CN105943406A - 3D printing composite material for mouth rehabilitation and preparation and using method of 3D printing composite material - Google Patents
3D printing composite material for mouth rehabilitation and preparation and using method of 3D printing composite material Download PDFInfo
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- CN105943406A CN105943406A CN201610335111.7A CN201610335111A CN105943406A CN 105943406 A CN105943406 A CN 105943406A CN 201610335111 A CN201610335111 A CN 201610335111A CN 105943406 A CN105943406 A CN 105943406A
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- monomer
- composite material
- printing composite
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- stomatological repair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
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- 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
Abstract
The invention relates to a 3D printing composite material for mouth rehabilitation and a preparation and using method of the 3D printing composite material. The 3D printing composite material for mouth rehabilitation is characterized by comprising the following components in parts by weight: 10-40 parts of low-viscosity monomer, 10-40 parts of enhanced monomer or low polymer, 150-200 parts of ceramic powder, 5-20 parts of expansion monomer, 5-15 parts of a dispersing agent, 2-6 parts of a short-wave photoinitiator, 1-3 parts of a long-wave photoinitiator, 1-3 parts of an ultraviolet absorber and 2-5 parts of polymerizable quaternary ammonium salt anti-bacterial monomer. The 3D printing composite material for mouth rehabilitation is small in curing shrinkage, short in curing time and high in anti-bacterial property, and is suitable for manufacturing a dental prosthesis.
Description
Technical field
The present invention relates to 3D printing composite material used for stomatological repair and the preparation and application thereof of a kind of light curable type,
Especially, the present invention relates to that there is answering of low-shrinkage, appropriate viscosity, high-mechanical property, excellent biocompatibility and antibiotic property
Condensation material, this material prints the mouth mending materials such as inlay, veneer, corona, bridge for 3D.
Background technology
Increase material manufacturing technology, print or rapid shaping also known as 3D, occur in last century Mo, be a kind of based on discrete and accumulation
The new manufacture of molding thought.This technological break-through complexity limit of traditional manufacturing technology, has decoupled complexity, small quantities of
Amount customizes the relation with cost, is referred to as the important tool of " industrial revolution for the third time ".The principle of 3D printer is first will to beat
The three-dimensional digital model of printed document carries out layered shaping, generates and prints " scanning " path needed for each layer or image, then passes through
Laser selective fusing dusty material, electric heating shower nozzle melt extrude the method successively " heap such as wire rod, ultraviolet light projection print image
Long-pending " molding, print platform declines the height of a thickness subsequently, and some 3D Method of printings also need to the operation carrying out spreading powder one class
Newly putting one layer of undressed material on molded surface, the carrying out then moved in circles successively " piles up " mistake of molding
Journey, finally can print to three-dimensional real object by three-dimensional digital model.
Dental field, nowadays commercialization dental CAD/CAM system gradually it is widely used in from the CAD/CAM eighties in 20th century
System has been successfully applied to the making of all-ceramic prosthesis, but its operation principle is mostly the raw-material cutting of preformation, is to subtract material system
Making method, major defect is raw-material a large amount of consumption, cuts remaining porcelain block and can only be lost because not being recycled
Abandon；Visible ceramic material surfaces fine crack under its submicroscope, this is owing to ceramic material matter is crisp, ruptures product in working angles
Raw.Additionally material and facility cost is high, and there is the shortcomings such as complex operation, program complexity.And 3D printing technique, have
The advantages such as volume is little, precision is high, integrated cost is low, shaping speed is fast, personalized customization, subtract material shaping skill additionally, also overcome
Art waste of material and every time can only process the restriction of parts, is therefore highly suitable to be applied for the making of mouth mending material.Base
Photocuring 3D printing technique in stereolithography (SLA), digital light process (DLP) and continuous liquid level polymerization (CLIP) can pass through
The photocurable liquid resin of suitable wavelength or the mixed slurry with liquid resin as substrate, molding has high surface finish, height
In precision and the 3D solid of high complexity, with mouth or model scanning technical tie-up, it is achieved the whole process that mouth mending material produces from
Dynamicization, in order to substitute the design of mouth mending material, the making such as traditional personalization corona, bridge, artificial tooth, thus is greatly improved reparation
Body completes efficiency, precision, and saves the chair other working time.
The most unrealized large-scale promotion of 3D printing technique and application, a main reason is to be limited to 3D to print material
Material.Can really be applied to industrial 3D printed material kind at present the most fewer, it is impossible to meet the requirement of commercial Application, pin
The application that the extraordinary 3D printed material adapting different industrial requirement exploitations prints for extension 3D is most important.Mesh
Front existing photocuring 3D printed material has focused largely on simple resinous material, and application is also many opens in entertainment intention, design
Send out, the field the strongest to printout Functional Requirement such as model display, such as subtract material processing for substituting 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 a kind of can be used in make mouth mending material 3D printing composite material and preparation and
Using method.
