CN114905737B - 3D printing method and high-speed photo-curing 3D printing equipment - Google Patents
3D printing method and high-speed photo-curing 3D printing equipment Download PDFInfo
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- CN114905737B CN114905737B CN202210586338.4A CN202210586338A CN114905737B CN 114905737 B CN114905737 B CN 114905737B CN 202210586338 A CN202210586338 A CN 202210586338A CN 114905737 B CN114905737 B CN 114905737B
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- 238000010146 3D printing Methods 0.000 title claims abstract description 43
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 59
- -1 nitroxide free radical compound Chemical class 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000001723 curing Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 66
- 238000007639 printing Methods 0.000 claims description 45
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 18
- 230000005764 inhibitory process Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 10
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000004611 light stabiliser Substances 0.000 claims description 9
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008358 core component Substances 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical group CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 15
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000003490 calendering Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 229920009441 perflouroethylene propylene Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229920006356 Teflon™ FEP Polymers 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 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
- B29C64/10—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
-
- 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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/255—Enclosures for the building material, e.g. powder containers
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
The application relates to a 3D printing method and a high-speed photo-curing 3D printing device, wherein the method comprises the following steps: providing a material pool with a light-transmitting release element, and adding liquid photosensitive resin into the material pool; a UV light image is projected layer by layer under the material pool by a UV light machine so as to form a curing layer on the upper surface of the release element; wherein the release element in the layer contains macromolecular nitroxide free radical compound, the nitroxide free radical compound is at least one of 2, 6-tetramethyl piperidine nitroxide free radical or derivative thereof, the molecular weight of the nitroxide free radical compound is 2000-100000Mw, the content of the nitroxide free radical compound in the release element is more than or equal to 0.5wt%, and the UV light image passes through the release element from bottom to top, so that the 3D photosensitive resin in the material pool is photosensitive cured layer by layer.
Description
Technical Field
The invention belongs to the technical field of photo-curing 3D printing, and particularly relates to high-speed photo-curing 3D printing equipment and a 3D printing method.
Background
3D printing, also known as additive manufacturing, is known as a new industrial revolution marking technology. 3D printing technology routes are numerous, wherein the photocuring 3D printing technology becomes a 3D printing mode with the highest potential due to the advantages of high precision, good surface quality and the like. In the field of photo-curing, a UV photo machine according to photo-curing molding is divided into a photo-curing 3D printing technology and is divided into a laser point light source (SLA for short) and a surface light source digital light projection (DLP for short), wherein the SLA molding mode is that an ultraviolet laser beam is scanned point by point on the surface of photosensitive resin according to each layered section information of the part under the control of a control system, so that a resin thin layer in a scanned area is cured by photo-polymerization reaction, and a thin layer of the part is formed. After one layer is solidified, the workbench is moved downwards by a layer thickness distance so that a new layer of liquid resin is coated on the surface of the original solidified resin, the surface of the resin with higher viscosity is scraped to be flat by the scraper, then the scanning processing of the next layer is carried out, the newly solidified layer is firmly bonded on the previous layer, and the process is repeated until the whole part is manufactured, and a three-dimensional entity prototype is obtained.
The surface light source is classified into a lower projection type and an upper projection type according to the position of the light source. The upper projection type UV ray machine is arranged on the upper surface, and the liquid of the printer is in a material pool, so that each layer of printing needs a scraper to enable the liquid to be leveled because of the leveling problem, and the whole printing efficiency is greatly reduced. The downward projection type surface UV ray machine is positioned below the material, and the printing platform realizes the forming of the three-dimensional object by moving layer by layer, so that the time of scraping knife and leveling is saved, and the printing mode with highest efficiency is realized.
