WO2017219742A1 - 一种牙科用复合树脂材料的制备方法及其制备的产品 - Google Patents

一种牙科用复合树脂材料的制备方法及其制备的产品 Download PDF

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Publication number
WO2017219742A1
WO2017219742A1 PCT/CN2017/080865 CN2017080865W WO2017219742A1 WO 2017219742 A1 WO2017219742 A1 WO 2017219742A1 CN 2017080865 W CN2017080865 W CN 2017080865W WO 2017219742 A1 WO2017219742 A1 WO 2017219742A1
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Prior art keywords
filler
composite resin
fibers
type
weight
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Ceased
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PCT/CN2017/080865
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English (en)
French (fr)
Inventor
仇越秀
王鸿娟
袁大鹏
孙宾
石凤
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LIAONING UPCERA CO Ltd
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LIAONING UPCERA CO Ltd
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Priority to JP2017557191A priority Critical patent/JP6727232B2/ja
Priority to ES17800995T priority patent/ES2897479T3/es
Priority to US15/569,543 priority patent/US10596077B2/en
Priority to KR1020177033360A priority patent/KR101963240B1/ko
Priority to EP17800995.7A priority patent/EP3305341B1/en
Publication of WO2017219742A1 publication Critical patent/WO2017219742A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/79—Initiators
    • 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
    • A61C13/0004—Computer-assisted sizing or machining of dental prostheses
    • 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
    • A61C13/087—Artificial resin teeth
    • 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
    • A61K6/80—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
    • 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
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/40—Glass
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron

Definitions

  • the present application relates to the field of dental restorations, and in particular to a method for preparing a dental composite resin material and a product thereof.
  • CAD Computer Aided Design/Computer Aided Manufacture
  • CAD/CAM systems have been able to successfully produce fixed restorations such as inlays, veneers, crowns, fixed bridges, etc.; however, during the entire treatment process, patients need to go to the hospital at least 2-3 times to complete the repair; The complicated review of the diagnosis made the patient feel greatly inconvenient; with the development of computer technology, a new technology of rapid treatment came into being, that is, the digital restoration technology of the dental chair (CAD/CAM next to the dental chair).
  • CAD/CAM 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 acquire the patient's tooth model, analyzes the data by computer, and immediately designs and Automatically complete the production of dentures (prostheses).
  • the patient only has to wait for about 30 minutes to wear the teeth and omits the complicated follow-up process.
  • the CAD/CAM next to the dental chair banned the temporary restoration, which made the restoration complete once, which reduced the number of patient visits and significantly improved the quality of the restoration.
  • Due to the model scanning the design of the prosthesis is digital technology and is calculated by computer. Therefore, the prosthesis can achieve better precision and accuracy.
  • the healing rate of the prosthesis is higher.
  • Traditional porcelain teeth and activities Dentures are easy to produce The problems of discoloration of the gums, inconsistency of the edges, etc. will be greatly reduced, and the satisfaction of the patient's treatment effect will also be significantly improved.
  • machinable ceramic materials mainly include: glass ceramics (also known as glass ceramics), glass infiltrated ceramic composite materials, alumina ceramics, zirconia ceramics and the like.
  • Composite materials mainly include: composite resin materials, resin infiltrated ceramic composite materials, polyetheretherketone (PEEK) materials, and the like.
  • the metal material is mainly dental titanium or the like.
  • the composite resin material has good toughness, workability, wear resistance, X-ray resistance and easy polishing, and its repairing effect is close to natural teeth, which is an ideal.
  • the existing composite resin material has a problem of low strength, and the bending strength can only reach about 240 MPa, which can only satisfy the repair of the inlay, the inlay, the veneer and the single crown in the dental restoration.
  • Body it is not possible to make a restoration such as a bridge body and a posterior tooth that requires weight bearing.
  • the embodiment of the present application discloses a preparation method of a dental composite resin material and a product thereof, which are used for solving the problem of low strength of the existing composite resin material.
  • the technical solutions are as follows:
  • the application first provides a method for preparing a dental composite resin material, comprising:
  • each raw material including ethylenically unsaturated monomers, reinforcing fibers, fillers, initiators, polymerization inhibitors, and colorants, wherein the total weight of the reinforcing fibers and fillers and the ethylenic bond
  • the weight ratio of the unsaturated monomer is from 90:10 to 10:90, preferably from 85:15 to 65:35; the weight of the initiator is from 0.05 to 1%, preferably from 0.1 to 0.3, based on the weight of the ethylenically unsaturated monomer.
  • the weight of the polymerization inhibitor is from 0.05 to 1%, preferably from 0.1 to 0.3% by weight based on the weight of the ethylenically unsaturated monomer; and the colorant is from 0.001 to 0.2% by weight based on the total weight of the ethylenically unsaturated monomer, the reinforcing fiber and the filler. , preferably 0.005-0.1%; the weight ratio of filler to reinforcing fiber is 10:90-55:45;
  • the curing temperature is 100-200 ° C, preferably 120-160 ° C, and the curing time is 0.5-3 hours. It is preferably 1.5 to 2 hours; the curing pressure is 10 to 200 MPa, preferably 10 to 100 MPa, and more preferably 20 to 60 MPa.
  • the raw material further includes an accelerator, wherein the promoter accounts for 0.05-1%, preferably 0.1-0.3%, by weight of the ethylenically unsaturated monomer, preferably, the accelerator It is N,N-dihydroxyethyl p-toluidine.
  • the raw material further includes at least one of a fluorescent-imparting agent, an indicator, a viscosity modifier, a wetting agent, an antioxidant, a stabilizer, and a diluent.
  • the ethylenically unsaturated monomer comprises one or a combination of a (meth) acrylate, a hydroxy-functional (meth) acrylate, and an epoxy resin.
