CN108623752A - A kind of UV-cured resin and preparation method, stereoforming method of biology base - Google Patents
A kind of UV-cured resin and preparation method, stereoforming method of biology base Download PDFInfo
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- CN108623752A CN108623752A CN201810316679.3A CN201810316679A CN108623752A CN 108623752 A CN108623752 A CN 108623752A CN 201810316679 A CN201810316679 A CN 201810316679A CN 108623752 A CN108623752 A CN 108623752A
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- cured resin
- biology base
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The present invention provides a kind of UV-cured resin of biology base, is made of the raw material of following mass parts：50~75 parts of resin matrix, 25~50 parts of diluent, 1~3 part of photoinitiator, the resin matrix are bio-based materials, and the diluent can reduce viscosity, simultaneously participate in photocuring reaction, and the photoinitiator can cause monomer polymerization crosslinking curing.The UV-cured resin of biology base provided by the invention has good mechanical property, it is 3~5 times of current business ultraviolet light solidification stereo shaping resin material, printing precision is high, complicated porous bone structure can be manufactured, above there is tremendous potential in the application of biomedical aspect, especially bioengineered tissue and artificial bone.
Description
Technical field
The present invention relates to a kind of solidifications of the ultraviolet light of stereolithograghy field of material technology more particularly to biology base to set
Fat and preparation method, stereoforming method.
Background technology
Biology base photocuring 3D printing resin formula project has the international advanced and important market demand capacity.At present
3D printing material staple market is based on the material wire of technique Fused Deposition Modeling (FDM), the liquid resin of photocuring (SLA)
Material, the sintering of plastics powder of selective laser sintering (SLS) and sintered metal powder and other biological material etc..
The cured material of ultraviolet light has the advantages that curing rate is fast, formed precision is high, any surface finish is good, object high mechanical strength.Light
Cure stereo shaping technology, model is cut to according to cross section profile transverse and longitudinal according to the Slice Software of computer first set it is more
The software having cuting slice, then imported into photocuring printer by thick 2 consistent dimensional planes layer by layer, is controlled and is risen according to model information
The height that platform moves a synusia in vertical direction is dropped, is layering until printing material object.
The company or seminar of domestic research and development photocuring consumptive material are seldom at present, in the world strong such consumptive material of research and development
Seldom, and equipment manufacturer is depended on.And the research of biology base photo-curing material is rarely reported, and becomes domestic and international 3D printing
The blank of R＆D direction.The advantage that photocuring printing consumables based on biology base has other printed materials irreplaceable, has
The object of very high importance and necessity, printing has biodegradability, biocompatibility, the safety etc. of skin contact
Function, while reaching the flexibility requirements of the certain degree of hardness required by concrete application scene and intensity or wearable device.Difference
In other UV-cured resins, mainly the deficiency based on petrochemical industry class synthesis material, bio-based resin can realize production, printing
Molding, printout use the more environmentally-friendly cleaning of overall process, pollutant are greatly reduced.However, the life developed extensively both at home and abroad at present
Object 3D printing material has technical maturity inadequate, remote from industrialized scale, is of limited application, high and main of cost
All kinds of disadvantages suitable for inefficient nozzle FDM printings.Therefore, it is necessary to one kind being based on photocuring technology bio-based materials, make
Such materials industrialization possibility increases, and use cost reduces, with wearable device suitable for extensive bio-compatible and wide
The general agricultural high to environmental requirement, medicine, the practical application areas such as biology.
Invention content
In view of this, the present invention provides a kind of UV-cured resin for the biology base having excellent mechanical performances, also
Provide a kind of preparation method and stereoforming method of UV-cured resin simple for process.
The present invention provides a kind of UV-cured resin of biology base, is made of the raw material of following mass parts：Resin matrix
50~75 parts, 25~50 parts of diluent, 1~3 part of photoinitiator, the resin matrix is bio-based materials, the diluent energy
Viscosity is reduced, simultaneously participates in photocuring reaction, the photoinitiator can cause monomer polymerization crosslinking curing.