A kind of 3D printing composite material used for stomatological repair, it is characterised in that in parts by weight, including following components:
Wherein in an embodiment, described low viscosity monomer is simple function group or polyfunctional monomer, described low viscosity
Monomer is selected from acrylic ester monomer, methacrylate-based monomer, vinyl monomer, vinyl ethers monomer and epoxies
At least one in monomer；Preferred methacrylate class, such as pentaerythritol tetramethylacrylate, carbamic acid dimethyl
Acrylate (UDMA), triethylene-glycol dimethylacrylate (TEGDMA), 1,4-butanediol dimethylacrylate, second
Oxidation pentaerythritol tetramethylacrylate, 1,6-HD dimethylacrylate.
Wherein in an embodiment, described enhancing monomer or oligomer are selected from bisphenol-A-dimethyl allene acid glycidyl
Ester (bis-GMA), urethane methacrylate oligomer, methyl methacrylate oligomer, Epoxy Acrylates are oligomeric
At least one in thing；There is higher mechanical performance, wearability and low-shrinkage.
Wherein in an embodiment, the absworption peak wavelength of described short wavelength light initiator is less than 400nm, and the described long glistening light of waves draws
Send out the absworption peak wavelength of agent more than 400nm.
Wherein in an embodiment, described short wavelength light initiator is selected from acylphosphine oxide, bis-acylphosphine oxides, hexichol
Ethanol ketone (Benzoinum), benzoin ether, liquid storax, thioxanthone, benzil, benzil ketals, 1-Phenylethanone. and benzophenone
In at least one.
Wherein in an embodiment, the maximum absorption band wavelength of described short wavelength light initiator is less than 400nm, preferably
Between 280nm to 400nm, preferred between 320nm to 400nm, between most preferably 350nm to 400nm.
Wherein in an embodiment, described long wave light trigger is selected from α-diketone, metallocene and acyl group
At least one in germanium compound.
Wherein in an embodiment, the maximum absorption band wavelength of described long wave light trigger is more than 400nm, preferably exists
Between 400nm to 600nm, preferred between 400nm to 500nm, between most preferably 420nm to 470nm.
Wherein in an embodiment, described 3D printing composite material used for stomatological repair also comprises 1 part～3 parts of cationic photopolymerizations
Initiator, described cation light initiator is selected from aromatic diazo salt, organic aluminium compound, silane compound, Diaryl iodonium
Salt, triaryl sulfonium salts, triaryl selenium salt, alkyl sulfosalt, sulfonyloxy ketone, triaryl silica ether, ferrocene and Fang Mao
At least one in iron salt.
Wherein in an embodiment, described UV absorbers selected from benzotriazole, benzophenone, salicylate,
At least one in hindered amine as light stabilizer, cyanoacrylate, triazine and nano titanium oxide, described UV absorbers
Maximum absorption band wavelength is less than 400nm；It is preferably between 280nm to 400nm, preferred between 320nm to 400nm,
Between most preferably 350nm to 400nm, absorbent preferably in the effective wavelength range of described long wave light trigger almost
Do not absorb luminous energy.
Wherein in an embodiment, described Expanding Monomer is former selected from spiro orthoester class, spiro orthocarbonate class, dicyclo
At least one of esters of gallic acid and ketal lactone apoplexy due to endogenous wind, preferably spiro orthocarbonate class, such as 3,9-diethyl-3,9-propylene oxygen first
The miscellaneous hendecane of base-1,5,7,11-four oxygen spiral shell (BAOM) and 3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-four oxygen spiral shell miscellaneous ten
One alkane (DHOM).
Wherein in an embodiment, described polymerizable quaternary ammonium salt antibacterial monomer is selected from methacryloxypropyl dodecyl bromide
Pyridine (MDPB), and
In at least one；Wherein-R1For in straight chained alkyl, branched alkyl, multi-ring alkyl and the aryl containing 1～12 carbon
One ,-R2For
In one ,-R3For
And containing the one in the straight chained alkyl of 1～12 carbon, branched alkyl, multi-ring alkyl, aryl, X-For chloride ion, bromine
One in ion, hexafluoro-phosphate radical.
Wherein in an embodiment, described ceramic powder selected from preparing spherical SiO 2, titanium dioxide, zirconium dioxide, three
At least one in fluorination ytterbium, tantalum oxide, barium sulfate, quartz, glass and glass ceramics powder body.
Wherein in an embodiment, described dispersant is selected from polyamide, poly-propoxyl group ammonium salt, quaternary ammonium acetate and phosphoric acid
At least one in ester.
Wherein in an embodiment, described 3D printing composite material used for stomatological repair also comprises parts by weight more than 0 part
And the light inhibitor less than 3 parts, described light inhibitor is selected from tetraethylthiuram disulfide and naphthoyl methylene quinuclidine four
One in phenylboronate.
Wherein in an embodiment, described 3D printing composite material used for stomatological repair also comprises parts by weight more than 0 part
And the defoamer less than 5 parts, described defoamer is selected from mineral oils, silicone, polyethers, polyesters, lower aliphatic alcohols
In at least one.
Wherein in an embodiment, described 3D printing composite material used for stomatological repair also comprises other additives, such as
Aqueous solvent or ethanol, stabilizer, levelling agent, aromatic, pigment, Fluoride release composition, fluorescent whitening agent, plasticizer.
