CN111303577A - Visible photosensitive liquid resin for additive manufacturing, and preparation method and application method thereof - Google Patents
Visible photosensitive liquid resin for additive manufacturing, and preparation method and application method thereof Download PDFInfo
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- CN111303577A CN111303577A CN202010126370.5A CN202010126370A CN111303577A CN 111303577 A CN111303577 A CN 111303577A CN 202010126370 A CN202010126370 A CN 202010126370A CN 111303577 A CN111303577 A CN 111303577A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
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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
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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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- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/02—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a visible photosensitive liquid resin for additive manufacturing, and a preparation method and a use method thereof. The visible photosensitive liquid resin for additive manufacturing is stable at room temperature and easy to store. The preparation method is simple to operate, and the photoinitiator can be directly dissolved in the resin monomer; the production cost is low; the preparation process is energy-saving, and only needs to be carried out at room temperature without conditions such as heating, pressurizing and the like. By using the visible photosensitive liquid resin for additive manufacturing, the scan-molded solid model basically does not generate volume shrinkage and has stable size; the spatial resolution of visible light to resin is good, and the size precision of the molded model is good; the forming process is energy-saving and environment-friendly, and only visible light is used for scanning liquid resin; the molding process is easy and convenient to operate, and a powder spreading mechanism is not needed.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to the technical field of additive manufacturing, and particularly relates to visible photosensitive liquid resin for additive manufacturing, and a preparation method and a use method thereof.
Background
The additive manufacturing technology is generally also called as a 3D printing technology, and is a rapid manufacturing technology for forming materials by overlapping layer by layer based on a digital model file, the technology can rapidly manufacture three-dimensional parts for design verification or verification as functional prototypes, a mould is not needed, the processing period is effectively shortened, rapid manufacture of complex three-dimensional structural parts is easy to realize, and meanwhile, the technology can also be widely applied to the field of individuation.
Among the 3D printing technologies, the stereolithography technology is classified and extracted by its high precision, high manufacturing efficiency, and low cost. Compared with the traditional injection molding method, the process of preparing the workpiece by photocuring is not limited by the geometric dimension at all, so that the photocuring rapid molding technology at the present stage is widely applied to the fields of modeling, electronic and electric products, biomedicine and aerospace.
Most of the existing photosensitive resin for 3D printing is solid powder material, the powder bed melting forming technology is required to be utilized for additive manufacturing by adopting the solid powder resin, and in order to realize the resin powder bed melting forming, a flat and compact powder bed must be formed firstly, which puts high requirements on a powder laying mechanism. In addition, the polymer material can be crystallized in the cooling process, and the shrinkage caused by cooling and the large volume uneven shrinkage of the workpiece are caused together, so that the polymer material can be obviously deformed and warped in the powder bed melting and forming process, the mechanical property of the material is seriously influenced, and the 3D printing part can not meet the requirement of industrial use.
The liquid photosensitive resin has the advantages of good fluidity, no need of heating and melting in the molding process, direct room-temperature photocuring molding, no volume shrinkage in the curing process and the like, so research focuses on the development of the liquid photosensitive resin in recent years, CN 10977023A discloses an SLA flexible photosensitive resin, CN 107868443A discloses a 3D printing photosensitive resin, CN 110452340A discloses a 3D printing photosensitive resin and a preparation method thereof, and CN 110396266A discloses a 3D printing photosensitive resin.
Disclosure of Invention
The invention aims to provide a visible photosensitive liquid resin for additive manufacturing, a preparation method and a use method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows: a visible light-sensitive liquid resin for additive manufacturing comprises the following components in percentage by mass based on 100% of the total mass of the visible light-sensitive liquid resin for additive manufacturing:
(1) 95-99 wt% of acrylate resin or epoxy resin;
(2) 0.5-2.5 wt% of an organophosphine photoinitiator;
(3) 0.5-2.5 wt% of iodonium salt or sulfonium salt photoinitiator.
