WO2022258030A1 - 一种3d打印用组合物、3d打印方法、装置 - Google Patents

一种3d打印用组合物、3d打印方法、装置 Download PDF

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WO2022258030A1
WO2022258030A1 PCT/CN2022/097957 CN2022097957W WO2022258030A1 WO 2022258030 A1 WO2022258030 A1 WO 2022258030A1 CN 2022097957 W CN2022097957 W CN 2022097957W WO 2022258030 A1 WO2022258030 A1 WO 2022258030A1
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group
printing
layer
acrylate
composition
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PCT/CN2022/097957
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English (en)
French (fr)
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吕如松
杨前程
傅佳艺
陈保全
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珠海赛纳三维科技有限公司
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Publication of WO2022258030A1 publication Critical patent/WO2022258030A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • 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
    • B29C64/245—Platforms or substrates
    • 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
    • B29C64/264—Arrangements for irradiation
    • 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
    • B29C64/295—Heating elements
    • 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
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers

Definitions

  • the present application relates to a composition for 3D printing, a 3D printing method, and a device, and relates to the technical field of 3D printing.
  • Stereo-curing 3D printing technology mainly includes three-dimensional inkjet printing technology (3DP), stereolithography technology (SLA), digital light processing technology (DLP), continuous liquid surface manufacturing technology (CLIP), etc.
  • This type of technology mainly uses liquid photosensitive resin As a raw material, under the condition of light irradiation, the photosensitive resin undergoes a polymerization reaction and is rapidly cured to form a 3D object.
  • Light-curing 3D printing technology has the characteristics of high molding precision, high printing efficiency, and mature technology. It is one of the earliest developed and commercialized 3D printing technologies.
  • light-curing 3D printing technology requires photosensitive resins with high purity and low viscosity. Good stability and low volatility;
  • chemical properties it is required that the photosensitive resin can be quickly polymerized and solidified under light conditions, and it is required to have good mechanical properties and dimensional stability after curing. Due to the limitations of the chemical and physical properties of the existing 3D printing materials, it hinders the application of light-curing 3D printing technology in industrial fields such as aerospace, molds, automobiles and other fields.
  • the present application provides a composition for 3D printing, a 3D printing method and a device, and the 3D object printed by the composition has good dimensional stability and mechanical properties.
  • the first aspect of the present application provides a composition for 3D printing, the composition includes 5-30% of blocked diisocyanate, 5-40% of active hydrogen-containing compound, and 5% of the first photocurable component according to weight percentage.
  • -40% photocurable monomer 20-80%, photocurable oligomer 0-30%, photoinitiator 0.5-10%, catalyst 0-1%, additive 0.05-8%, filler 0-15% and Colorant 0-5%;
  • the blocked diisocyanate has a structure shown in formula 1:
  • R 9 and R 10 are independently selected from one of the following structures:
  • R 1 , R 2 , R 4 and R 5 are independently selected from linear or branched chain alkyl groups with 1-20 carbon atoms; C3-C20 groups with monocyclic, bridged bicyclic and bridged tricyclic groups group; aryl group with 6-18 carbon atoms; arylalkyl or alkylaryl group with 6-18 carbon atoms; 3- A heteroaryl group with 20 carbon atoms, a heterocyclic group with 3-20 carbon atoms containing at least one atom of O, N, Si, S, and P;
  • R is one selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, allyl, (meth)acryloyloxyethyl kind;
  • R 3 is selected from linear or branched alkylene groups with 1-18 carbon atoms, alicyclic groups with 5-18 carbon atoms, arylene groups with 6-18 carbon atoms, and arylene groups with 6-20 arylalkylene or alkylarylene with carbon atoms, naphthalene ring with substituted or unsubstituted groups;
  • the molecular structure of the first photocuring component includes a vinyl group and a heterocyclic group, and the heterocyclic group can undergo a thermochemical reaction with the blocking agent formed after deblocking the blocked diisocyanate;
  • the blocked diisocyanate has a deblocking temperature at least 20° C. higher than the printing temperature of the composition.
  • the unblocking temperature of the blocked diisocyanate is T, and 100 ⁇ T ⁇ 150°C.
  • the heterocyclic group is selected from epoxy group, butoxy ring group, tetrahydrofuran group, dioxane group, dioxane group, trioxane group, propane group Lactone group, butyrolactone group, aziridane group, azetidinyl group, cyclothiobutane group, hexamethylcyclotrisiloxane group, octamethylcyclotetrasilane group One or more of oxyalkyl groups and 2,5-dioxolan-1-one groups.
  • the first photocurable component is selected from the group consisting of glycidyl acrylate, hydroxybutyl glycidyl acrylate, acryloxyglycerol carbonate, 1,2-epoxy-9-decene, 3, 4-epoxy-1-butene, 1,2-epoxy-5-hexene, allyl glycidyl ether, glycidyl methacrylate, 1,2-epoxy-5-hexene, 3 -(allyloxy)oxetane, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, allyl 4-oxo-2-oxetane carboxylate, 2- Oxytetrahydrofuran-3-ylmethacrylate, 3-(allyloxy)-5-ethyldihydro-2(3H)-furanone, 2,4,6-trivinyl-2,4, One or more of 6-trimethylcyclotris
  • the active hydrogen-containing compound is selected from polyols, polyamines, polyol amines, liquid unsaturated polyester resins, liquid epoxy resins, liquid phenolic resins, liquid silicone resins containing active hydrogen groups 1.
  • the liquid rubbers whose end groups contain active hydrogen groups.
  • the molar ratio of active hydrogen groups in the active hydrogen-containing compound to isocyanate groups in the blocked diisocyanate is (0.9-1.0):1.
  • the polyhydric alcohol is selected from ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol (HDO), neopentyl glycol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, cyclohexanedimethanol, 2-ethyl-1,3-hexanediol, 3-hydroxyethyloxyethyl-1 - one or more of hydroxyethyl phenylene ether, hydrogenated bisphenol A, cyclohexanediol, and oligomer polyols;
  • the polyamine is selected from ethylenediamine, propylenediamine, butylenediamine, cyclohexanediamine, hexamethylenediamine, 1,8-diaminooctane, 2,5-diamino- One or more of 2,5-dimethylhexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, oligomer polyamine;
  • the polyol amine is selected from ethanolamine, aminoethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2,2-di Methylethanol, 2-amino-2-ethyl-1-3-propanediol, tris(hydroxymethyl)aminomethane, 1-amino-1-methyl-2-hydroxycyclohexane and 2-amino-2- One or more of methyl-1-butanol.
  • the oligomer polyol is selected from polyester polyol, poly ⁇ -caprolactone polyol, polycarbonate polyol, polyether polyol, polyoxyacrylic polyol, polytetrahydrofuran polyol one or more of .
  • the liquid rubber whose end group contains active hydrogen groups is selected from hydroxyl-terminated polybutadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber, One or more of amine-based polybutadiene liquid rubber, amine-terminated nitrile liquid rubber, mercapto-terminated polybutadiene liquid rubber, and mercapto-terminated nitrile rubber.
  • the active hydrogen group-containing liquid silicone resin is selected from one or more of hydroxyl-modified silicone oil, carboxyl-modified silicone oil, amine-modified silicone oil, and mercapto-modified silicone oil.
  • the photocurable monomer is selected from one or more of monofunctional monomers, difunctional monomers, and multifunctional monomers.
  • the monofunctional monomer is selected from 2-acrylic acid-2-methoxy ester, ethoxy ethoxy ethyl acrylate, methoxy polyethylene glycol monoacrylate, methoxy Polyethylene glycol methacrylate, 2-phenoxyethyl acrylate, (2-ethyl-2-methyl-1,3-dioxopentyl-4-yl) acrylate, alkoxynonyl Ethylphenol acrylate, ethylated nonylphenol acrylate, 2-[[(butylamino)carbonyl]oxo]ethyl acrylate, isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methyl Acrylate, 3,3,5-trimethylcyclohexane acrylate, 3,3,5-trimethylcyclohexane methacrylate, acryloyl morpholine, cyclotrimethylolpropane formal acrylic acid ester, 3-e
  • the difunctional monomer is selected from 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (1000) Diacrylate, Polyethylene Glycol (200) Dimethacrylate, Polyethylene Glycol (400) Dimethacrylate, Tricyclodecane Dimethanol Diacrylate, Triethylene Glycol Divinyl Ether, polybutadiene acrylate, dioxanediol diacrylate, 1,9-nonanediol diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate One or more of esters, ethylene glycol dimethacrylate, and tripropylene glycol diacrylate.