While efficient relative to other printing modes, projection-type photo-curing 3D printing suffers from a serious problem: the release film has high adhesion and poor molding surface quality. The release film of the current DLP type printer mainly adopts a material with low surface energy to realize the release effect in a physical mode. The adhesion force can cause the polymeric layer to adhere to the release film interface, and the separation of the printing component from the release film interface requires mechanical motion intervention for peeling, such as pulling and sliding, and the resulting separation force is proportional to the area, which can damage the printing component and result in poor reliability, and the huge mechanical separation force limits the printable geometry and area, severely reducing the printing speed. Another problem is that with increasing the number of prints, the release film has a reduced release capability, increased adhesion and reduced material transmittance, so that the release film needs to be replaced once every one week of printing, and the release film does not cause any trouble when meeting the low-frequency printing requirements of laboratories or non-businesses, but for 3D printers in commercial scenes, frequent replacement of the release film causes problems such as reduced production efficiency, increased maintenance cost, unstable printing quality, and the like.
Disclosure of Invention
The purpose of the application is to provide a 3D printing method and equipment capable of realizing high-speed printing without frequently replacing release elements.
In order to achieve the above object, the present invention adopts the following technical scheme, and a 3D printing method includes:
providing a material pool with a light-transmitting release element, and adding liquid photosensitive resin into the material pool;
a UV light image is projected layer by layer under the material pool by a UV light machine so as to form a curing layer on the upper surface of the release element; wherein,
the release element in the layer contains macromolecular nitroxide free radical compound, the nitroxide free radical compound is at least one of 2, 6-tetramethyl piperidine nitroxide free radical or the derivative compound thereof, the molecular weight of the nitroxide free radical compound is 2000-100000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 0.5wt%.
The principle of the application is as follows: the TEMPO compound containing the macromolecular nitroxide free radical is introduced into the release element, and the effect of low release force is achieved by utilizing chemical repulsion, so that high-speed 3D printing is realized. In the printing process, the photosensitive resin is contained in a material tank for a long time, and a polymerization inhibitor is consumed by a monomer in the photosensitive resin and a solvent (such as alcohol, isopropanol and propylene carbonate) for cleaning the material tank.
The application is suitable for liquid photosensitive resin, such as HD80, HD90, DT10, DT20 and other types of Suzhou Bo New Material science and technology Co.
In a preferred technical scheme, the molecular weight of the nitroxide free radical compound is 3000-80000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 1wt%.
Another technical scheme of the application is as follows: a high speed photo-curing 3D printing apparatus comprising:
a frame having a horizontal base;
the material pool is used for containing liquid photosensitive resin and is fixedly arranged on the horizontal base station;
the UV ray machine is positioned below the material pool and is used for outputting UV light images layer by layer;
the printing platform is arranged on the frame above the material pool in a lifting manner;
the light-transmitting release element is arranged at the bottom of the material pool, a macromolecular nitroxide free radical compound is added in the release element, the nitroxide free radical compound is at least one of 2, 6-tetramethyl piperidine nitroxide free radical or a derivative thereof, the molecular weight of the nitroxide free radical compound is 2000-100000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 0.5wt%; the UV light image passes through the release element from bottom to top, so that the 3D printing sol in the material pool is photosensitive and solidified layer by layer.
In the preferred technical scheme, the molecular weight of the nitroxide free radical compound is 3000-80000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 1wt%.
Further, the tensile strength of the release element is more than or equal to 18Mpa, and the thickness is 0.05-0.5mm.
Further, the elongation of the release element is less than or equal to 20%.
Optionally, the weight percentage of the nitroxide compound in the release element is 0.01% -15%.
In one embodiment of the present application, the release element is a transparent single-layer film, the core component of the release element is made by mixing a base material with the nitroxide free radical compound, and the base material is one or more than two of tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer, amorphous fluoropolymer, and poly 4-methyl 1-pentene.
In one embodiment of the present application, the release element is a composite membrane with at least two layers, the release element includes a polymerization inhibitor layer and a base layer, the core component of the polymerization inhibitor layer is made by mixing a material forming the base layer with the oxygen-nitrogen radical compound, and the material of the base layer is selected from one or more than two of tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer, amorphous fluoropolymer, poly 4-methyl 1-pentene.
In one embodiment of the present application, the release element is prepared according to the following method: (a) mixing a hindered amine light stabilizer with a base material; (b) forming a release member; (c) And then placing the release element in a dichloromethane solution of 3-chloroperoxybenzoic acid for soaking treatment, so that the hindered amine light stabilizer on the surface of the release element is converted into the nitroxide free radical compound, and the base material is one or more than two of tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer, amorphous fluoropolymer and poly 4-methyl 1-pentene.