The invention relates to a visible photosensitive liquid resin for additive manufacturing, which is characterized in that: the acrylic resin monomer comprises acrylic resin monomer pure products or a mixture of two or more acrylic resin monomers; the epoxy resin is a pure epoxy resin monomer or a mixture of two or more epoxy resin monomers.
The invention relates to a visible photosensitive liquid resin for additive manufacturing, which is characterized in that: the single-component acrylic resin monomer pure product comprises bis-GMA, bis-GEA, UDMA, HEMA, HPMA, SDDMA, TEGDMA, TEGDA, PEG200DMA and Ebecryl series component acrylic resin monomers.
The invention relates to a visible photosensitive liquid resin for additive manufacturing, which is characterized in that: the pure product of the epoxy resin monomer comprises bisphenol A type epoxy resin, bisphenol F type epoxy resin and an epoxidized olefin compound.
The invention relates to a visible photosensitive liquid resin for additive manufacturing, which is characterized in that: the organic phosphine photoinitiator is (substituted) aryl phosphine, di (substituted) aryl phosphine or tri (substituted) aryl phosphine organic compound.
The invention relates to a visible photosensitive liquid resin for additive manufacturing, which is characterized in that: the iodonium salt is a di (substituted) aryl iodonium salt or a triaryl sulfonium salt.
The invention relates to a visible photosensitive liquid resin for additive manufacturing, which is characterized in that: the anions in the di (substituted) aryl iodonium salts and triarylsulfonium salts include hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetrakis- (pentafluorophenyl) borate, and trifluoromethylsulfonate.
The invention relates to a preparation method of visible photosensitive liquid resin for additive manufacturing, which comprises the following operation steps:
(1) at room temperature, adding 0.5-2.5 wt% of organic phosphine photoinitiator into 95-99 wt% of acrylate resin or epoxy resin, and uniformly mixing;
(2) and (2) adding 0.5-2.5 wt% of iodonium salt or sulfonium salt into the resin solution prepared in the step (1) in an environment protected from light, and uniformly mixing to obtain the visible photosensitive liquid resin for additive manufacturing.
The invention relates to a using method of a visible photosensitive liquid resin for additive manufacturing, which comprises the following steps:
(1) creating a three-dimensional model for printing, and importing the three-dimensional model into computer application software of a 3D printer;
(2) pouring a proper amount of prepared visible photosensitive liquid resin for additive manufacturing into a containing device of a 3D printer;
(3) setting a visible laser wavelength of 400-500 nm, a power of 10-1000 mW, a resolution of 10-100 mu m and a scanning speed of 1-100 mm/s for a 3D printer;
(4) starting the 3D printer, and scanning the visible photosensitive liquid resin in the containing device into a solid model according to the shape and the size of the introduced three-dimensional model;
(5) and after the scanning is finished, taking down the model, and removing the support to obtain the additive manufacturing solid model with a smooth surface and good spatial resolution.
The visible photosensitive liquid resin for additive manufacturing is stable at room temperature and easy to store. The preparation method is simple to operate, and the photoinitiator can be directly dissolved in the resin monomer to prepare the required visible light sensitive liquid resin; the production cost is low, and the used raw materials, namely the acrylate monomer, the epoxy resin monomer, the organic phosphine compound, the iodonium salt and the sulfonium salt are all cheap industrial products; the preparation process is energy-saving, and only needs to be carried out at room temperature without conditions such as heating, pressurizing and the like. By using the visible photosensitive liquid resin for additive manufacturing, the scan-molded solid model basically does not generate volume shrinkage and has stable size; the spatial resolution of visible light to resin is good, and the size precision of the molded model is good; the forming process is energy-saving and environment-friendly, and only visible light is used for scanning liquid resin; the molding process is easy and convenient to operate, and a powder spreading mechanism is not needed.
Detailed Description
The invention is described in detail below by way of specific examples, it being necessary to note that: this example is only suitable for further illustration of the invention, but does not limit its scope. Various modifications which do not depart from the spirit of the invention will become apparent to those skilled in the art from this disclosure and are intended to be included within the scope of the invention.