  • it comprises bisphenol A-glycidyl methacrylate, ethoxy bisphenol A dimethacrylate, urethane dimethacrylate, diethylene glycol dimethacrylate, One or a combination of hydroxyethyl methacrylate, polyethylene glycol dimethacrylate, and bisphenol A epoxy resin.
  • the reinforcing fiber comprises one or a combination of carbon fiber, glass fiber, quartz fiber, siliceous fiber, ceramic fiber and polymer fiber; the reinforcing fiber is a fiber bundle, A fiber cloth or a fiber block; the single fiber of the reinforcing fiber has a diameter ranging from 0.1 to 25 ⁇ m, preferably from 0.5 to 10 ⁇ m; and the reinforcing fiber has a refractive index ranging from 1.40 to 1.70, preferably from 1.45 to 1.60.
  • the filler includes a type I filler and a type II filler;
  • the type I filler is a filler having a particle size ranging from 0.01 ⁇ m to 10 ⁇ m, and the type I filler is selected from the group consisting of inorganic fillers and / or a prepolymerized organic filler insoluble in the composite resin monomer precursor;
  • the I type filler preferably comprises quartz, bismuth glass, bismuth glass, borosilicate glass, silica-zirconia composite powder, silicon oxide At least one of a cerium oxide composite powder, a polycarbonate filled or unfilled with an inorganic material, a polyepoxide powder, and a polymerized methacrylic resin;
  • the refractive index of the type I filler ranges from 1.48 to 1.60
  • the type II filler is a filler having a particle size ranging from 10 to 100 nm;
  • the type II filler preferably comprises at least one of a silica nano
  • the filler is subjected to surface modification treatment before being mixed with other raw materials
  • the modification treatment method includes: coupling agent modification, plasma surface treatment modification or chemical connection. Branch modification.
  • the coloring agent includes one or a combination of a red coloring agent, a yellow coloring agent, and a black coloring agent;
  • the red coloring agent is preferably iron oxide red
  • the yellow coloring agent is selected from One or a combination of iron oxide yellow, yttrium yellow, vanadium zirconium yellow, and yttrium yellow
  • the black colorant is preferably iron oxide black.
  • the initiator is selected from the group consisting of dicumyl peroxide, t-butyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, and t-butyl peroxybenzoate.
  • the esters; the polymerization inhibitor is 2,6-di-tert-butyl-p-cresol.
  • the reinforcing fiber is pretreated before impregnation; the pretreatment comprises washing the reinforcing fiber and modifying the surface thereof;
  • the cleaning method includes a heat treatment method, a solvent immersion method or an acid-base corrosion method; and the modification treatment method includes: a coupling agent modification, a plasma surface treatment modification or a chemical graft modification.
  • the present application also provides a dental composite resin material prepared by the above method.
  • the dental composite resin material provided by the present application has extremely high mechanical strength, and the flexural strength reaches 600 MPa or more by experiments, and can be used to manufacture a dental restoration of a load-bearing part, such as a bridge, a load-bearing crown, and the whole Dentures, as well as stents for implant restoration;
  • the dental composite resin material provided by the present application does not detect residual ethylenically unsaturated monomers (no cytotoxicity), and has good biosafety.
  • the dental composite resin material provided by the present application has a permeability close to that of a natural tooth, and the light transmittance is up to 40% or more, up to 55%, and can be used for preparing a full-form denture.
  • the application provides a method for preparing a dental composite resin material, comprising:
  • each raw material including ethylenically unsaturated monomers, reinforcing fibers, fillers, initiators, polymerization inhibitors, and colorants, wherein the total weight of the reinforcing fibers and fillers and the ethylenic bond
  • the weight ratio of the unsaturated monomer is from 90:10 to 10:90, preferably from 85:15 to 65:35; the weight of the initiator is from 0.05 to 1%, preferably from 0.1 to 0.3, based on the weight of the ethylenically unsaturated monomer.
  • the weight of the polymerization inhibitor is from 0.05 to 1%, preferably from 0.1 to 0.3% by weight based on the weight of the ethylenically unsaturated monomer; and the colorant is from 0.001 to 0.2% by weight based on the total weight of the ethylenically unsaturated monomer, the reinforcing fiber and the filler. , preferably 0.005-0.1%; the weight ratio of filler to reinforcing fiber is 10:90-55:45;
  • the ethylenically unsaturated monomer comprises one or a combination of (meth) acrylate, hydroxy-functional (meth) acrylate, and epoxy resin, preferably, including Bisphenol A-bis-dimethacrylate glycidyl ester (Bis-GMA), ethoxylated bisphenol A dimethacrylate (Bis-EMA), urethane dimethacrylate (UDMA), bismethyl Triethylene glycol acrylate (TEGDMA), hydroxyethyl methacrylate (HEMA), polyethylene glycol dimethacrylate (PEGDMA) and bisphenol A epoxy resin (epoxy resin E-44) One or a combination thereof.
  • Bisphenol A-bis-dimethacrylate glycidyl ester Bis-GMA
  • EMA ethoxylated bisphenol A dimethacrylate
  • UDMA urethane dimethacrylate
  • TEGDMA bismethyl Triethylene glycol acrylate
  • HEMA hydroxyethyl me
  • the reinforcing fiber comprises one or a combination of carbon fiber, glass fiber, quartz fiber, siliceous fiber, ceramic fiber and polymer fiber; the reinforcing fiber may be a fiber bundle, a fiber cloth or a fiber block.
  • the diameter of the individual fibers of the reinforcing fibers ranges from 0.1 to 25 ⁇ m, preferably from 0.5 to 10 ⁇ m; the refractive index of the reinforcing fibers ranges from 1.40 to 1.70, preferably from 1.45 to 1.60.