Compared with the prior art, the invention has the following beneficial effects: according to the 3D printing equipment disclosed by the invention, the release element is manufactured by adopting the macromolecular nitroxide free radical compound, and the nitroxide free radical in the release element can continuously capture the free radical of the 3D printing photosensitive resin, so that the polymerization inhibition performance is obtained on the surface of the release element, the lower surface adhesion force is obtained, the service life of the release element is long, frequent replacement is not needed, the 3D printing equipment can realize ultrahigh-speed printing, the usability of the printing equipment is greatly improved, the macromolecular nitroxide free radical compound can stably fix polymerization inhibition components on the surface of the release element, the polymerization inhibition components cannot migrate into the photosensitive resin and the cleaning solvent, and meanwhile, the tensile strength, the tearing strength and the durability of the release element are improved.
Drawings
FIG. 1 is a schematic structural diagram of a 3D printing device according to an embodiment of the present application;
fig. 2 is a schematic diagram of the photo-curing principle of the 3D printing device of the present application;
FIG. 3 is a schematic diagram of a material pond according to an embodiment of the present application;
FIG. 4 is a schematic structural view of a release member according to an embodiment of the present application using a single film;
fig. 5 is a schematic structural diagram of a release element according to an embodiment of the present application using a composite film.
Wherein: 101. a light machine; 102. a material pool; 103. a photosensitive resin; 104. a Z-axis lifting mechanism; 105. a printing platform; 200. a release film; 106. printing a piece; 301. a material pool bottom plate; 302. a gasket; 304. a tank body; 201. a base layer; 202. and a polymerization inhibitor layer.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the invention in detail, the following description will refer to the embodiments in combination with the accompanying drawings, wherein the "upper" and "lower" positional relationships described in the present specification correspond to the upper and lower directions in fig. 1 and 2 respectively.
The application discloses a release element, high-speed photo-curing 3D printing equipment applying the release element, and a 3D printing method of the printing equipment. Referring to fig. 1, the high-speed photocuring 3D printing device of the present application includes a frame, a horizontal workbench is provided in the middle of the frame, a material pool 102 is fixedly provided on the horizontal workbench, an optical machine 101 is fixedly installed below the horizontal workbench, a printing platform 105 is provided above the horizontal workbench in a liftable manner, a Z-axis lifting mechanism 104 is provided at the rear part of the frame, and the printing platform 105 vertically ascends or descends through the Z-axis lifting mechanism 104. Referring to fig. 2-3, the tank 102 includes a tank floor 301, a gasket 302, and a trough 304. The bottom of the material pool 102 is provided with the release element, and the release film is taken as an example for the description in this specification. The material pool bottom plate 301 is a frame-shaped structure with a hollowed-out center, the release film 200 is clamped and fixed between the material pool bottom plate 301 and the gasket 302, and the material pool bottom plate 301 is locked and connected to the bottom of the groove body 304 through a fastener.
When the photo-curing 3D printer works, projection light emitted upwards by the optical machine 101 passes through the release film 200, and the photosensitive resin 103 above the release film 200 is cured to form a printing piece 106, each cured layer of material needs to be separated from the release film once, the upper part of the printing piece 106 is attached to the printing platform 105 and moves upwards by one layer height along with the printing platform 105, 3D printing sol rapidly fills the gap between the printing piece and the release film, so that the lower part of the printing piece 106 is immersed in the photosensitive resin, and the next frame of slice image is printed. In the application, by adding the nitroxide free radical compound into the release film, an interface exists between the photosensitive resin 103 and the release film 200, and the polymerization reaction of the photosensitive resin is stopped on the interface, so that a liquid photosensitive resin always exists between the printing piece 106 and the release film 200, and the adhesion between the low printing piece and the release film is realized, thereby realizing ultra-high-speed 3D printing.