The preparation method of the 3D printing composite material used for stomatological repair described in any of the above-described item, comprises the following steps:
1) by low viscosity monomer, monomer or oligomer, Expanding Monomer, polymerizable quaternary ammonium salt antibacterial monomer, dispersant are strengthened
Pre-composition is obtained after mixing；
2) after ceramic powder being added described pre-composition, ball-milling treatment obtains mixture；And
3) shortwave, long wave, cation light initiator and UV absorbers add continuation ball milling in described mixture obtain
To described 3D printing composite material used for stomatological repair.
The using method of above-mentioned 3D printing composite material used for stomatological repair, comprises the following steps:
1) use the maximum emission peak wavelength light source less than 400nm, process (DLP) by stereolithography (SLA), digital light
Or liquid level is polymerized (CLIP) technology continuously, according to 3D printing composite material used for stomatological repair described in the mathematical model photocuring of oral cavity,
Obtain tri-dimensional oral prosthesis, such as inlay, veneer, corona, bridge.
2) described tri-dimensional oral prosthesis is put into maximum emission peak wavelength certain more than the photocuring case of 400nm is carried out
The subsequent cure of time, to strengthen the mechanical performance of described tri-dimensional oral prosthesis.
Above-mentioned 3D printing composite material used for stomatological repair, under the maximum emission peak wavelength photoirradiation less than 400nm, shortwave
Light trigger causes resin monomer polymerization thus solidifies rapidly, and UV absorbers regulates curing depth during resin polymerization
And extent of polymerization, Expanding Monomer can produce volumetric expansion in the polymerization process that cation light initiator causes thus subtract simultaneously
The contraction of little slurry generation when solidification and internal stress, make the parts printed have less deformation, more preferable 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,
Big emission peak wavelength is more than under the photoirradiation of 400nm, and long wave light trigger causes resin monomer or oligomeric remaining in dummy
Thing is polymerized, thus improves the resin polymerization degree of dummy, and the bonding more compacted, as the ceramic powders of enhancing phase, increases its machine
Tool intensity and wearability, polymerisable quaternary ammonium salt antibacterial monomer is aggregated in resin monomer/oligomer in Light Curing
Together, thus provide good anti-microbial property for dummy, and decrease the possibility in use separated out.
Application photocuring 3D prints and directly can be printed ceramic powders resin compounded by the oral cavity mathematical model designed
The mouth mending material of material.By this 3D Method of printing and material, traditional subtract material method make mouth mending material can be by
It is substituted off, not only has that volume is little, precision is high, saves the advantage such as material, integrated cost is low, shaping speed is fast, personalized customization,
And dummy is greatly improved complete efficiency and save the chair other working time.
Detailed description of the invention
Mainly in combination with specific embodiment, 3D printing composite material used for stomatological repair and preparation and application thereof are made below
Further details of explanation.
A kind of 3D printing composite material used for stomatological repair, it is characterised 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 processes (DLP) and continuous
The 3D printing techniques such as liquid level polymerization (CLIP).
Resinous substrates is the continuous phase in material, for boning as the ceramic powder particle strengthening phase, passes through selectivity
The process of photopolymerization forms the 3D solid corresponding with mathematical model.Resinous substrates is by low viscosity monomer and strengthens monomer or low
Polymers forms.Low viscosity monomer is simple function group or polyfunctional monomer, selected from acrylic ester monomer, methyl acrylic ester
At least one in 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,
Glycerol two/trimethyl acrylic ester.Strengthen monomer or oligomer has higher mechanical performance, wearability and low-shrinkage, choosing
From bisphenol-A-dimethyl allene acid glycidyl ester (bis-GMA), urethane methacrylate oligomer, methyl methacrylate
At least one in ester oligomer, Epoxy Acrylates oligomer.
Expanding Monomer is dicyclo or the tricyclic compound that a class can produce volumetric expansion in the course of the polymerization process, mostly is containing miscellaneous
The dicyclo of atom or tricyclic compound, the hetero atom of most of monomers is oxygen, and minority is then sulfur, and nitrogen etc. is similar with epoxy resin,
Expanding Monomer polymerization belongs to the ring-opening polymerisation that cation causes.Expanding Monomer for reduce slurry solidification time produce contraction and
Internal stress, makes the parts printed have less deformation, more preferable dimensional accuracy and less micro-crack defect.The most also may be used
To improve the cylinder block strength of polymeric material, improve polymerization-filling degree, reduce little molecule leaching content, make the biology performance of system
Optimized.Expanding Monomer is selected from spiro orthoester class, spiro orthocarbonate class, bicyclo orthoester class and ketal lactone apoplexy due to endogenous wind
At least one, preferably spiro orthocarbonate class, such as 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid, 5,7,11-tetra-oxygen spiral shells miscellaneous ten
One alkane (BAOM) and the 3,9-diethyl-3,9-miscellaneous hendecane of dihydroxymethyl-1,5,7,11-four oxygen spiral shell (DHOM).