  • HDDA 1,6-hexanediol diacrylate
  • tripropylene glycol diacrylate polyethylene glycol (600) diacrylate, polyethylene glycol (1000) Diacrylate,
  • the multifunctionality monomer is selected from dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated glycerin triacrylate, 3(2-hydroxyethyl Base) isocyanuric acid triacrylate, caprolactone modified tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, One or more of 3(propoxy)glycerol triacrylate.
  • the photocurable oligomer is selected from one or more of urethane acrylate, polyester acrylate, and epoxy acrylate.
  • the photoinitiator is a free radical photoinitiator.
  • the catalyst is selected from tertiary amine catalysts and composite catalysts thereof.
  • the catalyst is selected from triethylenediamine and its composite catalyst, triethylamine and its composite catalyst, N,N-methyldicyclohexylamine and its composite catalyst, N-form N-ethylmorpholine and its composite catalyst, N-ethylmorpholine and its composite catalyst, N, N'-dimethylpiperazine and its composite catalyst, N, N'-diethylpiperazine and its composite catalyst Complex catalysts, one or more of 1,1,3,3-tetramethylpiperidine and complex catalysts thereof.
  • the auxiliary agent is selected from one or more of polymerization inhibitors, leveling agents, defoamers, and dispersants.
  • the second aspect of the present application provides a 3D printing method, including the following steps:
  • At least one printing layer stacked layer by layer is obtained according to the layer printing data to obtain the 3D object.
  • the method further includes heating the material layer to cause a thermal polymerization reaction of the composition to obtain a printing layer.
  • the method further includes heating the layer-by-layer stacked at least one printing layer to cause thermal polymerization of the composition to obtain the 3D object.
  • the heating includes four stages, wherein the heating temperature of the first stage is 80-100°C, and the time is 3-10h, and the heating temperature of the second stage is increased to 110-130°C, and the time is 3-10h , the heating temperature of the third stage is raised to 130-150°C for 3-10h, and the heating temperature of the fourth stage is raised to 150-200°C for 3-10h.
  • the third aspect of the present application provides a device for implementing any one of the above methods, the device comprising a molding chamber, a distributor, a support platform and a radiation source;
  • the dispenser, the support platform and the radiation source are arranged in the molding chamber, the dispenser and the radiation source are arranged above the support platform, and the dispenser is used to print data on the layer according to the layer.
  • a material layer is formed by spraying any of the above-mentioned compositions on the support platform, and the radiation source is used to irradiate the material layer to obtain a printing layer.
  • the device further includes a first heating component arranged in the molding chamber to provide thermal energy for the material layer, so that the composition undergoes a thermal polymerization reaction to obtain a printing layer.
  • the device further includes a second heating component, and the second heating component is arranged outside the molding chamber to heat at least one printing layer stacked layer by layer, so that the composition undergoes a thermal polymerization reaction to obtain the 3D objects.
  • the viscosity of the composition for 3D printing provided by the application is adjustable, suitable for inkjet printing and/or stereolithography molding technology, and has good thermal stability; and the size of the 3D object printed by using the composition provided by the application Good stability and mechanical properties.
  • Fig. 1 is a schematic flow chart of a 3D printing method provided by an embodiment of the present application
  • Fig. 2 is a schematic structural diagram of a 3D printing device provided by an embodiment of the present application.
  • 1-material container 2-ink tube; 3-dispenser; 7-3D printing composition; 8-3D object; 9-radiation source; 10-first heating component; 11-guiding rail; 12-supporting platform; 13 - Lifting parts; 14 - Controller; 15 - Leveling parts; 20 - Forming chamber.
  • the first aspect of the present application provides a composition for 3D printing, the composition includes 5-30% of blocked diisocyanate, 5-40% of active hydrogen-containing compound, and 5% of the first photocurable component according to weight percentage.
  • -40% photocurable monomer 20-80%, photocurable oligomer 0-30%, photoinitiator 0.5-10%, catalyst 0-1%, additive 0.05-8%, filler 0-15% and Colorant 0-5%;
  • the blocked diisocyanate has a structure shown in formula 1:
  • R 9 and R 10 are independently selected from one of the following structures:
  • R 1 , R 2 , R 4 and R 5 are independently selected from linear or branched chain alkyl groups with 1-20 carbon atoms; C3- C20 group; aryl group with 6-18 carbon atoms; arylalkyl or alkylaryl group with 6-18 carbon atoms; at least one atom containing O, N, Si, S, P has A heteroaryl group with 3-20 carbon atoms, a heterocyclic group with 3-20 carbon atoms containing at least one atom of O, N, Si, S, P;
  • R is one selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, allyl, (meth)acryloyloxyethyl kind;
  • R 3 is selected from linear or branched alkylene groups with 1-18 carbon atoms, alicyclic groups with 5-18 carbon atoms, arylene groups with 6-18 carbon atoms, and arylene groups with 6-20 arylalkylene or alkylarylene with carbon atoms, naphthalene ring with substituted or unsubstituted groups;
  • the molecular structure of the first photocuring component includes a vinyl group and a heterocyclic group, and the heterocyclic group can undergo a thermochemical reaction with the blocking agent formed after deblocking the blocked diisocyanate;
  • the present application provides a composition for 3D printing, which includes 5-30% of blocked diisocyanate, and the diisocyanate containing 5-40% active hydrogen compound, 5-40% of the first photocurable component that undergoes polymerization under photoinitiator and photoirradiation conditions to form a photocurable crosslinked network, 20-80% photocurable monomer, low photocurable 0-30% of polymer and 0.5-10% of photoinitiator, and other catalysts, auxiliary agents, fillers and colorants; wherein, blocked diisocyanate has the structure shown in formula 1, according to formula 1, it can be seen that two The isocyanate group is connected through R3 to obtain a diisocyanate, and R3 is selected from a straight chain or branched chain alkylene group with 1-18 carbon atoms, an alicyclic group with 5-18 carbon atoms, alicyclic group with 6-18 An arylene group having carbon atoms, an arylalkylene group or an alkylarylene group having 6
  • the viscosity of the 3D printing composition provided by the application is adjustable, suitable for inkjet printing and/or stereolithography molding technology, and has better thermal stability; and the dimensional stability and mechanical properties of the 3D object printed using the composition provided by the application are better.
  • the thermal unblocking of blocked diisocyanate occurs only at a certain temperature, knowing the thermal unblocking temperature of blocked diisocyanate has a positive effect on the printing of 3D objects, specifically, the unblocking of the blocked diisocyanate
  • the temperature is at least 20°C higher than the printing temperature of the composition; further, the unblocking temperature of the blocked diisocyanate is T, and 100 ⁇ T ⁇ 150°C, therefore, the thermal stability of the blocked diisocyanate provided by the application better.
  • the blocked diisocyanate provided by the application can be purchased directly, or can be synthesized by oneself, and its synthesis method is not limited, such as the method disclosed in the Chinese patent whose publication number is CN110582725A can be adopted, or the method disclosed below in the application can be adopted, specifically:
  • diisocyanate has a structure shown in formula 2, and the blocking agent is selected from one or both of the structures shown in any one of formula 3 to formula 7:
  • formula 3 and formula 4 are ketoximes
  • formula 5 is imidazole
  • formula 6 is pyrazole
  • formula 7 is hindered amine
  • the diisocyanate is selected from isophorone diisocyanate (IPDI for short), IPDI trimer, toluene diisocyanate (TDI for short), hydrogenated TDI, TDI dimer, TDI trimer, diphenylmethane diisocyanate (referred to as MDI), polymerized MDI, liquefied MDI hydrogenated MDI, hexamethylene diisocyanate (referred to as HDI), HDI trimer, naphthalene diisocyanate (referred to as NDI), p-phenylene diisocyanate (referred to as PPDI), 1,4- Cyclohexane diisocyanate (CHDI for short), xylylene diisocyanate (XDI for short), dimethyl biphenyl diisocyanate (TODI for short), trimethylhexamethylene diisocyanate (TMDI for short), triphenyl One or more of methyl methane triisocyanate (
  • the capping agent is selected from at least one of ketoxime groups, imidazole groups, pyrazole groups and hindered amines, and is characterized in that it can perform irreversible thermochemical reactions with the first photocurable component, The end-blocking agent is consumed, and the balance of the deblocking reversible reaction is promoted to move toward the deblocking direction.
