CN117067589A - SLA light curing 3D printing part with blocked surface toxicity, method and application - Google Patents
SLA light curing 3D printing part with blocked surface toxicity, method and application Download PDFInfo
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- CN117067589A CN117067589A CN202310831618.1A CN202310831618A CN117067589A CN 117067589 A CN117067589 A CN 117067589A CN 202310831618 A CN202310831618 A CN 202310831618A CN 117067589 A CN117067589 A CN 117067589A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 31
- 231100000419 toxicity Toxicity 0.000 title claims abstract description 28
- 230000001988 toxicity Effects 0.000 title claims abstract description 28
- 229920000052 poly(p-xylylene) Polymers 0.000 claims abstract description 43
- 238000007639 printing Methods 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 9
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- 238000005516 engineering process Methods 0.000 abstract description 5
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- 238000009501 film coating Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 19
- 238000002386 leaching Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
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- 239000003344 environmental pollutant Substances 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 238000000016 photochemical curing Methods 0.000 description 2
- -1 photoinitiators Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
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- VRBFTYUMFJWSJY-UHFFFAOYSA-N 28804-46-8 Chemical compound ClC1CC(C=C2)=CC=C2C(Cl)CC2=CC=C1C=C2 VRBFTYUMFJWSJY-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 231100000215 acute (single dose) toxicity testing Toxicity 0.000 description 1
- 238000011047 acute toxicity test Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229920000249 biocompatible polymer Polymers 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000014461 bone development Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007681 cardiovascular toxicity Effects 0.000 description 1
- 231100000060 cardiovascular toxicity Toxicity 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
- B33Y80/00—Products made by additive manufacturing
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Robotics (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
The invention relates to an SLA light curing 3D printing piece with blocked surface toxicity, a method and application thereof. And covering a Parylene film layer on the surface of the SLA light-cured 3D printing piece by using a Parylene film coating process. The Parylene film layer is a Parylene film layer or a Parylene D film layer. Use of a SLA photo-cured 3D print with blocked surface toxicity in medical and biological prints. Provides a new idea and method for the popularization and application of the 3D printing technology in daily life or biomedical research.
Description
Technical Field
The invention relates to the technical field of 3D printing piece toxicity blocking, in particular to a SLA light curing 3D printing piece with blocked surface toxicity, a method and application thereof.
Background
3D printing has been widely used in recent years. Over decades, a variety of 3D printing methods have been developed, including fused deposition modeling, stereolithography, powder-liquid 3D printing, and selective laser sintering. The FDM method provides a variety of biocompatible polymers. However, as the complexity of 3D printing increases, this biocompatibility weakens or even disappears. Stereolithography printing has the advantages of extraordinary resolution, manufacturing speed and smooth surface, and is widely applied in the fields of medicine and biology, such as tissue engineering, organ printing, artificial bone development, drug delivery and the like.
However, stereolithography printing techniques have achieved biocompatibility certification for only a small fraction of commercially available photopolymerizable resins. In addition, of the necessary compounds or additives for stereolithography, more than 20 have been found to be toxic to organisms and found to remain in the finished product. Some toxic compounds such as 1-HCHPK may cause developmental defects, neurotoxicity, cardiovascular toxicity, etc. Toxicity of the 3D part of the stereolithography printing technique can be reduced by supercritical carbon dioxide treatment, ultrasonic treatment of the material in isopropanol, and uv exposure. However, the above method has the problems of complex technology, high cost, insufficient toxin expelling and the like.
Parylene, a generic term for members of the xylene polymer family, is a thermoplastic polymer formed on the surface of a substrate using vacuum deposition polymerization techniques. Currently, among them, parylene N and its halogenated derivatives, para-parylene C and para-parylene D are commercially valuable. Parylene c exhibits excellent properties in medical applications such as low water absorption, high dielectric constant, low coefficient of friction and moderate elongation at break. It has been successfully used for the protective coating of medical metals and metal alloys. However, whether the coating can be applied to a coating of a 3D printing material for isolating toxicity is not reported in research at present.
