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WO2024141095A1 - Procédé de fabrication d'un article imprimé en 3d à l'aide d'une composition de silicone photodurcissable - Google Patents

Procédé de fabrication d'un article imprimé en 3d à l'aide d'une composition de silicone photodurcissable Download PDF

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Publication number
WO2024141095A1
WO2024141095A1 PCT/CN2023/143684 CN2023143684W WO2024141095A1 WO 2024141095 A1 WO2024141095 A1 WO 2024141095A1 CN 2023143684 W CN2023143684 W CN 2023143684W WO 2024141095 A1 WO2024141095 A1 WO 2024141095A1
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Prior art keywords
weight
silicone composition
photocurable silicone
sio
printer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/143684
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English (en)
Inventor
Liya JIA
Yuanzhi YUE
Genli WU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elkem Silicones Shanghai Co Ltd
Original Assignee
Elkem Silicones Shanghai Co Ltd
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Filing date
Publication date
Application filed by Elkem Silicones Shanghai Co Ltd filed Critical Elkem Silicones Shanghai Co Ltd
Publication of WO2024141095A1 publication Critical patent/WO2024141095A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • Silicone materials are increasingly used in 3D printing due to their unique chemical and mechanical properties, for example, flexibility, elasticity, weather resistance, radiation resistance, biocompatibility, high and low temperature resistance, pressure resistance, non-toxicity, etc.
  • a silicone elastomer has excellent flexibility and elasticity and is easy to cut and sew, so it is particularly suitable for replicating blood vessels, hearts, muscles or skin.
  • Viscosity is one of the most important parameters for 3D printing photocuring silicone technology, which is one of the key factors affecting quality of the final product.
  • Photocurable silicone materials with high viscosity are generally not suitable for 3D printing due to poor fluidity and even thixotropy.
  • most commercialized 3D Printer is more suitable to print the silicone materials with relatively lower viscosity with good flowability.
  • the existing 3D printing using materials with lower viscosity usually limits the range of materials suitable for 3D printing.
  • materials with lower viscosity are unfavorable to better mechanical properties and thus affects the quality of the final product.
  • Another object of the present invention is to provide a three-dimensional (3D) printed article formed in accordance with the method of the invention.
  • Another further object of the present invention is to provide a three-dimensional (3D) printer for photocurable silicone composition in accordance with present invention.
  • high viscosity refers to a viscosity of higher than 500 mPa. sat 25°C, for example between 3000 mPa. sand 5 000 000 mPa. sat 25°C, between 10 000 mPa. s and 3 000 000mPa. sat 25°C, between 20 000 mPa. s and 1 000 000mPa. sat 25°C, or between 50 000 mPa. s and 1 000 000 mPa. sat 25°C.
  • step (1) flattening the photocurable silicone composition provided in step (1) , for example, by self-leveling of the composition, or by using a flattening device;
  • the flattening device is used to load the photocurable silicone composition evenly on to printing area.
  • the flattening device may be a scraper, a roller, a sprayer, or a brush.
  • the flattening device may be a scraper simply having scraping function, or a scraper having both scraping function and feeding function.
  • the flattening device may be made of rigid or flexible material, or may have various cross-sectional shape such as rectangle, oval, and square.
  • the thickness of each layer in step (3) is from 5 to 500 ⁇ m, or from 10 to 200 ⁇ m, or from 10 to 100 ⁇ m, or from 15 to 50 ⁇ m, or from 20 to 30 ⁇ m.
  • the 3D printer is DLP printer, preferably pull-up type DLP printer or sinking type DLP printer.
  • the secondary curing of the 3D printed article in step (6) is carried out under UV or visible radiation for a period of 0.01 to 200 min, for example 0.05 to 100 min, 0.1 to 50 min, 1 to 50 min, 5 to 30 min, or 10 to 20 min, preferably 0.1 to 40 min, more preferably 1 to 30 min.
  • the secondary curing of the 3D printed article in step (6) is carried out by heating at a temperature in the range of 50°C to 200°C, preferably 60°C to 130°C, more preferably 80°C to 120°C for a period of 0.1 to 120 min, preferably 1 to 50 min, more preferably 5 to 40 min.
  • the secondary curing of the 3D printed article in step (6) is carried out by heating at a temperature in the range of 60°C to 200°C, 80 to 100°C, 85 to 90°C, for a period of 0.1 to 110 min, 1 to 100 min, 5 to 50 min, 10 to 30 min.
