CN109650909A - A kind of calcium phosphate bone induction bioceramic scaffold and preparation method thereof based on photocuring 3D printing technique - Google Patents
A kind of calcium phosphate bone induction bioceramic scaffold and preparation method thereof based on photocuring 3D printing technique Download PDFInfo
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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Abstract
The invention discloses a kind of, and the calcium phosphate bone based on photocuring 3D printing technique induces bioceramic scaffold and preparation method thereof, belongs to biomedical materials field.The method through the invention can effectively prepare high solids content, low viscosity, dispersibility and the preferable ceramic slurry of mobility.By photocuring 3D printing technique and subsequent degreasing sintered, can prepare has inside through pore structure, shape, size, porosity and macro morphology accurately control and have the porous calcium phosphate ceramic bracket of osteoinductive, for bone tissue reparation filling and individualized therapy.
Description
Technical field
The invention belongs to biomedical material technologies, more particularly to a kind of phosphorus based on photocuring 3D printing technique
Sour calcium self-bone grafting bioceramic scaffold and preparation method thereof.
Technical background
All the time, the bone defect due to caused by wound, tumour, metabolic disease etc. is always clinical a great problem, past
Toward the part or all of afunction of patient bone is caused, quality of life is seriously affected.Bone defect for size less than 1cm can lead to
Autogenous repairing is crossed, and size is more than the bone defect of 1cm, then can only pass through interventional therapy.
Although autologous bone transplanting is still considered as " goldstandard " of large segmental bone defect treatment, also facing source always has
The risks such as limit, second operation wound, unknown complication.Homogeneous allogenic bone and animal derived bone xenograft have " natural
The characteristic of bone " or " class bone ", but the risk of transmission and immunological rejection can not be avoided completely.Therefore, research and development to disease damage or lack
The bone tissue of mistake carries out effectively repairing the artificial bone renovating material with reconstruction, has extensive clinical demand and huge warp
Ji value.Among these, the artificial bone with ostosis effect, osteoconductive and osteoinductive will occupy more in bone collection
Important position.
Calcium phosphate (Ga-P) bioceramic has excellent biocompatibility, good osteoconductive and osteoinductive, is
One of ideal material of bone defect healing.Studies have shown that there is the porous structure and microscale-nanoscale microcellular structure being mutually communicated,
It can promote bone tissue regeneration induction, reach the lived repairing effect of tool.Commonly the preparation method of porous material bracket includes
Traditional freeze-drying, pore creating material method, gas foaming method etc..But there are still certain defects and deficiency for these methods, are difficult
The pore structure size and porosity of accurate control internal stent, and be difficult accurately to prepare the bone defect portion with irregular pattern
Position recovery support.
Recently as the fast development of advanced manufacturing technology, 3D printing technique shows unique excellent at many aspects
Gesture.It constructs object by layer-by-layer printing based on digital model file, can be simultaneously in precise forming part
Outer labyrinth, this just provides new manufacturing philosophy and method for the personalized preparation of bone renovating material.DLP and SLA skill
Art is the mainstream technology in photocuring 3D ceramics printing technique, it is then light to be thrown video signal again by digital processing
Shadow emits, and is the 3D printing method that print speed is fast, printing precision is high.Exploitation and photocuring 3D ceramics printing technique phase
Matched osteoinductive calcium phosphate biological ceramic will have very big application potential in hard tissue repair field.
Summary of the invention
In view of the deficiencies of the prior art, the calcium phosphate bone induction based on photocuring 3D printing technique that the present invention provides a kind of
Bioceramic scaffold and preparation method thereof.The method through the invention can effectively prepare high solids content, low viscosity, dispersion
Property and the preferable ceramic slurry of mobility.By photocuring printing technique and subsequent degreasing sintered, can prepare have it is interior
Pore structure is run through in portion, and shape, size, porosity and macro morphology accurately control and have the porous calcium phosphate of osteoinductive
Ceramics bracket, for bone tissue reparation filling and individualized therapy.