Example 1
A10 mL glass bottle was tightly wrapped with tinfoil on the outside thereof and was protected from light. 2 g bisGMA (analytically pure, Sigma-Aldrich, USA) and 2 g TEGDMA (analytically pure, Sigma-Aldrich, USA) are added into the treated glass bottle in sequence at room temperature, and the mixture is stirred for 0.5 h at the speed of 50 rpm by electric stirring to mix the two acrylic resin monomers uniformly; 0.05 g of diphenylphosphine (analytical grade, Sigma-Aldrich, USA) is then added to the glass bottle and stirring is continued for 0.5 h; finally, 0.05 g of bis (4-tert-butyl) phenyliodonium hexafluorophosphate (analytically pure, Sigma-Aldrich, USA) was added, and stirring was continued for 0.5 h to obtain a visible light-sensitive liquid resin for additive manufacturing.
And storing the prepared visible photosensitive liquid resin for additive manufacturing in dark for later use.
And creating a three-dimensional model for printing by using Creo software, and importing the three-dimensional model into computer application software of the NEJE DK-8-KZ laser printer. A square glass mold with the inner cavity size of 20 mm in length, 20 mm in width and 10 mm in height is manufactured by using organic glass with the thickness of 5 mm, and is fixed on a working platform of a NEJE DK-8-KZ laser printer. And weighing a proper amount of the prepared visible photosensitive liquid resin, and pouring the visible photosensitive liquid resin into a square glass mold. The NEJE DK-8-KZ laser printer is set to be at a visible laser wavelength of 405 nm, energy of 10 mW, resolution of 10 mu m and a scanning speed of 1 mm/s. And starting the NEJE DK-8-KZ laser printer, and scanning the visible photosensitive liquid resin in the square glass mold into a solid model according to the shape and the size of the introduced three-dimensional model. After the scanning is finished, the edge of the formed solid model is clear and smooth, which shows that the visible photosensitive liquid resin prepared by the embodiment has high resolution ratio to visible light.
Example 2
At room temperature, 10 g of Ebecryl 40 (analytically pure, Shanghai Kay chemical Co., Ltd.) and 0.2 g of tri (1-naphthyl) phosphine (analytically pure, Shanghai Kay chemical Co., Ltd.) were sequentially added to a 50 mL glass bottle, and the two acrylic resin monomers were uniformly mixed by electrically stirring at a speed of 60 rpm for 0.5 h. The vials were then protected from light with tinfoil. Then 0.2 g of bis (4-methyl) phenyliodonium tetrafluoroborate (analytically pure, Shanghai Kahn chemical Co., Ltd.) is added, and the stirring is continued for 0.5 h, thus obtaining the visible photosensitive liquid resin for additive manufacturing.
And storing the prepared visible photosensitive liquid resin for additive manufacturing in dark for later use.
And creating a three-dimensional model for printing by using Creo software, and importing the three-dimensional model into computer application software of the LD-002R photocuring 3D laser printer. And weighing a proper amount of the prepared visible photosensitive liquid resin, and pouring the visible photosensitive liquid resin into a resin tank at the bottom of the LD-002R photocuring 3D laser printer. The LD-002R photocuring 3D laser printer is set to have visible laser wavelength of 500 nm, energy of 1000mW, resolution of 50 μm and scanning speed of 10 mm/s. And starting a printer, and scanning the visible photosensitive liquid resin in the resin tank into a solid model according to the shape and the size of the introduced three-dimensional model. After the scanning is finished, the support is removed, and the edge of the formed solid model is clear and smooth, which shows that the visible photosensitive liquid resin prepared by the embodiment has high resolution ratio to visible light.
Example 3
5 g of (3, 4-epoxyhexane) carboxylic acid 3,4- (epoxyhexane) methyl ester (analytical grade, TCI Co., Japan) and 0.1 g of triphenylphosphine analytical grade (analytical grade, Alfa Aesar Co., England) were charged in this order into a 10 mL brown glass bottle at room temperature, and the resin was stirred with electric motor at 50 rpm for 0.5 hour; then, 0.1 g of UVI-6992 (analytical grade, TCI Co., Japan) was added to the glass bottle and stirring was continued for 0.5 h to obtain a visible light-sensitive liquid resin for additive manufacturing.
