原料:研磨球:球磨助剂的质量比为1:1:1-3:6:2，优选为2:4:1，球磨时间为0.5-2h；
将所述原料混合物与所述增强纤维混合，得到复合树脂材料前驱粉体。
在本申请的一种具体实施方式中，所述着色剂包含红色着色剂、黄色着色剂及黑色着色剂中的一种或其组合，其中，所述红色着色剂占所述原料重量的0.001-0.06％，优选为氧化铁红；所述黄色着色剂占所述原料重量的0.001-0.04％，包含氧化铁黄、铋黄、钒锆黄及铈镨黄中的一种或其组合；所述黑色着色剂占所述原料重量的0-0.03％，优选为氧化铁黑。
在实际应用中，着色剂一般为金属氧化物，如氧化铁、氧化锆、氧化钒、以及氧化铈等。另外，可以根据不同的实际需求调节红色着色剂、黄色着色剂及黑色着色剂的比例，从而制备不同颜色的透光率和颜色渐变的牙科材料。
本申请实施例还提供了应用上述任一项方法制备的透光率和颜色渐变的牙科材料。
下面将结合具体实施例对本申请的技术方案进行描述，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本申请的保护范围。
表1 为4种不同透光率的复合树脂材料前驱粉体的配方及工艺参数。
表1
Figure PCTCN2018087109-appb-000004
Figure PCTCN2018087109-appb-000005
注：表1中的树脂单体、填料、引发剂和着色剂所对应的数值为重量份，每一重量份可以为100g。
表2 为粉体1-4基于Lab表色系的色度值以及透光率。
表2
Figure PCTCN2018087109-appb-000006
粉体1-4对应的色度值以及透光率如表2所示，从表2可以看出，粉体1-4的透光率依次降低，其中，粉体1-4的色度是基于Lab表色系，将上述粉体在预设条件下固化后利用色差仪或者分光测色仪测量得到。另外，透光率是在将上述粉体在预设条件下固化后，在测试光线波长为550nm时，利用透光率测试仪测量得到。
实施例1
按照表1中粉体1、粉体2、粉体4的配方及相关工艺参数，将原料混合后，即可制备出3种不同颜色的粉体1、粉体2和粉体4。然后将粉体1加入到模具中作为第一层，压平后再加入粉体2，并将粉体2作为第二层，压平后再加入粉体4，并将粉体4作为第三层，其中粉体1的厚度为4mm、粉体2的厚度为6mm、粉体4的厚度为4mm，然后在4MPa的压力下干压成型，得到透光率和颜色渐变的牙科材料预成型坯体，然后对透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为115℃、压力为160MPa、保温时间0.5h，即可制备出具有三层透光率和颜色渐变的牙科材料。
其中，第一层与第三层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下，且|第一层与第三层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差)|≤1。
利用上述三种粉体制备的透光率和颜色渐变的牙科材料，其第一层的透光率大于第二层的透光率；第二层的透光率大于第三层的透光率，从第一层到第三层颜色依次加深。在患者使用该复合树脂材料时，第一层对应牙齿切 端的部位，第三层对应牙齿的颈部。
实施例2
根据表1中粉体1、粉体3和粉体4的配方和工艺参数，制备3种复合树脂材料前驱粉体。然后将粉体4加入到模具中作为第一层，压平后再加入粉体3，并将粉体3作为第二层，压平后再加入粉体1，并将粉体1作为第三层，其中，粉体1的厚度为3mm、粉体3的厚度为7mm、粉体4的厚度为4mm，然后在10MPa的压力下干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为131℃、压力为250MPa、保温时间3h，即可制备出具有三层透光率和颜色渐变的牙科材料。
其中，第一层与第三层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下，且|第一层与第三层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差)|≤1。
