CN105943406B - 3D printing composite material used for stomatological repair and its preparation and application - Google Patents
3D printing composite material used for stomatological repair and its preparation and application Download PDFInfo
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- CN105943406B CN105943406B CN201610335111.7A CN201610335111A CN105943406B CN 105943406 B CN105943406 B CN 105943406B CN 201610335111 A CN201610335111 A CN 201610335111A CN 105943406 B CN105943406 B CN 105943406B
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 230000008439 repair process Effects 0.000 title claims abstract description 45
- 229960001957 stomatological preparations Drugs 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 125000001999 4-Methoxybenzoyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C(*)=O 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- JHQMEZRRZJJNAI-UHFFFAOYSA-N [(2-methylphenyl)-phenylphosphoryl]-phenylmethanone Chemical compound CC1=CC=CC=C1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 JHQMEZRRZJJNAI-UHFFFAOYSA-N 0.000 description 1
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical class C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- JVCXFJJANZMOCM-UHFFFAOYSA-N phenyl(trimethylgermyl)methanone Chemical compound C[Ge](C)(C)C(=O)C1=CC=CC=C1 JVCXFJJANZMOCM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- ROMWNDGABOQKIW-UHFFFAOYSA-N phenyliodanuidylbenzene Chemical compound C=1C=CC=CC=1[I-]C1=CC=CC=C1 ROMWNDGABOQKIW-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/61—Cationic, anionic or redox initiators
-
- 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
- A61K6/69—Medicaments
-
- 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
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
-
- 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
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/893—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of 3D printing composite material used for stomatological repair and its preparation and application.A kind of 3D printing composite material used for stomatological repair, which is characterized in that in parts by weight, including following components: 10 parts~40 parts of low viscosity monomer；Enhance monomer or 10 parts~40 parts of oligomer；150 parts~200 parts of ceramic powder；5 parts~20 parts of Expanding Monomer；5 parts~15 parts of dispersing agent；2 parts~6 parts of shortwave photoinitiator；1 part~3 parts of long wave photoinitiator；1 part~3 parts of UV absorbers；And polymerizable 2 parts~5 parts of quaternary ammonium salt antibacterial monomer.Above-mentioned 3D printing composite material cure shrinkage used for stomatological repair is smaller, curing time is short, antibiotic property is strong, to be suitable for production mouth mending material.
Description
Technical field
The present invention relates to the 3D printing composite material used for stomatological repair and its preparation and application of a kind of light curable type,
Particularly, the present invention relates to answering with low-shrinkage, appropriate viscosity, high-mechanical property, excellent biocompatibility and antibiotic property
Condensation material, this material is for mouth mending materials such as 3D printing inlay, veneer, corona, bridges.
Background technique
Increases material manufacturing technology, also known as 3D printing or rapid shaping, appear in last century Mo, are a kind of based on discrete and accumulation
Form the new manufacture of thought.The technological break-through complexity limit of traditional manufacturing technology has decoupled complexity, small quantities of
Amount customizes the relationship with cost, the referred to as important tool of " the third time industrial revolution ".The principle of 3D printer is first will to beat
The three-dimensional digital model of printed document carries out layered shaping, generates " scanning " path or image needed for printing each layer, then passes through
Laser selective melts the methods of dusty material, electric heating spray head melting extrusion wire rod, ultraviolet light projection print image successively " heap
Product " molding, subsequent print platform decline the height of a thickness, the process that some 3D printing methods also need to carry out powdering one kind
One layer of untreated material is newly set on molded surface, layer-by-layer " accumulation " the molding mistake of the progress then to move in circles
Three-dimensional digital model can finally be printed to three-dimensional real object by journey.
Gradually it is widely used in dental field from CAD/CAM the 1980s, dental CAD/CAM system is nowadays commercialized
System has been successfully applied to the production of all-ceramic prosthesis, but its working principle is mostly the pre- cutting at raw material, is to subtract material system
Method is made, major defect is a large amount of consumption of raw material, and cutting remaining porcelain block can only be lost because that cannot be recycled
It abandons；Visible ceramic material surfaces fine crack under its submicroscope is ruptured in cutting process and is produced this is because ceramic material matter is crisp
Raw.In addition material and facility is at high cost, and there are the shortcomings such as cumbersome, program is complicated.And 3D printing technique, have
Small in size, the advantages that precision is high, overall cost is low, shaping speed is fast, personalized customization, subtracts material forming skill in addition, also overcoming
Art waste of material and the limitation that a component can only be processed every time, therefore it is highly suitable to be applied for the production of mouth mending material.Base
It can pass through in the photocuring 3D printing technique of stereolithography (SLA), digital light processing (DLP) and continuous liquid level polymerization (CLIP)
The photocurable liquid resin of suitable wavelength or using liquid resin as the mixed slurry of matrix, molding have high surface finish, height
The 3D solid of precision and high complexity, in mouth or model scanning technical tie-up, realize mouth mending material production it is whole from
Dynamicization, to substitute design, the production of the mouth mending materials such as traditional personalization corona, bridge, artificial tooth, to greatly improve reparation
Body completes efficiency, precision, and saves the working time by chair.
Large-scale promotion and application is also not implemented in 3D printing technique at present, and a main reason is to be limited to 3D printing material
Material.It is also fewer that industrial 3D printing material category can be really applied at present, be unable to satisfy the requirement of industrial application, needle
It is most important for the application field for extending 3D printing to the extraordinary 3D printing material that different industrial requirement exploitations is adaptable.Mesh
Preceding existing photocuring 3D printing material has focused largely on simple resinous material, using also mostly entertainment intention, design open
The field not strong to printout Functional Requirement such as hair, model display such as subtracts material processing for substitution traditional industry production method
The 3D printing composite material that mouth mending material is developed is substantially also in space state.