  • A-1 at least one organopolysiloxane polymer having the following formula (1) : M*D x M* (1)
  • ⁇ D is (R) 2 SiO 2/2 ;
  • ⁇ R is a substituted or unsubstituted hydrocarbyl having 1 to 20 carbons, preferably chosen from the group consisting of methyl, ethyl, propyl, trifluoropropyl, and phenyl, and most preferably R is a methyl group,
  • ⁇ D is (R) 2 SiO 2/2 ;
  • At least one organopolysiloxane resin comprising a (meth) acrylate group optionally, at least one organopolysiloxane resin comprising a (meth) acrylate group
  • A-2 is different from A-1.
  • the organopolysiloxane resin comprising a (meth) acrylate group B is chosen from MQ resins, MDQ resins, TD resins, MDT resins and MTQ resins containing a (meth) acrylate group.
  • the photocurable silicone composition comprises:
  • the photocurable silicone composition comprises:
  • At least one organopolysiloxane compound A’ comprising, per molecule at least two C 2 -C 6 alkenyl radicals bonded to silicon atoms,
  • At least one organohydrogenopolysiloxane compound B’ comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom,
  • the photocurable silicone composition comprises:
  • Another object of the invention relates to a 3D printed article formed in accordance with the method of present invention.
  • Another object of the invention relates to use of the 3D printed article according to the invention or formed in accordance with the method of the invention, especially in hygienic application, medical application, healthcare application, electronics, aerospace, transportation, industrial spare parts, filtration materials, agricultural application, clothing, footwear product, household application, industrial application, building or construction applications, sealing and bonding application, consumer goods, food application such as the application in contact with food.
  • Another object of the invention relates to a photocurable silicone composition for 3D printing, comprising:
  • A-1 at least one organopolysiloxane polymer having the following formula (1) : M*D x M* (1)
  • ⁇ R is a substituted or unsubstituted hydrocarbyl having 1 to 20 carbons, preferably chosen from the group consisting of methyl, ethyl, propyl, trifluoropropyl, and phenyl, and most preferably R is a methyl group,
  • At least one organopolysiloxane polymer having the following formula (2) M D y (D ACR ) w M (2)
  • ⁇ M is: R 2 (R) 2 SiO 1/2 ; (R) 3 SiO 1/2 or R 4 (R) 2 SiO 1/2 ;
  • ⁇ D ACR is (R 2 ) (R) SiO 2/2 ;
  • ⁇ R 2 is a moiety of the following general formulas:
  • At least one organopolysiloxane resin comprising a (meth) acrylate group optionally, at least one organopolysiloxane resin comprising a (meth) acrylate group
  • the photocurable silicone composition comprises at least one of the components B and D.
  • A-2 is different from A-1.
  • the photocurable silicone composition proper viscosity and good mechanical properties play key roles to successfully obtain printed articles via 3D printing technologies involving photocuring such as DLP or SLA, notably for the manufacturing of complex article.
  • the use of the specific method according to the invention would bring many advantageous effects, for example, wider printable viscosity range of, especially high viscosity of the photocurable silicone composition useful in 3D printing, better mechanical properties for 3D printed objects, higher production efficiency, faster printing speed, higher precision, less or no support structure.
  • the printing process according to the invention is particularly suitable for DLP printing technology, especially for pull-up or sinking DLP printing technology.
  • DLP printing technology especially for pull-up or sinking DLP printing technology.
  • sinking DLP printing technology an object having a complex shape can be obtained with high precision, without or less use of support structure.
  • the 3D printing systems useful in the present invention includes different 3D printing technologies such as SLA, DLP, LCD, CLIP, etc.
  • ⁇ M is: R 2 (R) 2 SiO 1/2 ; (R) 3 SiO 1/2 or R 4 (R) 2 SiO 1/2
  • the photocurable silicone composition comprises at least one of the components B and D.
  • ⁇ D is (R) 2 SiO 2/2 ;
  • ⁇ x ⁇ 60 for example 60 ⁇ x ⁇ 500,000, 80 ⁇ x ⁇ 100,000, 100 ⁇ x ⁇ 50,000, 200 ⁇ x ⁇ 10,000, 500 ⁇ x ⁇ 5000, 600 ⁇ x ⁇ 1000, 50 ⁇ x ⁇ 300, or 100 ⁇ x ⁇ 300, preferably 60 ⁇ x ⁇ 500 000, and most preferably 90 ⁇ x ⁇ 5000,
  • ⁇ R is a substituted or unsubstituted hydrocarbyl having 1 to 20 carbons, preferably chosen from the group consisting of methyl, ethyl, propyl, trifluoropropyl, and phenyl, and most preferably R is a methyl group,
  • the organopolysiloxane polymer (polydimethylsiloxane with 3-acryloxy 2-hydroxypropoxypropyl end-groups) A-1 has the following formula (4) :
  • the organopolysiloxane polymer A-1 may be oils with a dynamic viscosity at 25°C of between 1 mPa. sand 5 000 000 mPa. s. for example between 1 mPa. sand 1 000 000 mPa. s, between 10 mPa. sand 500 0 00 mPa. s, between 50 mPa. sand 100 000 mPa. s, between 100 mPa. sand 50 000 mPa. s, or between 500 mPa. sand 1000 mPa. s, preferably between 10 mPa. sand 100 000 mPa. s.