Accordingly, the invention provides an SLA light curing 3D printing part with blocked surface toxicity, a method and application thereof, which are used for blocking the surface toxicity of the SLA light curing 3D printing part, and a specific blocking method and specific application of the printing part.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an SLA light curing 3D printing piece for blocking the surface toxicity of an SLA light curing 3D printing piece, a specific blocking method and specific application of the printing piece, and an SLA light curing 3D printing piece, a method and application thereof, which are used for overcoming the defects in the prior art.
The technical scheme of the invention is realized as follows: a SLA light curing 3D printing piece with blocked surface toxicity, wherein the surface of the printing piece is uniformly covered with a Parylene film layer.
A method of blocking surface toxicity of an SLA photo-cured 3D print as described above, comprising the steps of:
firstly, printing an SLA light curing 3D printing piece according to the required size and specification by an SLA light curing 3D printer;
and secondly, covering a Parylene film layer on the surface of the SLA light-cured 3D printing piece by utilizing a Parylene film coating process.
The Parylene film layer is a Parylene film layer or a Parylene D film layer.
Use of a SLA photo-cured 3D print with blocked surface toxicity in medical and biological prints.
The invention has the following positive effects: the project blocked the toxicity of SLA photo-cured 3D prints by spraying a Parylene film layer. Toxicity was compared between the sprayed and non-sprayed groups by an acute toxicity test. Non-targeted screening of organic pollutants in the SLA light-cured 3D printing part leaching liquid is carried out, and the result shows that in different sampling time points, the screened compound types in the SLA light-cured 3D printing part leaching liquid of the Parylene film layer are less than those of the SLA light-cured 3D printing part leaching liquid without spraying the Parylene film layer; in the two materials, substances obtained by screening in and out liquid have an ascending trend along with the extension of infiltration time. In the SLA light curing 3D printing part leaching solution without the Parylene film layer, the screened pollutants are mainly carboxylic acid esters, amides, organic amines and other industrial product pollutants.
Experiments and non-targeted screening of organic pollutants show that toxicity of the SLA photo-curing 3D printing part can be obviously isolated by using the Parylene film layer, and application potential of the SLA photo-curing 3D printing part in biomedicine is improved. The product, the method machine and the use of the product and the method for isolating the toxicity of the SLA light curing 3D printing part by a low-cost, high-efficiency and direct method are provided, and a new thought and method are provided for the popularization and application of the 3D printing technology in daily life or biomedical research.
Drawings
FIG. 1 is a distribution diagram of non-targeted screening of organic contaminant species.
FIG. 2 is a graph showing the distribution of the detection of contaminants in leachate at various time points.
Detailed Description
A SLA light curing 3D printing piece with blocked surface toxicity, wherein the surface of the printing piece is uniformly covered with a Parylene film layer.
A method of blocking surface toxicity of an SLA photo-cured 3D print as described above, comprising the steps of:
firstly, printing an SLA light curing 3D printing piece according to the required size and specification by an SLA light curing 3D printer;
and secondly, covering a Parylene film layer on the surface of the SLA light-cured 3D printing piece by utilizing a Parylene film coating process.
The Parylene film layer is a Parylene film layer or a Parylene D film layer.
Use of a SLA photo-cured 3D print with blocked surface toxicity in medical and biological prints.
The Parylene coating is a novel shape coating material, is polymerized by paraxylene, and can be divided into N type, C type, D type, HT type and other types according to different molecular structures. The parylene N has the strongest penetrating power, and can effectively form a film on the surfaces of various fine seams or blind holes. The dielectric constant is extremely low, the dissipation factor is small, and the rubber is mainly used in the rubber and optical fields. The parylene has very low permeability of water molecules and corrosive gases, has a deposition growth rate faster than that of an N type, and is the material with the widest application and the best protection effect at present. Parylend has flame retardancy. Has relatively better physical and electrical properties at higher temperatures and also has better thermal stability than N, C. Parylentht has high dielectric strength, low dielectric constant and good thermal stability. The film is continuous and compact, has no pinholes, has a short-term temperature resistance of 450 ℃ and a long-term temperature resistance of 350 ℃, has strong ultraviolet resistance, and is suitable for being used as a protective material of high-frequency microwave devices.