Summary of the invention
Based on this, it is necessary to provide it is a kind of can be used in make mouth mending material 3D printing composite material and its preparation and
Application method.
A kind of 3D printing composite material used for stomatological repair, which is characterized in that in parts by weight, including following components:
The low viscosity monomer is simple function group or polyfunctional monomer, the low viscosity in one of the embodiments,
Monomer is selected from acrylic ester monomer, methacrylate-based monomer, vinyl monomer, vinyl ethers monomer and epoxies
At least one of monomer；Preferred methacrylate class, such as pentaerythritol tetramethylacrylate, carbamic acid dimethyl
Acrylate (UDMA), triethylene-glycol dimethylacrylate (TEGDMA), 1,4- butanediol dimethylacrylate, second
Aoxidize pentaerythritol tetramethylacrylate, 1,6-HD dimethylacrylate.
The enhancing monomer or oligomer are selected from bisphenol-A-dimethyl allene acid glycidyl in one of the embodiments,
Ester (bis-GMA), urethane methacrylate oligomer, methyl methacrylate oligomer, Epoxy Acrylates are oligomeric
At least one of object；Mechanical performance, wearability and low-shrinkage with higher.
The absorption peak wavelength of the shortwave photoinitiator is less than 400nm in one of the embodiments, and the long glistening light of waves draws
The absorption peak wavelength for sending out agent is greater than 400nm.
The shortwave photoinitiator is selected from acylphosphine oxide, bis-acylphosphine oxides, hexichol in one of the embodiments,
Ethyl alcohol ketone (styrax), benzoin ether, liquid storax, thioxanthone, benzil, benzil ketals, acetophenone and benzophenone
At least one of.
The maximum absorption band wavelength of the shortwave photoinitiator is less than 400nm in one of the embodiments, preferably
Between 280nm to 400nm, more preferably between 320nm to 400nm, between most preferably 350nm to 400nm.
The long wave photoinitiator is selected from α-diketone, metallocene and acyl group in one of the embodiments,
At least one of germanium compound.
The maximum absorption band wavelength of the long wave photoinitiator is greater than 400nm in one of the embodiments, preferably exists
Between 400nm to 600nm, more preferably between 400nm to 500nm, between most preferably 420nm to 470nm.
The 3D printing composite material used for stomatological repair also includes 1 part~3 parts cationic photopolymerizations in one of the embodiments,
Initiator, the cation light initiator are selected from aromatic diazo salt, organic aluminium compound, silane compound, Diaryl iodonium
Salt, triaryl sulfonium salts, triaryl selenium salt, alkyl sulfosalt, sulfonyloxy ketone, triaryl silicon oxygen ether, ferrocene and Fang Mao
At least one of molysite.
In one of the embodiments, the UV absorbers be selected from benzotriazole, benzophenone, salicylate,
At least one of hindered amine light stabilizer, cyanoacrylate, triazine and nano-titanium dioxide, the UV absorbers
Maximum absorption band wavelength is less than 400nm；Preferably between 280nm to 400nm, more preferably between 320nm to 400nm,
Between most preferably 350nm to 400nm, absorbent preferably in the effective wavelength range of the long wave photoinitiator almost
Do not absorb luminous energy.
The Expanding Monomer is selected from spiro orthoester class, spiro orthocarbonate class, bicyclic original in one of the embodiments,
At least one of esters of gallic acid and ketal lactone class, preferably spiro orthocarbonate class, such as 3,9- diethyl -3,9- propylene oxygen first
Four oxygen spiral shell miscellaneous ten of the four miscellaneous hendecane of oxygen spiral shell (BAOM) of base -1,5,7,11- and 3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11-
One alkane (DHOM).
The polymerizable quaternary ammonium salt antibacterial monomer is selected from methacryloxypropyl dodecyl bromide in one of the embodiments,
Pyridine (MDPB), and
At least one of；Wherein-R1For in straight chained alkyl, branched alkyl, multi-ring alkyl and aryl containing 1~12 carbon
One kind ,-R2For
One of ,-R3For
And one of straight chained alkyl containing 1~12 carbon, branched alkyl, multi-ring alkyl, aryl, X-For chloride ion, bromine
One of ion, hexafluoro-phosphate radical.
The ceramic powder is selected from preparing spherical SiO 2, titanium dioxide, zirconium dioxide, three in one of the embodiments,
It is fluorinated at least one of ytterbium, tantalum oxide, barium sulfate, quartz, glass and glass ceramics powder.
The dispersing agent is selected from polyamide, poly- propoxyl group ammonium salt, quaternary ammonium acetate and phosphoric acid in one of the embodiments,
At least one of ester.
The 3D printing composite material used for stomatological repair also includes that parts by weight are greater than 0 part in one of the embodiments,
And the light inhibitor less than 3 parts, the light inhibitor are selected from tetraethylthiuram disulfide and naphthalene formyl methylene quinuclidine four
One of phenylboronate.
The 3D printing composite material used for stomatological repair also includes that parts by weight are greater than 0 part in one of the embodiments,
And the defoaming agent less than 5 parts, the defoaming agent are selected from mineral oils, organic silicon, polyethers, polyesters, lower aliphatic alcohols
At least one of.
The 3D printing composite material used for stomatological repair also includes other additives in one of the embodiments, such as
Aqueous solvent or ethyl alcohol, stabilizer, levelling agent, aromatic, pigment, Fluoride release ingredient, fluorescent whitening agent, plasticizer.