The present invention is achieved through the following technical solutions:
A kind of photosensitive resin premixed liquid being used to prepare calcium phosphate bone induction porous bioceramic scaffold, including oligomer, activity
Diluent, photoinitiator and sensitizer.Prepolymer is the basic resin of photocurable formulation, constitutes the basic framework of cured article,
The performance of prepolymer resin determines solidify after material basic performance.Reactive diluent generally contains the small of polymer functional group
Molecule is mainly used for the viscosity of regulation system, also has an impact to solidification rate and material property.Photoinitiator can be in the work of luminous energy
Become reactive intermediate (free radical or ion) under, be the key component of photocuring system, is related to formula system in light spoke
When penetrating, can oligomer and reactive diluent rapid crosslinking curing.Sensitizer be it is a kind of do not absorb radiation and will not cause polymerization,
But the molecule of the effectual active rate of photoinitiator can be improved.
Alternately, in above-mentioned photosensitive resin premixed liquid, the mass fraction of each component are as follows: oligomer 45 ~ 65%,
Reactive diluent 35 ~ 55%, photoinitiator 1 ~ 7%, sensitizer 1 ~ 5%.Oligomer and reactive diluent are photosensitive resin premixed liquid
Main part, the curing molding of resin can be guaranteed by accounting for 90% or more of mass fraction in total；The dosage of photoinitiator is to solidification speed
Rate has decisive role, and dosage is more, and solidification rate is faster, but photoinitiator dosage it is excessive when, a large amount of heat produced by polymerizeing
It is not easy to control that amount makes reaction, while the initiator that photodissociation does not occur often moves to rack surface, influences the performance of bracket.
Alternately, in above-mentioned photosensitive resin premixed liquid, the oligomer is epoxy acrylate, polyurethane third
It is one or more in olefin(e) acid ester, polyester acrylate.
Alternately, in above-mentioned photosensitive resin premixed liquid, the reactive diluent is methacrylic acid isoborneol
Ester (IBOMA), trimethylolpropane trimethacrylate (TMPTA), tripropylene glycol and acrylate (TPGDA), 1,6-HD
It is one or more in diacrylate (HDDA)；
Alternately, in above-mentioned photosensitive resin premixed liquid, the photoinitiator is 819,184,173, in TPO, TPO-L
It is one or more.
Alternately, in above-mentioned photosensitive resin premixed liquid, the sensitizer is 4- dimethylaminobenzoic acid second
Ester (EDB), to the one or more of the different monooctyl ester of dimethylamine benzoic acid (EHA).
The present invention also provides a kind of photocuring 3D printing calcium phosphate bones to induce ceramic slurry, including calcium phosphate ceramic powder
Or its nano pulp, dispersing agent and any one of the above photosensitive resin premixed liquid.Calcium phosphate ceramic is the core of slurry,
It is ultimately formed the main body of porous bioceramic scaffold；Dispersing agent can effectively avoid the reunion of ceramic powder, guarantee that it is being starched
Fully disperse in material, improves the mobility of slurry.The print object of photocuring 3D ceramics printing technique is photosensitive resin, therefore
Making the preferable ceramics of mobility-photosensitive resin mixed slurry seems increasingly important.For the quality for guaranteeing ceramic printing shaping
And phenomena such as splitting, deforming of not collapsing in subsequent sintering skimming processes, higher solid content are also a necessary condition；
But if the ceramic powder in ceramics-photosensitive resin mixed slurry is excessive, the viscosity of slurry can be improved seriously to influence to flow
Dynamic property, causes 3D printing process to be obstructed.The preparation of slurry is printed other than the fluency and integrality that guarantee printing shaping how
Guarantee the bioactivity of print carriage and osteoinductive is also the key for preparing sclerous tissues' implantation renovating bracket material of new generation.