Ceramic powder as obturator, can make dummy possess higher in 3D printing composite material used for stomatological repair
Hardness, intensity and wearability.Ceramic powder selected from preparing spherical SiO 2, titanium dioxide, zirconium dioxide, borontrifluoride ytterbium, tantalum oxide,
At least one in barium sulfate, quartz, glass and glass ceramics powder body, powder particle average diameter 0.005 μm to 10 μm it
Between, preferably between 0.1 μm to 5 μm, preferred between 0.1 μm to 1 μm, most preferably 0.1 μm to 0.3 μm it
Between.
Resin monomer or oligomer itself can not effectively absorb the energy of exposure light, it is therefore desirable to add in the composite
Light trigger, light trigger itself the most directly participates in polyreaction, but with absorbing light irradiation energy, and can transfer energy to resin
Molecule, generates reactive intermediate trigger monomer or the polyreaction of oligomer.The selection of light trigger is it is required that its absorbing light
Spectrum matches with the spectral distribution property of light source, additionally depends on light trigger dissolubility in material slurry, adds light-initiated
Degree of stability under material leaves no light condition in after agent etc..Especially, the use of light trigger has been largely fixed light
The speed of curing reaction.
Light trigger includes free radical photo-initiation and cation light initiator.
Free radical photo-initiation comprises short wavelength light initiator and long wave light trigger, the wherein maximum suction of short wavelength light initiator
Receive spike length and be less than 400nm, preferably between 280nm to 400nm, preferred between 320nm to 400nm, most preferably
For 350nm to 400nm between；The maximum absorption band wavelength of long wave light trigger is more than 400nm, preferably arrives at 400nm
Between 600nm, preferred between 400nm to 500nm, between most preferably 420nm to 470nm.
Short wavelength light initiator selected from acylphosphine oxide, bis-acylphosphine oxides, diphenylhydroxyethanone (Benzoinum), benzoin ether,
At least one in liquid storax, thioxanthone, benzil, benzil ketals, 1-Phenylethanone. and benzophenone, such as 2,4,6-tri-
Double (2,4, the 6-trimethylbenzoyl) phosphine oxide of methyl benzoyl diphenyl phosphine oxide, phenyl, benzyl dimethyl ketal,
1-hydroxy-cyclohexyl phenyl ketone, α-Dialkoxy acetophenones.
At least one in α-diketone, metallocene and acyl group germanium compound of long wave light trigger, such as
Camphorquinone, 1-phenyl-1,2-propanedione, 9,10-phenanthrenequione, dibenzoyl diethyl germanium, double (4-anisoyl)-two
Germanium ethide, benzoyltrimethyl germanium, double 2,6-bis-fluoro-3-pyrroles phenyl titanocenes.As preferably, α-binary can be selected
Ketone, such as camphorquinone, 1-phenyl-1,2-propanedione and mixture thereof, can coordinate 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, selected from aromatic diazo salt, organo-aluminium
Complex, silane compound, diaryl group iodized salt, triaryl sulfonium salts, triaryl selenium salt, alkyl sulfosalt, sulphonyl oxygen
At least one in base ketone, triaryl silica ether, ferrocene and iron arene complexes, such as diphenyl iodine hexafluorophosphate, 4,4'-
Dimethyl diphenyl iodine hexafluorophosphate, diphenyl iodine trifluoro-methanyl sulfonate, double 2,6-bis-fluoro-3-pyrroles phenyl two cyclopentadienyl
Titanium and (4-Phenylsulfanyl-phenyl) diphenyl sulfur hexafluorophosphate.
3D printing composite material used for stomatological repair adds UV absorbers and suitably can reduce according to demand printed
Response speed in journey and curing depth.The maximum absorption band wavelength of UV absorbers is less than 400nm, preferably at 280nm
Between 400nm, preferred 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 light trigger.It is selected from benzotriazole, benzophenone, salicylic acid
At least one in ester, hindered amine as light stabilizer, cyanoacrylate, triazine and nano titanium oxide, such as 2,4-dihydroxy
Benzophenone, ESCALOL 567, Octabenzone, 2-(2 '-hydroxyl-3 ', 5 '-
Two tertiary phenyl)-5-chlorination benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) 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 group-3,3-diphenylacrylate ester, double (2,2,6,6-tetramethyl-4-piperidyl)-sebacate.
Polymerizable quaternary ammonium salt antibacterial monomer is selected from methacryloxypropyl dodecyl bromopyridine (MDPB), and
In at least one；Wherein-R1For in straight chained alkyl, branched alkyl, multi-ring alkyl and the aryl containing 1～12 carbon
One ,-R2For
In one ,-R3For
And containing the one in the straight chained alkyl of 1～12 carbon, branched alkyl, multi-ring alkyl, aryl, X-For chloride ion, bromine
One in 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).Selection can be able to synthesize with the quaternary ammonium salt antibacterial monomer of resinous substrates copolymerization
Going out the anti-biotic material of non-stripping property, quaternary ammonium salt is the organic antibacterial agent of a kind of high-efficiency broad spectrum, has that sterilization speed is fast, antibacterial efficacy
Persistently, low toxicity, low corrosion, good colour, the advantage such as be uniformly dispersed, simultaneously because of its by antibacterial functions group by chemical bond
Form secure attachment, in resinous substrates, therefore overcomes common organic antibacterial agents poor heat stability, easily decomposes dissolution, decomposition
Product is poisonous waits deficiency, and shows long-term biological effect.