The preparation method of 3D printing composite material used for stomatological repair described in any of the above embodiments, comprising the following steps:
1) by low viscosity monomer, enhancing monomer or oligomer, Expanding Monomer, polymerizable quaternary ammonium salt antibacterial monomer, dispersing agent
Pre-composition is obtained after mixing；
2) ball-milling treatment obtains mixture after the pre-composition being added in ceramic powder；And
3) continuation ball milling in the mixture is added in shortwave, long wave, cation light initiator and UV absorbers to obtain
To the 3D printing composite material used for stomatological repair.
The application method of above-mentioned 3D printing composite material used for stomatological repair, comprising the following steps:
1) it is less than the light source of 400nm using maximum emission peak wavelength, by stereolithography (SLA), digital light processing (DLP)
Or continuous liquid level polymerization (CLIP) technology, the 3D printing composite material used for stomatological repair according to the mathematical model photocuring of oral cavity,
Obtain tri-dimensional oral prosthesis, such as inlay, veneer, corona, bridge.
2) tri-dimensional oral prosthesis is put into photocuring case of the maximum emission peak wavelength greater than 400nm and is carried out centainly
The subsequent cure of time, to enhance the mechanical performance of the tri-dimensional oral prosthesis.
Above-mentioned 3D printing composite material used for stomatological repair, under light irradiation of the maximum emission peak wavelength less than 400nm, shortwave
Photoinitiator causes resin monomer polymerization to solidify rapidly, and UV absorbers adjust curing depth during resin polymerization
And extent of polymerization, while Expanding Monomer can generate volume expansion in the polymerization process that cation light initiator causes to subtract
The contraction and internal stress that small slurry is generated when solidifying make the component printed have smaller deformation, better dimensional accuracy
With less micro-crack defect.Then the mouth mending material that printing obtains is placed in photocuring case and carries out subsequent cure, most
Under light irradiation of the big emission peak wavelength greater than 400nm, long wave photoinitiator causes resin monomer or oligomeric remaining in dummy
Object polymerization, to improve the resin polymerization degree of dummy, ceramic powders of the more compact bonding as reinforced phase increase its machine
Tool intensity and wearability, polymerizable quaternary ammonium salt antibacterial monomer are aggregated in Light Curing with resin monomer/oligomer
Together, to provide good anti-microbial property for dummy, and reduce the possibility being precipitated in use.
Ceramic powders resin compounded directly can be printed by designed oral cavity mathematical model using photocuring 3D printing
The mouth mending material of material.By this 3D printing method and material, traditional material method production mouth mending material that subtracts can be by
It is substituted off, not only has many advantages, such as that small in size, precision is high, saving material, overall cost is low, shaping speed is fast, personalized customization,
And it greatly improves dummy to complete efficiency and save the working time by chair.
Specific embodiment
3D printing composite material used for stomatological repair and its preparation and application are made mainly in combination with specific embodiment below
Further details of explanation.
A kind of 3D printing composite material used for stomatological repair, which is characterized in that in parts by weight, including following components:
Above-mentioned 3D printing composite material used for stomatological repair can be used for stereolithography (SLA), digital light processing (DLP) and continuously
Liquid level polymerize 3D printing techniques such as (CLIP).
Resinous substrates are that the continuous phase in material for bonding the ceramic powder particle as reinforced phase passes through selectivity
The process of photopolymerization forms 3D solid corresponding with mathematical model.Resinous substrates are by low viscosity monomer and enhancing monomer or low
Polymers composition.Low viscosity monomer is simple function group or polyfunctional monomer, is selected from acrylic ester monomer, methyl acrylic ester
At least one of monomer, vinyl monomer, vinyl ethers monomer and epoxy monomer, preferred methacrylate class,
Such as pentaerythritol tetramethylacrylate, carbamic acid dimethylacrylate (UDMA), triethylene-glycol dimethyl propylene
Olefin(e) acid ester (TEGDMA), 1,4- butanediol dimethylacrylate, ethoxyquin pentaerythritol tetramethylacrylate, 1,6- oneself two
Alcohol dimethylacrylate, two/tri-/tetra- ethylene glycol dimethylacrylates, trimethylol-propane trimethacrylate,
Two/trimethyl acrylic ester of glycerol.Enhance monomer or oligomer mechanical performance with higher, wearability and low-shrinkage, choosing
From bisphenol-A-dimethyl allene acid glycidyl ester (bis-GMA), urethane methacrylate oligomer, methyl methacrylate
At least one of ester oligomer, Epoxy Acrylates oligomer.
Expanding Monomer is a kind of bicyclic or tricyclic compound that can generate volume expansion in the course of the polymerization process, mostly containing miscellaneous
The bicyclic or tricyclic compound of atom, the hetero atom of most of monomers are oxygen, it is a small number of then be sulphur, nitrogen etc. is similar with epoxy resin,
Expanding Monomer polymerization belongs to the ring-opening polymerisation of cation initiation.Expanding Monomer be used to reduce contraction that slurry is generated when solidify with
Internal stress makes the component printed have smaller deformation, better dimensional accuracy and less micro-crack defect.May be used also simultaneously
To improve the cylinder block strength of polymer material, polymerization-filling degree is improved, small molecule leaching content is reduced, makes the biology performance of system
Optimized.Expanding Monomer is in spiro orthoester class, spiro orthocarbonate class, bicyclo orthoester class and ketal lactone class
At least one, preferably spiro orthocarbonate class, such as 3,9- diethyl -3,9- propylene oxygen methyl-1,5,7,11- tetra- oxygen spiral shells miscellaneous ten
The four miscellaneous hendecane of oxygen spiral shell (DHOM) of one alkane (BAOM) and 3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11-.