Further, the nitroxide radical compound added to the release element is at least one of 2, 6-tetramethyl piperidyloxy nitroxide radical or its derivative with molecular weight between 2000-100000 Mw. Wherein, the weight percentage content of the nitroxide free radical compound in the release element is 0.5-15%, and the transparency of the release element is more than or equal to 50%. In the downward projection type printing equipment, the photosensitive resin is always soaked on the surface of the release element, the photosensitive resin is subjected to curing reaction under the irradiation of the UV image, a chemical exclusion area is formed by the macromolecular nitroxide free radical compound of the release element, and solids formed by the photo-curing reaction of the photosensitive resin cannot adhere to the release element, so that 3D printing with low release force, high speed and long service life is realized. The selected nitroxide free radical compound with molecular weight of more than 2000Mw can resist the long-time use environment of photosensitive resin and cleaning solvent, and can not cause the rapid failure of the surface polymerization inhibition layer.
Preferably, the tensile strength of the release element is more than or equal to 18Mpa, the thickness is 0.05-0.5mm, and the elongation is less than or equal to 20%. The tensile strength and the elongation also influence the service life of the release film, and the deformation of the film material after long-term printing is avoided.
The following describes how the release member of the present application is prepared and used in connection with specific examples.
Preparation of a monolayer release film as shown in FIG. 4
Example 1
1) Mixing 1:1 of polyglycidyl methacrylate and 4-hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical (4-OH-TEMPO) and fully reacting to obtain a reactant containing hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical with molecular weight of 5000Mw, mixing 1 part (weight part) of the reactant with 100 parts (weight part) of poly 4-methyl 1-pentene (brand DX 845) of Mitsui chemical company, and uniformly stirring;
2) Adding the mixture into an extruder for melt plasticizing extrusion, wherein the heating temperature of four areas of the screw extruder is 270 ℃, 280 ℃ and 285 ℃ respectively;
3) And (3) feeding the mixture extruded by the screw extruder into a casting machine through a T-shaped die to carry out casting molding, wherein the die head temperature of the casting machine is 285 ℃, and then carrying out biaxial stretching after cooling to obtain the transparent sheet with the film thickness of 0.05-0.5mm. Through testing, the membrane has the transmittance of 88 percent, the tensile strength of 27.5MPa and the elongation of 18.2 percent.
Example 2
The molar ratio was set to 1:1, mixing and fully reacting the poly glycidyl methacrylate with 4-hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical (4-OH-TEMPO) to obtain a reactant containing hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical with molecular weight of 7000Mw, taking 3 parts by mass of the reactant, mixing with 100 parts by mass of tetrafluoroethylene and hexafluoropropylene copolymer (brand Teflon FEP 9494), and uniformly stirring; and (3) carrying out tape casting and stretching to form a film after screw extrusion to obtain a transparent film with the thickness of 0.1mm and the transmittance of 82%.
Example 3
The polyglycidyl methacrylate and 4-hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical (4-OH-TEMPO) are mixed according to a mole ratio of 1:1, obtaining a reactant containing hydroxyl-2, 6-tetramethyl piperidine oxy-nitrogen free radical with the molecular weight of 15000Mw, mixing 5 parts (mass parts) of the reactant with 100 parts (mass parts) of tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer (Teflon ™ PFA 350), and uniformly stirring; and (3) carrying out tape casting and stretching to form a film after screw extrusion to obtain a transparent film with the thickness of 0.2mm and the transmittance of 75%.
Example 4.
The polyglycidyl methacrylate and 4-hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical (4-OH-TEMPO) are mixed according to a mole ratio of 1:1 to obtain a reactant containing hydroxyl-2, 6-tetramethyl piperidine oxy-nitrogen free radical with molecular weight of 20000Mw, mixing the 9 parts (mass parts) of reactant with 100 parts (mass parts) of poly 4-methyl-1-pentene (with the brand of DX 845) of Sanjing company, plasticizing, extruding and casting to form a film, and obtaining a transparent film with thickness of 0.3mm and transmittance of 70%.