The Parylene can be vapor deposited under vacuum, the good penetrability of the Parylene active molecules can form a transparent insulating coating with uniform thickness and no pinholes at the inner part and the bottom part of the element, a complete high-quality protective coating is provided for the element, the damage of acid, alkali, salt mist, mold and various corrosive gas pieces is resisted, and the Parylene is not liquid, so that the Parylene cannot gather in the coating process, and a bridging meniscus is formed. The 0.1-100 mu m film coating prepared by adopting a vacuum vapor deposition process (CVD) has the advantages of uniform thickness, compactness, no pinholes, transparency, no stress, no auxiliary agent, no damage to a workpiece, excellent electrical insulation and protection, and is the most effective dampproof, mildew-proof, corrosion-proof and salt mist-proof coating material in the current generation.
The SLA light curing 3D printing technology needs to use various resin monomers, photoinitiators, auxiliary agents, plasticizers, stabilizers and the like, most of which can leak out of water and are toxic to organisms, so that the problems of water quality pollution and biological hazard caused by the leakage are needed to be solved. The invention combines the Parylene film coating process with the SLA light curing 3D printing technology, and isolates most toxic substances in the SLA light curing 3D printing part by utilizing excellent waterproof performance and corrosion resistance of Parylene C or Parylene D, thereby effectively preventing the toxic substances from leaking in some underwater application occasions of the part and protecting the water body and human health. Compared with the uncoated group, the survival rate of zebra fish embryos cultured in the SLA light curing 3D printing culture dish of the coated group is obviously improved, the development condition of each organ is good, and the deformity rate is obviously reduced. The method shows that the Parylene film layer has excellent toxicity isolation capability, provides a new method for solving the long-term problem of toxicity leakage of the 3D printing part, has simple process, can be manufactured in batches, has low cost, and is expected to be applied in large scale in commerce.
The results of the non-targeted screening of organic contaminants in the SLA photo-cured 3D print leachate covered with parylene c film layer were tested as follows:
leaching solution: taking 250ml deionized water into printing material, preserving at room temperature, and respectively taking water samples at 2d,5d and 14d and preserving at-40 ℃. Then, 20ml of leaching solution is placed in a separating funnel, 10ml of dichloromethane liquid-liquid extraction is added, the dichloromethane layer is collected after passing through anhydrous sodium sulfate, the extraction is repeated for 3 times, all the dichloromethane layers are combined, the concentration is reduced to near dryness, about 1ml of methanol is added for redissolution, 500ul of leaching solution is taken to pass through a microporous filter membrane to a sample injection vial, 500ul of leaching solution is taken to pass through the microporous filter membrane, and the leaching solution and the methanol compound solution are combined and mixed uniformly to be tested.
Instrument: thermo UPLC 3000 series Q Orbitrap Mass. Chromatographic conditions: chromatographic column: waters ACQUITY BEH C18 column, 2.1mm X100 mm,1.7 μm. Mobile phase: 0.01% formic acid water (A) -acetonitrile (B). Flow rate: 0.3ml/min. Column incubator: 35 ℃. Sample injection volume: 5ul. Elution gradient: 0min,90% A:10% d; 0-2 min,90% A:10% d; 2-3 min,70% A:30% d; 3-4 min,50% A:50% d; 4-6 min,40% A:60% d; 6-9 min,0% A:100% d; 9-10 min,0% A:100% d; 10-11.5 min,90% A:10% d; 11.5-12 min,90% A:10% D.