And storing the prepared visible photosensitive liquid resin for additive manufacturing in dark for later use.
A square glass mold with the inner cavity size of 20 mm in length, 20 mm in width and 10 mm in height is manufactured by using organic glass with the thickness of 5 mm, and is fixed on a working platform of a NEJE DK-8-KZ laser printer. And weighing a proper amount of the prepared visible photosensitive liquid resin, and pouring the visible photosensitive liquid resin into a square glass mold. The NEJE DK-8-KZ laser printer is set to be at a visible laser wavelength of 405 nm, energy of 100mW, resolution of 100 mu m and scanning speed of 100 mm/s. And starting the NEJE DK-8-KZ laser printer, and scanning the visible photosensitive liquid resin in the square glass mold into a solid model according to the shape and the size of the introduced three-dimensional model. After the scanning is finished, the edge of the formed solid model is clear and smooth, which shows that the visible photosensitive liquid resin prepared by the embodiment has high resolution ratio to visible light.
Example 4
At room temperature, 10 g of diphenol propane epoxy resin (analytically pure, TCI company, Japan) and 0.2 g of tri (1-naphthyl) phosphine (analytically pure, Kay chemical Co., Ltd., Shanghai) were sequentially added into a 50 mL brown glass bottle, and stirred electrically for 0.5 h; then, 0.2 g of UVI-6976 (analytically pure, TCI Co., Japan) was added thereto, and stirring was continued for 0.5 h to obtain a visible light-sensitive liquid resin for additive manufacturing.
And storing the prepared visible photosensitive liquid resin for additive manufacturing in dark for later use.
And creating a three-dimensional model for printing by using Creo software, and importing the three-dimensional model into computer application software of the LD-002R photocuring 3D laser printer. And weighing a proper amount of the prepared visible photosensitive liquid resin, and pouring the visible photosensitive liquid resin into a resin tank at the bottom of the LD-002R photocuring 3D laser printer. The LD-002R photocuring 3D laser printer is set to be at the visible laser wavelength of 405 nm, the energy of 100mW, the resolution of 60 mu m and the scanning speed of 40 mm/s. And starting a printer, and scanning the visible photosensitive liquid resin in the resin tank into a solid model according to the shape and the size of the introduced three-dimensional model. After the scanning is finished, the edge of the formed solid model is clear and smooth, which shows that the visible photosensitive liquid resin prepared by the embodiment has high resolution ratio to visible light.
Claims (9)
1. A visible light-sensitive liquid resin for additive manufacturing comprises the following components in percentage by mass based on 100% of the total mass of the visible light-sensitive liquid resin for additive manufacturing:
(1) 95-99 wt% of acrylate resin or epoxy resin;
(2) 0.5-2.5 wt% of an organophosphine photoinitiator;
(3) 0.5-2.5 wt% of iodonium salt or sulfonium salt photoinitiator.
2. The visible light-sensitive liquid resin for additive manufacturing according to claim 1, wherein: the acrylic resin is a pure product of acrylic resin monomers or a mixture of two or more acrylic resin monomers; the epoxy resin is a pure epoxy resin monomer or a mixture of two or more epoxy resin monomers.
3. The visible light-sensitive liquid resin for additive manufacturing according to claim 2, wherein: the pure product of the acrylic resin monomer comprises bis-GMA, bis-GEA, UDMA, HEMA, HPMA, SDDMA, TEGDMA, TEGDA, PEG200DMA and Ebecryl series component acrylic resin monomer.
4. The visible light-sensitive liquid resin for additive manufacturing according to claim 2, wherein: the pure epoxy resin monomer comprises bisphenol A epoxy resin, bisphenol F epoxy resin and an epoxidized olefin compound.
5. The visible light-sensitive liquid resin for additive manufacturing according to claim 1, wherein: the organic phosphine photoinitiator is (substituted) aryl phosphine, di (substituted) aryl phosphine or tri (substituted) aryl phosphine organic compound.