Ceramic powder is used as obturator in 3D printing composite material used for stomatological repair, dummy can be made to have higher
Hardness, intensity and wearability.Ceramic powder be selected from preparing spherical SiO 2, titanium dioxide, zirconium dioxide, borontrifluoride ytterbium, tantalum oxide,
At least one of barium sulfate, quartz, glass and glass ceramics powder, powder particle average diameter 0.005 μm to 10 μm it
Between, preferably between 0.1 μm to 5 μm, more preferably between 0.1 μm to 1 μm, most preferably 0.1 μm to 0.3 μm it
Between.
Resin monomer or oligomer itself cannot effectively absorb the energy of exposure light, it is therefore desirable to add in the composite
Photoinitiator, photoinitiator itself do not participate in polymerization reaction directly, but light irradiation energy can be absorbed, and transfer energy to resin
Molecule generates the polymerization reaction that reactive intermediate causes monomer or oligomer.The selection of photoinitiator is it is required that it absorbs light
Spectrum is matched with the spectral distribution property of light source, additionally depends on solubility of the photoinitiator in material slurry, is added light-initiated
Material is stored in the stability etc. under no light condition after agent.Especially, the use of photoinitiator has been largely fixed light
The speed of curing reaction.
Photoinitiator includes free radical photo-initiation and cation light initiator.
Free radical photo-initiation includes shortwave photoinitiator and long wave photoinitiator, and wherein the maximum of shortwave photoinitiator is inhaled
It is long less than 400nm to receive spike, preferably between 280nm to 400nm, more preferably between 320nm to 400nm, most preferably
It is between 350nm to 400nm；The maximum absorption band wavelength of long wave photoinitiator is greater than 400nm, preferably arrives in 400nm
Between 600nm, more preferably between 400nm to 500nm, between most preferably 420nm to 470nm.
Shortwave photoinitiator be selected from acylphosphine oxide, bis-acylphosphine oxides, diphenylhydroxyethanone (styrax), benzoin ether,
At least one of liquid storax, thioxanthone, benzil, benzil ketals, acetophenone and benzophenone, such as 2,4,6- tri-
Bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of methyl benzoyl diphenyl phosphine oxide, phenyl, benzyl dimethyl ketal,
1- hydroxy-cyclohexyl phenyl ketone, α-Dialkoxy acetophenones.
Long wave photoinitiator is selected from least one of α-diketone, metallocene and acyl group germanium compound, such as
Camphorquinone, 1- phenyl -1,2- propanedione, 9,10- phenanthrenequione, dibenzoyl diethyl germanium, bis- (4- methoxybenzoyl bases)-two
Germanium ethide, benzoyltrimethyl germanium, the fluoro- 3- pyrroles's phenyl titanocenes of double 2,6- bis-.Preferably, can choose α-binary
Ketone, such as camphorquinone, 1- phenyl -1,2- propanedione and its mixture, can cooperate amine aided initiating to be used together, such as first
Base dimethylaminoethyl acrylate, dimethylaminoethyl benzoyl ethyl ester, N, accelerine.
Cation light initiator is used to cause the ring-opening polymerization of Expanding Monomer, is selected from aromatic diazo salt, organo-aluminium
Complex compound, silane compound, diaryl iodonium salt, triaryl sulfonium salts, triaryl selenium salt, alkyl sulfosalt, sulphonyl oxygen
At least one of base ketone, triaryl silicon oxygen ether, ferrocene and iron arene complexes, such as diphenyl iodine hexafluorophosphate, 4,4'-
Dimethyl diphenyl iodine hexafluorophosphate, diphenyl iodine trifluoro-methanyl sulfonate, fluoro- two cyclopentadienyl of 3- pyrroles's phenyl of double 2,6- bis-
Titanium and (4- Phenylsulfanyl-phenyl) diphenyl sulphur hexafluorophosphate.
Addition UV absorbers can suitably be reduced according to demand in 3D printing composite material used for stomatological repair printed
Reaction speed and curing depth in journey.The maximum absorption band wavelength of UV absorbers is less than 400nm, preferably in 280nm
To between 400nm, more preferably between 320nm to 400nm, between most preferably 350nm to 400nm, absorbent is best
Luminous energy is hardly picked up in the effective wavelength range of long wave photoinitiator.It can be selected from benzotriazole, benzophenone, salicylic acid
At least one of ester, hindered amine light stabilizer, cyanoacrylate, triazine and nano-titanium dioxide, such as 2,4- dihydroxy
Benzophenone, ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2 '-hydroxyls -3 ', 5 ' -
Two tertiary phenyl) -5- chlorination benzotriazole, 2- (2 '--5 '-aminomethyl phenyl of hydroxyl) benzotriazole, 2- (2H- benzotriazole -2-
Base) -6- dodecyl -4- methylphenol, 2- (2- hydroxyl -4- hexyloxy-phenyl) -4,6- diphenyl -1,3,5- triazine, 2- second
Alkyl-hexyl -2- cyano -3,3- diphenylacrylate ester, bis- (2,2,6,6- tetramethyl -4- piperidyl)-sebacates.