  • the compound containing ketoxime group is selected from acetone oxime, butanone oxime, 5-methyl-2-hexanone oxime, 2-heptanone oxime, 2,2,4,4-tetramethyl-3-pentanone oxime , 5-methyl-3-heptanone oxime, bis-2-thienyl ketone oxime, bis(2-pyridine) ketone oxime, 6,7-dihydrobenzo[B]thiophene-4(5H)-ketoxime , cyclohexanone oxime, cyclopentanone oxime, cycloheptanone oxime, cyclooctone oxime, cyclopentadecanone oxime, acetophenone oxime, phenyl-2-pyridyl ketone oxime, 2-indanone oxime, diphenyl Methanone oxime, 4-hydroxyacetophenone oxime, 3-hydroxy-3-methyl-2-butanone oxi
  • the molar ratio of the isocyanate group in the diisocyanate to the active group in the blocking agent is 1: (1.0-1.4). It can be understood that the blocking groups at both ends of the isocyanate group can be the same or different.
  • the vinyl group in the first photocurable component is used to participate in the polymerization reaction to form a photocurable crosslinked network
  • the heterocyclic group is used to react with the blocking agent after the blocked diisocyanate is unblocked
  • the heterocyclic group is selected from epoxy group, butoxy ring group, tetrahydrofuran group, dioxane group, dioxane group, trioxane group, propiolactone group group, butyrolactone group, aziridine group, azetidinyl group, cyclothiobutane group, hexamethylcyclotrisiloxane group, octamethylcyclotetrasiloxane group One or more of group, 2,5-dioxolane-1-one group.
  • the first photocurable component is selected from the group consisting of glycidyl acrylate, hydroxybutyl glycidyl acrylate, acryloxyglyceryl carbonate, 1,2-epoxy-9-decene, 3,4- Epoxy-1-butene, 1,2-epoxy-5-hexene, allyl glycidyl ether, glycidyl methacrylate, 1,2-epoxy-5-hexene, 3-( Allyloxy)oxetane, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, allyl 4-oxo-2-oxetane carboxylate, 2-oxo Tetrahydrofuran-3-ylmethacrylate, 3-(allyloxy)-5-ethyldihydro-2(3H)-furanone, 2,4,6-trivinyl-2,4,6- One or more of trimethylcyclotrisiloxan
  • the active hydrogen-containing compound is used to react with the diisocyanate after unblocking the blocked diisocyanate
  • the active hydrogen-containing compound is selected from polyols, polyamines, polyol amines, liquid One or more of unsaturated polyester resins, liquid epoxy resins, liquid phenolic resins, liquid silicone resins containing active hydrogen groups, and liquid rubbers whose end groups contain active hydrogen groups.
  • the molar ratio of active hydrogen groups in the active hydrogen-containing compound to isocyanate groups in the blocked diisocyanate is (0.9-1.0):1.
  • the polyhydric alcohol is selected from ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol (HDO), neopentyl glycol, 1,5-pentanediol Diol, 1,6-hexanediol, 1,9-nonanediol, cyclohexanedimethanol, 2-ethyl-1,3-hexanediol, 3-hydroxyethyloxyethyl-1-hydroxy One or more of ethyl phenylene ether, hydrogenated bisphenol A, cyclohexanediol, and oligomer polyols;
  • the polyamine is selected from ethylenediamine, propylenediamine, butylenediamine, cyclohexanediamine, hexamethylenediamine, 1,8-diaminooctane, 2,5-diamino- One or more of 2,5-dimethylhexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, oligomer polyamine;
  • the polyol amine is selected from ethanolamine, aminoethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2,2-di Methylethanol, 2-amino-2-ethyl-1-3-propanediol, tris(hydroxymethyl)aminomethane, 1-amino-1-methyl-2-hydroxycyclohexane and 2-amino-2- One or more of methyl-1-butanol.
  • the oligomer polyol refers to an oligomer containing two hydroxyl groups having a structure shown in Formula 8 , wherein R is selected from the long chain of ether molecules, the long chain of ester molecules, and the olefin molecule long chain;
  • the oligomer polyol is selected from one of polyester polyol, poly ⁇ -caprolactone polyol, polycarbonate polyol, polyether polyol, polyoxyacrylic polyol, polytetrahydrofuran polyol one or more species.
  • the oligomer polyamine refers to an oligomer containing two amino groups having a structure shown in formula 9 , wherein R is selected from the long chain of ether molecules, the long chain of ester molecules, and the olefin molecule long chain;
  • the oligomer polyamine is selected from one or more of polyether diamines, polyester diamines, and aliphatic diamines.
  • the active hydrogen groups are selected from one or more of terminal hydroxyl groups, carboxyl terminal groups, terminal amine groups, and terminal mercapto groups.
  • the The liquid rubber containing active hydrogen groups at the end is selected from hydroxyl-terminated polybutadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber, and amino-terminated polybutadiene liquid rubber
  • liquid rubbers containing active hydrogen groups such as rubber, amino-terminated nitrile liquid rubber, mercapto-terminated polybutadiene liquid rubber, and mercapto-terminated nitrile rubber.
  • liquid unsaturated polyester resin is selected from one of orthophthalic unsaturated polyester resins, isophthalic unsaturated polyester resins, p-phenylene unsaturated polyester resins, and bisphenol A unsaturated polyester resins. one or more kinds;
  • liquid epoxy resin is selected from glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin one or more of the resins;
  • liquid phenolic resin is selected from one or more of alcohol-soluble phenolic resins, oil-soluble phenolic resins, and modified phenolic resins;
  • the active hydrogen group in the liquid silicone resin containing active hydrogen groups is selected from at least one of hydroxyl, carboxyl, amine, and mercapto groups, specifically, the liquid organic silicon resin containing active hydrogen groups
  • the silicone resin is selected from one or more of hydroxyl-modified silicone oil, carboxyl-modified silicone oil, amino-modified silicone oil, mercapto-modified silicone oil, and the like.
  • the photocurable monomer refers to a small molecular compound containing vinyl in the molecular structure, which is used to adjust the viscosity and performance of the composition, and is specifically selected from monofunctional monomers, difunctional monomers, One or more of the multifunctional monomers.
  • the monofunctional monomer is selected from 2-acrylic acid-2-methoxy ester, ethoxy ethoxy ethyl acrylate, methoxy polyethylene glycol monoacrylate, methoxy Polyethylene glycol methacrylate, 2-phenoxyethyl acrylate, (2-ethyl-2-methyl-1,3-dioxopentyl-4-yl) acrylate, alkoxynonyl Ethylphenol acrylate, ethylated nonylphenol acrylate, 2-[[(butylamino)carbonyl]oxo]ethyl acrylate, isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methyl Acrylate, 3,3,5-trimethylcyclohexane acrylate, 3,3,5-trimethylcyclohexane methacrylate, acryloyl morpholine, cyclotrimethylolpropane formal acrylic acid ester, 3-e
  • the difunctional monomer is selected from 1,6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (1000) Diacrylate, Polyethylene Glycol (200) Dimethacrylate, Polyethylene Glycol (400) Dimethacrylate, Tricyclodecane Dimethanol Diacrylate, Triethylene Glycol Divinyl Ether, polybutadiene acrylate, dioxanediol diacrylate, 1,9-nonanediol diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate One or more of esters, ethylene glycol dimethacrylate, and tripropylene glycol diacrylate;
  • HDDA 1,6-hexanediol diacrylate
  • tripropylene glycol diacrylate 1,6-hexanediol diacrylate
  • the multifunctionality monomer is selected from dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated glycerin triacrylate, 3(2-hydroxyethyl Base) isocyanuric acid triacrylate, caprolactone modified tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, One or more of 3(propoxy)glycerol triacrylate.
  • the photocurable oligomer is selected from one or more of urethane acrylate, polyester acrylate, and epoxy acrylate.
  • the polyurethane acrylate can be one of BR-344, BR-374, BR-970BT, BR-345, BR-541S, BR-774SD, BR-543, and BR-970H produced by Bomar Corporation of the United States.