  • the content of (meth) acrylate group in the organopolysiloxane A-1 is 0.0001-30%by weight, preferably 0.001-10%by weight, relative to the total weight of organopolysiloxane A-1.
  • the organopolysiloxane polymer A-2 is chosen from the group consisting of polymers (5) to (8) :
  • a is from 1 to 20, for example from 2 to 18, or from 4 to 16, or from 6 to 10, and preferably a is from 1 to 10, b is from 1 to 500, and preferably b is from 10 to 500;
  • n is from 10 to 400, for example from 20 to 350, from 50 to 300, from 80 to 300, or from 100 to 250, preferably n is from 50 to 200, and even more preferably n is from 50 to 150;
  • n is from 1 to 500, for example from 10 to 400, from 100 to 350, or from 150 to 300, and preferably n is from 1 to 200;
  • a is from 2 to 50, from example from 2 to 40, from 5 to 30, or from 10 to 20, and preferably a is from 2 to 20;
  • b is from 0 to 500, for example from 1-300, from 5 to 200, from 15 to 150, or from 50 to 100, and preferably b is from 10 to 400.
  • the organopolysiloxane A-2 may be oils with a dynamic viscosity at 25°C of between 1 mPa. sand 1 000 000 mPa. s, preferably between 10 mPa. sand 100 000 mPa. s.
  • the content of (meth) acrylate group in the organopolysiloxane A-2 is 0.0001-30%by weight, preferably 0.001-10%by weight, relative to the total weight of organopolysiloxane A-2.
  • the organopolysiloxane resin comprising a (meth) acrylate group B has, per molecule, at least two different units chosen from those of formula R’ 3 SiO 1/2 (M unit) , R’ 2 SiO 2/2 (D unit) , R’SiO 3/2 (T unit) and SiO 4/2 (Q unit) with at least one of the units being a T or Q unit and has a (meth) acrylate group, in which the acrylate group may be optionally substituted, and thus may be, for example, methacrylate group.
  • the R’ radicals are identical or different and are chosen from linear or branched alkyl radicals or vinyl, phenyl or 3, 3, 3-trifluoropropyl radicals.
  • the alkyl radicals have from 1 to 6 carbon atoms. More particularly, mention may be made, as examples of alkyl R’ radicals, of methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals. These resins preferably have a double bond content of between 0.05 and 0.5mol/100g, more preferably between 0.1 and 0.4mol/100g. Examples of resins that may be mentioned include MQ resins, MDQ resins, TD resins, MDT resins and MTQ resins containing a (meth) acrylate group.
  • the organopolysiloxane resin comprising a (meth) acrylate group B may have a dynamic viscosity at 25°C of between 1 mPa. sand 1 000 000 mPa. s, preferably between 10 mPa. sand 100 000 mPa. s, more preferably between 2000 mPa. sand 5000 mPa. s,
  • the photoinitiator C employed in the photocurable silicone composition according to the present invention is preferably a radical photoinitiator which can be chosen from the group consisting of ⁇ -hydroxy ketones, benzoin ethers, aromatic ⁇ -amino ketones and acylphosphine oxides. More preferably, the photoinitiator C is an acylphosphine oxide and even more preferably the photoinitiator C is ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphinate (CAS No. 84434-11-7) .
  • the acrylic type photocurable silicone composition according to the present invention optionally comprises at least one filler D.
  • the filler is preferably mineral filler. It may especially be siliceous. When it is a siliceous material, it may act as a reinforcing or semi-reinforcing filler.
  • the reinforcing siliceous filler is chosen from colloidal silica, powder of fumed silica and of precipitated silica, or a mixture thereof.
  • the powder has a mean particle size generally less than 0.1 ⁇ m (micrometers) , a BET specific surface area of greater than 30 m2/g, preferably between 30 and 350 m2/g.
  • the silica may be incorporated in unmodified form or after having been treated with organosilicon compounds usually used for this purpose.
  • the semi-reinforcing siliceous filler such as diatomaceous earth or ground quartz may also be used.