  • the filler comprises a type I filler and a type II filler;
  • the type I filler is a filler having a particle size ranging from 0.01 ⁇ m to 10 ⁇ m, and the type I filler has a particle size range of preferably 0.01 ⁇ m to 5 ⁇ m, more preferably 0.01 ⁇ m. 1 ⁇ m
  • the type I filler may be an inorganic filler, or a prepolymerized organic filler which is insoluble in the composite resin monomer precursor, or a combination of the two;
  • the type I filler includes but is not limited to quartz, bismuth glass, bismuth.
  • At least one of the type I fillers has a refractive index ranging from 1.48 to 1.60, preferably from 1.50 to 1.58;
  • the type II filler is a filler having a particle size ranging from 10 to 100 nm, and the type II filler has a particle size range of preferably from 10 to 70 nm, more
  • the 15-type filler comprises at least one of a silica nanopowder and a zirconia nanopowder; and the weight ratio of the type I filler to the type II filler is from 3:1 to 1:1.
  • the present application uses ethylenically unsaturated monomers, reinforcing fibers and fillers having similar refractive indices, so that the dental composite resin material prepared by the present application can be made closer to natural teeth.
  • the combination of the reinforcing fiber and the resin material can significantly increase the strength of the resin material, and meet the requirements for preparing a restoration such as a bridge body and a posterior tooth.
  • the Applicant has unexpectedly discovered that the addition of fillers can increase the polishability and wear resistance of the material.
  • the use of a Type I filler and a Type II filler can provide the dental composite resin material provided herein with a semi-permeable and opalescent effect similar to that of natural teeth.
  • the coloring agent includes one or a combination of a red coloring agent, a yellow coloring agent, and a black coloring agent;
  • the red coloring agent is preferably iron oxide red
  • the yellow coloring agent is selected from the group consisting of iron oxide yellow, One or a combination of yellow, vanadium zirconium and yellow
  • the black colorant is preferably iron oxide black. It is to be understood that the amount of the various colorants and the ratio between them can be adjusted according to actual needs so that the color of the material is close to the color of the natural tooth.
  • the initiator may be selected from the group consisting of dicumyl peroxide, t-butyl peroxide, benzoyl peroxide, t-butyl peroxyacetate, and t-butyl peroxybenzoate.
  • the polymerization inhibitor may be 2,6-di-tert-butyl-p-cresol, and of course, other initiators and polymerization inhibitors may also be selected.
  • the raw material may further include a promoter, the promoter may comprise 0.05-1%, preferably 0.1-0.3% by weight of the ethylenically unsaturated monomer, and the promoter may be an N,N-dihydroxyethyl pair. Toluidine.
  • various additives suitable for use in an oral environment may be included in the raw material, including but not limited to fluorescent-imparting reagents, indicators, viscosity modifiers, wetting agents, antioxidants, stabilizers. And at least one of the diluents.
  • the raw materials other than the reinforcing fibers may be dispersed and uniformly mixed by mechanical stirring or ultrasonic vibration.
  • the reinforcing fiber in order to be able to improve the bonding between the reinforcing fibers and the resin Intensity, before the reinforcing fiber is immersed in the composite resin monomer precursor, the reinforcing fiber may be pretreated; the pretreatment comprises washing the reinforcing fiber and modifying the surface thereof;
  • the cleaning method includes, but is not limited to, a heat treatment method, a solvent immersion method or an acid-base etching method;
  • the heat treatment method refers to high-temperature calcination, such as calcination at 400 ° C for 1 hour;
  • the solvent immersion method refers to the use of an organic solvent, for example. Soaking in acetone for 5 hours;
  • acid-base corrosion treatment refers to soaking with a certain concentration of hydrochloric acid solution or sodium hydroxide solution for a certain period of time, such as 0.5 hours.
  • different cleaning methods may be adopted depending on the material of the reinforcing fiber.
  • the glass fiber may be subjected to an acid-base etching method
  • the silicon fiber may be subjected to a high-temperature calcination method
  • the polymer fiber may be a solvent soaking method.
  • the cleaned reinforcing fiber may be subjected to a modification treatment, and the modification treatment method includes, but not limited to, a coupling agent modification, a plasma surface treatment modification, or a chemical graft modification.
  • the methods of the modification treatment are all known in the prior art, and those skilled in the art can know the method for carrying out the above modification treatment, which is not limited herein.
  • the literature silane coupling agent for carbon microspheres
  • Surface chemical modification Li Sha, Duan Feifei, et al., Functional Materials, 2011, Vol. 1, No. 42, pp. 25-28, p.
  • the coupling agent used includes ⁇ -methacryloxypropyltrimethoxysilane (KH-570), ⁇ -mercaptopropyltriethoxysilane (KH-580), and ⁇ -aminopropyltrimethoxysilane. (JH-A111) and so on.
  • the filler may be subjected to surface modification treatment before the filler is mixed with other raw materials, and the modification treatment method includes: coupling agent modification, plasma surface treatment modification.
  • the modification treatment method includes: coupling agent modification, plasma surface treatment modification.
  • sexual or chemical graft modification, etc. please refer to the description about reinforcing fibers.
  • the curing temperature is 100-200 ° C, preferably 120-160 ° C, and the curing time is 0.5-3 hours. It is preferably 1.5 to 2 hours; the curing pressure is 10 to 200 MPa, preferably 10 to 100 MPa, and more preferably 20 to 60 MPa.
  • the above-mentioned curing treatment by pressure heating increases the area in which the ethylenically unsaturated monomer and the initiator contact each other under a certain pressure, improves the curing reaction efficiency, reduces the residual of the polymer monomer, and improves the composite resin.
  • the material is biocompatible and effectively increases the strength of the composite resin material.
  • pressurized heating device and the like used in the present application are all commonly used in the art, and the purpose of the present application can be achieved.
  • the present application is not limited herein.
  • Shenzhen Chuangjiahong Machinery Equipment Co., Ltd. can be used.
  • the company's hot pressing equipment can be used.