Alternately, in above-mentioned photocuring 3D printing calcium phosphate ceramic slurry, the mass fraction of each component are as follows: 50
~ 90% calcium phosphate ceramic powder or its nano pulp, 10 ~ 50% photosensitive resin premixed liquid, 2 ~ 5% dispersing agents.Slurry can be passed through
Component ratio, model structure design to adjust the mechanical property of prepared self-bone grafting bracket, hole shape/size and porosity.
Calcium phosphate is the ultimate constituent of product, and when its mass fraction is lower than 50%, the bracket green body of printing can collapse during the sintering process
Or cracking: when its content is higher than 90%, the lotion solid content of printing is too high, and the mobility of lotion is too poor so that it cannot beat
Print.A small amount of dispersing agent can improve the combination at interface between resin and calcium phosphate granules, further increase the mobility of lotion
And convenient for printing.
Alternately, in above-mentioned photocuring 3D printing calcium phosphate ceramic slurry, the calcium phosphate ceramic powder or
Nano pulp is tricalcium phosphate (α-TCP and β-TCP), hydroxyapatite (HA), tetracalcium phosphate, a kind of or more in calcium dihydrogen phosphate
Kind
Alternately, in above-mentioned photocuring 3D printing calcium phosphate ceramic slurry, the dispersing agent is silane coupling agent KH-
550, one of KH-560, KH-570 or a variety of.
Alternately, in above-mentioned photocuring 3D printing calcium phosphate ceramic slurry, the calcium phosphate ceramic powder or
The purity of nano pulp is 95.00 ~ 99.99%.Calcium phosphate is the active constituent of product, determines the final repairing effect of bracket,
The higher the better for its purity.Based on current calcium phosphate synthesis technology, the purity selected is described above.
The present invention also provides a kind of preparation methods of calcium phosphate bone induction porous bioceramic scaffold, including following step
It is rapid:
(1) preparation of photosensitive resin premixed liquid: oligomer, reactive diluent, photoinitiator, sensitizer are sufficiently mixed；
(2) preparation of photocuring 3D printing ceramic slurry: photosensitive resin premixed liquid prepared in step (1) and calcium phosphate are made pottery
Porcelain powder or nano pulp, dispersing agent are placed in ball mill in proportion and are mixed, and are suitble to print with certain viscosity to prepare
Ceramic slurry；
(3) photocuring 3D printing: step (2) are prepared into obtained ceramic slurry and are placed under photocuring printer, by adjusting beating
Print parameter makes the superposition molding of slurry layer upon layer, obtains with the calcium phosphate porous bioceramic scaffold biscuit of osteoinductive；
(4) degreasing sintered: the biscuit of ceramics in step (3) being placed in degreasing in sintering furnace and is calcined, the higher bone of consistency is obtained
The calcium phosphate porous bioceramic scaffold of inductivity.
Alternately, in the above preparation method, the printing technique in the step (3) is digital light processing
(DLP) and the 3D printing technique of stereolithography apparatus (SLA).
Alternately, in the above preparation method, uv equipment print parameters are as follows: wavelength 300-500nm, printing
25 ~ 100 μm of thickness, Single Slice Mode time are 2 ~ 20s.
Alternately, in the above preparation method, in the step (4), the ceramics bracket biscuit of printing shaping
It is degreasing sintered using normal sintering furnace or microwave agglomerating furnace, 800 DEG C are warming up to the rate of 2 ~ 10 DEG C/min, keeps the temperature 2-5h, so
1050 ~ 1200 DEG C are warming up to the rate of 2 ~ 10 DEG C/min again afterwards, 1-5h is kept the temperature, then cools to room temperature with the furnace.
Alternately, in the above preparation method, volume contraction parameter after being sintered according to printed sample, it is reversed to amplify
Initial model size repeats the preparation step, to guarantee the shape of the calcium phosphate porous bioceramic scaffold of osteoinductive
Accurate dimension.
The present invention also provides a kind of calcium phosphate porous bioceramic scaffolds prepared using the above method.
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
Beneficial effects of the present invention:
(1) bioceramic suitable for photocuring 3D printing is prepared by effective control to each group distribution ratio in the present invention
Slurry, the slurry have many advantages, such as high solids content, low viscosity, good fluidity.