3D printing composite material used for stomatological repair also includes dispersant.The effect of dispersant is the most homogeneous dispersion
Ceramic powder particle also prevents the reunion caking of powder particle and precipitates.Adding appropriate dispersant can promote material in molding
During formed continuously, atresia and the thin film of homogenizing.If dispersant adds too much, the light-cured performance of material can be by unfavorable
Affect and interlayer adhesion when printing is affected.If dispersant adds very few, then can may interfere with homogeneous material
Formed.The concrete dispersant quantity being suitable for adding is relevant to the powder classification of use and its surface area, needs to be adjusted accordingly.
At least one in polyamide, poly-propoxyl group ammonium salt, quaternary ammonium acetate and phosphate ester of dispersant.Further, poly-third oxygen
Base ammonium salt is preferably at least one in diethyl poly-propoxy methyl ammonium chloride and diethyl poly-propoxyl group dihydroxy ammonium phosphate.
Further, the polyamide hyper-dispersant under polyamide is preferably Noveon company SOLSPERSE 32000 and 39000 trade mark；
Diethyl poly-propoxy methyl ammonium chloride is preferably the poly-propoxyl group of diethyl under Degussa company VARIQUAT CC-59 trade mark
Ammonio methacrylate；Diethyl poly-propoxyl group dihydroxy ammonium phosphate is preferably under Degussa company VARIQUAT CC-42NS trade mark
Diethyl poly-propoxyl group dihydroxy ammonium phosphate；Quaternary ammonium acetate is preferably under Degussa company VARIQUAT CC-55 trade mark
Quaternary ammonium acetate；Phosphate ester is preferably RHODAFAC RS-610 and RE 610 of Rhodia company.Certainly, phosphate ester also may be used
Think unsaturated phosphate ester, the MAXEMUL 6106 and 6112 of preferably Uniqema company.
3D printing composite material used for stomatological repair also can comprise the parts by weight light inhibitor more than 0 part and less than 3 parts, with
Enabling material to be polymerized on the 3D printer of (CLIP) technology use at continuous liquid level, light inhibitor is selected from the tetraethyl base autumn
One in blue nurse and naphthoyl methylene quinuclidine tetraphenyl borate salts.
3D printing composite material used for stomatological repair also can comprise the parts by weight defoamer more than 0 part and less than 5 parts, permissible
Reducing surface tension, suppression foam produces or eliminates the foam produced, and defoamer is selected from mineral oils, silicone, polyethers
Class, polyesters, lower aliphatic alcohols apoplexy due to endogenous wind at least one.
3D printing composite material used for stomatological repair also can comprise other additives, such as aqueous solvent or ethanol, stabilizer, stream
Flat agent, aromatic, pigment, Fluoride release composition, fluorescent whitening agent, plasticizer.
The using method of above-mentioned 3D printing composite material used for stomatological repair is as follows:
Use maximum emission peak wavelength less than the light source of 400nm, by stereolithography (SLA), digital light process (DLP) or
Liquid level polymerization (CLIP) technology continuously, solidifies above-mentioned material used for stomatological repair through successively selectivity, straight by oral cavity mathematical model
Connect and obtain tri-dimensional oral prosthesis, such as inlay, veneer, corona, bridge.Forming three-dimensional mouth mending material is placed into maximum subsequently
Emission peak wavelength carries out subsequent cure, to strengthen the mechanical performance of dummy more than in the photocuring case of 400nm.
Above-mentioned 3D printing composite material used for stomatological repair, under the maximum emission peak wavelength photoirradiation less than 400nm, shortwave
Light trigger causes resin monomer polymerization thus solidifies rapidly, and UV absorbers regulates curing depth during resin polymerization
And extent of polymerization, Expanding Monomer can produce volumetric expansion in the polymerization process that cation light initiator causes thus subtract simultaneously
The contraction of little slurry generation when solidification and internal stress, make the parts printed have less deformation, more preferable 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,
Big emission peak wavelength is more than under the photoirradiation of 400nm, and long wave light trigger causes resin monomer/oligomer remaining in dummy
Polymerization, thus improve the resin polymerization degree of dummy, the bonding more compacted, as the ceramic powders of enhancing phase, increases its machinery
Intensity and wearability, polymerisable quaternary ammonium salt antibacterial monomer condenses together with resinous substrates in Light Curing, thus
Provide good anti-microbial property for dummy, and decrease the possibility in use separated out.
Application photocuring 3D prints and directly can be printed ceramic powders resin compounded by the oral cavity mathematical model designed
The mouth mending material of material.By this 3D Method of printing and material, traditional subtract material method make mouth mending material can be by
It is substituted off, not only has that volume is little, precision is high, saves the advantage such as material, integrated cost is low, shaping speed is fast, personalized customization,
And dummy is greatly improved complete efficiency and save the chair other working time.
The preparation method of above-mentioned 3D printing composite material used for stomatological repair, including following:
Step S110, by low viscosity monomer, strengthen monomer or oligomer, Expanding Monomer, polymerizable quaternary ammonium salt antibacterial monomer,
Pre-composition is obtained after dispersant.