  • the raw materials were weighed according to the formulation of Example 1 in Table 1, and the weighed materials other than the glass fiber bundle were mechanically stirred to be dispersed and mixed to obtain a composite resin monomer precursor;
  • the so-called glass fiber bundle is calcined at a temperature of 400 ° C for 1 h; after cooling to room temperature, a coupling agent modification treatment is carried out.
  • the glass fiber bundle can be immersed in ethanol containing KH570 hydrolyzate (KH570 hydrolysis) The liquid to ethanol volume ratio was 1:3), treated at 65 ° C for 2 hours, and then dried at 100 ° C for 4 hours.
  • the dried reinforcing fiber was immersed in the composite resin monomer precursor for 2 hours, and the impregnation pressure was controlled at about 0.1 MPa to obtain a reinforcing fiber adsorbed with the composite resin monomer precursor; then, the use of the first embodiment in Table 1 was employed.
  • Curing Process Conditions The reinforcing fibers to which the composite resin monomer precursor is adsorbed are subjected to a curing treatment to obtain a dental composite resin material.
  • the dental composite resin material was prepared according to the preparation method described in the first embodiment using the raw material formulation and the preparation conditions described in Table 1. Wherein, in the second embodiment, the filler glass powder, the nano-silica and the nano-zirconia are subjected to a coupling agent modification treatment before being mixed with other raw materials, and the treatment method and the glass fiber bundle treatment method in the first embodiment
  • the color of the dental composite resin material prepared in Example 6 is the A2 color of the VITA 16 color color palette
  • the color of the dental composite resin material prepared in Example 7 is the A3 color of the VITA 16 color color palette.
  • the color of the dental composite resin material prepared in Example 8 was gingival color.
  • test method of flexural strength refers to YY/T 0710-2009/ISO 10477-2004 "Dental Polymer-based Crown Bridge Materials"
  • test method of flexural modulus refers to ISO 10477:2004 Ed.2 dentistry polymer base Crown and bridge materials
  • test method for fracture toughness refer to ISO6872-2008 dental ceramic materials
  • the light transmittance test method refers to JC/T 2020-2010 translucent fine ceramic transmittance test method.
  • the dental composite resin materials prepared in the examples of the present application are excellent in various properties.
  • the high strength and toughness enable the material to maintain a good shape during the application of the tooth restoration, whether during the processing or during the wearing and use of the patient, without causing collapse or breakage. This makes the material more widely used in dental restoration to meet the needs of the market.