利用上述三种粉体制备的透光率和颜色渐变的牙科材料，其第三层的透光率大于第二层的透光率；第二层的透光率大于第一层的透光率，从第三层到第一层颜色依次加深。第三层对应牙齿切端的部位，第一层对应牙齿的颈部。
实施例3
根据表1中粉体1-4的配方和工艺参数，制备4种复合树脂材料前驱粉体。然后将粉体1加入到模具中作为第一层，压平后再加入粉体2，并将粉体2作为第二层，压平后再加入粉体3，并将粉体3作为第三层，压平后再加入粉体4，并将粉体4作为第四层，其中，粉体1的厚度为4mm、粉体2的厚度为4mm、粉体3的厚度为3mm、粉体4的厚度为3mm，然后在20MPa的压力下干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体，进行热固化处理，处理温度为185℃、压力为300MPa、保温时间4h，即可制备出具有四层透光率和颜色渐变的牙科材料。
其中，第一层与第三层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下，第三层与第四层之间的色度差为1以上且11以下；且|第一层与第四层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差+第三层与第四层之间的色度差)|≤1。
上述四种粉体制备的透光率和颜色渐变的牙科材料，其第一层的透光率大于第二层的透光率；第二层的透光率大于第三层的透光率；第三层的透光率大于第四层的透光率，从第一层到第四层颜色依次加深。第一层对应牙齿切端的部位，第四层对应牙齿的颈部。
在实际应用中，还可以采用如实施例4-6所示的方法得到透光率和颜色渐变的牙科材料。
需要说明的是，在实施实施例4-6时，使用1#-4#四种模具，四种模具形状相同，且4#模具容积＞3#模具容积＞2#模具容积＞1#模具容积。
实施例4
先将粉体4放入1#模具中、并在4MPa的压力下进行干压成型，得到第一坯体；再将粉体2放入2#模具中，将第一坯体放入2#模具中，使粉体2包裹第一坯体的同时使第一坯体位于粉体2的中部，在4MPa的压力下进行干压成型，得到第二坯体；再将粉体1放入4#模具中，将第二坯体放入4#模具中，使粉体1包裹第二坯体的同时使第二坯体位于粉体1的中部，在4MPa的压力下进行干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。然后对透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为115℃、压力为160MPa、保温时间为0.5h，即可制备出具有三层透光率和颜色渐变的牙科材料。
在本实施例中制备的透光率和颜色渐变的牙科材料中，粉体1作为最外层，粉体2作为次外层，粉体4作为最内层，其中，最外层与最内层之间的色度差为2以上且15以下；最外层与次外层之间的色度差为1以上且11以下；次外层与最内层之间的色度差为1以上且11以下，且|最外层与最内层之间的色度差-(最外层与次外层之间的色度差+次外层与最内层之间的色度差)|≤1。
可以理解的是，本申请实施例4制备的透光率和颜色渐变的牙科材料，透 光率从最外层至最内层依次降低；颜色从最外层到最内层依次加深。
实施例5
根据表1中粉体1、粉体3和粉体4的配方和工艺参数，制备3种复合树脂材料前驱粉体。先将粉体4放入1#模具中、在10MPa的压力下进行干压成型，得到第一坯体；再将粉体3放入3#模具中，将第一坯体放入3#模具中，使粉体3包裹第一坯体的同时使第一坯体位于粉体3的中部，在10MPa的压力下进行干压成型，得到第二坯体，再将粉体1放入4#模具中，将第二坯体放入4#模具中，使粉体1包裹第二坯体的同时使第二坯体位于粉体1的中部，在10MPa的压力下进行干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为131℃、压力为250MPa、保温时间为3h，即可制备出具有三层透光率和颜色渐变的牙科材料。