Preferably, it is mixed and added into before dispersant, polymerizable quaternary ammonium salt antibacterial monomer first by low viscosity with Expanding Monomer
Monomer and enhancing monomer or oligomer mix homogeneously.
Preferably, if during mixture that Expanding Monomer is two kinds of Expanding Monomer, and resin monomer/oligomer mixes and adds
Enter before dispersant, polymerizable quaternary ammonium salt antibacterial monomer first by two kinds of Expanding Monomer mix homogeneously.
Step S120, ceramic powder is added described pre-composition after ball-milling treatment obtain mixture.
Preferably, ceramic powder is added gradually in pre-composition several times, it is further preferred that join premix in three times
In thing.
Preferably, ball-milling treatment is carried out in ceramic pot.
Preferably, ball-milling treatment is to add different size of spherical ceramic grinding media to carry out ball milling.Further, ball
The quality of shape ceramic grinding media is suitable with the quality of mixed slurry.Further, a diameter of in spherical ceramic grinding media
The mass ratio of the spherical ceramic grinding media of 10mm and a diameter of 3mm is 1:1.
Preferably, the time of ball-milling treatment is 8～48 hours.
Preferably, the rotating speed of ball milling is 10～30rpm.
Step S130, light trigger and UV absorbers are added ball milling in mixture obtain 3D used for stomatological repair and print
Composite.
Preferably, light trigger includes shortwave, long wave, cation light initiator.
Preferably, in this step, the time of ball milling is 1～3 hour.
Preferably, this step is carried out before carrying out printing.
The preparation method of above-mentioned 3D printing composite material used for stomatological repair, simple to operate.
It is below specific embodiment part:
Embodiment 1
The preparation of the 3D printing composite material used for stomatological repair of embodiment 1 comprises the following steps:
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 isophthalic acid of 20g, 5,7,11-tetra-
The miscellaneous hendecane of oxygen spiral shell (BAOM), joins in above-mentioned resin compound.
Measure 5g polymerizable quaternary ammonium salt antibacterial monomer methacryloxypropyl dodecyl bromopyridine (MDPB), join above-mentioned
In mixture.
Measure 5g diethyl poly-propoxy methyl ammonium chloride (the VARIQUAT CC-59 of Degussa company) as dispersant
Joining in said mixture, agitation as appropriate uniformly obtains liquid mixture.
Obtaining satisfactory powder after being sieved by spherical Zirconium dioxide powder, the average diameter of powder particle is 0.3 micro-
Rice.Measure 150g Zirconium dioxide powder, the most secondary be added step-wise in aforesaid liquid mixture and carry out every time after adding
Stirring is fully to mix.
The mixture obtained through previous step is subsequently placed in ceramic pot, and (diameter divides to add 200g different size
Not Yue Wei 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, then ceramic pot is placed on roller ball mill
On machine speed with 10rpm carry out for time the ball milling of 8 hours.
Last before carrying out printing, ceramic pot adds the 2 of 2g, 4,6-trimethyl benzoyl diphenyl base oxygen
Change phosphine is as short wavelength light initiator, and the dibenzoyl diethyl germanium of 1g is as long wave light trigger, the diphenyl iodine six of 1g
Fluorophosphate is as cation light initiator.And add the Octabenzone of 3g as UV Absorption
Agent.Add the mineral oil antifoam agent of 5g.Continue ceramic pot to be put on tumbling ball mill and carry out 1 hour 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), is mixed and stirred for both resins.
Measure the spiro orthocarbonate class Expanding Monomer 3,9-diethyl-3,9-propylene oxygen methyl isophthalic acid of 5g, 5,7,11-tetra-oxygen
The miscellaneous hendecane of spiral shell (BAOM), joins in above-mentioned resin compound.
Measure 5g polymerizable quaternary ammonium salt antibacterial monomer methylacryoyloxyethyl-n-hexadecyl-dimethyl hexafluorophosphoric acid
Ammonium (DMAE-CH), joins in said mixture.
Measure 15g polyamide hyper-dispersant (SOLSPERSE 32000 of Noveon company) and join in said mixture,
Agitation as appropriate uniformly obtains liquid mixture.
Obtaining satisfactory powder after being sieved by globular glass ceramic powders, the average diameter of powder particle is about 0.1
Micron.Measure 200g glass ceramic powder, the most secondary be added step-wise in aforesaid liquid mixture and laggard adding every time
Row stirring is fully to mix.
The mixture obtained through previous step is subsequently placed in ceramic pot, and (diameter divides to add 275g different size
Not Yue Wei 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, then ceramic pot is placed on roller ball mill
On machine speed with 15rpm carry out for time the ball milling of 24 hours.