(2) present invention carries out printing shaping using bioceramic slurry of the photocuring 3D printing technique to preparation, obtains into
The calcium phosphate biological ceramic bracket that type effect is good, print speed is fast, printing precision is high.
(3) calcium phosphate biological ceramic bracket prepared by the present invention has macroporous structure (400 μm~600 μ to interpenetrate
M), it is also enriched on macropore inner wall many micro-nano holes (50 μm or less), porosity 60%~80%,
(4) calcium phosphate biological ceramic bracket prepared by the present invention has connectivity macropore (400 μm~600 μ for allowing tissue to grow into
M), and hole wall has micron abundant and small nano-size pores, and forms the three-dimensional porous of class osteoplaque apatite layer on surface
Calcium phosphate ceramic has osteoinductive, belongs to a new generation with tissue regeneration induction ability in bone renovating bracket material.
Detailed description of the invention:
Fig. 1 is to print the calcium phosphate biological ceramic rack standard sample prepared using this method.
Fig. 2 is scanning electron microscope (SEM) photo of sample segment under different amplification in embodiment.
After Fig. 3 is self-bone grafting porous calcium phosphate stenter to implant new zealand white rabbit muscle of back 4 months of this method preparation,
The coloration result figure of the hard tissue slicing of bone tissue sample.
Specific embodiment:
Specific embodiment by the following examples is again described in further detail above content of the invention.But it does not answer
When the range that this is interpreted as the above-mentioned theme of the present invention is only limitted to example below.Do not depart from the spirit and principles in the present invention it
Any modification inside made, and the equivalent replacement or improvement made according to ordinary skill knowledge and customary means,
It should include within the scope of the present invention.
Embodiment 1:
(1) preparation of photosensitive resin premixed liquid: selecting the epoxy acrylate of 50wt% for oligomer, and the TMPTA of 44wt% is to live
Property diluent, the 819 of 5wt% are photoinitiator, and the EDB of 1wt% is sensitizer, are sufficiently mixed 20min with magnetic stirring apparatus.
(2) hydroxyapatite (quality accounting 60%) by purity for 99.9%, configured photosensitive resin premixed liquid (quality
Accounting 37%), KH-570 silane coupling agent be placed in ball mill as dispersing agent (quality accounting 3%), revolving speed 150r/min, ball milling
10h obtains ceramic-resin slurry.
(3) ceramic-resin slurry being placed under DLP photo solidification machine and is printed, wavelength 405nm prints 50 μm of thickness,
5s/ layers of light application time, be layering accumulation molding, obtains biscuit of ceramics.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, ceramic porosity 65%.Prepared bracket is as shown in Figure 2.
By aforesaid operations, porous hydroxyl apatite bioceramic bracket may finally be obtained, bracket, which has, mutually to be passed through
Logical macroporous structure has a large amount of capillary micro-nano holes in rack surface, wherein the macroporous structure (> 100 μm) of macroscopic view can pass through
3D printing realizes that the capillary micropore on big hole wall can decompose during the sintering process by light-cured resin and leave vacancy and hydroxyl
Base apatite crystal grain shrinks to be formed.Experiment display, the bioceramic scaffold have osteoinductive, can be used for field of biomedicine bone
Tissue repair.
Embodiment 2
(1) preparation of photosensitive resin premixed liquid: selecting the epoxy acrylate of 59wt% for oligomer, and the TMPTA of 35wt% is to live
Property diluent, the 819 of 5wt% are photoinitiator, and the EDB of 1wt% is sensitizer, are sufficiently mixed 20min with magnetic stirring apparatus.
(2) with step (2) in embodiment 1.
(3) with step (3) in embodiment 1.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, ceramic porosity 65%.
The content of reactive diluent in the present embodiment has selected the minimum of optional mass fraction range, and sample can be at
Function printing.
Embodiment 3
(1) with step (1) in embodiment 1.