  • the unit of the numerical value corresponding to the raw material in Table 1 is part by weight, and may be 100 g per part by weight.
  • the more complete the curing of the composite resin material the less the residual monomer monomer, the lower the water absorption value, the dissolution value and the chemical solubility value of the material, and the better the biocompatibility of the material.
  • the water absorption, solubility and chemical solubility of the prepared dental composite resin material prepared in Example 1 and the commercially available Bioloren Trilor CAD/CAM fiber reinforced resin product were respectively tested, as shown in Table 3, in which the water absorption value and dissolution were carried out.
  • YY/T 0710-2009/ISO 10477-2004 "Dental Polymer-Based Crown Bridge Materials" for the test method for values.
  • the test method for chemical solubility refers to ISO6872-2008 dental ceramic materials.
  • the dental composite resin material prepared in Example 1 has lower water absorption value, solubility value and chemical solubility than the Bioloren Trilor product, indicating that the preparation method of the present application is advantageous for reducing the polymer. Since the monomer remains, the biocompatibility and safety of the dental composite resin material can be improved.

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Abstract

一种牙科用复合树脂材料的制备方法及其制备的产品。该方法包括：（1）称取各原料，原料包括烯键式不饱和单体、增强纤维、填料、引发剂、阻聚剂及着色剂；（2）将所称取的除增强纤维外的原料混合，得到复合树脂单体前驱物；（3）将所称取的增强纤维浸渍于复合树脂单体前驱物中1-5小时，浸渍压力小于等于0.1MPa，得到吸附有复合树脂单体前驱物的增强纤维；（4）将吸附有复合树脂单体前驱物的增强纤维进行固化处理，得到牙科用复合树脂材料。该牙科用复合树脂材料挠曲强度达600MPa以上，光透过率达40％以上。

Description

一种牙科用复合树脂材料的制备方法及其制备的产品
本申请要求于2016年06月23日提交中国专利局、申请号为201610463669.3发明名称为“一种牙科用复合树脂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体领域，特别涉及一种牙科用复合树脂材料的制备方法及其制备的产品。
背景技术
计算机辅助设计和计算机辅助制作(Computer Aided Design/Computer Aided Manufacture，CAD/CAM)技术最早是在20世纪70年代初期，由法国Francois Duret教授开创性地引入口腔固定修复体的设计与制作中，该技术引发了口腔修复领域的一场重大的技术革命；其中，CAD是指以计算机作为主要技术手段来生成和运用各种数字信息和图形信息，以进行产品的设计；CAM是指由计算机控制的数控加工设备，如数控铣床等，对产品进行自动加工成型的制作技术。目前，CAD/CAM系统已能成功地制作嵌体、贴面、冠、固定桥等固定修复体；但是，在整个治疗过程中，患者至少需要去医院2-3次才能完成修复；如此频繁而又复杂的复诊让患者感到极大地不便；随着计算机技术的发展，一种快速治疗的新技术应运而生，那就是牙科椅旁数字化修复技术(牙科椅旁CAD/CAM)。
牙科椅旁CAD/CAM，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，由计算机分析数据，立即设计并自动完成假牙(修复体)的制作。病人只需等待约30分钟，就可以戴牙完成，省略了复杂的复诊过程。牙科椅旁CAD/CAM取缔了临时性的修复体，使修复体的制作一次完成，减少了病人就诊次数，而且明显能提高修复体的质量。由于模型扫描，修复体的设计制作都采用了数码技术，并由计算机计算完成，因而修复体可以达到更好的精密度和准确性，修复体的治疗成功率更高，传统烤瓷牙和活动假牙容易产 生的牙龈变色，边缘不密合等问题将大大减少，病人的治疗效果满意度也将显著提高。
牙科椅旁CAD/CAM的发展也带动了配套材料的进步，目前，已发展出三大类可用于牙科椅旁CAD/CAM的配套材料：可切削的陶瓷材料、复合材料及金属材料。可切削的陶瓷材料主要包括：玻璃陶瓷(又称微晶玻璃)、玻璃渗透的陶瓷复合材料、氧化铝陶瓷、氧化锆陶瓷等。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。金属材料主要为牙科钛金属等。
在上述的各种材料中，复合树脂材料具有良好的韧性、可加工性、耐磨性，并具有X线阻射的作用和易抛光的特质，且其修复效果接近天然牙齿，是一种理想的牙科椅旁CAD/CAM的配套材料。但是，现有的复合树脂材料存在强度较低的问题，弯曲强度最高仅能达到约240MPa，仅能满足制作牙科修复体中的嵌体、高嵌体、贴面和单冠等不承重的修复体，不能制作需要承重的桥体和后牙等修复体。
发明内容
本申请实施例公开了一种牙科用复合树脂材料的制备方法及其制备的产品，用于解决现有的复合树脂材料强度较低的问题。技术方案如下：
本申请首先提供了一种牙科用复合树脂材料的制备方法，包括：