Mass spectrometry conditions: scanning mode: scanning is carried out in positive ion mode and negative ion mode respectively, and the ion source: ESI,375 ℃, ion spray voltage 3500V, sheath gas 40arb, assist gas 10arb, reverse blow gas 0,S-lens RF 50; auxiliary air pressure: 10arb, the spray gas and the collision gas are high-purity nitrogen, the scanning mode adopts data dependency scanning (data dependent scan), the detection is carried out in an anion mode, the mode comprises primary full scanning with the resolution of 70000 and secondary scanning with the data dependency resolution of 17500, the scanning range is 100-1500 m/z, the primary scanning automatic gain is controlled to be 1.0e6, and the ion implantation time is 100 ms; the data-dependent two-stage scan automatic gain control was set to 1.0e5, the maximum ion implantation time was set to 100 ms, the isolation window was set to 3.0 m/z, the collision energy (NCE) was set to 30,40,50eV,Loop count to 3, and the dynamic exclusion was set to 10.0s.
And (3) data processing: and (3) introducing the TIC diagram obtained by QE analysis into compound discoverer, performing operations such as peak extraction, filtering, alignment, deconvolution and the like, performing molecular formula fitting by using the accurate mass number obtained by mass spectrometry, and converting the accurate mass number into visual data containing information such as retention time, accurate mass number, fitting molecular formula, peak response value and the like. And (3) matching according to the m/zCloud, chemSpider database and the self-built compound database by using information such as accurate mass number, fragment information, isotope proportion, neutral loss and the like to obtain compound information, and screening and qualitatively analyzing the compound according to the matching degree and score and further carrying out statistical analysis.
Data results: as shown in fig. 1, the contaminants screened in the leachate are mainly carboxylic acid esters, amides, organic amines, boranes, azonia and other chemical contaminants; and a small amount of organic phosphate, phenol, biphenyl, benzene series, and an inducer. As shown in FIG. 2 (color pictures are used in FIG. 2 because of the comparison and distinction between 0-coated and 1-uncoated) the distribution of the detection of contaminants in the leachate at different time points (0-coated and 1-uncoated). In different sampling time points, the types of the compounds screened in the leaching solution of the coating material are less than those of the leaching solution of the non-coating material; in the two materials, substances obtained by screening in and out liquid have an ascending trend along with the extension of infiltration time. In the non-coated leaching solution, the screened pollutants are mainly carboxylic acid esters, amides, organic amines and other industrial product pollutants.
Claims (4)
1. An SLA photo-cured 3D print with blocked surface toxicity, characterized by: the surface of the printing piece is uniformly covered with a Parylene film layer.
2. A method of blocking surface toxicity of a SLA photo-cured 3D printing according to claim 1, wherein: the method comprises the following steps:
firstly, printing an SLA light curing 3D printing piece according to the required size and specification by an SLA light curing 3D printer;
and secondly, coating a Parylene layer on the surface of the SLA light-cured 3D printing piece by using a Parylene coating process.
3. The surface toxicity blocking method of a surface toxicity blocked SLA photo-cured 3D printing according to claim 2, wherein: the Parylene film layer is a Parylene film layer or a Parylene D film layer.
4. Use of a SLA photo-cured 3D print with blocked surface toxicity in medical and biological prints.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310831618.1A CN117067589A (en) | 2023-07-07 | 2023-07-07 | SLA light curing 3D printing part with blocked surface toxicity, method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310831618.1A CN117067589A (en) | 2023-07-07 | 2023-07-07 | SLA light curing 3D printing part with blocked surface toxicity, method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117067589A true CN117067589A (en) | 2023-11-17 |
Family
ID=88705100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310831618.1A Pending CN117067589A (en) | 2023-07-07 | 2023-07-07 | SLA light curing 3D printing part with blocked surface toxicity, method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117067589A (en) |
-
2023
- 2023-07-07 CN CN202310831618.1A patent/CN117067589A/en active Pending
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