Further, it is made of the raw material of following mass parts：61.7 parts of resin matrix, 37 parts of diluent, photoinitiator 1.3
Part.
Further, the resin matrix is polyurethanes oligomer made from polylactide polyol, the diluent
For methacrylic acid tirethylene glycol ester, the photoinitiator is bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl.
The present invention also provides a kind of preparation methods of the UV-cured resin of above-mentioned biology base, include the following steps：
Photoinitiator is dissolved in diluent by S1, obtains uniform solution；
Uniform solution is mixed with resin matrix, obtains mixture by S2；
S3 stirs the mixture for a period of time, after stirring, removes the bubble in mixture to get to UV light
Change resin.
Further, in step S3,30min is stirred the mixture under the rotating speed of 1000r/min using dispersion machine.
Further, in step S3, the process for removing the bubble in mixture is：Mixture is placed in vacuum pump,
Under the pressure of -1bar, the bubble in mixture is removed.
The present invention also provides a kind of applications of the UV-cured resin of above-mentioned biology base, are cured using the ultraviolet light and are set
Fat cures stereo shaping technology by ultraviolet light can print the material object of 3D models.
The present invention also provides a kind of stereoforming methods of the UV-cured resin of above-mentioned biology base, including following step
Suddenly：The digitlization 3D models that need to be printed are established, hierarchy slicing is carried out to digitlization 3D models；The UV-cured resin is filled
It fills out in the hopper of photocuring printer, and established digitlization 3D models is imported in photocuring printer and start to print
Journey, under the action of the ultraviolet source of the photocuring printer, the UV-cured resin cures stereo shaping, obtains
The material object of 3D models.
Further, the thickness of each layer digital 3D models is set as 0.01~0.2mm.
Further, the power of the ultraviolet source is 25W, wavelength 405nm.
Compared with prior art, the invention has the advantages that：
(1) there is biodegradability, bio-compatible using the object of UV-cured resin provided by the invention printing
The functions such as the safety of property, skin contact, there is great potential in terms of bioengineered tissue；
(2) UV-cured resin provided by the invention has good mechanical property, is current commercial ultraviolet light solidification
Stereo shaping uses 3~5 times of resin material so that it can be applied in more extensive, more specifically occasion.
(3) structure can be made by stereolithograghy technology using UV-cured resin provided by the invention to answer
Miscellaneous object, and multiple same items can be manufactured in same print procedure, efficiency is greatly improved, while also reducing production
Cost, improves production scale, and industrialization possibility is very big.
Description of the drawings
Fig. 1 is the flow diagram of the preparation method of the UV-cured resin of biology base provided by the invention.
Fig. 2 is that the present invention utilizes Hubei Province bone image that UV-cured resin prints made from embodiment 2, wherein Fig. 2
(a) it is the 3D models of Hubei Province bone image, Fig. 2 (b) is the material picture of Hubei Province bone image, and Fig. 2 (c) is the light microscope of Hubei Province bone image
Image.
Fig. 3 is that the present invention utilizes the breastbone image that UV-cured resin prints made from embodiment 2, wherein Fig. 3
(d) it is the 3D models of breastbone image, Fig. 3 (e) is the material picture of breastbone image, and Fig. 3 (f) is the light microscope of breastbone image
Image.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
The embodiment provides a kind of UV-cured resins of biology base, by the raw material group of following mass parts
At：50~75 parts of resin matrix, 25~50 parts of diluent, 1~3 part of photoinitiator, wherein resin matrix is that polylactide is polynary
Polyurethanes oligomer made from alcohol, is a kind of bio-based materials, and diluent is methacrylic acid tirethylene glycol ester
(TEGDMA), the viscosity that can reduce formula, simultaneously participates in photocuring reaction, and photoinitiator is bis- (2,4, the 6- front threes of phenyl
Base benzoyl) phosphine oxide (Irgacure 819), monomer polymerization crosslinking curing can be caused.