  • the non-siliceous mineral material it may be included as semi-reinforcing or bulking mineral filler.
  • the non-siliceous filler that may be used, alone or as a mixture, are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, non-expanded vermiculite, calcium carbonate optionally surface-treated with fatty acids, zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime. It is within the capability of the person skilled in the art to choose the particle size and the BET surface area of these fillers according to the actual demands.
  • silica is used.
  • the acrylic type photocurable silicone composition according to the present invention optionally contains at least one solvent F.
  • the solvent F is selected from the group consisting of hexane, toluene, methanol, ethanol, dioxane, acetone, dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethylacetate, glycerol, ⁇ -valerolactone, polyethylene glycol, polypropylene glycol, decamethylcyclopentasiloxane and mixtures thereof.
  • the solvent F is used to compatilize the photoinitiator C with other components of the photocurable silicone composition.
  • said other auxiliary agent or additive is chosen from photosensitizer, adhesion promoter, pigments, delustrants, matting agents, heat and/or light stabilizers, antistatic agents, flame retardants, antibacterial agent, antifungal agent, thixotropic agent, photocuring inhibitor, retardant and any combination thereof.
  • the acrylic type photocurable silicone composition according to the present invention may have proportions of the components that are standard in the technical field under consideration, given that the intended application must also be taken into account.
  • the acrylic type photocurable silicone composition according to the present invention may comprise 20 to 90%by weight, or 45 to 80%by weight, or 50 to 60%by weight, of the organopolysiloxane polymer A-1, based on the total weight of the composition.
  • the acrylic type photocurable silicone composition according to the present invention may comprise 0 to 30%by weight, or 2 to 15%by weight, or 3 to 10%by weight of the organopolysiloxane polymer A-2, based on the total weight of the composition.
  • the acrylic type photocurable silicone composition according to the present invention may comprise 0 to 50%by weight, or 5 to 40%by weight, or 10 to 30%by weight of the organopolysiloxane resin comprising a (meth) acrylate group B, based on the total weight of the composition.
  • the acrylic type photocurable silicone composition according to the present invention may comprise 0.01 to 5%by weight, or 0.2 to 1.5%by weight, or 0.6 to 1%by weight of the photoinitiator C, based on the total weight of the composition.
  • the acrylic type photocurable silicone composition according to the present invention may comprise from 0 to 45%by weight, or 5 to 35%by weight, or 10 to 32%by weight of the filler D, based on the total weight of the composition.
  • the photocurable silicone composition according to the present invention may have a dynamic viscosity at 25°C of between 1 mPa. sand 3 000 000 mPa. s, preferably between 10 mPa. sand 1 000 000 mPa. s, and more preferably between 100 mPa. sand 500 000 mPa. s.
  • (F’) optionally at least one crosslinking inhibitor F’.
  • - and the symbols Z which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably selected from the group formed by alkyl groups containing from 1 to 8 carbon atoms and aryl groups containing between 6 and 12 carbon atoms, and even more preferentially selected from the group formed by methyl, ethyl, propyl, 3, 3, 3-trifluoropropyl, xylyl, tolyl and phenyl radicals,
  • the symbols Z 1 which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably selected from the group formed by alkyl groups containing from 1 to 8 carbon atoms inclusive and aryl groups containing between 6 and 12 carbon atoms, and even more preferentially selected from the group formed by methyl, ethyl, propyl, 3, 3, 3-trifluoropropyl, xylyl, tolyl and phenyl radicals.
  • Z and Z 1 are selected from the group formed by methyl and phenyl radicals
  • W is selected from the following list: vinyl, propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 10-undecenyl, 5, 9-decadienyl and 6-11-dodecadienyl, and preferably, W is a vinyl.
  • organopolysiloxanes may have a linear, branched or cyclic structure. Their degree of polymerization is preferably between 2 and 5000.
  • siloxyl units "D” selected from the group formed by the siloxyl units W 2 SiO 2/2 , WZSiO 2/2 and Z 1 2 SiO 2/2
  • siloxyl units "M” selected from the group formed by the siloxyl units W 3 SiO 1/2 , WZ 2 SiO 1/2 , W 2 ZSiO 1/2 and Z 1 3 SiO 1/2 .
  • the symbols W, Z and Z 1 are as described above.
  • end units "M” mention may be made of trimethylsiloxy, dimethylphenylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy groups.
  • units "D” mention may be made of dimethylsiloxy, methylphenylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyldecenylsiloxy or methyldecadienylsiloxy groups.