在本实施例中制备的透光率和颜色渐变的牙科材料中，粉体1作为最外层，粉体3作为次外层，粉体4作为最内层，其中，最外层与最内层之间的色度差为2以上且15以下；最外层与次外层之间的色度差为1以上且11以下；次外层与最内层之间的色度差为1以上且11以下，且|最外层与最内层之间的色度差-(最外层与次外层之间的色度差+次外层与最内层之间的色度差)|≤1。
本申请实施例5制备的透光率和颜色渐变的牙科材料，透光率从最外一层至最内一层依次降低；颜色从最外层到最内层依次加深。
实施例6
根据表1中粉体1-4的配方和工艺参数，制备4种复合树脂材料前驱粉体。先将粉体4放入1#模具中、在20MPa的压力下进行干压成型，得到第一坯体；再将粉体3放入2#模具中，将第一坯体放入2#模具中，使粉体3包裹第一坯体的同时使第一坯体位于粉体3的中部，在20MPa的压力下进行干压成型，得到第二坯体；再将粉体2放入3#模具中，将第二坯体放入3#模具中，使粉体2包裹第二坯体的同时使第二坯体位于粉体2的中部，在20MPa的压力下进行干压成型，得到第三坯体，再将粉体1放入4#模具中，将第三坯体放入4#模具中，使粉体1包裹第三坯体的同时使第三坯体位于粉体1的中部，在20MPa的压力 下进行干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体，进行热固化处理，处理温度为185℃、压力为300MPa、保温时间为4h，即可制备出具有四层透光率和颜色渐变的牙科材料。
可以将粉体1固化后的材料称为第一层，类似的，将粉体2固化后的材料称为第二层；将粉体3固化后的材料称为第三层；将粉体4固化后的材料称为第四层。
其中，第一层与第四层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下；第三层与第四层之间的色度差为1以上且11以下，且|第一层与第四层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差+第三层与第四层之间的色度差)|≤1。
本申请实施例6制备的透光率和颜色渐变的牙科材料，透光率从最外一层至最内一层依次降低，即第一层的透光率大于第二层的透光率；第二层的透光率大于第三层的透光率；且第三层的透光率大于第四层的透光率，其颜色从最外层到最内层依次加深。
对比例7
对比例7与实施例1的区别在于，热固化压力为13MPa，对比例7的配方以及各种工艺参数与实施例1完全相同。
对比例8
对比例8与实施例2的区别在于，热固化压力为16MPa，对比例8的配方以及各种工艺参数与实施例2完全相同。
对比例9
对比例9与实施例3的区别在于，热固化压力为20MPa，对比例9的配方以及各种工艺参数与实施例3完全相同。
对比例10
对比例10与实施例4的区别在于，热固化压力为130MPa，对比例10的配方以及各种工艺参数与实施例4完全相同。
对比例11
对比例11与实施例5的区别在于，热固化压力为150MPa，对比例11的配方以及各种工艺参数与实施例5完全相同。
分别测定实施例1-6和对比例7-11所制备的透光率和颜色渐变的牙科材料的挠曲强度、压缩强度及断裂韧性，结果如表3所示。
挠曲强度的测试方法参照YY/T 0710-2009/ISO 10477-2004标准；压缩强度的测试方法参照ISO 4049:2009标准；断裂韧性的测试方法参照ISO6872-2015标准。
表3 为实施例1-6制备以及对比例7-12制备的牙科材料的性能
表3
Figure PCTCN2018087109-appb-000007
Figure PCTCN2018087109-appb-000008
从表3可以看出，实施例1-3相对于对比例7-9的挠曲强度从不到213MPa左右提高到了248MPa以上；压缩强度从557MPa提高到了581MPa以上；断裂韧性从1.3MPa提高到了1.67MPa以上。应用本申请实施例制备的透光率和颜色渐变的牙科材料的挠曲强度、压缩强度以及断裂韧性有了很大的提高，进而提高了材料的耐磨性。