(1)称取各原料，所述各原料包括烯键式不饱和单体、增强纤维、填料、引发剂、阻聚剂及着色剂，其中，所述增强纤维及填料的总重量与烯键式不饱和单体重量的比为90∶10-10∶90，优选为85∶15-65∶35；引发剂重量占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％；阻聚剂重量占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％；着色剂占烯键式不饱和单体、增强纤维及填料总重量的0.001-0.2％，优选为0.005-0.1％；填料与增强纤维的重量比为10∶90-55∶45；
(2)将所称取的、除增强纤维外的原料混合，得到复合树脂单体前驱物；
(3)将所称取的增强纤维浸渍于所述复合树脂单体前驱物中1-5小时，优选为2-3小时，浸渍压力小于等于0.1MPa，得到吸附有复合树脂单体前驱物的 增强纤维；
(4)将吸附有复合树脂单体前驱物的增强纤维进行固化处理，得到牙科用复合树脂材料，其中，固化温度为100-200℃，优选为120-160℃，固化时间为0.5-3小时，优选为1.5-2小时；固化压力为10-200MPa，优选为10-100MPa，更优选为20-60MPa。
在本申请的一种具体实施方式中，所述原料还包括促进剂，促进剂占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％，优选地，所述促进剂为N，N-二羟乙基对甲苯胺。
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、粘度调节剂、润湿剂、抗氧化剂、稳定剂及稀释剂中的至少一种。
在本申请的一种具体实施方式中，所述烯键式不饱和单体包含(甲基)丙烯酸酯、羟基官能化的(甲基)丙烯酸酯及环氧树脂中的一种或其组合，优选地，包含双酚A-双甲基丙烯酸缩水甘油酯、乙氧基双酚A二甲基丙烯酸酯、氨基甲酸酯双甲基丙烯酸酯、双甲基丙烯酸二缩三乙二醇酯、甲基丙烯酸羟乙酯、聚乙二醇二甲基丙烯酸酯及双酚A环氧树脂中的一种或其组合。
在本申请的一种具体实施方式中，所述增强纤维包含碳纤维、玻璃纤维、石英纤维、硅质纤维、陶瓷纤维和聚合物纤维中的一种或其组合；所述增强纤维为纤维束、纤维布或纤维块；所述增强纤维的单根纤维的直径范围为0.1-25μm，优选为0.5-10μm；所述增强纤维的折射率范围为1.40-1.70，优选为1.45-1.60。
在本申请的一种具体实施方式中，所述填料包括I型填料和II型填料；所述I型填料为粒度范围在0.01μm-10μm的填料，所述I型填料选自于无机填料和/或不溶于所述复合树脂单体前驱物的预聚合有机填料；所述I型填料优选包括石英、钡玻璃、镧玻璃、硼硅酸盐玻璃、氧化硅-氧化锆复合粉体、氧化硅-氧化镱复合粉体、填充或未填充无机材料的聚碳酸酯、聚环氧化物粉末及聚合的甲基丙烯酸类树脂中的至少一种；所述I型填料的折射率范围为1.48-1.60，优选为1.50-1.58；所述II型填料为粒度范围在10-100nm的填料；所述II型填料优选包括氧化硅纳米粉体、氧化锆纳米粉体中的至少一种；所述 I型填料与所述II型填料的重量比为3∶1-1∶1。
在本申请的一种具体实施方式中，在与其它原料混合之前，对所述填料进行表面改性处理，改性处理的方法包括：偶联剂改性、等离子体表面处理改性或化学接枝改性。
在本申请的一种具体实施方式中，所述着色剂包括红色着色剂、黄色着色剂及黑色着色剂中的一种或其组合；红色着色剂优选为氧化铁红，黄色着色剂选自于氧化铁黄、铋黄、钒锆黄及铈镨黄中的一种或其组合，黑色着色剂优选为氧化铁黑。
在本申请的一种具体实施方式中，所述引发剂选自二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧乙酸叔丁酯及过氧化苯甲酸叔丁酯中的一种或其组合；所述阻聚剂为2，6-二叔丁基对甲苯酚。
在本申请的一种具体实施方式中，在浸渍之前对所述增强纤维进行预处理；所述预处理包括对所述增强纤维进行清洗并对其表面进行改性处理；
其中，清洗的方法包括热处理法、溶剂浸泡法或酸碱腐蚀法；改性处理的方法包括：偶联剂改性、等离子体表面处理改性或化学接枝改性。
本申请还提供了一种由上述方法制备的牙科用复合树脂材料。
采用本申请的提供的方法制备的牙科用复合树脂材料具有以下有益效果：
(1)本申请提供的牙科用复合树脂材料具有极高的机械强度，经实验测定挠曲强度达到600MPa以上，可用以制作承重部位的牙科修复体，如，牙桥，承重的牙冠，全口义齿，以及种植修复用的支架等；
(2)本申请提供的牙科用复合树脂材料未检出烯键式不饱和单体残余(无细胞毒性)，具有很好的生物安全性。
(3)本申请提供的牙科用复合树脂材料具有与天然牙接近的透度，光透过率可达40％以上，最高可达55％，可用来制备全形态义齿。
具体实施方式
本申请提供了一种牙科用复合树脂材料的制备方法，包括：
(1)称取各原料，所述各原料包括烯键式不饱和单体、增强纤维、填料、引发剂、阻聚剂及着色剂，其中，所述增强纤维及填料的总重量与烯键式不饱和单体重量的比为90∶10-10∶90，优选为85∶15-65∶35；引发剂重量占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％；阻聚剂重量占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％；着色剂占烯键式不饱和单体、增强纤维及填料总重量的0.001-0.2％，优选为0.005-0.1％；填料与增强纤维的重量比为10∶90-55∶45；
在本申请的具体实施方式中，烯键式不饱和单体包含(甲基)丙烯酸酯、羟基官能化的(甲基)丙烯酸酯及环氧树脂中的一种或其组合，优选地，包含双酚A-双甲基丙烯酸缩水甘油酯(Bis-GMA)、乙氧基双酚A二甲基丙烯酸酯(Bis-EMA)、氨基甲酸酯双甲基丙烯酸酯(UDMA)、双甲基丙烯酸二缩三乙二醇酯(TEGDMA)、甲基丙烯酸羟乙酯(HEMA)、聚乙二醇二甲基丙烯酸酯(PEGDMA)及双酚A环氧树脂(环氧树脂E-44)中的一种或其组合。
在本申请的具体实施方式中，增强纤维包含碳纤维、玻璃纤维、石英纤维、硅质纤维、陶瓷纤维和聚合物纤维中的一种或其组合；增强纤维可以为纤维束、纤维布或纤维块；增强纤维的单根纤维的直径范围为0.1-25μm，优选为0.5-10μm；增强纤维的折射率范围为1.40-1.70，优选为1.45-1.60。