  • it can be one or more of 6113, 6115J-80, 6101, 8000A produced by China Taiwan Changxing Company; it can be CN9178 NS, CN9010 NS, CN 996 NS, CN985B88, CN985B88, One or more of CN975NS; one or more of Ebecryl 8296, Ebecryl 8296, Ebecryl 8807, Ebecryl 205, Ebecryl 220, Ebecryl 4587, Ebecryl 5129 produced by Allnex, Germany.
  • the polyester acrylate can be one or more of Ebecryl 810, Ebecryl 450, Ebecryl 452, Ebecryl 547, Ebecryl 571, Ebecryl 800, Ebecryl 852, Ebecryl 856 etc. produced by Germany Allnex; One or more of MIRAMER PS420, MIRAMER PS4040, MIRAMER PS4500; one or more of LR9004, PE9024, PE44F, PE55F produced by BASF, Germany;
  • Epoxy acrylate can be one or more of 3016, 3316, and 3005 produced by IGM Company in Italy; one or more of LR 8765, LR 8986, LR 9019, and LR 8765 produced by BASF in Germany; One or more of MIRAMER PE210, MIRAMER PE110H, MIRAMER PE230, MIRAMER EA2235, MIRAMER EA2259 produced by the source company;
  • the photoinitiator is a free radical photoinitiator
  • the free radical photoinitiator can be selected from benzoin ether, benzoin ⁇ , ⁇ -dimethylbenzil ketal, ⁇ , ⁇ -diethoxyacetophenone, 2-hydroxyl-2-methyl-1 -Phenyl-1 acetone (referred to as 1173), 1-hydroxy-cyclohexyl benzophenone (referred to as 184), 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, [2-methyl Base 1-(4-methylmercaptophenyl)-2-morpholineacetone-1], [2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)butanone-1], benzene Formyl formate, 2,4,6-trimethylphenyl acyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylphenyl acyl-diphenylphosphine oxide (TPO for short) , bis(2,4,6-trimethylphenylacyl)pheny
  • the catalyst is used to catalyze the thermochemical reaction between the heterocyclic group and the blocking agent generated after deblocking the blocked diisocyanate, and is specifically selected from tertiary amine catalysts and their composite catalysts one or more of .
  • the catalyst is selected from triethylenediamine and its composite catalyst, triethylamine and its composite catalyst, N, N-methyldicyclohexylamine and its composite catalyst, N-methyl Phyline and its composite catalyst, N-ethylmorpholine and its composite catalyst, N, N'-dimethylpiperazine and its composite catalyst, N, N'-diethylpiperazine and its composite catalyst , One or more of 1,1,3,3-tetramethylpiperidine and its composite catalyst.
  • the auxiliary agent is selected from one or more of polymerization inhibitors, leveling agents, defoamers, and dispersants.
  • the function of the polymerization inhibitor is mainly to prevent the polymerization reaction of free radicals and improve the storage stability of the composition.
  • the polymerization inhibitor can be selected from one of phenols, quinones or nitrites. or more, such as hydroquinone, p-quinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, three (N-nitroso One or more of base-N-phenylhydroxylamine) aluminum salts (inhibitor 510).
  • the leveling agent is mainly used to improve the fluidity of the composition and the wetting performance of the substrate, while adjusting the surface tension of the composition so that it can be printed normally. This application does not specifically limit the selection of leveling agents.
  • the main function of the defoamer is to suppress, reduce and eliminate air bubbles in the composition.
  • the present application does not specifically limit the selection of the defoamer.
  • there are many products on the market such as BYK1798, BYK055, BYK088, BYK020, BYK025 of BYK Company, TEGO Airex 920, TEGO Airex 921, TEGO Airex 986, TEGO Foamex 810, TEGO Foamex N of Tego Company, etc.
  • the main function of the dispersant is to improve the dispersion stability of the particulate matter in the composition.
  • the present application does not specifically limit the selection of the dispersant.
  • there are many products on the market such as BYK102, BYK106, BYK108, BYK110, BYK111, BYK180, Tego Dispers 655, Dispers675, Dispers 710, Dispers 630, Dispers 670, etc.
  • the filler is selected from one or more of silica, carbon black, barium sulfate, aluminum hydroxide, kaolin, and talc.
  • colorant can be pigment or dyestuff, preferred pigment is colorant among the present application, and pigment can be selected from C.I.PigmentWhite 6, C.I.Pigment Red 3, C.I.Pigment Red 5, C.I.Pigment Red 7, C.I.Pigment Red9 , C.I.Pigment Red 12, C.I.Pigment Red 13, C.I.Pigment Red 21, C.I.Pigment Red31, C.I.Pigment Red49:1, C.I.Pigment Red 58:1, C.I.Pigment Red 175; C.I.PigmentYellow 63, C.I.Pigment Yellow.Pigment Yellow3, C.I.Pigment 12.
  • C.I.Pigment Yellow 16 C.I.Pigment Yellow 83; C.I.Pigment Blue 1, C.I.Pigment Blue 10, C.I.Pigment BlueB, Phthalocyanine Blue BX, Phthalocyanine Blue BS, C.I.PigmentBlue61:1.
  • the viscosity of the 3D printing composition provided by the application is adjustable, suitable for inkjet printing and/or stereolithography, and has good thermal stability; and the 3D printing obtained by using the composition provided by the application The dimensional stability and mechanical properties of the object are better.
  • the second aspect of the present application provides a 3D printing method, including the following steps:
  • At least one printing layer stacked layer by layer is obtained according to the layer printing data to obtain the 3D object.
  • the method further includes heating the material layer to cause a thermal polymerization reaction of the composition to obtain a printing layer.
  • the method further includes heating the layer-by-layer stacked at least one printing layer to cause thermal polymerization of the composition to obtain the 3D object.
  • the heating includes four stages, wherein the heating temperature of the first stage is 80-100°C, and the time is 3-10h, and the heating temperature of the second stage is increased to 110-130°C, and the time is 3-10h , the heating temperature of the third stage is raised to 130-150°C for 3-10h, and the heating temperature of the fourth stage is raised to 150-200°C for 3-10h.
  • the third aspect of the present application provides a device for implementing any one of the above methods, the device comprising a molding chamber, a distributor, a support platform and a radiation source;
  • the dispenser, the support platform and the radiation source are arranged in the molding chamber, the dispenser and the radiation source are arranged above the support platform, and the dispenser is used to print data on the layer according to the layer.
  • the composition described above is sprayed on the support platform to form a material layer, and the radiation source is used to irradiate the material layer to form a printing layer.
  • the device further includes a first heating component arranged in the molding chamber to provide thermal energy for the material layer, so that the composition undergoes a thermal polymerization reaction to obtain a printing layer.
  • the device further includes a second heating component, the second heating component is arranged outside the molding chamber to heat the at least one printing layer stacked layer by layer, so that the composition undergoes a thermal polymerization reaction The 3D object is obtained.
  • the application also provides comparative examples 1-4 for comparison with examples 1-2, specifically, comparative example 1 does not include ketoxime-blocked diisocyanate, and comparative example 2 does not include the first photocurable component , the first photocurable component in Comparative Example 3 is n-butyl glycidyl ether, including epoxy groups but not vinyl groups in its molecular structure, including non-blocked isocyanate in Comparative Example 4, Comparative Examples 1-4 See Table 2 for each component and weight percentage in the provided composition.
  • FIG. 1 is a flow chart of the method for printing a 3D object provided in an embodiment of the present application, as shown in Figure 1 , including the following steps:
  • the model data of the 3D object to be printed is sliced and layered and data processed to obtain the layer printing data.
  • the layer printing data is the data representing the cross section of the 3D object.
  • at least one layer of printing data can be obtained, and all layers of printing data can be superimposed layer by layer to obtain a digital model of the 3D object.
  • This application is not limited to the acquisition method of layer printing data, and any acquisition method of layer printing data in the 3D object printing process in the field can be used.
  • the model data of the 3D object needs to be obtained, and the model Data format conversion, such as conversion into STL format, PLY format, WRL format and other formats that can be recognized by slicing software, use slicing software to slice and layer the model to obtain slice layer data, and use data processor to slice layer data Data processing is performed to obtain layer printing data, and the layer printing data includes information representing the shape of the object and/or information representing the color of the object.