实施例4-6相对于对比例10-11的挠曲强度从不到223MPa提高到了252MPa以上；压缩强度从566MPa提高到了593MPa以上；断裂韧性从1.58MPa提高到了1.76MPa以上。应用本申请实施例制备的透光率和颜色渐变的牙科材料的挠曲强度、压缩强度以及断裂韧性有了很大的提高，进而提高了材料的耐磨性。
另一方面，在本申请的一种具体实施方式中，所述填料与树脂单体的重量比为31:69-69:31，优选为43:57-62:38，引发剂重量为树脂单体重量的0.1-3％，优选为0.1-2％，着色剂重量为树脂单体和填料总重量的0.001-0.2％，优选为0.002-0.1％；干压成型的压力为11-19MPa，优选为11-16MPa；所述热固化处理条件为，温度为151-169℃，优选为155-165℃，压力为210-300MPa，优选为240-290MPa，保温时间为1.1-1.8h，优选为1.6-1.8h。
下面将结合具体实施例对本申请的技术方案进行描述。
表4 为4种不同透光率的复合树脂材料前驱粉体的配方及工艺参数。
表4
Figure PCTCN2018087109-appb-000009
Figure PCTCN2018087109-appb-000010
注：表4中的树脂单体、填料、引发剂和着色剂所对应的数值为重量份，每一重量份可以为100g。
表5 为粉体5-8基于Lab表色系的色度值以及透光率。
表5
Figure PCTCN2018087109-appb-000011
Figure PCTCN2018087109-appb-000012
粉体5-8对应的色度值以及透光率如表5所示，从表5可以看出，粉体5-8的透光率依次降低，其中，粉体5-8的色度是基于Lab表色系，将上述粉体在预设条件下固化后利用色差仪或者分光测色仪测量得到。另外，透光率是在将上述粉体在预设条件下固化后，在测试光线波长为550nm时，利用透光率测试仪测量得到。
实施例12
按照表4中粉体5、粉体6、粉体8的配方及相关工艺参数，将原料混合后，即可制备出3种不同颜色的粉体5、粉体6和粉体8。然后将粉体5加入到模具中作为第一层，压平后再加入粉体6，并将粉体6作为第二层，压平后再加入粉体8，并将粉体8作为第三层，其中粉体5的厚度为4mm、粉体6的厚度为6mm、粉体8的厚度为4mm，然后在11MPa的压力下干压成型，得到透光率和颜色渐变的牙科材料预成型坯体，然后对透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为155℃、压力为210MPa、保温时间为1.1h，即可制备出具有三层透光率和颜色渐变的牙科材料。
其中，第一层与第三层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下，且|第一层与第三层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差)|≤1。
利用上述三种粉体制备的透光率和颜色渐变的牙科材料，其第一层的透光率大于第二层的透光率；第二层的透光率大于第三层的透光率，从第一层到第三层颜色逐渐加深。在患者使用该复合树脂材料时，第一层对应牙齿切端的部位，第三层对应牙齿的颈部。
实施例13
根据表4中粉体5、粉体7和粉体8的配方和工艺参数，制备3种复合树脂材料前驱粉体。然后将粉体8加入到模具中作为第一层，压平后再加入粉体7，并将粉体7作为第二层，压平后再加入粉体5，并将粉体5作为第三层，其中，粉体5的厚度为3mm、粉体7的厚度为7mm、粉体8的厚度为4mm，然后在16MPa的压力下干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为165℃、压力为240MPa、保温时间为1.6h，即可制备出具有三层透光率和颜色渐变的牙科材料。
其中，第一层与第三层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下，且|第一层与第三层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差)|≤1。