(2) hydroxyapatite (quality accounting 50%) by purity for 99.9%, configured photosensitive resin premixed liquid (quality
Accounting 47%), KH-570 silane coupling agent be placed in ball mill as dispersing agent (quality accounting 3%), revolving speed 150r/min, ball milling
10h obtains ceramic-resin slurry.
(3) with step (3) in embodiment 1.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, ceramic porosity 73%.
Hydroxyapatite quality accounting (solid content) in the present embodiment has selected the minimum of optional range, and sample can
Successful print, the bioceramic scaffold have osteoinductive, can be used for field of biomedicine bone tissue reparation.
Embodiment 4
(1) preparation of photosensitive resin premixed liquid: the polyester acrylate of the epoxy acrylate, 25wt% that select 25wt% is oligomeric
Object, the HDDA of TMPTA, 20wt% of 24wt% are reactive diluent, 2wt% 819, the 1173 of 1wt%, the TPO of 2wt% draws for light
Agent is sent out, the EDB of 1%wt is sensitizer, is sufficiently mixed 20min with magnetic stirring apparatus；
(2) hydroxyapatite (quality accounting 60%) by purity for 99.9%, configured photosensitive resin premixed liquid (quality accounting
35%), KH-570 silane coupling agent (quality accounting 3%), KH-550 silane coupling agent (quality accounting 2%) are placed in ball mill, are turned
Fast 200r/min, ball milling 10h obtain ceramic-resin slurry.
(3) ceramic-resin slurry being placed under DLP photo solidification machine and is printed, wavelength 405nm prints 50 μm of thickness,
4s/ layers of light application time, be layering accumulation molding, obtains biscuit of ceramics.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, and ceramic porosity 65% can be used for field of biomedicine bone tissue and repair
It is multiple.
The type of oligomer, reactive diluent and photoinitiator in photosensitive resin premixed liquid is increased in the present embodiment.
The TMPTA diluent solidification rate of three-functionality-degree is very fast but viscosity is higher, and the solidification rate of the HDDA diluent of bifunctionality is slightly
Slow but viscosity is lower, and dilution effect is more preferable, the better effect that the two is used cooperatively；A variety of photoinitiators are used cooperatively can be in difference
Wave-length coverage can cause solidification, it is faster than single photoinitiator curing rate.
Embodiment 5
(1) preparation of photosensitive resin premixed liquid: the polyester acrylate of the epoxy acrylate, 25wt% that select 25wt% is oligomeric
Object, the HDDA of TMPTA, 20wt% of 26wt% be reactive diluent, the 819 of 1wt%, the 1173 of 1wt%, the TPO of 1wt% be that light draws
Agent is sent out, the EDB of 1%wt is sensitizer, is sufficiently mixed 20min with magnetic stirring apparatus；
(2) with step (2) in embodiment 4.
(3) with step (3) in embodiment 4.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, and ceramic porosity 65% can be used for field of biomedicine bone tissue and repair
It is multiple.
The dosage of photoinitiator is reduced to 3% in the present embodiment, photocuring effect and curing time be not substantially by shadow
It rings.Photoinitiator dosage be not it is The more the better, when the dosage of photoinitiator is excessive, a large amount of heat produced by polymerizeing makes to react
It is not easy to control.
Embodiment 6
(1) with step (1) in embodiment 5.
(2) hydroxyapatite (quality accounting 70%) for being 99.0% by purity, configured photosensitive resin premixed liquid (quality
Accounting 27%), KH-570 silane coupling agent (quality accounting 1%), KH-560 silane coupling agent (quality accounting 2%) be placed in ball mill
In, revolving speed 200r/min, ball milling 10h obtain ceramic-resin slurry.
(3) with step (3) in embodiment 4.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, and ceramic porosity 60% can be used for field of biomedicine bone tissue and repair
It is multiple.
Embodiment improves the solid content of calcium phosphate ceramic, remain to preferably form under this photocuring printing technology.