  • the model Data format conversion such as conversion into STL format, PLY format, WRL format and other formats that can be recognized by slicing software
  • use data processor to slice layer data Data processing is performed to obtain layer printing data
  • the layer printing data includes information representing the shape of the object and/or information representing the color of the object.
  • the printing data of each layer spray any one of the compositions described above to form a material layer, and irradiate the material layer so that the material layer is at least partially cured to obtain a printed layer, wherein the curing It refers to the use of a radiation source to irradiate the material layer, so that the photocuring system in it undergoes a photocuring reaction and becomes a solidified or semi-solidified state.
  • step S200 After forming a printing layer according to step S200, repeat this step according to the printing data of different layers, that is, continue to form a material layer on the surface of the previous printing layer, irradiate the material layer to form a new printing layer, and stack multiple printing layers in sequence, to get the final 3D object.
  • the method further includes heating the material layer to cause thermal polymerization of the composition to obtain a printing layer.
  • the method It also includes heating the at least one printing layer stacked layer by layer, so that the composition undergoes a thermal polymerization reaction to obtain the 3D object.
  • the heating temperature should not be too high, as long as it can trigger the unblocking of the active group-blocked diisocyanate to release the isocyanate group, and the temperature is too high will lead to aging of the 3D object .
  • heating is performed after the at least one printing layer is stacked layer by layer, the heating is gradient heating, including four stages, wherein the heating temperature of the first stage is 80-100°C, and the time is 3-10h , the heating temperature of the second stage is increased to 110-130°C for 3-10h, the heating temperature of the third stage is increased to 130-150°C for 3-10h, and the heating temperature of the fourth stage is increased to 150-200 °C, heating for 3-10h.
  • the role of gradient heating in this application is to make thermal unsealing and thermal polymerization proceed slowly, the laminated printing layer is not easy to deform during heat treatment, and it is not easy to generate pores inside the model, so as to improve dimensional stability and performance uniformity.
  • the printing method of the 3D object provided by the present application uses any one of the above-mentioned compositions for printing, which is beneficial to improve the mechanical properties and dimensional stability of the 3D object.
  • FIG. 2 is a schematic structural diagram of a 3D printing device provided by an embodiment of the present application.
  • the 3D printing device at least includes: The molding chamber 20, the distributor 3, the support platform 12 and the radiation source 9, the distributor 3, the support platform 12 and the radiation source 9 are arranged in the molding chamber 20, the distributor 3 and the radiation source 9 are located above the support platform 12,
  • the dispenser 3 is used to spray the composition 7 on the supporting platform 12 to form a material layer according to the layer printing data
  • the radiation source 9 is used to irradiate the material layer to form a printing layer.
  • the distributor 3 can be one or both of a single-channel print head and a multi-channel print head, and the number of the print head 3 is at least one;
  • the radiation source 9 is one of UVLED lamps, mercury lamps, metal halide lamps, electrodeless lamps, xenon lamps and the like.
  • material container 1 also comprise material container 1 and ink tube 2
  • material container 1 is connected with ink tube 2
  • described ink tube 2 is connected with described dispenser 3
  • described material container 1 is used for storing above-mentioned any described 3D printing composition, and the 3D printing composition stored therein can be delivered to the printing head of the dispenser 3 through the ink tube 2 .
  • the material composition needs to be preheated in advance, and the preheating process can occur in the material container 1 and/or the ink tube 2, and/or print head 3, there is no specific limitation in this application.
  • the preheating temperature needs to be lower than the thermal unblocking temperature of the active group-blocked diisocyanate, preferably lower than 20°C, otherwise, the thermal polymerization reaction of the material composition will block the nozzle holes of the print head before inkjet printing.
  • the preheating component can be at least one of a metal heating sheet, a heating wire, and a heating spring;
  • a first heating unit 10 which is located in the molding chamber 20 to provide thermal energy for the material layer, so that the composition undergoes a thermal polymerization reaction to obtain a printing layer.
  • the first heating component 10 is selected from one or more of infrared lamps, heating plates, heat preservation plates, heat dissipation plates, microwave radiation sources, and temperature controllers.
  • the device also includes a lifting part 13, which is used to change the relative distance between the supporting platform 12 and the distributor 3 in the height direction (Z direction), so as to continuously form printing layers and stack them layer by layer to form a 3D object 8.
  • the dispenser 3 sprays the composition 7 for 3D printing onto the support platform 12 to form a material layer
  • the radiation source 9 irradiates light to cause the composition to undergo a photocuring reaction
  • the first heating member 10 heats the material layer to make the composition
  • the lifting member 13 moves the supporting platform 12 down a certain distance in the height direction (ie, the Z direction), so that there is enough space to accommodate a new printing layer.
  • a 3D object 8 is formed.
  • leveling component 15 is positioned between dispenser 3 and radiation source 9, is used for leveling material layer;
  • Leveling component 15 can be leveling stick, through leveling stick The swirling action carries away excess 3D printing material dispensed.
  • controller 14 for controlling the operation of at least one of the preheating component, the first heating component 10 , the distributor 3 , the radiation source 9 , the lifting mechanism 13 and the leveling component 15 .
  • the controller 14 can control the distribution of the heated 3D printing composition 7 by the dispenser 3 according to the layer printing data, the controller 14 can control the radiation intensity and radiation time of the radiation source 9 on the material layer, and the controller 14 can control the first The heating temperature of the material by the heating part 10, the controller 14 can control the relative distance between the support platform 12 and the distributor 3 in the Z direction, etc.
  • the device also includes a guide rail 10 , the distributor 3 , the radiation source 9 , the first heating unit 10 and the leveling unit 15 are sequentially installed on the guide rail 11 and can move on the guide rail 11 .
  • the device does not include the first heating component, but includes a second heating component (not shown), and the second heating component is arranged in the molding chamber 20 Externally heat the at least one printed layer stacked layer by layer (corresponding to the 3D object 8 in FIG. 2 ), so that the composition in the 3D object 8 undergoes a thermal polymerization reaction to obtain the target 3D object.
  • the second heating component is selected from one or more of infrared lamps, microwave ovens, heating furnaces, ovens, and high-temperature vacuum ovens.
  • the controller 14 can also be used to control the second heating component to heat the 3D object 8.
  • the specific heating method is as described in the gradient heating method in the above-mentioned embodiment 11, and will not be repeated here.
  • the viscosity of the above composition at the printing temperature was tested with a DV-I digital display viscometer.
  • composition for 3D printing was continuously printed with a Senna photocurable inkjet printer for 4 hours, and the ink output of the nozzle before and after printing was tested. If there were no more than 10 broken lines before and after printing, the printing fluency was ok and the test was passed.
  • the 3D printing materials are applied to the Senna light-curing inkjet printer or SLA 3D printer, and the elastic material (Example 2, Example 5, Comparative Example 2) prints the 3D object of the required size according to GB/T 528-2009 , test the elongation at break and tensile strength of 3D objects according to GB/T 528-2009; hard materials (others) print 3D objects of the required size and specifications according to GB/T 1040.2-2006, according to GB/T 1040.2-2006 Test the elongation at break and tensile strength of 3D objects.
  • composition for 3D printing to the Sina light-curing inkjet printer or SLA 3D printer, and print squares with a length, width, and height of 10mm, 10mm, and 10mm respectively; after printing, heat treatment is performed, and the heating temperature of the first stage 90°C for 2h, the heating temperature for the second stage is 110°C for 3h, the heating temperature for the third stage is 140°C for 4h; naturally cool to 25°C, measure the length and width of the block after heat treatment , height, when the measured length, width, and height are all 10 ⁇ 0.1mm, that is, the dimensional stability is good, and the test is passed; otherwise, the test is not passed.
  • the viscosity of the 3D printing composition provided by the application is adjustable, and it is suitable for inkjet printing and/or stereolithography; and the 3D printing composition provided by the application
  • the object can be an elastic material or a hard material, and the 3D object printed by using the composition has good mechanical properties and dimensional stability.