用上述三种粉体制备的透光率和颜色渐变的牙科材料，其第三层的透光率大于第二层的透光率；第二层的透光率大于第一层的透光率，从第三层到第一层颜色逐渐加深。在患者使用该牙科材料时，第三层对应牙齿切端的部位，第一层对应牙齿的颈部。
实施例14
根据表4中粉体5-8的配方和工艺参数，制备4种复合树脂材料前驱粉体。将粉体5加入到模具中作为第一层，压平后再加入粉体6，并将粉体6作为第二层，压平后再加入粉体7，并将粉体7作为第三层，压平后再加入粉体8，并将粉体8作为第四层，其中，粉体5的厚度为4mm、粉体6的厚度为4mm、粉体7的厚度为3mm、粉体8的厚度为3mm，然后在19MPa的压力下干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体，进行热固化处理，处理温度为169℃、压力为290MPa、保温时间为1.8h，即可制备出具有四层透透光率和颜色渐变的牙科材料。
其中，第一层与第三层之间的色度差为2以上且15以下；第一层与第二层 之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下，第三层与第四层之间的色度差为1以上且11以下；且|第一层与第四层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差+第三层与第四层之间的色度差)|≤1。
利用上述四种粉体制备的透光率和颜色渐变的牙科材料，第一层的透光率大于第二层的透光率；第二层的透光率大于第三层的透光率；第三层的透光率大于第四层的透光率，从第一层到第四层颜色逐渐加深。在患者使用该牙科材料时，第一层对应牙齿切端的部位，第四层对应牙齿的颈部。
在实际应用中，还可以采用如实施例15-17所示的方法得到透光率和颜色渐变的牙科材料。
需要说明的是，在实施实施例15-17时，使用与实施例4-6中相同的1#-4#四种模具。
实施例15
根据表4中粉体5、粉体6和粉体8的配方和工艺参数，制备3种复合树脂材料前驱粉体。先将粉体8放入1#模具中、并在11MPa的压力下进行干压成型，得到第一坯体；再将粉体6放入2#模具中，将第一坯体放入2#模具中，使粉体6包裹第一坯体的同时使第一坯体位于粉体6的中部，在11MPa的压力下进行干压成型，得到第二坯体；再将粉体5放入4#模具中，将第二坯体放入4#模具中，使粉体5包裹第二坯体的同时使第二坯体位于粉体5的中部，在11MPa的压力下进行干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。然后对透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为155℃、压力为210MPa、保温时间为1.1h，即可制备出具有三层透光率和颜色渐变的牙科材料。
在本实施例中制备的透光率和颜色渐变的牙科材料中，粉体5作为最外层，粉体6作为次外层，粉体8作为最内层，其中，最外层与最内层之间的色度差为2以上且15以下；最外层与次外层之间的色度差为1以上且11以下；次外层与最内层之间的色度差为1以上且11以下，且|最外层与最内层之间的色度差-(最外层与次外层之间的色度差+次外层与最内层之间的色度差)|≤1。
本申请实施例15制备的透光率和颜色渐变的牙科材料，透光率从最外层至最内层依次降低；颜色从最外层到最内层依次加深。
实施例16
根据表4中粉体5、粉体7和粉体8的配方和工艺参数，制备3种复合树脂材料前驱粉体。先将粉体8放入1#模具中、在11MPa的压力下进行干压成型，得到第一坯体；再将粉体7放入3#模具中，将第一坯体放入3#模具中，使粉体7包裹第一坯体的同时使第一坯体位于粉体7的中部，在11MPa的压力下进行干压成型，得到第二坯体，再将粉体5放入4#模具中，将第二坯体放入4#模具中，使粉体5包裹第二坯体的同时使第二坯体位于粉体5的中部，在11MPa的压力下进行干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，处理温度为165℃、压力为240MPa、保温时间为1.6h，即可制备出具有三层透光率和颜色渐变的牙科材料。