The embodiments of the present invention also provide a kind of preparation methods of the UV-cured resin of above-mentioned biology base, including with
Lower step：
Step S1 weighs 1~3 part of photoinitiator and is dissolved into 25~50 parts of diluent, obtain based on mass component
Uniform solution.
Step S2 weighs 50~75 parts of resin matrix based on mass component, by the obtained uniform solutions of step S1 and tree
Aliphatic radical body mixes, and obtains mixture.
Step S3 stirs the mixture for 30min under the rotating speed of 1000r/min using dispersion machine, after stirring, will mix
It closes object to be placed in vacuum pump, under the pressure of -1bar, removes the bubble in mixture, obtain UV-cured resin.
The material object of 3D models can be printed by curing stereo shaping technology by ultraviolet light using above-mentioned UV-cured resin.
The present invention also provides a kind of stereoforming methods of the UV-cured resin of above-mentioned biology base, including following step
Suddenly：The digitlization 3D models that need to be printed are established, hierarchy slicing are carried out to digitlization 3D models, according to UV-cured resin formula
Hardening time setting the time for exposure be 8~15s, according to printing precision require setting digitlization 3D models every layer thickness be
0.01~0.2mm；UV-cured resin is loaded into the hopper of photocuring printer, and established 3D models are imported
Start print procedure in photocuring printer, the ultraviolet light that photocuring printer uses power to be 405nm for 25W, wavelength is light
Source, under the action of ultraviolet source, UV-cured resin cures stereo shaping, obtains the material object of 3D models.
With reference to embodiment to the preparation method of the UV-cured resin of biology base provided by the invention and it is three-dimensional at
Type method is described in detail.
Embodiment 1：
Based on mass component, weighs 2.2 parts of bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl and be dissolved into 29.5
In the methacrylic acid tirethylene glycol ester of part, uniform solution is obtained；Based on mass component, 56 parts of resin matrix is weighed, it will
Uniform solution is mixed with resin matrix, obtains mixture；It is stirred the mixture under the rotating speed of 1000r/min using dispersion machine
After stirring, mixture is placed in vacuum pump by 30min, under the pressure of -1bar, is removed the bubble in mixture, is obtained
To UV-cured resin；The digitlization 3D models that need to be printed are established, hierarchy slicing, setting exposure are carried out to digitlization 3D models
Time is 12s, and it is 0.02mm to require the every layer thickness of setting according to printing precision；UV-cured resin is loaded into photocuring to beat
In the hopper of print machine, and established 3D models are imported in photocuring printer and start print procedure, photocuring printer is adopted
The ultraviolet light for being 405nm with 25W wavelength is light source, and ultraviolet light projects on the lcd screen, in layer according to each chip formation
Solidified resin prints the material object of 3D models.
Embodiment 2：
Based on mass component, weighs 1.3 parts of bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl and be dissolved into 37 parts
Methacrylic acid tirethylene glycol ester in, obtain uniform solution；Based on mass component, 61.7 parts of resin matrix is weighed, it will
Uniform solution is mixed with resin matrix, obtains mixture；It is stirred the mixture under the rotating speed of 1000r/min using dispersion machine
After stirring, mixture is placed in vacuum pump by 30min, under the pressure of -1bar, is removed the bubble in mixture, is obtained
To UV-cured resin；The digitlization 3D models that need to be printed are established, hierarchy slicing, setting exposure are carried out to digitlization 3D models
Time is 10s, and it is 0.05mm to require the every layer thickness of setting according to printing precision；UV-cured resin is loaded into photocuring to beat
In the hopper of print machine, and established 3D models are imported in photocuring printer and start print procedure, photocuring printer is adopted
The ultraviolet light for being 405nm with 25W wavelength is light source, and ultraviolet light projects on the lcd screen, in layer according to each chip formation
Solidified resin prints the material object of 3D models.