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Abstract

一种3D打印用组合物、3D打印方法、装置，该3D打印用组合物按照重量百分含量包括封端二异氰酸酯5-30％、含活泼氢的化合物5-40％、第一光固化组分5-40％、光固化单体20-80％、光固化低聚物0-30％、光引发剂0.5-10％、催化剂0-1％、助剂0.05-8％、填料0-15％和着色剂0-5％。该3D打印用组合物粘度可调、热稳定性好，打印得到的3D物体的尺寸稳定性和力学性能较好，适用于喷墨打印和/或立体光固化成型技术。

Description

一种3D打印用组合物、3D打印方法、装置
本申请要求于2021年06月11日提交中国专利局、申请号为202110659489.3、申请名称为“一种3D打印用组合物、3D打印方法、装置”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及一种3D打印用组合物、3D打印方法、装置，涉及3D打印技术领域。
背景技术
光固化3D打印技术主要包括三维喷墨打印技术(3DP)、立体光刻技术(SLA)、数字光处理技术(DLP)、连续液面制造技术(CLIP)等，该类技术主要以液态光敏树脂为原材料，在光照射条件下，光敏树脂发生聚合反应，并快速固化成型得到3D物体。光固化3D打印技术具有成型精度高、打印效率高、工艺成熟等特点，是最早发展和最早商业化的3D打印技术之一。
随着光固化3D打印设备和工艺的不断发展，原材料成为了制约光固化3D打印技术发展的关键因素，例如，在物理性能方面，光固化3D打印技术要求光敏树脂的纯度高、粘度较低、稳定性好和挥发性低；在化学性能方面，要求光敏树脂在光照条件下能快速聚合固化成型，而且固化后要求有良好的力学性能和尺寸稳定性。由于现有的3D打印用材料自身化学和物理性能的局限，阻碍了光固化3D打印技术在工业领域如航空航天、模具、汽车等领域的应用。
发明内容
本申请提供一种3D打印用组合物、3D打印方法和装置，该组合物打印得到的3D物体的尺寸稳定性和力学性能较好。
本申请第一方面提供一种3D打印用组合物，所述组合物按照重量百分含量包括封端二异氰酸酯5-30％、含活泼氢的化合物5-40％、第一光固化组分5-40％、光固化单体20-80％、光固化低聚物0-30％、光引发剂0.5-10％、催化剂0-1％、助剂0.05-8％、填料0-15％和着色剂0-5％；
所述封端二异氰酸酯具有式1所示的结构：
Figure PCTCN2022097957-appb-000001
其中，R 9，R 10独立选自以下结构中的一种：
Figure PCTCN2022097957-appb-000002
R 1、R 2、R 4和R 5独立地选自具有1-20个碳原子的直链或支链烷基；具有单环、桥连的双环以及桥连的三环的C3-C20基团；具有6-18个碳原子的芳基；具有6-18个碳原子的芳基烷基或烷基芳基；含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂芳基，含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂环基；
R 8选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环己基、烯丙基、(甲基)丙烯酰氧基乙基中的一种；
R 3选自具有1-18个碳原子的直链或支链亚烷基、具有5-18个碳原子的亚脂环基、具有6-18个碳原子的亚芳基、具有6-20个碳原子的芳基亚烷基或烷基亚芳香基、具有取代或非取代基团的萘环基；
所述第一光固化组分的分子结构中包括乙烯基团和杂环基团，且所述杂环基团能与所述封端二异氰酸酯解封后形成的封端剂发生热化学反应；
所述光固化单体和所述光固化低聚物均不与所述封端剂发生所述热化学反应。
如上述组合物，所述封端二异氰酸酯的解封温度高于所述组合物打印温度至少20℃。
如上述组合物，所述封端二异氰酸酯的解封温度为T，且100≤T≤150℃。
如上述组合物，所述杂环基团选自环氧基团、丁氧环基团、四氢呋喃基团、二氧五环基团、二氧六环基团、三氧六环基团、丙内酯基团、丁内酯基团、杂氮环丙烷基团、杂氮环丁烷基团、环硫丁烷基团、六甲基环三硅氧烷基团、八甲基环四硅氧烷基团、2，5-二氧戊环-1-酮基团中的一种或多种。
如上述组合物，所述第一光固化组分选自丙烯酸缩水甘油酯、丙烯酸羟丁基缩水甘油醚、丙烯酰氧基碳酸甘油酯、1，2-环氧-9-癸烯、3，4-环氧-1-丁烯、1，2-环氧-5-己烯、烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、1，2-环氧基-5-己烯、3-(烯丙氧基)氧杂环丁烷、丙烯酸四氢糠基酯、甲基丙烯酸四氢糠基酯、烯丙基4-氧代-2-氧杂环丁烷羧酸酯、2-氧代四氢呋喃-3-基甲基丙烯酸酯、3-(烯丙氧基)-5-乙基二氢-2(3H)-呋喃酮、2，4，6-三乙烯基-2，4，6-三甲基环三硅氧烷、1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷中的一种或多种。
如上述组合物，所述含活泼氢的化合物选自多元醇、多元胺、多元醇胺、液体不饱和 聚酯树脂、液体环氧树脂、液体酚醛树脂、含活泼氢基团的液体有机硅树脂、端基含有活泼氢基团的液体橡胶中的一种或多种。
如上述组合物，所述含活泼氢的化合物中活泼氢基团与所述封端二异氰酸酯中异氰酸根的摩尔比为(0.9-1.0)∶1。
如上述组合物，所述多元醇选自乙二醇、丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇(HDO)、新戊二醇、1，5-戊二醇、1，6-己二醇、1，9-壬二醇、环己烷二甲醇、2-乙基-1，3-己二醇、3-羟乙基氧乙基-1-羟乙基苯二醚、氢化双酚A、环己二醇、低聚物多元醇中的一种或多种；
和/或，所述多元胺选自乙二胺、丙二胺、丁二胺、环己二胺、六亚甲基二胺、1，8-二氨基辛烷、2，5-二氨基-2，5-二甲基己烷、1-氨基-3，3，5-三甲基-5-氨甲基环己烷、低聚物多元胺中的一种或多种；
和/或，所述多元醇胺选自乙醇胺、氨基乙基乙醇胺、2-氨基-1-丙醇、2-氨基-2-甲基-1-丙醇、2-氨基-2，2-二甲基乙醇、2-氨基-2-乙基-1-3-丙二醇、三(羟甲基)氨基甲烷、1-氨基-1-甲基-2-羟基环己烷和2-氨基-2-甲基-1-丁醇中的一种或多种。
如上述组合物，所述低聚物多元醇选自聚酯多元醇、聚ε-己内酯多元醇、聚碳酸酯多元醇、聚醚多元醇、聚氧化丙烯酸多元醇、聚四氢呋喃多元醇中的一种或多种。
如上述组合物，所述端基含有活泼氢基团的液体橡胶选自端羟基聚丁二烯液体橡胶、端羧基聚丁二烯液体橡胶、端羟基丁腈橡胶、端羧基丁腈橡胶、端胺基聚丁二烯液体橡胶、端胺基丁腈液体橡胶、端巯基聚丁二烯液体橡胶、端巯基丁腈橡胶中的一种或多种。
如上述组合物，所述含活泼氢基团的液体有机硅树脂选自羟基改性硅油、羧基改性硅油、胺基改性硅油、巯基改性硅油中的一种或多种。
如上述组合物，所述光固化单体选自单官能度单体、双官能度单体、多官能度单体中的一种或多种。
如上述组合物，所述单官能度单体选自2-丙烯酸-2-甲氧基酯、乙氧基乙氧基乙基丙烯酸酯、甲氧基聚乙二醇单丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯、丙烯酸-2-苯氧基乙基酯、(2-乙基-2-甲基-1，3-二氧戊基-4-基)丙烯酸酯、烷氧化壬基苯酚丙烯酸酯、乙基化壬基苯酚丙烯酸酯、2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、1-金刚烷基甲基丙烯酸酯、3，3，5-三甲基环己烷丙烯酸酯、3，3，5-三甲基环己烷甲基丙烯酸酯、丙烯酰吗啉、环三羟甲基丙烷缩甲醛丙烯酸酯、3-乙基-3-环氧丙基丙烯酸甲酯、2-苯氧基乙基甲基丙烯酸酯、苯氧乙基丙烯酸酯、邻苯基苯氧乙基丙烯酸酯、N，N’-二甲基丙烯酰胺中的一种或多种；