在本实施例中制备的透光率和颜色渐变的牙科材料中，粉体5作为最外层，粉体7作为次外层，粉体8作为最内层，其中，最外层与最内层之间的色度差为2以上且15以下；最外层与次外层之间的色度差为1以上且11以下；次外层与最内层之间的色度差为1以上且11以下，且|最外层与最内层之间的色度差-(最外层与次外层之间的色度差+次外层与最内层之间的色度差)|≤1。
本申请实施例16制备的透光率和颜色渐变的牙科材料，透光率从最外一层至最内一层依次降低；颜色从最外层到最内层依次加深。
实施例17
根据表4中粉体5-8的配方和工艺参数，制备4种复合树脂材料前驱粉体。先将粉体8在1#模具中、在11MPa的压力下进行干压成型，得到第一坯体；再将粉体7放入2#模具中，将第一坯体放入2#模具中，使粉体7包裹第一坯体的同时使第一坯体位于粉体7的中部，在11MPa的压力下进行干压成型，得到第二坯体；再将粉体6放入3#模具中，将第二坯体放入3#模具中，使粉体6包裹第二坯体的同时使第二坯体位于粉体6的中部，在11MPa的压力下进行干压成型，得到第三坯体，再将粉体5放入4#模具中，将第三坯体放入4#模具中，使 粉体5包裹第三坯体的同时使第三坯体位于粉体5的中部，在11MPa的压力下进行干压成型，得到透光率和颜色渐变的牙科材料预成型坯体。
然后对得到透光率和颜色渐变的牙科材料预成型坯体，进行热固化处理，处理温度为169℃、压力为290MPa、保温时间为1.8h，即可制备出具有四层透光率和颜色渐变的牙科材料。
可以将粉体5固化后的材料称为第一层，类似的，将粉体6固化后的材料称为第二层；将粉体7固化后的材料称为第三层；将粉体8固化后的材料称为第四层。
其中，第一层与第四层之间的色度差为2以上且15以下；第一层与第二层之间的色度差为1以上且11以下；第二层与第三层之间的色度差为1以上且11以下；第三层与第四层之间的色度差为1以上且11以下，且|第一层与第四层之间的色度差-(第一层与第二层之间的色度差+第二层与第三层之间的色度差+第三层与第四层之间的色度差)|≤1。
本申请实施例17制备的透光率和颜色渐变的牙科材料，透光率从最外一层至最内一层依次降低，即第一层的透光率大于第二层的透光率；第二层的透光率大于第三层的透光率；第三层的透光率大于第四层的透光率；颜色从最外层到最内层依次加深。
对比例18
对比例18与实施例12的区别在于，热固化压力为13MPa，对比例18的配方以及各种工艺参数与实施例12完全相同。
对比例19
对比例19与实施例13的区别在于，热固化压力为16MPa，对比例19的配方以及各种工艺参数与实施例13完全相同。
对比例20
对比例20与实施例14的区别在于，热固化压力为20MPa，对比例20的配方以及各种工艺参数与实施例14完全相同。
对比例21
对比例21与实施例15的区别在于，热固化压力为130MPa，对比例21的配方以及各种工艺参数与实施例15完全相同。
对比例22
对比例22与实施例16的区别在于，热固化压力为150MPa，对比例22的配方以及各种工艺参数与实施例16完全相同。
分别测定实施例12-17和对比例18-22所制备的透光率和颜色渐变的牙科材料的挠曲强度、压缩强度及断裂韧性，结果如表6所示。
挠曲强度的测试方法参照YY/T 0710-2009/ISO 10477-2004标准；压缩强度的测试方法参照ISO 4049:2009标准；断裂韧性的测试方法参照ISO6872-2015标准。
表6 为实施例12-17制备以及对比例18-22制备的透光率和颜色渐变的牙科材料的性能
表6
Figure PCTCN2018087109-appb-000013
Figure PCTCN2018087109-appb-000014
从表6可以看出，实施例12-14相对于对比例18-20的挠曲强度从不到218MPa左右提高到了250MPa以上；压缩强度从549MPa提高到了591MPa以上；断裂韧性从1.28MPa提高到了1.72MPa以上。应用本申请实施例制备的透光率和颜色渐变的牙科材料的挠曲强度、压缩强度以及断裂韧性有了很大的提高，进而提高了材料的耐磨性。