Polymerizable quaternary ammonium salt antibacterial monomer is selected from methacryloxypropyl dodecyl bromopyridine (MDPB), and
At least one of；Wherein-R1For in straight chained alkyl, branched alkyl, multi-ring alkyl and aryl containing 1~12 carbon
One kind ,-R2For
One of ,-R3For
And one of straight chained alkyl containing 1~12 carbon, branched alkyl, multi-ring alkyl, aryl, X-For chloride ion, bromine
One of ion, hexafluoro-phosphate radical.Such as methylacryoyloxyethyl-n-hexadecyl-dimethyl ammonium hexafluorophosphate
(DMAE-CH), two (2- methylacryoyloxyethyl)-n-dodecanes-methyl ammonium hexafluorophosphate (MAE-DH), methacryloxypropyl
Ethyl-benzyl-alkyl dimethyl ammonium chloride (DMAE-BC), methylacryoyloxyethyl-n-hexadecyl-ditallowdimethyl ammonium bromide
(DMAE-CB), methylacryoyloxyethyl-dodecyl-ditallowdimethyl ammonium bromide (DMAE-BB), two (2- methacryloxypropyls
Ethyl)-dodecyl-methyl bromide ammonium (MAE-DB), two (2- methylacryoyloxyethyl)-n-hexadecyl-methyl bromides
Change ammonium (MAE-HB), two (2- acrylyl oxy-ethyl)-dodecyls-methyl bromide ammonium (AE-DB), two (2- acryloyl-oxy second
Base)-n-hexadecyl-methyl bromide ammonium (AE-HB).Select the quaternary ammonium salt antibacterial monomer that can be copolymerized with resinous substrates that can synthesize
The anti-biotic material of non-stripping property out, quaternary ammonium salt are a kind of organic antibacterial agents of high-efficiency broad spectrum, the fast, antibacterial efficacy with sterilization speed
Persistently, low toxicity, low corrosion, good colour, the advantages that being uniformly dispersed, while because it is that antibacterial functions group is passed through chemical bond
Form secure attachment in resinous substrates, therefore overcome common organic antibacterial agents thermal stability it is poor, be easy decompose dissolution, decompose
The deficiencies of product is toxic, and show long-term biological effect.
3D printing composite material used for stomatological repair further includes dispersing agent.The effect of dispersing agent is uniform dispersion in the slurry
Ceramic powder particle simultaneously prevents the reunion of powder particle from agglomerating and precipitating.Suitable dispersing agent, which is added, can promote material forming
Continuous, non-porous and homogeneous film is formed in the process.If dispersing agent is added excessively, it is unfavorable that the light-cured performance of material will receive
It influences and interlayer adhesion when printing is affected.If dispersing agent addition is very few, homogeneous material may be interfered
It is formed.The specific dispersing agent quantity for being suitble to be added is related to the powder classification and its surface area used, needs accordingly to be adjusted.
Dispersing agent is selected from least one of polyamide, poly- propoxyl group ammonium salt, quaternary ammonium acetate and phosphate.Further, poly- third oxygen
Base ammonium salt is preferably at least one of the poly- propoxy methyl ammonium chloride of diethyl and the poly- propoxyl group dihydroxy ammonium phosphate of diethyl.
Further, polyamide is preferably the polyamide hyper-dispersant under Noveon company SOLSPERSE 32000 and 39000 trade marks；
The poly- propoxy methyl ammonium chloride of diethyl is preferably the poly- propoxyl group of diethyl under Degussa company VARIQUAT CC-59 trade mark
Ammonio methacrylate；The poly- propoxyl group dihydroxy ammonium phosphate of diethyl is preferably under Degussa company VARIQUAT CC-42NS trade mark
The poly- propoxyl group dihydroxy ammonium phosphate of diethyl；Quaternary ammonium acetate is preferably under Degussa company VARIQUAT CC-55 trade mark
Quaternary ammonium acetate；Phosphate is preferably the RHODAFAC RS-610 and RE 610 of Rhodia company.Certainly, phosphate may be used also
Think unsaturated phosphate ester, the preferably MAXEMUL 6106 and 6112 of Uniqema company.
3D printing composite material used for stomatological repair also may include that parts by weight are greater than 0 part and the light inhibitor less than 3 parts, with
Material is set to use on the 3D printer that continuous liquid level polymerize (CLIP) technology, light inhibitor is selected from the tetraethyl base autumn
One of blue nurse and naphthalene formyl methylene quinuclidine tetraphenyl borate salts.
3D printing composite material used for stomatological repair also may include that parts by weight are greater than 0 part and the defoaming agent less than 5 parts, can be with
Surface tension is reduced, foam is inhibited to generate or eliminate the foam generated, defoaming agent is selected from mineral oils, organic silicon, polyethers
At least one of class, polyesters, lower aliphatic alcohols.
3D printing composite material used for stomatological repair also may include other additives, such as aqueous solvent or ethyl alcohol, stabilizer, stream
Flat agent, aromatic, pigment, Fluoride release ingredient, fluorescent whitening agent, plasticizer.
The application method of above-mentioned 3D printing composite material used for stomatological repair is as follows:
Be less than the light source of 400nm using maximum emission peak wavelength, by stereolithography (SLA), digital light processing (DLP) or
Continuous liquid level polymerize (CLIP) technology, solidifies above-mentioned material used for stomatological repair by successively selectivity, straight by oral cavity mathematical model
It connects to obtain tri-dimensional oral prosthesis, such as inlay, veneer, corona, bridge.Subsequent forming three-dimensional mouth mending material is placed into maximum
Emission peak wavelength carries out subsequent cure in the photocuring case greater than 400nm, to enhance the mechanical performance of dummy.
Above-mentioned 3D printing composite material used for stomatological repair, under light irradiation of the maximum emission peak wavelength less than 400nm, shortwave
Photoinitiator causes resin monomer polymerization to solidify rapidly, and UV absorbers adjust curing depth during resin polymerization
And extent of polymerization, while Expanding Monomer can generate volume expansion in the polymerization process that cation light initiator causes to subtract
The contraction and internal stress that small slurry is generated when solidifying make the component printed have smaller deformation, better dimensional accuracy
With less micro-crack defect.Then the mouth mending material that printing obtains is placed in photocuring case and carries out subsequent cure, most
Under light irradiation of the big emission peak wavelength greater than 400nm, long wave photoinitiator causes resin monomer/oligomer remaining in dummy
Polymerization, to improve the resin polymerization degree of dummy, ceramic powders of the more compact bonding as reinforced phase increase its machinery
Intensity and wearability, polymerizable quaternary ammonium salt antibacterial monomer condense together in Light Curing with resinous substrates, thus
Good anti-microbial property is provided for dummy, and reduces the possibility being precipitated in use.