Last before carrying out printing, the phenyl adding 6g in ceramic pot is double (2,4,6-trimethylbenzoyl)
Phosphine oxide is as short wavelength light initiator, and the camphorquinone of 3g is as long wave light trigger, the 4 of 3g, 4'-dimethyl diphenyl iodine six
Fluorophosphate is as cation light initiator.And add 2-(2H-benzotriazole-2-the base)-6-dodecyl-4-methylbenzene of 1g
Phenol is as UV absorbers.Add the tetraethylthiuram disulfide of 3g as light inhibitor.Continue to be put into rolling by ceramic pot
Carry out the ball milling of 2 hours on cylinder ball mill with the speed of 15rpm, obtain being sufficiently mixed uniform 3D used for stomatological repair and print compound
Material.
Embodiment 3
Electronic balance measures 10g triethylene-glycol dimethylacrylate (TEGDMA) and 40g methyl methacrylate
Oligomer, is mixed and stirred for both resins.
Measure spiro orthocarbonate class Expanding Monomer 3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-four oxygen of 15g
The miscellaneous hendecane of spiral shell (DHOM), joins in above-mentioned resin compound.
Measure 2g polymerizable quaternary ammonium salt antibacterial monomer two (2-acrylyl oxy-ethyl)-dodecyl-methyl bromide ammonium
(AE-DB), join in said mixture.
Measure 12g quaternary ammonium acetate (the VARIQUAT CC-55 of Degussa company) and join as dispersant above-mentioned mixed
In resin, agitation as appropriate uniformly obtains liquid mixture.
Obtaining satisfactory powder after being sieved by spherical silicon dioxide powder, the average diameter of powder particle is about 0.2
Micron.Measure 160g SiO 2 powder, the most secondary be added step-wise in aforesaid liquid mixture and laggard adding every time
Row stirring is fully to mix.
The mixture obtained through previous step is subsequently placed in ceramic pot, and (diameter divides to add 239g different size
Not Yue Wei 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, then ceramic pot is placed on roller ball mill
On machine speed with 30rpm carry out for time the ball milling of 48 hours.
Last before carrying out printing, the benzyl dimethyl ketal adding 5g in ceramic pot draws as short wavelength light
Sending out agent, double the 2 of 2.5g, 6-bis-fluoro-3-pyrroles phenyl titanocenes is as long wave light trigger, double the 2 of 2g, the fluoro-3-pyrroles of 6-bis-
Phenyl titanocenes is as cation light initiator.And add the ESCALOL 567 of 1.2g as ultraviolet light suction
Receive agent.Continue ceramic pot to be put on tumbling ball mill the ball milling carried out with the speed of 30rpm 3 hours, obtain being sufficiently mixed all
Even 3D printing composite material used for stomatological repair.
Embodiment 4
Electronic balance measures 1,4-butanediol dimethylacrylate and 35g bisphenol-A-dimethacrylate shrink of 30g
Glyceride (bis-GMA), is mixed and stirred for both resins.
Measure spiro orthocarbonate class Expanding Monomer 3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11-four oxygen of 10g
3,9-diethyl-3,9-propylene oxygen the methyl isophthalic acid of the miscellaneous hendecane of spiral shell (DHOM) and 5g, the miscellaneous hendecane of 5,7,11-tetra-oxygen spiral shell
(BAOM), join after mixing in above-mentioned resin compound.
Measure 3.6g polymerizable quaternary ammonium salt antibacterial monomer two (2-methylacryoyloxyethyl)-n-dodecane-methyl hexafluoro
Ammonium phosphate (MAE-DH), joins in said mixture.
Measure 14g diethyl poly-propoxyl group dihydroxy ammonium phosphate (the VARIQUAT CC-42NS of Degussa company) conduct
Dispersant joins in above-mentioned hybrid resin, and agitation as appropriate uniformly obtains liquid mixture.
Satisfactory powder, Zirconium dioxide powder is obtained after spherical zirconium dioxide and glass powder being sieved respectively
The average diameter of granule is about 0.3 micron, and the average diameter of glass powder granule is about 3 microns.Measure 120g titanium dioxide zirconium powder
End, the most secondary be added step-wise in aforesaid liquid mixture and be stirred fully mixing after add every time, with
After measure 80g glass powder, be added step-wise in aforesaid liquid mixture and be stirred fully carrying out after add every time
Mixing.
The mixture obtained through previous step is subsequently placed in ceramic pot, adds 297.6g different size (diameter
Respectively may be about 10mm and 3mm, quality respectively accounts for about half) spherical ceramic grinding media, then ceramic pot is placed on roller ball
On grinding machine speed with 30rpm carry out for time the ball milling of 48 hours.
Last before carrying out printing, ceramic pot adds the 1-hydroxy-cyclohexyl phenyl ketone of 3g as short wavelength light
Initiator, the 9 of 2g, 10-phenanthrenequione draws as helping as the dimethylaminoethyl methacrylate of long wave light trigger and 0.8g
Sending out agent, (4-Phenylsulfanyl-phenyl) diphenyl sulfur hexafluorophosphate of 1.8g is as cation light initiator.And add 1.2g's
2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole is as UV absorbers.And add 4g Chinese white and 5g fluorescent brightening
Agent is to improve the pure white aesthetics of mouth mending material.Continue ceramic pot to be put on tumbling ball mill and carry out with the speed of 20rpm
The ball milling of 2.5 hours, obtains being sufficiently mixed uniform 3D printing composite material used for stomatological repair.