The increase of ceramic solid content can be improved sinter molding and sintered mechanical property, simultaneously because calcium phosphate solid content
It improves, photosensitive resin premixed liquid is reduced, and the hole left after sintering is reduced, and the porosity of bracket is caused to have certain reduction.
Embodiment 7
(1) with step (1) in embodiment 5.
(2) by purity be 99.0% bata-tricalcium phosphate (quality accounting 35%), the hydroxyapatite (matter that purity is 99.0%
Measure accounting 30%), configured photosensitive resin premixed liquid (quality accounting 32%), KH-570 silane coupling agent (quality accounting 1%),
KH-560 silane coupling agent (quality accounting 2%) is placed in ball mill, revolving speed 200r/min, ball milling 10h, obtains ceramic-resin slurry
Material.
(3) with step (3) in embodiment 4.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1200 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, and ceramic porosity 63% can be used for field of biomedicine bone tissue and repair
It is multiple.
Bata-tricalcium phosphate is increased in the present embodiment.Bata-tricalcium phosphate is greater than hydroxyl phosphorus in the intracorporal solution rate of people
Lime stone, the adjustable integral support of addition degradation rate, improve the activity of bracket.It is compared to embodiment 1, this implementation
Example is suitable for the defect more demanding to degradation speed.
Embodiment 8
(1) preparation of photosensitive resin premixed liquid: the polyester acrylate of the epoxy acrylate, 25wt% that select 25wt% is oligomeric
Object, the HDDA of TMPTA, 20wt% of 25wt% be reactive diluent, the 819 of 2wt%, the TPO of 2wt% be photoinitiator, 1%wt's
EDB is sensitizer, is sufficiently mixed 20min with magnetic stirring apparatus；
(2) hydroxyapatite (quality accounting 75%) for being 99.0% by purity, configured photosensitive resin premixed liquid (quality accounting
22%), KH-570 silane coupling agent (quality accounting 1%), KH-560 silane coupling agent (quality accounting 2%) are placed in ball mill, are turned
Fast 200r/min, ball milling 10h obtain ceramic-resin slurry.
(3) with step (3) in embodiment 4.
(4) it by after the biscuit of ceramics removal support of printing shaping, is placed in Muffle furnace and is sintered degreasing.With 5 DEG C/min
Rate heat up, 3h is kept the temperature after being warming up to 800 DEG C, is then warming up to 1100 DEG C again with the rate of 5 DEG C/min, keeps the temperature 5h,
Then furnace cooling obtains porous calcium phosphate ceramic bracket, ceramic porosity 63%.
The present embodiment is compared to other embodiments, and final sintering temperature is lower, the final crystal grain meeting of ceramics bracket
Smaller, crystallinity is lower, has better bioactivity in vivo, on the other hand, the mechanical property of bracket can be lower than above-mentioned reality
Apply example.
Embodiment 9
It is total in vitro with mesenchymal stem cell (MSCs) after porous calcium phosphate ceramic bracket sterilizing prepared by embodiment 1-6
Culture 3 weeks, respectively when cultivating 1 day, 5 days, 7 days and 21 days, using diacetic acid fluorescein/propidium iodide (FDA/PI) to cell
It is dyed, then use confocal laser scanning microscope and is taken pictures, cell attachment is in porous ceramic channel inner wall as the result is shown
Growth is broken up on the material, is proliferated obviously.Material has induction bone tissue regeneration and speeds the function that bone defect repairing is rebuild
Energy.
Embodiment 10
After porous calcium phosphate bracket (stent diameter 12.0mm, with a thickness of the 2.0mm) sterilizing for using the mode of embodiment 1 to prepare
It is implanted into new zealand white rabbit muscle of back.The sample for having portion bone tissue is taken out after implantation 4 months, is put into 4% poly
The fixed sample of formaldehyde is dehydrated after 14 days and resin embedding, carries out hard tissue slicing, and slice thickness is 15 μm, finally carries out to slice
H and E dyeing.Its coloration result is as shown in figure 3, wherein dark brown is the porous calcium phosphate bracket of implantation, Qi Bishang
Light-colored part be newborn bone tissue.This it appears that having gone out new bone tissue in internal stent adherent growth from figure,
It, there are also a certain distance, thus indicates that apart from skull itself bone tissue and has induced newborn bone in prepared internal stent
Tissue, it was demonstrated that bracket has a good osteoinductive.