Ultraviolet curing resin material made from embodiment 2 is tested for the property, its viscosity is at 25 DEG C
504mPaS, cure shrinkage 6.27%, according to measuring mechanical property-ASTM (American Society for
Testing and Materials, American Society Testing and Materials) standard D638 plastic tensile strength tests measure it is solid
The ultraviolet curing resin material average tensile strength is 68MPa after change, does not reinforce and adds according to ASTM standard D790-
The ultraviolet curing resin material is flat after the standard test method of the bending property of strong plastics and electrical insulating material measures solidification
Equal bending strength is 115MPa, and average bending modulus is 5.8GPa, and business cures the drawing of stereo shaping resin with ultraviolet light at present
It is about 23MPa to stretch intensity with bending strength, and the mechanical property of ultraviolet curing resin material provided by the invention is that business is used
3~5 times of material, performance greatly promotes, while compared with traditional manufacture, can be had using stereolithograghy technology
Effect reduces the bubble in sample, so that the mechanical property of product improves about 62%, it is referring to figs. 2 and 3, real to utilize
Hubei Province bone image that UV-cured resin made from example 2 prints is applied, Fig. 2 (a) is the 3D models of Hubei Province bone image, and Fig. 2 (b) is
The material picture of Hubei Province bone image, Fig. 2 (c) are the optical microscope image of Hubei Province bone image, and Fig. 3 is using purple made from embodiment 2
The breastbone image that outer light-cured resin prints, Fig. 3 (d) are the 3D models of breastbone image, and Fig. 3 (e) is the reality of breastbone image
Object image, Fig. 3 (f) are the optical microscope image of breastbone image, utilize the ultraviolet light of the present invention as can be seen from Figures 2 and 3
Solidified resin can manufacture complicated porous bone structure by photocuring printing technique, and precision is very high, due to the present invention
Used in resin matrix be bio-based materials, have biodegradability, bio-compatibility, and the material possess it is excellent
Mechanical property, therefore above have tremendous potential in the application of biomedical aspect, especially bioengineered tissue and artificial bone.
Embodiment 3：
Based on mass component, weighs 2.8 parts of bis- (2,4, the 6- trimethylbenzoyl) phosphine oxides of phenyl and be dissolved into 48 parts
Methacrylic acid tirethylene glycol ester in, obtain uniform solution；Based on mass component, 72 parts of resin matrix is weighed, it will be equal
One solution is mixed with resin matrix, obtains mixture；It is stirred the mixture under the rotating speed of 1000r/min using dispersion machine
After stirring, mixture is placed in vacuum pump by 30min, under the pressure of -1bar, is removed the bubble in mixture, is obtained
To UV-cured resin；The digitlization 3D models that need to be printed are established, hierarchy slicing, setting exposure are carried out to digitlization 3D models
Time is 9s, and it is 0.15mm to require the every layer thickness of setting according to printing precision；UV-cured resin is loaded into photocuring to beat
In the hopper of print machine, and established 3D models are imported in photocuring printer and start print procedure, photocuring printer is adopted
The ultraviolet light for being 405nm with 25W wavelength is light source, and ultraviolet light projects on the lcd screen, in layer according to each chip formation
Solidified resin prints the material object of 3D models.
Using UV-cured resin provided by the invention printing object have biodegradability, biocompatibility,
The functions such as the safety of skin contact, there is great potential in terms of bioengineered tissue；Ultraviolet light solidification tree provided by the invention
Fat has good mechanical property, is 3~5 times that current commercial ultraviolet light solidification stereo shaping uses resin material so that its
It can be applied in more extensive, more specifically occasion；Pass through photocuring solid using UV-cured resin provided by the invention
Complicated object can be made in forming technique, and multiple same items can be manufactured in same print procedure, greatly carry
High efficiency, while production cost is also reduced, production scale is improved, industrialization possibility is very big.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of UV-cured resin of biology base, which is characterized in that be made of the raw material of following mass parts：Resin matrix 50
~75 parts, 25~50 parts of diluent, 1~3 part of photoinitiator, the resin matrix is bio-based materials, and the diluent can drop
Low viscosity, simultaneously participates in photocuring reaction, and the photoinitiator can cause monomer polymerization crosslinking curing.