Each technical characteristic of embodiment described above can combine arbitrarily, for making description succinct, not to above-mentioned reality
The all possible combination of each technical characteristic executed in example is all described, but, as long as the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope that this specification is recorded.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that, come for those of ordinary skill in the art
Saying, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (15)
1. a 3D printing composite material used for stomatological repair, it is characterised in that in parts by weight, including following components:
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described low viscosity monomer is
Simple function group or polyfunctional monomer, described low viscosity monomer is selected from acrylic ester monomer, methacrylate-based monomer, second
At least one in thiazolinyl class monomer, vinyl ethers monomer and epoxy monomer；Described enhancing monomer or oligomer are selected from double
Phenol A-dimethyl allene acid glycidyl ester (bis-GMA), urethane methacrylate oligomer, methyl methacrylate are low
At least one in polymers, Epoxy Acrylates oligomer.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described short wavelength light initiator
Absworption peak wavelength less than 400nm, the absworption peak wavelength of described long wave light trigger is more than 400nm.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described short wavelength light initiator
Selected from acylphosphine oxide, bis-acylphosphine oxides, diphenylhydroxyethanone (Benzoinum), benzoin ether, liquid storax, thioxanthone, benzene
At least one in even acyl, benzil ketals, 1-Phenylethanone. and benzophenone.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described long wave light trigger
At least one in α-diketone, metallocene and acyl group germanium compound.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that also comprise 1 part～3 parts of sun
Ionic photoinitiator, described cation light initiator is selected from aromatic diazo salt, organic aluminium compound, silane compound, two virtues
Base iodine salt, triaryl sulfonium salts, triaryl selenium salt, alkyl sulfosalt, sulfonyloxy ketone, triaryl silica ether, ferrocene
And at least one in iron arene complexes.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described UV Absorption
Agent is selected from benzotriazole, benzophenone, salicylate, hindered amine as light stabilizer, cyanoacrylate, triazine and nanometer titanium dioxide
At least one in titanium, the maximum absorption band wavelength of described UV absorbers is less than 400nm.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described Expanding Monomer is selected from
At least one of spiro orthoester class, spiro orthocarbonate class, bicyclo orthoester class and ketal lactone apoplexy due to endogenous wind.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described polymerizable quaternary ammonium salt
Antibacterial monomer is selected from methacryloxypropyl dodecyl bromopyridine (MDPB), and
In at least one；Wherein-R1For in straight chained alkyl, branched alkyl, multi-ring alkyl and the aryl containing 1～12 carbon
Kind ,-R2For
In one ,-R3For
And containing the one in the straight chained alkyl of 1～12 carbon, branched alkyl, multi-ring alkyl, aryl, X-For chloride ion, bromide ion,
One in hexafluoro-phosphate radical.
3D printing composite material used for stomatological repair the most according to claim 1, it is characterised in that described ceramic powder selects
From preparing spherical SiO 2, titanium dioxide, zirconium dioxide, borontrifluoride ytterbium, tantalum oxide, barium sulfate, quartz, glass and glass ceramics powder
At least one in body.
11. 3D printing composite materials used for stomatological repair according to claim 1, it is characterised in that described dispersant is selected from
At least one in polyamide, poly-propoxyl group ammonium salt, quaternary ammonium acetate and phosphate ester.
12. 3D printing composite materials used for stomatological repair according to claim 1, it is characterised in that also comprise parts by weight
Light inhibitor more than 0 part and less than 3 parts, described light inhibitor is selected from tetraethylthiuram disulfide and naphthoyl methylene Kui
One in peaceful ring tetraphenyl borate salts.
13. 3D printing composite materials used for stomatological repair according to claim 1, it is characterised in that also comprise parts by weight
Defoamer more than 0 part and less than 5 parts, described defoamer is selected from mineral oils, silicone, polyethers, polyesters, rudimentary fat
At least one of fat alcohol apoplexy due to endogenous wind.
The preparation method of the 3D printing composite material used for stomatological repair described in 14. 1 kinds of claim 1, it is characterised in that include
Following steps:
1) by low viscosity monomer, monomer or oligomer, Expanding Monomer, polymerizable quaternary ammonium salt antibacterial monomer, dispersant are strengthened
After obtain pre-composition；
2) after ceramic powder being added described pre-composition, ball-milling treatment obtains mixture；And
3) shortwave, long wave, cation light initiator and UV absorbers are added continuation ball milling in described mixture and obtains institute
State 3D printing composite material used for stomatological repair.
The using method of the 3D printing composite material used for stomatological repair described in 15. 1 kinds of claim 1, it is characterised in that include
Following steps:
1) use the maximum emission peak wavelength light source less than 400nm, process or liquid level polymerization continuously by stereolithography, digital light
Technology, according to the 3D printing composite material used for stomatological repair described in any one of mathematical model photocuring claim 1～13 of oral cavity,
Obtain tri-dimensional oral prosthesis.
2) described tri-dimensional oral prosthesis is put into maximum emission peak wavelength follow-up solid more than the photocuring case of 400nm is carried out
Change, to strengthen the mechanical performance of described tri-dimensional oral prosthesis.
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