实施例15-17相对于对比例21-22的挠曲强度从不到220MPa提高到了257MPa以上；压缩强度从553MPa提高到了596MPa以上；断裂韧性从1.35MPa提高到了1.78MPa以上。应用本申请实施例制备的透光率和颜色渐变的牙科材料的挠曲强度、压缩强度以及断裂韧性有了很大的提高，进而提高了材料的耐磨性。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (14)

  1. 透光率和颜色渐变的牙科材料的制备方法，其特征在于，所述方法包括：
    (1)、制备至少三种不同透光率的复合树脂材料前驱粉体，其中，每一种透光率的复合树脂材料前驱粉体的制备过程包括：称取原料，所述原料包括树脂单体、填料、引发剂及着色剂，将原料混合后得到复合树脂材料前驱粉体，其中，填料与树脂单体的重量比为10:90-90:10，优选为70:30-85:15，引发剂重量为树脂单体重量的0.1-3％，优选为0.1-2％，着色剂重量为树脂单体和填料总重量的0.001-0.2％，优选为0.002-0.1％；所述树脂单体包括烯键式不饱和单体和\或环氧树脂；
    (2)、按照透光率从低到高的顺序，或从高到低的顺序，依次将所述至少三种不同透光率的复合树脂材料前驱粉体加入到模具中，在3-20MPa，优选为4-10MPa的压力下，干压成型，得到透光率和颜色渐变的牙科材料预成型坯体；其中，在将每一种复合树脂材料前驱粉体加入到模具中后，将该前驱粉体的上表面平整至平坦；
    或
    (2′)，将所述至少三种不同透光率的复合树脂材料前驱粉体中，第一种透光率复合树脂材料前驱粉体在3-20MPa，优选为4-10MPa的压力下干压成型，得到第一坯体；将所述第一坯体包裹于所述至少三种不同透光率的复合树脂材料前驱粉体中的第二种透光率复合树脂材料前驱粉体中，在3-20MPa，优选为4-10MPa的压力下干压成型，得到第二坯体；重复进行包裹、干压成型操作，直至将所述至少三种透光率复合树脂材料前驱粉体干压成型后，得到透光率和颜色渐变的牙科材料预成型坯体，其中，所述透光率和颜色渐变的牙科材料预成型坯体中各层前驱粉体从内到外的透光率依次升高；
    (3)、将步骤(2)或者步骤(2′)所制备的透光率和颜色渐变的牙科材料预成型坯体进行热固化处理，得到透光率和颜色渐变的牙科材料，其中，热固化处理条件为，温度为115-185℃，优选为131-171℃，压力为大于160MPa，优选为160-300MPa，更优选为200-250MPa，保温时间为0.5-4h，优选为0.5-3 h。
  2. 根据权利要求1所述的方法，其特征在于，所述透光率和颜色渐变的牙科材料还具有多层色，相邻两层的复合树脂材料之间，基于Lab表色系的色度差大于等于1，且小于等于11；
    所述透光率和颜色渐变的牙科材料中不相邻各层的复合树脂材料之间，基于Lab表色系的色度差的最大值大于等于2，且小于等于15；
    所述透光率和颜色渐变的牙科材料中所有相邻各层复合树脂材料之间的色度差之和，与所述透光率和颜色渐变的牙科材料中色度值最高的一层复合树脂材料与色度值最低的一层复合树脂材料之间的色度差之差不大于2；
    其中，
    基于Lab表色系的色度差的计算公式为，
    Figure PCTCN2018087109-appb-100001
    且，ΔE为色度差；ΔL为两层间的L值之差；Δa为两层间的a值之差；Δb为两层间的b值之差。
  3. 根据权利要求1所述的方法，其特征在于，所述透光率和颜色渐变的牙科材料还具有多层透光率，相邻两层的透光率和颜色渐变的牙科材料之间的透光率的差为0.5-10％；不相邻两层复合树脂材料之间的透光率的差为1-15％；且透光率最高的一层复合树脂材料的可见光(波长为550nm)透光率为50-75％，透光率最低的一层复合树脂材料的透光率为30-60％，所述透光率最高的一层复合树脂材料与所述透光率最低的一层复合树脂材料之间的其他各层复合树脂材料的透光率为40-70％。