2. the UV-cured resin of biology base as described in claim 1, which is characterized in that by the raw material group of following mass parts
At：61.7 parts of resin matrix, 37 parts of diluent, 1.3 parts of photoinitiator.
3. the UV-cured resin of biology base as described in claim 1, which is characterized in that the resin matrix is poly- third friendship
Polyurethanes oligomer made from ester polyol, the diluent are methacrylic acid tirethylene glycol ester, the photoinitiator
For bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl.
4. a kind of preparation method of the UV-cured resin of claims 1 to 3 any one of them biology base, feature exist
In including the following steps：
Photoinitiator is dissolved in diluent by S1, obtains uniform solution；
Uniform solution is mixed with resin matrix, obtains mixture by S2；
S3 stirs the mixture for a period of time, after stirring, removes the bubble in mixture and cures tree to get to ultraviolet light
Fat.
5. preparation method as claimed in claim 4, which is characterized in that in step S3, utilize dispersion machine turning in 1000r/min
30min is stirred the mixture under speed.
6. preparation method as claimed in claim 4, which is characterized in that in step S3, remove the process of the bubble in mixture
For：Mixture is placed in vacuum pump, under the pressure of -1bar, the bubble in mixture is removed.
7. a kind of application of the UV-cured resin of claims 1 to 3 any one of them biology base, which is characterized in that profit
The material object of 3D models can be printed by curing stereo shaping technology by ultraviolet light with the UV-cured resin.
8. a kind of stereoforming method of the UV-cured resin of claims 1 to 3 any one of them biology base, feature
It is, includes the following steps：The digitlization 3D models that need to be printed are established, hierarchy slicing is carried out to digitlization 3D models；It will be described
UV-cured resin is loaded into the hopper of photocuring printer, and established digitlization 3D models importing photocuring is beaten
Start print procedure in print machine, under the action of the ultraviolet source of the photocuring printer, the UV-cured resin
Cure stereo shaping, obtains the material object of 3D models.
9. the stereoforming method of the UV-cured resin of biology base as claimed in claim 8, which is characterized in that each layer
The thickness of digitlization 3D models is set as 0.01~0.2mm.
10. the stereoforming method of the UV-cured resin of biology base as claimed in claim 8, which is characterized in that described
The power of ultraviolet source is 25W, wavelength 405nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810316679.3A CN108623752A (en) | 2018-04-10 | 2018-04-10 | A kind of UV-cured resin and preparation method, stereoforming method of biology base |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109593165A (en) * | 2018-10-30 | 2019-04-09 | 中科三维成型技术（深圳）有限公司 | PLA biology base photosensitive resin and application thereof and application method |
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| CN105936667A (en) * | 2016-03-17 | 2016-09-14 | 华东理工大学 | Method for improving mechanical properties of polycaprolactone-based biological elastomer |
| CN106189048A (en) * | 2016-07-29 | 2016-12-07 | 苏州秉创科技有限公司 | A kind of bio-based 3D printing consumables |
| CN106519161A (en) * | 2016-10-25 | 2017-03-22 | 深圳光华伟业股份有限公司 | Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105936667A (en) * | 2016-03-17 | 2016-09-14 | 华东理工大学 | Method for improving mechanical properties of polycaprolactone-based biological elastomer |
| CN106189048A (en) * | 2016-07-29 | 2016-12-07 | 苏州秉创科技有限公司 | A kind of bio-based 3D printing consumables |
| CN106519161A (en) * | 2016-10-25 | 2017-03-22 | 深圳光华伟业股份有限公司 | Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109593165A (en) * | 2018-10-30 | 2019-04-09 | 中科三维成型技术（深圳）有限公司 | PLA biology base photosensitive resin and application thereof and application method |
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Application publication date: 20181009 |