Preparation of the composite Release film shown in FIG. 5
Example 5
The composite release film is prepared by adopting a double-layer coextrusion calendaring mode, wherein the upper layer of the release film is a polymerization inhibition layer 202, the lower layer of the release film is a base layer 201, and the polymerization inhibition layer 202 contains a nitroxide free radical compound. The preparation method of the polymerization inhibitor layer 202 is as follows: the polyglycidyl methacrylate and 4-hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical (4-OH-TEMPO) are mixed according to the mole ratio of 1:1 to obtain a compound of a reactant containing hydroxy-2, 6-tetramethyl piperidine oxy-nitrogen free radical with the molecular weight of 20000Mw, taking 6 parts by mass of the reactant to be mixed with 100 parts by mass of poly 4-methyl-1-pentene (with the trade name of DX 845) of Sanjing chemical company, and uniformly stirring. The base material is poly 4-methyl 1-pentene (with the brand of DX 845) of Sanjing chemical company, the polymerization inhibitor layer material is extruded by a first screw extruder, the base material is extruded by a second screw extruder, and then the base material is calendered by a double-layer co-extrusion die head to form a film, wherein the thickness of the polymerization inhibitor layer is 0.05mm, the thickness of the base layer is 0.15mm, the total thickness is 0.2mm, and the transmittance is 86%.
Example 6.
The composite release film is prepared by adopting a double-layer coextrusion calendaring mode, wherein the upper layer of the release film contains high molecular weight Hindered Amine Light Stabilizer (HALS), and the lower layer is prepared by adopting a base material. The preparation method comprises the following steps: 3 parts by mass of a high molecular weight hindered amine light stabilizer (HALS, chimassorb 944) and 100 parts by mass of poly 4-methyl-1-pentene (trade name DX 845) from Mitsui chemical company were mixed and stirred uniformly. The base material of the release film is poly 4-methyl 1-pentene (with the trade name of DX 845) of Sanjing chemical company, the upper material is extruded by a first screw extruder, the base material is extruded by a second screw extruder, and then the film is calendered by a double-layer co-extrusion die head to form a film, so that the upper layer of composite film containing the hindered amine light stabilizer with the molecular weight of 3000Mw is obtained. Wherein, the thickness of the upper layer film is 0.04mm, the thickness of the base layer is 0.12mm, the total thickness is 0.16mm, and the transmittance is 89%.
And (3) soaking the composite film in a dichloromethane solution of 3-chloroperoxybenzoic acid to convert the hindered amine light stabilizer on the surface of the composite film into a nitroxide free radical, so that the composite release film suitable for photocuring 3D printing is formed.
The release films of examples 1 to 6 were tested and the test results are summarized in the following table.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Molecular weight Mw | 5000 | 7000 | 15000 | 30000 | 50000 | 3000 |
| Transmittance% | 88 | 82 | 75 | 70 | 86 | 89 |
| Tensile Strength/Mpa | 27.5 | 18.5 | 25.5 | 22.5 | 28.2 | 27.5 |
| Elongation% | 18.2 | 26.8 | 22.04 | 15.6 | 19.5 | 18.6 |
The transmittance test method adopts an optical transmittance measuring instrument to measure in the ultraviolet band. The tensile strength and elongation were tested by a universal tester at 23 ℃.
In order to compare the performance difference between the release film and the conventional 3D printing release film in actual printing, the applicant also selected the following two comparative examples for reference.
Comparative example 1 a tetrafluoroethylene and hexafluoropropylene copolymer FEP film with a thickness of 0.15mm was used.
Comparative example 2 a tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer PFA film having a thickness of 0.15mm was used.
Comparative example 3 a release film made of a film of p-hydroxyanisole and a copolymer of tetrafluoroethylene and hexafluoropropylene, FEP, having a thickness of 0.15mm, was selected, wherein the content of p-hydroxyanisole was 1.5%.
Comparative example 4 a release film was selected from the group consisting of 4-hydroxy-2, 6-tetramethylpiperidine oxy-nitrogen radical and tetrafluoroethylene and hexafluoropropylene copolymer FEP film having a thickness of 0.15mm, wherein the content of 4-hydroxy-2, 6-tetramethylpiperidine oxy-nitrogen radical was 1.5%.