在本申请的具体实施方式中，填料包括I型填料和II型填料；I型填料为粒度范围在0.01μm-10μm的填料，I型填料粒度范围优选0.01μm-5μm，更优选为0.01μm-1μm，I型填料可以是无机填料，也可以是不溶于所述复合树脂单体前驱物的预聚合有机填料，也可以是二者的组合；I型填料包括但不限于石英、钡玻璃、镧玻璃、硼硅酸盐玻璃、氧化硅-氧化锆复合粉体、氧化硅-氧化镱复合粉体、填充或未填充无机材料的聚碳酸酯、聚环氧化物粉末及聚合的甲基丙烯酸类树脂中的至少一种；I型填料的折射率范围为1.48-1.60，优选为1.50-1.58；所述II型填料为粒度范围在10-100nm的填料，II型填料粒度范围优选10-70nm，更优选15-50nm；II型填料优选包括氧化硅纳米粉体、氧化锆纳米粉体中的至少一种；I型填料与所述II型填料的重量比为3∶1-1∶1。
本申请采用折射率相接近的烯键式不饱和单体、增强纤维及填料，可以使得本申请制备出的牙科用复合树脂材料的外观更接近于天然牙。而将增强纤维与树脂材料复合在一起，能够显著提高树脂材料的强度，使之满足制备需要承重的桥体和后牙等修复体的需求。另外，申请人出人意料的发现，填料的加入能够增加材料的抛光性和耐磨性。进一步地，申请人出人意料的发现，将I型填料和II型填料混配使用，可以使本申请提供的牙科用复合树脂材料具有与天然牙齿类似的半透性和乳光效果。
在本申请的具体实施方式中，着色剂包括红色着色剂、黄色着色剂及黑色着色剂中的一种或其组合；红色着色剂优选为氧化铁红，黄色着色剂选自于氧化铁黄、铋黄、钒锆黄及铈镨黄中的一种或其组合，黑色着色剂优选为氧化铁黑。可以理解的是，各种着色剂的用量及它们之间的配比可以根据实际需要来进行调节，以使材料的颜色接近于天然牙齿的颜色。
在本申请的具体实施方式中，引发剂可以选自二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧乙酸叔丁酯及过氧化苯甲酸叔丁酯中的一种或其组合；阻聚剂可以为2，6-二叔丁基对甲苯酚，当然，也可以选择其它的引发剂及阻聚剂。优选地，原料中还可以包括促进剂，促进剂占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％，所述促进剂可以为N，N-二羟乙基对甲苯胺。
在本申请的具体实施方式中，原料中还可以包括适合在口腔环境中使用的各类添加剂，包括但不限于赋予荧光的试剂、指示剂、粘度调节剂、润湿剂、抗氧化剂、稳定剂及稀释剂中的至少一种。
(2)将所称取的、除增强纤维外的原料混合，得到复合树脂单体前驱物；
在具体实施过程中，可以通过机械搅拌或超声波震荡的方式将除增强纤维外的原料分散、混合均匀。
(3)将所称取的增强纤维浸渍于所述复合树脂单体前驱物中1-5小时，优选为2-3小时，浸渍压力小于等于0.1MPa，得到吸附有复合树脂单体前驱物的增强纤维；
在本申请的具体实施方式中，为了能够提高增强纤维和树脂之间的结合 强度，在将增强纤维浸渍于复合树脂单体前驱物中之前，可以对增强纤维进行预处理；预处理包括对增强纤维进行清洗并对其表面进行改性处理；
其中，清洗的方法包括但不限于热处理法、溶剂浸泡法或酸碱腐蚀法；所说的热处理法指的是高温煅烧，如在400℃煅烧1小时；溶剂浸泡法指的是用有机溶剂例如丙酮浸泡5小时；酸碱腐蚀处理指的是用一定浓度盐酸溶液或氢氧化钠溶液浸泡一定时间如0.5小时。需要说明的是，根据增强纤维材质的不同，可以采用不同的清洗方法，例如玻璃纤维可以采用酸碱腐蚀法，硅质纤维可以采用高温煅烧法，聚合物纤维可以采用溶剂浸泡法等。
进一步地，还可以对清洗后的增强纤维进行改性处理，改性处理的方法包括但不限于偶联剂改性、等离子体表面处理改性或化学接枝改性等。所列举的改性处理的方法均为现有技术，本领域技术人员可以获知实施上述改性处理的方法，本申请在此不进行限定，例如可以采用文献(硅烷偶联剂对碳微球的表面化学修饰，李莎、段菲菲等，功能材料2011年第1期42卷25-28页)中记载的方法对增强纤维进行偶联剂改性处理，该文献通过引用其全文并入本文中，本申请在此不进行赘述。所用的偶联剂包括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。
同理，在本申请的具体实施方式中，在将填料与其它原料混合之前，可以对所述填料进行表面改性处理，改性处理的方法包括：偶联剂改性、等离子体表面处理改性或化学接枝改性等，具体可以参见关于增强纤维的记载。
(4)将吸附有复合树脂单体前驱物的增强纤维进行固化处理，得到牙科用复合树脂材料，其中，固化温度为100-200℃，优选为120-160℃，固化时间为0.5-3小时，优选为1.5-2小时；固化压力为10-200MPa，优选为10-100MPa，更优选为20-60MPa。
采用上述的加压加热的固化处理，使得烯键式不饱和单体和引发剂在一定的压力下相互接触的面积增加，提高了固化反应效率，降低了聚合物单体残余，提高了复合树脂材料的生物相容性，并且有效地提高复合树脂材料的强度。
需要说明的是，本申请所用的加压加热设备等均为本领域常用的设备，能实现本申请的目的即可，本申请在此不进行限定，例如可以采用深圳市创佳鸿机械设备有限公司的热压设备。
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前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1
按表1中实施例1的配方称取各原料，将所称取的、除玻璃纤维束外的其它原料机械搅拌进行分散、混合，得到复合树脂单体前驱物；
将所称取的玻璃纤维束在400℃的温度下煅烧1h；冷却至室温后再进行偶联剂改性处理，具体的，可以将玻璃纤维束浸渍在含有KH570水解液的乙醇中(KH570水解液与乙醇体积比为1∶3)，在65℃处理2小时，然后在100℃的温度下干燥4小时。
将干燥后的增强纤维浸渍于复合树脂单体前驱物中2小时，浸渍压力控制在0.1MPa左右，得到吸附有复合树脂单体前驱物的增强纤维；然后再采用表1中实施例1中的固化工艺条件对吸附有复合树脂单体前驱物的增强纤维进行固化处理，即得到牙科用复合树脂材料。
实施例2-8
采用表1中所记载的原料配方及制备工艺条件，根据实施1所记载的制备方法制备牙科用复合树脂材料。其中，在实施例2中，填料镧玻璃粉、纳米氧化硅及纳米氧化锆在与其它原料混合之前，先进行偶联剂改性处理，处理方法与实施例1中的玻璃纤维束的处理方法相同；实施例6制备出的牙科用复合树脂材料的颜色为VITA 16色比色板的A2色，实施例7制备出的牙科用复合树脂材料的颜色为VITA 16色比色板的A3色，实施例8制备出的牙科用复合树脂材料的颜色为牙龈色。
力学性能测试
分别测定实施例1-8所制备的牙科用复合树脂材料及市售的Bioloren公司的Trilor CAD/CAM纤维增强树脂产品的挠曲强度、弯曲模量、及断裂韧性及光透过率，结果如表2所示。
其中，挠曲强度的测试方法参照YY/T 0710-2009/ISO 10477-2004《牙科学聚合物基冠桥材料》；弯曲模量的测试方法参照ISO 10477：2004Ed.2牙科学高聚物基的牙冠和齿桥材料；断裂韧性的测试方法参照ISO6872-2008牙科陶瓷材料，光透过率的测试方法参照JC/T 2020-2010透光性精细陶瓷透过率的测试方法。