Ceramic powders resin compounded directly can be printed by designed oral cavity mathematical model using photocuring 3D printing
The mouth mending material of material.By this 3D printing method and material, traditional material method production mouth mending material that subtracts can be by
It is substituted off, not only has many advantages, such as that small in size, precision is high, saving material, overall cost is low, shaping speed is fast, personalized customization,
And it greatly improves dummy to complete efficiency and save the working time by chair.
The preparation method of above-mentioned 3D printing composite material used for stomatological repair, include the following:
Step S110, by low viscosity monomer, enhancing monomer or oligomer, Expanding Monomer, polymerizable quaternary ammonium salt antibacterial monomer,
Pre-composition is obtained after dispersant.
It is preferably mixed and added into Expanding Monomer before dispersing agent, polymerizable quaternary ammonium salt antibacterial monomer first by low viscosity
Monomer and enhancing monomer or oligomer are uniformly mixed.
Preferably, if mixing and adding with resin monomer/oligomer when Expanding Monomer is the mixture of two kinds of Expanding Monomers
First two kinds of Expanding Monomers are uniformly mixed before entering dispersing agent, polymerizable quaternary ammonium salt antibacterial monomer.
Step S120, ball-milling treatment obtains mixture after the pre-composition being added in ceramic powder.
Preferably, ceramic powder is added gradually in pre-composition several times, it is further preferred that being added to premix in three times
In object.
Preferably, ball-milling treatment carries out in ceramic pot.
Preferably, ball-milling treatment is that different size of spherical ceramic grinding media is added to carry out ball milling.Further, ball
The quality of shape ceramic grinding media and the quality of mixed slurry are suitable.Further, diameter is in spherical ceramic grinding media
The mass ratio for the spherical ceramic grinding media that 10mm and diameter are 3mm is 1:1.
Preferably, the time of ball-milling treatment is 8~48 hours.
Preferably, the revolving speed of ball milling is 10~30rpm.
Step S130, ball milling in mixture is added in photoinitiator and UV absorbers and obtains 3D printing used for stomatological repair
Composite material.
Preferably, photoinitiator includes shortwave, long wave, cation light initiator.
Preferably, the time of ball milling is 1~3 hour in the step.
Preferably, which carries out before carrying out printing.
The preparation method of above-mentioned 3D printing composite material used for stomatological repair, it is easy to operate.
The following are specific embodiment parts:
Embodiment 1
The preparation of the 3D printing composite material used for stomatological repair of embodiment 1 the following steps are included:
Electronic balance measures 10g pentaerythritol tetramethylacrylate and 10g urethane methacrylate oligomer, will
Both resins are mixed and stirred for.
Measure the spiro orthocarbonate class Expanding Monomer 3,9- diethyl -3,9- propylene oxygen methyl-1 of 20g, 5,7,11- tetra-
The miscellaneous hendecane of oxygen spiral shell (BAOM), is added in above-mentioned resin compound.
The polymerizable quaternary ammonium salt antibacterial monomer methacryloxypropyl dodecyl bromopyridine (MDPB) of 5g is measured, is added to above-mentioned
In mixture.
It measures the poly- propoxy methyl ammonium chloride of 5g diethyl (the VARIQUAT CC-59 of Degussa company) and is used as dispersing agent
It is added in said mixture, is suitably uniformly mixing to obtain liquid mixture.
Satisfactory powder will be obtained after the screening of spherical Zirconium dioxide powder, the average diameter of powder particle is 0.3 micro-
Rice.150g Zirconium dioxide powder is measured, it is secondary in three batches to be added step-wise in aforesaid liquid mixture and carried out after each be added
Stirring is sufficiently to be mixed.
It is subsequently placed in ceramic pot by the mixture that previous step obtains, 200g different size (diameter point is added
Not Yue Wei 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, ceramic pot is then placed on roller ball mill
On machine with the speed of 10rpm carry out for when 8 hours ball millings.
Finally before carrying out printing, 2,4, the 6- trimethyl benzoyl diphenyl base oxygen of 2g are added in ceramic pot
Change phosphine as shortwave photoinitiator, the dibenzoyl diethyl germanium of 1g is as long wave photoinitiator, the diphenyl iodine six of 1g
Fluorophosphate is as cation light initiator.And the 2-hydroxy-4-n-octoxybenzophenone of 3g is added as UV Absorption
Agent.The mineral oil antifoam agent of 5g is added.Ceramic pot is continued to be put into and is carried out 1 hour on tumbling ball mill with the speed of 10rpm
Ball milling obtains being sufficiently mixed uniform 3D printing composite material used for stomatological repair.
Embodiment 2
Electronic balance measures 40g carbamic acid dimethylacrylate (UDMA) and 10g bisphenol-A-dimethacrylate contracting
Water glyceride (bis-GMA), both resins are mixed and stirred for.
Measure the spiro orthocarbonate class Expanding Monomer 3,9- diethyl -3,9- propylene oxygen methyl-1 of 5g, tetra- oxygen of 5,7,11-
The miscellaneous hendecane of spiral shell (BAOM), is added in above-mentioned resin compound.
Measure the polymerizable quaternary ammonium salt antibacterial monomer methylacryoyloxyethyl-n-hexadecyl-dimethyl hexafluorophosphoric acid of 5g
Ammonium (DMAE-CH), is added in said mixture.