Claims (9)
1. a kind of photosensitive resin premixed liquid for being used to prepare calcium phosphate bone induction bioceramic scaffold, which is characterized in that including low
Polymers, reactive diluent, photoinitiator and sensitizer.
2. photosensitive resin premixed liquid according to claim 1, which is characterized in that the mass fraction of each component are as follows: oligomer
45 ~ 65%, reactive diluent 35 ~ 55%, photoinitiator 1 ~ 7%, sensitizer 1 ~ 5%.
3. photosensitive resin premixed liquid according to claim 1, which is characterized in that oligomer is epoxy acrylate, poly- ammonia
It is one or more in ester acrylate, polyester acrylate；Reactive diluent is isobornyl methacrylate (IBOMA), three
Hydroxymethyl-propane triacrylate (TMPTA), tripropylene glycol and acrylate (TPGDA), 1,6 hexanediol diacrylate
(HDDA) one or more in；Photoinitiator is 819,184,173, one of TPO, TPO-L or a variety of；Sensitizer is 4- bis-
Methylaminobenzoate ethyl ester (EDB), at least one of the different monooctyl ester of dimethylamine benzoic acid (EHA).
4. a kind of photocuring 3D printing calcium phosphate bone induces ceramic slurry, which is characterized in that including calcium phosphate ceramic powder or its
Nano pulp, dispersing agent and photosensitive resin premixed liquid described in claim 1.
5. photocuring 3D printing calcium phosphate bone according to claim 4 induces ceramic slurry, which is characterized in that each component
Mass fraction are as follows: 50 ~ 90% calcium phosphate ceramic powder or its nano pulp, 10 ~ 50% photosensitive resin premixed liquid, 2 ~ 5% dispersions
Agent.
6. photocuring 3D printing calcium phosphate bone according to claim 4 induces ceramic slurry, which is characterized in that the phosphoric acid
Calcium ceramic powder or nano pulp are tricalcium phosphate (α-TCP and β-TCP), hydroxyapatite (HA), tetracalcium phosphate, biphosphate
It is one or more in calcium；Dispersing agent is one of silane resin acceptor kh-550, KH-560, KH-570 or a variety of.
7. photocuring 3D printing calcium phosphate bone according to claim 4 induces ceramic slurry, which is characterized in that the phosphoric acid
The purity of calcium ceramic powder or nano pulp is 95.00 ~ 99.99%.
8. a kind of preparation method of calcium phosphate bone induction bioceramic scaffold, which comprises the following steps:
(1) preparation of photosensitive resin premixed liquid: oligomer, reactive diluent, photoinitiator, sensitizer are sufficiently mixed；
(2) preparation of photocuring 3D printing ceramic slurry: photosensitive resin premixed liquid prepared in step (1) and calcium phosphate are made pottery
Porcelain powder or nano pulp, dispersing agent are placed in ball mill in proportion and are mixed, and are suitble to light solid with certain viscosity to prepare
Change the ceramic slurry of 3D printing；
(3) photocuring 3D printing: step (2) are prepared into obtained ceramic slurry and are placed under photocuring printer, by adjusting beating
Print parameter makes the superposition molding of slurry layer upon layer, obtains with the calcium phosphate porous bioceramic scaffold biscuit of osteoinductive；
(4) degreasing sintered: the biscuit of ceramics in step (3) being placed in degreasing in sintering furnace and is calcined, the higher bone of consistency is obtained
The calcium phosphate porous bioceramic scaffold of inductivity.
9. a kind of calcium phosphate porous bioceramic scaffold prepared using claim 8 the method.
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