和/或，所述双官能度单体选自1，6-己二醇二丙烯酸酯(HDDA)、二缩三丙二醇二丙 烯酸酯、聚乙二醇(600)二丙烯酸酯、聚乙二醇(1000)二丙烯酸酯、聚乙二醇(200)二甲基丙烯酸酯、聚乙二醇(400)二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三乙二醇二乙烯基醚、丙烯酸聚丁二烯、二氧陆圜二醇二丙烯酸酯、1，9-壬二醇二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、一缩三丙二醇二丙烯酸酯中的一种或多种。
和/或，所述多官能度单体选自二季戊四醇五丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、丙氧化甘油三丙烯酸酯、3(2-羟乙基)异氰尿酸三丙烯酸酯、己内酯改性三(2-丙烯酰氧乙基)异氰尿酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯中的一种或多种。
如上述组合物，所述光固化低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯、环氧丙烯酸酯中的一种或多种。
如上述组合物，所述光引发剂为自由基光引发剂。
如上述组合物，所述催化剂选自叔胺类催化剂及其复配催化剂。
如上述组合物，所述催化剂选自三亚乙基二胺及其复配催化剂、三乙胺及其复配催化剂、N，N-甲基二环环己胺及其复配催化剂、N-甲基吗啉及其复配催化剂、N-乙基吗啉及其复配催化剂、N，N′-二甲基哌嗪及其复配催化剂、N，N′-二乙基哌嗪及其复配催化剂，1，1，3，3-四甲基哌啶及其复配催化剂中的一种或多种。
如上述组合物，所述助剂选自阻聚剂、流平剂、消泡剂、分散剂中的一种或多种。
本申请第二方面提供一种3D打印方法，包括如下步骤：
获取3D物体的至少一个层打印数据；
根据每个层打印数据喷射上述任一所述的组合物以形成材料层，并对所述材料层提供辐射得到打印层；
根据所述层打印数据得到逐层层叠的至少一个打印层，得到所述3D物体。
如上述方法，所述方法还包括，对所述材料层进行加热，使所述组合物发生热聚合反应，得到打印层。
如上述方法，所述方法还包括，对所述逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应，得到所述3D物体。
如上述方法，所述加热包括四个阶段，其中，第一阶段的加热温度为80-100℃，时间为3-10h，第二阶段的加热温度提高至110-130℃，时间为3-10h，第三阶段的加热温度提高至130-150℃，时间为3-10h，第四阶段的加热温度提高至150-200℃，加热3-10h。
本申请第三方面提供一种实施上述任一所述方法的装置，所述装置包括成型腔室、分配器、支撑平台和辐射源；
其中，所述分配器、支撑平台和辐射源设置于所述成型腔室内，所述分配器和所述辐射源设置于所述支撑平台的上方，所述分配器用于根据层打印数据在所述支撑平台上喷射上述任一所述的组合物形成材料层，所述辐射源用于对所述材料层进行辐射以得到打印层。
如上述装置，所述装置还包括第一加热部件，所述第一加热部件设置于所述成型腔室内为所述材料层提供热能，使所述组合物发生热聚合反应得到打印层。
如上述装置，所述装置还包括第二加热部件，所述第二加热部件设置于所述成型腔室外对逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应得到所述3D物体。
本申请的实施，至少具有以下优势：
本申请提供的3D打印用组合物粘度可调，适用于喷墨打印和/或立体光固化成型技术，具有较好的热稳定性；并且使用本申请提供的组合物打印得到的3D物体的尺寸稳定性和力学性能较好。
附图说明
图1为本申请一实施例提供的3D打印方法的流程示意图；
图2为本申请一实施例提供的3D打印装置的结构示意图。
附图标记说明：
1-材料容器；2-墨管；3-分配器；7-3D打印用组合物；8-3D物体；9-辐射源；10-第一加热部件；11-导轨；12-支撑平台；13-升降部件；14-控制器；15-校平部件；20-成型腔室。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请的实施例，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请第一方面提供一种3D打印用组合物，所述组合物按照重量百分含量包括封端二异氰酸酯5-30％、含活泼氢的化合物5-40％、第一光固化组分5-40％、光固化单体20-80％、光固化低聚物0-30％、光引发剂0.5-10％、催化剂0-1％、助剂0.05-8％、填料0-15％和着色剂0-5％；
所述封端二异氰酸酯具有式1所示的结构：
Figure PCTCN2022097957-appb-000003
其中，R 9，R 10独立选自以下结构中的一种：
Figure PCTCN2022097957-appb-000004
其中，R 1、R 2、R 4和R 5独立地选自具有1-20个碳原子的直链或支链烷基；具有单环、桥连的双环以及桥连的三环的C3-C20基团；具有6-18个碳原子的芳基；具有6-18个碳原子的芳基烷基或烷基芳基；含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂芳基，含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂环基；
R 8选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环己基、烯丙基、(甲基)丙烯酰氧基乙基中的一种；
R 3选自具有1-18个碳原子的直链或支链亚烷基、具有5-18个碳原子的亚脂环基、具有6-18个碳原子的亚芳基、具有6-20个碳原子的芳基亚烷基或烷基亚芳香基、具有取代或非取代基团的萘环基；
所述第一光固化组分的分子结构中包括乙烯基团和杂环基团，且所述杂环基团能与所述封端二异氰酸酯解封后形成的封端剂发生热化学反应；
所述光固化单体和所述光固化低聚物均不与所述封端剂发生所述热化学反应。
本申请提供一种3D打印用组合物，以所述组合物总重量为100％计算，其包括封端二异氰酸酯5-30％、用于和封端二异氰酸酯解封后的二异氰酸酯反应的含活泼氢的化合物5-40％、在光引发剂和光照射条件下发生聚合反应形成光固化交联网络的第一光固化组分5-40％、光固化单体20-80％、光固化低聚物0-30％以及光引发剂0.5-10％，以及其他催化剂、助剂、填料和着色剂；其中，封端二异氰酸酯具有式1所示的结构，根据式1可以看出，两个异氰酸酯基团通过R 3连接得到二异氰酸酯，R 3选自具有1-18个碳原子的直链或支链亚烷基、具有5-18个碳原子的亚脂环基、具有6-18个碳原子的亚芳基、具有6-20个碳原子的芳基亚烷基或烷基亚芳基、具有取代或非取代的萘环基，具体地，具有1-18个碳原子的直链或支链亚烷基是指通式为-C nH 2n-(1≤n≤18)的基团，例如，-CH 2CH 2-、-CH 2CH 2CH 2CH 2-、-CH(CH 3)CH 2-等、具有5-18个碳原子的亚脂环基是指碳原子数为5-18个，且结构中至少包括一个碳环的基团、具有6-18个碳原子的亚芳基是指碳原子数为6-18个，且结构中至少包括一个芳环的基团，例如，-C 6H 4-、-C 6H 3(CH 3)-等、具有6-20个碳原 子的芳基亚烷基或烷基亚芳基是指碳原子数为6-20个，结构中包括芳基亚烷基或烷基亚芳基，芳基亚烷基是指芳基基团附接到其上的亚烷基部分，烷基亚芳基是指烷基基团附接到其上的亚芳基部分、具有取代或非取代的萘环基是指结构中包括两个或两个以上的苯环，且苯环上可以有或没有取代基；二异氰酸酯的两端分别与含有取代基团的封端剂连接，具体地，R 