  4. 根据权利要求1所述的方法，其特征在于，所述填料与树脂单体的重量比为31:69-69:31，优选为43:57-62:38，引发剂重量为树脂单体重量的0.1-3％，优选为0.1-2％，着色剂重量为树脂单体和填料总重量的0.001-0.2％，优选为0.002-0.1％；
    所述热固化处理条件为，温度为151-169℃，优选为155-165℃，压力为210-300MPa，优选为240-290MPa，保温时间为1.1-1.8h，优选为1.6-1.8h。
  5. 根据权利要求1所述的方法，其特征在于，所述将原料混合后得到复合树脂材料前驱粉体，包括：
    将原料与球磨助剂混合，利用球磨法制备复合树脂材料前驱粉体，其中，原料:研磨球:球磨助剂的质量比为(1:1:1)-(3:6:2)，优选为2:4:1，球磨时间为0.5-2h。
  6. 根据权利要求1所述的方法，其特征在于，所述填料的粒度范围为不大于2.5μm，优选为不大于2μm，更优选为0.05-2μm；所述填料的折射率为1.40-1.7，优选为1.45-1.6。
  7. 根据权利要求1所述的方法，其特征在于，所述原料还包括阻聚剂，所述阻聚剂占所述树脂单体总重量的0.1-3％，优选为0.2-2％。
  8. 根据权利要求1所述的方法，其特征在于，所述原料还包括促进剂，所述促进剂占所述树脂单体总重量的0.1-3％，优选为0.2-2％。
  9. 根据权利要求1所述的方法，其特征在于，所述原料还包括赋予荧光的试剂、指示剂、抑制剂、加速剂、粘度调节剂、润湿剂、抗氧化剂、表面活性剂、稳定剂及稀释剂中的至少一种。
  10. 根据权利要求1所述的方法，其特征在于，所述填料还包括纳米粒子，其中，所述纳米粒子占所述填料重量的1-25％，优选为1-15％；所述纳米粒子的平均直径为35-100nm，优选为40-50nm。
  11. 根据权利要求1所述的方法，其特征在于，所述原料还包括增强纤维，所述增强纤维为所述填料重量的1-30％，优选为1-10％；所述增强纤维的直径为0.1-25μm，优选为0.5-10μm；所述增强纤维的长度为0.001-1mm，优选为0.1-0.5mm；所述增强纤维的折射率为1.4-1.7，优选为1.45-1.6；所述增强纤维包含玻璃纤维、石英纤维、硅质纤维、陶瓷纤维及聚合物纤维中的一种或其组合，所述聚合物纤维优选为聚乙烯纤维。
  12. 根据权利要求11所述的方法，其特征在于，所述将原料混合后得到复合树脂材料前驱粉体，包括：
    将除增强纤维以外的树脂单体、填料、引发剂及着色剂混合后进行球磨 混料，得到原料混合物，其中，原料:研磨球:球磨助剂的质量比为(1:1:1)-(3:6:2)，优选为2:4:1，球磨时间为0.5-2h；
    将所述原料混合物与所述增强纤维混合，得到复合树脂材料前驱粉体。
  13. 根据权利要求1所述的方法，其特征在于，所述着色剂包含红色着色剂、黄色着色剂及黑色着色剂中的一种或其组合，其中，所述红色着色剂占所述原料重量的0.001-0.06％，优选为氧化铁红；所述黄色着色剂占所述原料重量的0.001-0.04％，包含氧化铁黄、铋黄、钒锆黄及铈镨黄中的一种或其组合；所述黑色着色剂占所述原料重量的0-0.03％，优选为氧化铁黑。
  14. 根据权利要求1-13任一项所述的方法制备的透光率和颜色渐变的牙科材料。
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AU2018340731B2 (en) 2021-05-13
AU2018340731A1 (en) 2020-05-07
EP3689322A1 (en) 2020-08-05
EP3689322A4 (en) 2020-10-21
US11517507B2 (en) 2022-12-06
KR102306376B1 (ko) 2021-10-01
US20200268616A1 (en) 2020-08-27

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