The experimental means are as follows: the release films of the above examples and comparative examples were fixed to the bottom of the stock tank, and then photosensitive resin was added to debug the 3D printing apparatus. The printing format of the equipment is 216 x 121.5 x 400mm, and the photosensitive resin is test resin (model DT 10) of Suzhou Bo new material science and technology company. Adopting an ultraviolet LED optical module to carry out illumination curing, wherein the wavelength range is 405nm, and the optical power density is 8mw/cm 2 。
By adopting the 3D printer, a three-dimensional model with the graphic area accounting for 80% of the printing breadth is selected for testing the stripping force, the exposure time is 1s, and a mechanical test sensor is additionally arranged on a force arm on the printer. The three-dimensional model file is divided into layers with the thickness of 0.1mm by the Pollyprint slicing software of Bo-Liang corporation, the layers are exposed according to the thickness of the layers under the irradiation of an ultraviolet light machine under the control of a computer, and the photosensitive resin is cured and molded under the irradiation of the ultraviolet DLP light machine. The printing times count is to record the number of printing layers under the condition that the printing is successful, the surface of the printing piece is complete after being separated from the release element, and the appearance is not damaged. The results of the test are shown in the following table.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Peel force/N | 45 | 30 | 25 | 22 | 20 | 24 | 452 | 405 | 20 | 18 |
| Maximum printing speed mm/h | 300 | 600 | 650 | 650 | 700 | 650 | 50 | 60 | 700 | 700 |
| Printed product appearance | Good quality | Good quality | Good quality | Good quality | Good quality | Good quality | Good quality | Good quality | Good quality | Good quality |
| High speed service life/day | 10 | 15 | 25 | 25 | 30 | 20 | Cannot be printed at high speed | Cannot be printed at high speed | 2 | 4 |
From the table, it can be seen that, the release film that this application adopted makes release film and photosensitive resin form a chemically exclusive interface owing to the effect of nitrogen oxygen free radical polymerization inhibition, and the adhesion between newly formed condensate and the transparent release film is very low, and print platform need not just can separate condensate and release film through reciprocal lift, and new liquid supplements fast and gets into after print platform promotes, then carries out the exposure of next floor to realize the ultra-high speed printing process. It can be seen that examples 1-6 and comparative examples 3-4 in this application each have the advantages of low peel force, high print speed, and that the macromolecular nitroxide free radical compound release element in the examples can have a longer print life at high speed printing than comparative examples 3 and 4. The release force of the comparative example 1 and the comparative example 2 is large, the adhesion and deformation of the printed piece are serious, the appearance of the printed product is complete, the release film also needs to be replaced in time, the release film of the p-methoxyphenol polymerization inhibitor is adopted in the comparative example 3, the release force is small, high-speed printing can be realized, and after 2 days of printing, the polymerization inhibition effect is rapidly reduced because the micromolecule polymerization inhibitor groups in the film are consumed and migrate into the photosensitive resin and the cleaning solvent, and the release film also needs to be replaced.
In summary, the release element of the present application can provide a nitroxide radical compound with a large molecular weight, and can provide a stable polymerization inhibition effect for a long time, and the printing life is improved by 5-10 times compared with other polymerization inhibition release materials.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing embodiments and description merely illustrates the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, the scope of which is defined in the appended claims, specification and their equivalents.
Claims (9)
1. A method of 3D printing, the method comprising:
providing a material pool with a light-transmitting release element, and adding liquid photosensitive resin into the material pool;
a UV light image is projected layer by layer under the material pool by a UV light machine so as to form a curing layer on the upper surface of the release element; wherein,
the release element in the layer contains macromolecular nitroxide free radical compound, the nitroxide free radical compound is at least one of 2, 6-tetramethyl piperidine nitroxide free radical or the derivative compound thereof, the molecular weight of the nitroxide free radical compound is 2000-100000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 0.5wt%;
the nitroxide free radical compound is prepared from polyglycidyl methacrylate and 4-hydroxy-2, 6-tetramethyl piperidine nitroxide free radical in a molar ratio of 1:1 and fully reacting.
2. The method according to claim 1, characterized in that: the molecular weight of the nitroxide free radical compound is 3000-80000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 1wt%.