从表2中可以看出，本申请实施例制备的牙科用复合树脂材料，各项性能均十分优异。较高的强度、韧性，使得该材料在应用于牙齿修复时，不论在加工过程中，还是在患者佩戴、使用过程中，都可以保持良好的形态，而不至于出现崩口、断裂等现象。从而使这种材料可以更广泛地应用于牙齿修复，满足市场的需求。
表1 实施例1-8制备牙科用复合树脂材料的原料配方及制备工艺条件
Figure PCTCN2017080865-appb-000001
Figure PCTCN2017080865-appb-000002
注：表1中的原料所对应的数值的单位为重量份，每重量份可以为100g。
表2 实施例1-8所制备的牙科用复合树脂材料及Trilor产品的性能比较
Figure PCTCN2017080865-appb-000003
理化性能测试
复合树脂材料固化越完全，聚合物单体残余越少，则材料的吸水值、溶解值和化学溶解性数值越低，材料的生物相容性越好。分别测试实施例1制备的制备的牙科用复合树脂材料及市售的Bioloren公司的Trilor CAD/CAM纤维增强树脂产品的吸水值、溶解性及化学溶解性，见表3，其中，吸水值和溶解值的测试方法参照YY/T 0710-2009/ISO 10477-2004《牙科学聚合物基冠桥材料》，化学溶解性的测试方法参照ISO6872-2008牙科陶瓷材料。
表3 实施例1与Trilor产品的性能比较：
Figure PCTCN2017080865-appb-000004
从表3可以看出，实施例1制备的牙科用复合树脂材料与Bioloren公司的Trilor产品相比具有较低的吸水值、溶解值和化学溶解性，说明本申请的制备方法有利于降低聚合物单体残余，因此，可以提高牙科用复合树脂材料的生物相容性、安全性。
以上对本申请所提供的一种牙科用复合树脂材料的制备方法及其制备的产品进行了详细介绍。本文中应用了具体实施例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的方法及其中心思想。应当指出，对于本领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以对本申请进行若干改进和修饰，这些改进和修饰也落入本申请权利要求的保护。

Claims (11)

  1. 一种牙科用复合树脂材料的制备方法，其特征在于，包括：
    (1)称取各原料，所述各原料包括烯键式不饱和单体、增强纤维、填料、引发剂、阻聚剂及着色剂，其中，所述增强纤维及填料的总重量与烯键式不饱和单体重量的比为90∶10-10∶90，优选为85∶15-65∶35；引发剂重量占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％；阻聚剂重量占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％；着色剂占烯键式不饱和单体、增强纤维及填料总重量的0.001-0.2％，优选为0.005-0.1％；填料与增强纤维的重量比为10∶90-55∶45；
    (2)将所称取的、除增强纤维外的原料混合，得到复合树脂单体前驱物；
    (3)将所称取的增强纤维浸渍于所述复合树脂单体前驱物中1-5小时，优选为2-3小时，浸渍压力小于等于0.1MPa，得到吸附有复合树脂单体前驱物的增强纤维；
    (4)将吸附有复合树脂单体前驱物的增强纤维进行固化处理，得到牙科用复合树脂材料，其中，固化温度为100-200℃，优选为120-160℃，固化时间为0.5-3小时，优选为1.5-2小时；固化压力为10-200MPa，优选为10-100MPa，更优选为20-60MPa。
  2. 如权利要求1所述的方法，其特征在于，所述原料还包括促进剂，促进剂占烯键式不饱和单体重量的0.05-1％，优选为0.1-0.3％，优选地，所述促进剂为N，N-二羟乙基对甲苯胺。
  3. 如权利要求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、粘度调节剂、润湿剂、抗氧化剂、稳定剂及稀释剂中的至少一种。
  4. 如权利要求1所述的方法，其特征在于，所述烯键式不饱和单体包含(甲基)丙烯酸酯、羟基官能化的(甲基)丙烯酸酯及环氧树脂中的一种或其组合，优选地，包含双酚A-双甲基丙烯酸缩水甘油酯、乙氧基双酚A二甲基丙烯酸酯、氨基甲酸酯双甲基丙烯酸酯、双甲基丙烯酸二缩三乙二醇酯、甲基丙烯酸羟乙酯、聚乙二醇二甲基丙烯酸酯及双酚A环氧树脂中的一种或其组 合。
  5. 如权利要求1所述的方法，其特征在于，所述增强纤维包含碳纤维、玻璃纤维、石英纤维、硅质纤维、陶瓷纤维和聚合物纤维中的一种或其组合；所述增强纤维为纤维束、纤维布或纤维块；所述增强纤维的单根纤维的直径范围为0.1-25μm，优选为0.5-10μm；所述增强纤维的折射率范围为1.40-1.70，优选为1.45-1.60。
  6. 如权利要求1所述的方法，其特征在于，所述填料包括I型填料和II型填料；所述I型填料为粒度范围在0.01μm-10μm的填料，所述I型填料选自于无机填料和/或不溶于所述复合树脂单体前驱物的预聚合有机填料；所述I型填料优选包括石英、钡玻璃、镧玻璃、硼硅酸盐玻璃、氧化硅-氧化锆复合粉体、氧化硅-氧化镱复合粉体、填充或未填充无机材料的聚碳酸酯、聚环氧化物粉末及聚合的甲基丙烯酸类树脂中的至少一种；所述I型填料的折射率范围为1.48-1.60，优选为1.50-1.58；所述II型填料为粒度范围在10-100nm的填料；所述II型填料优选包括氧化硅纳米粉体、氧化锆纳米粉体中的至少一种；所述I型填料与所述II型填料的重量比为3∶1-1∶1。
  7. 如权利要求1所述的方法，其特征在于，在与其它原料混合之前，对所述填料进行表面改性处理，改性处理的方法包括：偶联剂改性、等离子体表面处理改性或化学接枝改性。
  8. 如权利要求1所述的方法，其特征在于，所述着色剂包括红色着色剂、黄色着色剂及黑色着色剂中的一种或其组合；红色着色剂优选为氧化铁红，黄色着色剂选自于氧化铁黄、铋黄、钒锆黄及铈镨黄中的一种或其组合，黑色着色剂优选为氧化铁黑。
  9. 如权利要求1所述的方法，其特征在于，所述引发剂选自二枯基过氧化物、叔丁基过氧化物、过氧化苯甲酰、过氧乙酸叔丁酯及过氧化苯甲酸叔丁酯中的一种或其组合；所述阻聚剂为2，6-二叔丁基对甲苯酚。
  10. 如权利要求1-9中任一项所述的方法，其特征在于，在浸渍之前对所述增强纤维进行预处理；所述预处理包括对所述增强纤维进行清洗并对其表面进行改性处理；
    其中，清洗的方法包括热处理法、溶剂浸泡法或酸碱腐蚀法；改性处理的方法包括：偶联剂改性、等离子体表面处理改性或化学接枝改性。
  11. 如权利要求1-10中任一项所述的方法制备的牙科用复合树脂材料。
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