15g polyamide hyper-dispersant (SOLSPERSE 32000 of Noveon company) is measured to be added in said mixture,
Suitably it is uniformly mixing to obtain liquid mixture.
Satisfactory powder will be obtained after the screening of globular glass ceramic powders, the average diameter of powder particle is about 0.1
Micron.Measure 200g glass ceramic powder, it is secondary in three batches be added step-wise to it is in aforesaid liquid mixture and laggard being added every time
Row stirring is sufficiently to be mixed.
It is subsequently placed in ceramic pot by the mixture that previous step obtains, 275g different size (diameter point is added
Not Yue Wei 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, ceramic pot is then placed on roller ball mill
On machine with the speed of 15rpm carry out for when 24 hours ball millings.
Finally before carrying out printing, the phenyl that 6g is added in ceramic pot is bis- (2,4,6- trimethylbenzoyl)
Phosphine oxide is as shortwave photoinitiator, and the camphorquinone of 3g is as long wave photoinitiator, 4, the 4'- dimethyl diphenyl iodine six of 3g
Fluorophosphate is as cation light initiator.And 2- (2H- benzotriazole -2- base) -6- dodecyl -4- methylbenzene of 1g is added
Phenol is as UV absorbers.The tetraethylthiuram disulfide of 3g is added as light inhibitor.Ceramic pot is continued to be put into rolling
It is compound to obtain being sufficiently mixed uniformly 3D printing used for stomatological repair for the ball milling for carrying out 2 hours on cylinder ball mill with the speed of 15rpm
Material.
Embodiment 3
Electronic balance measures 10g triethylene-glycol dimethylacrylate (TEGDMA) and 40g methyl methacrylate
Both resins are mixed and stirred for by oligomer.
Measure four oxygen of spiro orthocarbonate class Expanding Monomer 3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11- of 15g
The miscellaneous hendecane of spiral shell (DHOM), is added in above-mentioned resin compound.
Measure polymerizable two (2- acrylyl oxy-ethyl)-dodecyl of the quaternary ammonium salt antibacterial monomer-methyl bromide ammonium of 2g
(AE-DB), it is added in said mixture.
12g quaternary ammonium acetate (the VARIQUAT CC-55 of Degussa company) is measured as dispersing agent and is added to above-mentioned mix
In resin, it is suitably uniformly mixing to obtain liquid mixture.
Satisfactory powder is obtained after spherical silicon dioxide powder is sieved, the average diameter of powder particle is about 0.2
Micron.Measure 160g SiO 2 powder, it is secondary in three batches be added step-wise to it is in aforesaid liquid mixture and laggard being added every time
Row stirring is sufficiently to be mixed.
It is subsequently placed in ceramic pot by the mixture that previous step obtains, 239g different size (diameter point is added
Not Yue Wei 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, ceramic pot is then placed on roller ball mill
On machine with the speed of 30rpm carry out for when 48 hours ball millings.
Finally before carrying out printing, the benzyl dimethyl ketal that 5g is added in ceramic pot draws as short wavelength light
Agent is sent out, double fluoro- 3- pyrroles's phenyl titanocenes of 2,6- bis- of 2.5g are as long wave photoinitiator, the fluoro- 3- pyrroles of double 2,6- bis- of 2g
Phenyl titanocenes are as cation light initiator.And the ESCALOL 567 that 1.2g is added is inhaled as ultraviolet light
Receive agent.Ceramic pot is continued to be put on tumbling ball mill with the ball milling of the speed progress 3 hours of 30rpm, obtains being sufficiently mixed
Even 3D printing composite material used for stomatological repair.
Embodiment 4
Electronic balance measures the 1,4- butanediol dimethylacrylate of 30g and 35g bisphenol-A-dimethacrylate shrinks
Glyceride (bis-GMA), both resins are mixed and stirred for.
Measure four oxygen of spiro orthocarbonate class Expanding Monomer 3,9- diethyl -3,9- dihydroxymethyl -1,5,7,11- of 10g
3,9- diethyl -3,9- propylene oxygen the methyl-1 of the miscellaneous hendecane of spiral shell (DHOM) and 5g, the tetra- miscellaneous hendecane of oxygen spiral shell of 5,7,11-
(BAOM), it is added to after mixing in above-mentioned resin compound.
Measure polymerizable two (2- methylacryoyloxyethyl)-n-dodecane of the quaternary ammonium salt antibacterial monomer-methyl hexafluoro of 3.6g
Ammonium phosphate (MAE-DH), is added in said mixture.
Measure the poly- propoxyl group dihydroxy ammonium phosphate of 14g diethyl (the VARIQUAT CC-42NS of Degussa company) conduct
Dispersing agent is added in above-mentioned hybrid resin, is suitably uniformly mixing to obtain liquid mixture.
Satisfactory powder, Zirconium dioxide powder are obtained after spherical zirconium dioxide and glass powder are sieved respectively
The average diameter of particle is about 0.3 micron, and the average diameter of glass powder particle is about 3 microns.Measure 120g titanium dioxide zirconium powder
End, it is secondary in three batches to be added step-wise in aforesaid liquid mixture and be stirred after each be added sufficiently to be mixed, with
80g glass powder is measured afterwards, is added step-wise in aforesaid liquid mixture and is stirred after each be added sufficiently to carry out
Mixing.
It is subsequently placed in ceramic pot by the mixture that previous step obtains, 297.6g different size (diameter is added
Respectively may be about 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, ceramic pot is then placed on roller ball
On grinding machine with the speed of 30rpm carry out for when 48 hours ball millings.