3. A high speed photo-curing 3D printing apparatus comprising, characterized in that:
a frame having a horizontal base;
the material pool is used for containing liquid photosensitive resin and is fixedly arranged on the horizontal base station;
the UV ray machine is positioned below the material pool and is used for outputting UV light images layer by layer;
the printing platform is arranged on the frame above the material pool in a lifting manner;
the light-transmitting release element is arranged at the bottom of the material pool; the release element is added with a macromolecular nitroxide free radical compound, the nitroxide free radical compound is at least one of 2, 6-tetramethyl piperidine nitroxide free radical or a derivative thereof, the molecular weight of the nitroxide free radical compound is 2000-100000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 0.5wt%; the UV light image passes through the release element from bottom to top, so that the 3D printing sol in the material pool is photosensitive and solidified layer by layer; the nitroxide free radical compound is prepared from polyglycidyl methacrylate and 4-hydroxy-2, 6-tetramethyl piperidine nitroxide free radical in a molar ratio of 1:1 and fully reacting.
4. A high speed photo-curing 3D printing device as claimed in claim 3, characterized in that: the molecular weight of the nitroxide free radical compound is 3000-80000Mw, and the content of the nitroxide free radical compound in the release element is more than or equal to 1wt%.
5. A high speed photo-curing 3D printing device as claimed in claim 3, characterized in that: the tensile strength of the release element is more than or equal to 18Mpa, and the thickness is 0.05-0.5mm.
6. A high speed photo-curing 3D printing device as claimed in claim 3, characterized in that: the elongation of the release element is less than or equal to 20 percent.
7. A high speed photo-curing 3D printing device as claimed in claim 3, characterized in that: the release element is a transparent single-layer film, the core component of the release element is prepared by mixing a base material and the nitroxide free radical compound, and the base material is one or more than two of tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer, amorphous fluoropolymer and poly 4-methyl 1-pentene.
8. A high speed photo-curing 3D printing device as claimed in claim 3, characterized in that: the release element is a composite membrane with at least two layers, the release element comprises a polymerization inhibition layer and a base layer, the core component of the polymerization inhibition layer is prepared by mixing materials forming the base layer with the nitroxide free radical compound, and the material of the base layer is selected from one or more than two of tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer, amorphous fluoropolymer and poly 4-methyl 1-pentene.
9. A high speed photo-curing 3D printing device as claimed in claim 3, characterized in that: the release element is prepared according to the following method: (a) Mixing a high molecular weight hindered amine light stabilizer with a base material, wherein the hindered amine light stabilizer is Chimassorb 944; (b) co-extruding by a screw extruder to form a release element; (c) And then placing the release element in a dichloromethane solution of 3-chloroperoxybenzoic acid for soaking treatment, so that the hindered amine light stabilizer on the surface of the release element is converted into the nitroxide free radical compound, and the base material is one or more than two of tetrafluoroethylene and hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer, amorphous fluoropolymer and poly 4-methyl 1-pentene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107012737A (en) * | 2017-04-20 | 2017-08-04 | 上海金大塑胶有限公司 | A kind of preparation method of release liners |
| CN207172756U (en) * | 2017-07-12 | 2018-04-03 | 东莞市三维三打印科技有限公司 | Ultraviolet light solidifies 3D printer |
| CN110126272A (en) * | 2019-05-21 | 2019-08-16 | 广东石油化工学院 | A kind of photocuring 3D printer |
| CN113429947A (en) * | 2021-07-01 | 2021-09-24 | 本时智能技术发展(上海)有限公司 | Polymerization-resistant functionalized heat-conducting particle and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012737A (en) * | 2017-04-20 | 2017-08-04 | 上海金大塑胶有限公司 | A kind of preparation method of release liners |
| CN207172756U (en) * | 2017-07-12 | 2018-04-03 | 东莞市三维三打印科技有限公司 | Ultraviolet light solidifies 3D printer |
| CN110126272A (en) * | 2019-05-21 | 2019-08-16 | 广东石油化工学院 | A kind of photocuring 3D printer |
| CN113429947A (en) * | 2021-07-01 | 2021-09-24 | 本时智能技术发展(上海)有限公司 | Polymerization-resistant functionalized heat-conducting particle and application thereof |
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