6. The visible light-sensitive liquid resin for additive manufacturing according to claim 1, wherein: the iodonium salt is a di (substituted) aryl iodonium salt or a triaryl sulfonium salt.
7. The visible light-sensitive liquid resin for additive manufacturing according to claim 6, wherein: the anions in the di (substituted) aryl iodonium salts and triarylsulfonium salts include hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetrakis- (pentafluorophenyl) borate, and trifluoromethylsulfonate.
8. A method for preparing the visible light-sensitive liquid resin for additive manufacturing according to claim 1, comprising the following steps:
(1) at room temperature, adding 0.5-2.5 wt% of organic phosphine photoinitiator into 95-99 wt% of acrylate resin or epoxy resin, and uniformly mixing;
(2) and (2) adding 0.5-2.5 wt% of iodonium salt or sulfonium salt into the resin solution prepared in the step (1) in an environment protected from light, and uniformly mixing to obtain the visible photosensitive liquid resin for additive manufacturing.
9. A method of using the visible light-sensitive liquid resin for additive manufacturing of claim 1:
(1) creating a three-dimensional model for printing, and importing the three-dimensional model into computer application software of a 3D printer;
(2) pouring a proper amount of prepared visible photosensitive liquid resin for additive manufacturing into a containing device of a 3D printer;
(3) setting a visible laser wavelength of 400-500 nm, a power of 10-1000 mW, a resolution of 10-100 mu m and a scanning speed of 1-100 mm/s for a 3D printer;
(4) starting the 3D printer, and scanning the visible photosensitive liquid resin in the containing device into a solid model according to the shape and the size of the introduced three-dimensional model;
(5) and after the scanning is finished, taking down the model, and removing the support to obtain the additive manufacturing solid model with a smooth surface and good spatial resolution.
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Citations (5)
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|---|---|---|---|---|
| US7144927B1 (en) * | 1999-12-17 | 2006-12-05 | S & C Polymer Silicon-und Composite-Spezialitaten GmbH | Photoinitiator system with acylphosphine oxide initiators |
| US20120259031A1 (en) * | 2009-12-17 | 2012-10-11 | Dsm Ip Assets, B.V. | Led curable liquid resin compositions for additive fabrication |
| US20160264696A1 (en) * | 2015-03-10 | 2016-09-15 | National Taiwan University Of Science And Technology | Photocurable resin and three-dimensional printing system |
| CN107312133A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院化学研究所 | A kind of visible light solidifying material and 3D printing device and product for 3D printing |
| CN107501442A (en) * | 2017-08-15 | 2017-12-22 | 宁波七诺新材料科技有限公司 | For 3D printing technique by visible light-initiated photoinitiator composite and application |
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2020
- 2020-02-28 CN CN202010126370.5A patent/CN111303577A/en active Pending
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| US7144927B1 (en) * | 1999-12-17 | 2006-12-05 | S & C Polymer Silicon-und Composite-Spezialitaten GmbH | Photoinitiator system with acylphosphine oxide initiators |
| US20120259031A1 (en) * | 2009-12-17 | 2012-10-11 | Dsm Ip Assets, B.V. | Led curable liquid resin compositions for additive fabrication |
| US20160264696A1 (en) * | 2015-03-10 | 2016-09-15 | National Taiwan University Of Science And Technology | Photocurable resin and three-dimensional printing system |
| CN107312133A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院化学研究所 | A kind of visible light solidifying material and 3D printing device and product for 3D printing |
| CN107501442A (en) * | 2017-08-15 | 2017-12-22 | 宁波七诺新材料科技有限公司 | For 3D printing technique by visible light-initiated photoinitiator composite and application |
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| Title |
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| KAMPMEIER J.A.: "Phosphoranyl Radicals as Reducing Agents: SRN1 Chains with Onium Salts and Neutral Nucleophiles", 《J. ORG. CHEM.》 * |
| 吕建波: "紫外光固化涂料的氧阻聚效应", 《电镀与涂饰》 * |
| 贺军辉等: "碘盐/胺光引发聚合体系的初级反应研究", 《感光科学与光化学》 * |
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