Finally before carrying out printing, the 1- hydroxy-cyclohexyl phenyl ketone of 3g is added in ceramic pot as short wavelength light
Initiator, 9, the 10- phenanthrenequione of 2g is used as to help as the dimethylaminoethyl methacrylate of long wave photoinitiator and 0.8g to be drawn
Agent is sent out, (4- Phenylsulfanyl-phenyl) diphenyl sulphur hexafluorophosphate of 1.8g is as cation light initiator.And it is added 1.2g's
2- (2 '--5 '-aminomethyl phenyl of hydroxyl) benzotriazole is as UV absorbers.And 4g white pigment and 5g fluorescent brightening is added
Agent is to improve the pure white aesthetics of mouth mending material.Ceramic pot is continued to be put into and is carried out on tumbling ball mill with the speed of 20rpm
2.5 hours ball millings obtain being sufficiently mixed uniform 3D printing composite material used for stomatological repair.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
1. a kind of 3D printing composite material used for stomatological repair, which is characterized in that in parts by weight, including following components:
The maximum absorption band wavelength of the shortwave photoinitiator is between 280nm to 400nm, the maximum of the long wave photoinitiator
Absorption peak wavelength is between 400nm to 600nm；
The low viscosity monomer be simple function group or polyfunctional monomer, the low viscosity monomer be selected from acrylic ester monomer,
At least one of methacrylate-based monomer, vinyl monomer, vinyl ethers monomer and epoxy monomer；
It is low that the enhancing monomer or oligomer are selected from bisphenol-A-dimethyl allene acid glycidyl ester, urethane methacrylate
At least one of polymers, methyl methacrylate oligomer, Epoxy Acrylates oligomer；
The ceramic powder is selected from preparing spherical SiO 2, titanium dioxide, zirconium dioxide, borontrifluoride ytterbium, tantalum oxide, barium sulfate, stone
At least one of English, glass and glass ceramics powder；
The Expanding Monomer is in spiro orthoester class, spiro orthocarbonate class, bicyclo orthoester class and ketal lactone class
It is at least one；
The shortwave photoinitiator be selected from acylphosphine oxide, bis-acylphosphine oxides, diphenylhydroxyethanone, benzoin ether, liquid storax,
At least one of thioxanthone, benzil, benzil ketals, acetophenone and benzophenone；
The long wave photoinitiator is selected from least one of α-diketone, metallocene and acyl group germanium compound；
The UV absorbers are selected from benzotriazole, benzophenone, salicylate, hindered amine light stabilizer, alpha-cyanoacrylate
At least one of ester, triazine and nano-titanium dioxide；
The polymerizable quaternary ammonium salt antibacterial monomer be selected from methacryloxypropyl dodecyl bromopyridine andAt least one of；Wherein-R1For straight chained alkyl, branched alkyl, polynaphthene containing 1~12 carbon
One of base and aryl ,-R2For One of ,-R3For And in straight chained alkyl containing 1~12 carbon, branched alkyl, multi-ring alkyl, aryl
One kind, X-For one of chloride ion, bromide ion, hexafluoro-phosphate radical.
2. 3D printing composite material used for stomatological repair according to claim 1, which is characterized in that also include 1 part~3 parts sun
Ionic photoinitiator, the cation light initiator are selected from aromatic diazo salt, organic aluminium compound, silane compound, two virtues
Base salt compounded of iodine, triaryl sulfonium salts, triaryl selenium salt, alkyl sulfosalt, sulfonyloxy ketone, triaryl silicon oxygen ether, ferrocene
And at least one of iron arene complexes.
3. 3D printing composite material used for stomatological repair according to claim 1, which is characterized in that the UV absorbers
Maximum absorption band wavelength be less than 400nm.
4. 3D printing composite material used for stomatological repair according to claim 1, which is characterized in that the dispersing agent is selected from poly-
At least one of amide, poly- propoxyl group ammonium salt, quaternary ammonium acetate and phosphate.
5. 3D printing composite material used for stomatological repair according to claim 1, which is characterized in that also big comprising parts by weight
Light inhibitor in 0 part and less than 3 parts, the light inhibitor are selected from tetraethylthiuram disulfide and naphthalene formyl methylene quinine
One of ring tetraphenyl borate salts.
6. 3D printing composite material used for stomatological repair according to claim 1, which is characterized in that also big comprising parts by weight
Defoaming agent in 0 part and less than 5 parts, the defoaming agent are selected from mineral oils, organic silicon, polyethers, polyesters, lower aliphatic
At least one of alcohols.
7. a kind of preparation method of 3D printing composite material used for stomatological repair described in claim 1, which is characterized in that including with
Lower step:
1) by low viscosity monomer, enhancing monomer or oligomer, Expanding Monomer, polymerizable quaternary ammonium salt antibacterial monomer, dispersant
After obtain pre-composition；
2) ball-milling treatment obtains mixture after the pre-composition being added in ceramic powder；And
3) continuation ball milling in the mixture is added in shortwave, long wave, cation light initiator and UV absorbers and obtains institute
State 3D printing composite material used for stomatological repair.
8. a kind of preparation method of tri-dimensional oral prosthesis, which comprises the following steps:
1) it is less than the light source of 400nm using maximum emission peak wavelength, polymerize by stereolithography, digital light processing or continuous liquid level
Technology, according to the described in any item 3D printing composite materials used for stomatological repair of oral cavity mathematical model photocuring claim 1~6,
Obtain tri-dimensional oral prosthesis；
2) by the tri-dimensional oral prosthesis be put into maximum emission peak wavelength greater than 400nm photocuring case in carry out it is subsequent solid
Change, to enhance the mechanical performance of the tri-dimensional oral prosthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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