  • Said organopolysiloxanes A’ may be oils with a dynamic viscosity from about 10 to 100 000 mPa. sat 25°C, generally from about 10 to 70 000 mPa. sat 25°C, or gums with a dynamic viscosity of about 1 000 000 mPa. sor more at 25°C.
  • the organohydrogenopolysiloxane compound B’ is an organopolysiloxane containing at least two hydrogen atoms per molecule, bonded to an identical or different silicon atom, and preferably containing at least three hydrogen atoms per molecule directly bonded to an identical or different silicon atom.
  • the symbols Z 2 which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably selected from the group formed by alkyl groups containing from 1 to 8 carbon atoms and aryl groups containing between 6 and 12 carbon atoms, and even more preferentially selected from the group formed by methyl, ethyl, propyl, 3, 3, 3-trifluoropropyl, xylyl, tolyl and phenyl radicals.
  • the groups represented by R 1 , R 2 , and R 3 can be unsubstituted or substituted, linear, branched or cyclic alkyl groups or aryl, alkyl aryl or aryl alkyl groups, in particular alkyl or aryl groups.
  • the substituted group which may be on groups Cp, R 1 , R 2 and R 3 is one or more groups that do not interfere in a hydrosilation reaction such as alkyl and silyl groups or halogens like F, Cl or Br.
  • a light source such as LED arranged under the release film
  • the loading of the photocurable silicone composition may be realized by different method, for example, by using a pull-up system or a sinking forming system.
  • the photocurable silicone composition may be loaded onto a printing area from a grooved scraper device.
  • the sinking forming system such as sinking forming DLP printer
  • the photocurable silicone composition may be loaded onto a forming cylinder from storage cylinder by scraper moving.
  • the loading of the photocurable silicone composition refers to the photocurable silicone composition moving in the same cylinder by self-levelling or moving by scraper.
  • the secondary curing of the 3D printed article is carried out under UV or visible radiation for a period of 0.01 to 200 min, preferably 0.1 to 40 min, more preferably 1 to 30 min, and/or by heating at a temperature in the range of 50°C to 200°C, preferably 60°C to 130°C, more preferably 80°C to 120°C for a period of 0.1 to 120 min, preferably 1 to 50 min, more preferably 5 to 40 min, until the printed article is fully formed.
  • Fig. 4 shows a pull-up DLP printer, wherein the meanings for symbols are indicated below.
  • resin material such as photocurable silicone composition
  • reaction system When the reaction is finished, the reaction system is cooled down naturally. The product is transferred to a pear-shaped separated funnel and saturated aqueous sodium chloride solution is added and extracted with dichloromethane solution. Then the water phase is washed to neutral, and then anhydrous magnesium sulfate is added to remove water. After spin distillation, distillation under reduced pressure removes the remaining small molecules to obtain a transparent and product with a certain of viscosity.
  • Viscosity The viscosity is measured at 25°C according to ASTM D445.
  • the hardness of the cured sample based on the photocurable silicone composition is measured at 25°C according to ASTM D2240. The details of the measuring conditions are listed in the table 2.
  • the testing sample of cured silicone is prepared as the following method. The liquid sample according to examples in table 2 is firstly poured into mold with the thickness of 2 mm. Then the sample together with the mold is placed on printing platform of DLP printer at 25°C and the UV irradiation is at 405 nm for 40s. The energy density of UV irradiation is 85 mW/cm 2 . The post curing is carried out under heating condition at 150°C for 1 hour.
  • the photocurable silicone composition of the present invention allows good mechanical properties under high exposure intensity.
  • Table 3 The exposure intensity and exposure time used in printing the sample block according to the printing process of the invention and the printing precision of the sample block obtained.
  • process parameters for parametric slicing, and key process parameters are as follows: wavelength of light: 405 nm, the exposure intensity is 45mW/cm2, the exposure time is 5s and the layer thickness is 0.1 mm; in order to realize success printing, a support structure is designed and added in the STL model.
  • the residual resin material on the surface is removed by ultrasonic cleaning with ethanol, and then cured with UV for 15-30 min until the 3D printed object is completely cured.

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Abstract

L'invention concerne de manière générale le domaine d'une impression tridimensionnelle (3D), et en particulier un procédé de fabrication d'un article imprimé 3D à l'aide d'une composition de silicone photodurcissable, un article imprimé 3D formé selon le procédé et une imprimante 3D utilisée.
PCT/CN2023/143684 2022-12-30 2023-12-29 Procédé de fabrication d'un article imprimé en 3d à l'aide d'une composition de silicone photodurcissable Ceased WO2024141095A1 (fr)

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CNPCT/CN2022/144378 2022-12-30
CN2022144378 2022-12-30

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