1、R 2、R 4和R 5独立地选自具有1-20个碳原子的直链或支链烷基；具有单环、桥连的双环以及桥连的三环的C3-C20基团；具有6-18个碳原子的芳基；具有6-18个碳原子的芳基烷基或烷基芳基；含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂芳基，含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的的杂环基；所述封端二异氰酸酯具有一定的解封温度，当温度达到该解封温度后，封端二异氰酸酯解封生成包括R 9、R 10基团的封端剂和二异氰酸酯，二异氰酸酯与含有活泼氢的化合物发生热化学反应生成高分子链或交联型聚合物，并与第一光固化组分、光固化单体、光固化低聚物以及光引发剂形成的光固化交联网络形成光固化交联网络和聚合物交联网络的互穿网络，提高了3D物体的力学性能，尤其是拉伸强度、断裂伸长率、冲击韧性、耐撕裂性，而解封后脱落的封端剂与第一光固化组分的分子结构中的杂环基团发生热化学反应，封端剂被接枝到光固化交联网络上，使得组合物中没有小分子物质存在，提高了3D物体的尺寸稳定性，长期放置不存在变形，并且由于解封后的封端剂被反应消耗，进一步加快了封端二异氰酸酯基团的解封速率，综上，本申请提供的3D打印用组合物粘度可调，适用于喷墨打印和/或立体光固化成型技术，具有较好的热稳定性；并且使用本申请提供的组合物打印得到的3D物体的尺寸稳定性和力学性能较好。
由于封端二异氰酸酯在一定温度下才会发生热解封，因此，了解封端二异氰酸酯的热解封温度对3D物体的打印有积极的作用，具体地，所述封端二异氰酸酯的解封温度高于所述组合物打印温度至少20℃；进一步地，所述封端二异氰酸酯的解封温度为T，且100≤T≤150℃，因此，本申请提供的封端二异氰酸酯热稳定性较好。
本申请提供的封端二异氰酸酯可以直接购买，也可以自己合成，其合成方法不受限制，如可以采用公开号为CN110582725A的中国专利所揭示的方法，也可以采用本申请中以下揭示的方法，具体地：
S1、选取二异氰酸酯和封端剂，具体地，二异氰酸酯具有式2所示的结构，封端剂选自式3～式7任一所示的结构中的一种或两种：
O＝C＝N-R 3-N＝C＝O  式2
Figure PCTCN2022097957-appb-000005
Figure PCTCN2022097957-appb-000006
其中，式3和式4是酮肟，式5是咪唑，式6是吡唑，式7是位阻胺。
进一步地，二异氰酸酯选自异氟尔酮二异氰酸酯(简称IPDI)、IPDI三聚体、甲苯二异氰酸酯(简称TDI)、氢化TDI、TDI二聚体、TDI三聚体、二苯基甲烷二异氰酸酯(简称MDI)、聚合MDI、液化MDI氢化MDI、六亚甲基二异氰酸酯(简称HDI)、HDI三聚体、萘二异氰酸酯(简称NDI)、对苯二异氰酸酯(简称PPDI)、1，4-环己烷二异氰酸酯(简称CHDI)、苯二亚甲基二异氰酸酯(简称XDI)、二甲基联苯二异氰酸酯(简称TODI)、三甲基六亚甲基二异氰酸酯(简称TMDI)、三苯基甲烷三异氰酸酯(简称TTI)中的一种或多种。
本申请中封端剂选自含有酮肟基团、咪唑基团、吡唑基团以及位阻胺类中至少一种，其特征在于均可与第一光固化组份进行不可逆热化学反应，消耗掉封端剂，促进解封可逆反应的平衡向解封方向移动。
含有酮肟基团的化合物选自丙酮肟、丁酮肟、5-甲基-2-己酮肟、2-庚酮肟、2，2，4，4-四甲基-3-戊酮肟、5-甲基-3-庚酮肟、二-2-噻吩基酮肟、二(2-吡啶)酮肟、6，7-二氢苯并[B]噻吩-4(5H)-酮肟、环己酮肟、环戊酮肟、环庚酮肟、环辛酮肟、环十五酮肟、苯乙酮肟、苯基-2-吡啶基酮肟、2-茚酮肟、二苯甲酮肟、4-羟基苯乙酮肟、3-羟基-3-甲基-2-丁酮肟、1，3-二羟基丙酮肟、对甲基环己酮肟、四氟苯乙酮肟、对羟基苯乙酮肟、2，2，6，6-四甲基-4-二乙哌啶二酮肟、甲基异丁基酮肟、丁二酮肟、1，2-环己二酮肟等含有酮肟基团中的一种或多种；
含有位阻胺的化合物选自N-叔丁基甲胺、N-叔丁基乙胺、N-叔丁基正丙胺、N-叔丁基异丙胺、N-叔丁基正丁胺、N-叔丁基异丁胺、二叔丁基胺、N-环己基-N-叔丁胺、N-烯丙基-N-叔丁胺、2-叔丁基氨基丙烯酸乙酯的一种或几种；
二异氰酸酯中异氰酸酯基团与封端剂中活性基团的摩尔比为1∶(1.0-1.4)，可以理解的是，异氰酸酯基团两端的封端基团可以相同或不同。
S2、将封端剂放置于搅拌器中搅拌，同时缓慢滴入二异氰酸酯，保证反应体系温度低于40℃；
S3、待二异氰酸酯缓慢滴加完成后，室温搅拌30min；
S4、升温至40-90℃，继续反应4-12h，即得到封端二异氰酸酯。
如上述组合物，所述第一光固化组分中的乙烯基用于参与聚合反应形成光固化交联网络，杂环基团用于和封端二异氰酸酯解封后的封端剂反应，具体地，所述杂环基团选自环 氧基团、丁氧环基团、四氢呋喃基团、二氧五环基团、二氧六环基团、三氧六环基团、丙内酯基团、丁内酯基团、杂氮环丙烷基团、杂氮环丁烷基团、环硫丁烷基团、六甲基环三硅氧烷基团、八甲基环四硅氧烷基团、2，5-二氧戊环-1-酮基团中的一种或多种。
具体地，所述第一光固化组分选自丙烯酸缩水甘油酯、丙烯酸羟丁基缩水甘油醚、丙烯酰氧基碳酸甘油酯、1，2-环氧-9-癸烯、3，4-环氧-1-丁烯、1，2-环氧-5-己烯、烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、1，2-环氧基-5-己烯、3-(烯丙氧基)氧杂环丁烷、丙烯酸四氢糠基酯、甲基丙烯酸四氢糠基酯、烯丙基4-氧代-2-氧杂环丁烷羧酸酯、2-氧代四氢呋喃-3-基甲基丙烯酸酯、3-(烯丙氧基)-5-乙基二氢-2(3H)-呋喃酮、2，4，6-三乙烯基-2，4，6-三甲基环三硅氧烷、1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷中的一种或多种。
如上述组合物，所述含活泼氢的化合物用于和封端二异氰酸酯解封后的二异氰酸酯反应，具体地，所述含活泼氢的化合物选自多元醇、多元胺、多元醇胺、液体不饱和聚酯树脂、液体环氧树脂、液体酚醛树脂、含活泼氢基团的液体有机硅树脂、端基含有活泼氢基团的液体橡胶中的一种或多种。
进一步地，所述含活泼氢的化合物中活泼氢基团与所述封端二异氰酸酯中异氰酸根的摩尔比为(0.9-1.0)∶1。
具体地，所述多元醇选自乙二醇、丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇(HDO)、新戊二醇、1，5-戊二醇、1，6-己二醇、1，9-壬二醇、环己烷二甲醇、2-乙基-1，3-己二醇、3-羟乙基氧乙基-1-羟乙基苯二醚、氢化双酚A、环己二醇、低聚物多元醇中的一种或多种；
和/或，所述多元胺选自乙二胺、丙二胺、丁二胺、环己二胺、六亚甲基二胺、1，8-二氨基辛烷、2，5-二氨基-2，5-二甲基己烷、1-氨基-3，3，5-三甲基-5-氨甲基环己烷、低聚物多元胺中的一种或多种；
和/或，所述多元醇胺选自乙醇胺、氨基乙基乙醇胺、2-氨基-1-丙醇、2-氨基-2-甲基-1-丙醇、2-氨基-2，2-二甲基乙醇、2-氨基-2-乙基-1-3-丙二醇、三(羟甲基)氨基甲烷、1-氨基-1-甲基-2-羟基环己烷和2-氨基-2-甲基-1-丁醇中的一种或多种。
具体地，所述低聚物多元醇是指具有式8所示结构的含有两个羟基基团的低聚物，其中，R 6选自醚类分子长链、酯类分子长链、烯烃分子长链；
HO-R 6-OH式8。
进一步地，所述低聚物多元醇选自聚酯多元醇、聚ε-己内酯多元醇、聚碳酸酯多元醇、聚醚多元醇、聚氧化丙烯酸多元醇、聚四氢呋喃多元醇中的一种或多种。
具体地，所述低聚物多元胺是指具有式9所示结构的含有两个氨基基团的低聚物，其中，R 7选自醚类分子长链、酯类分子长链、烯烃分子长链；
H 2N-R 7-NH 2式9。
所述低聚物多元胺选自聚醚二元胺、聚酯二元胺、脂肪族二元胺中的一种或多种。
进一步地，所述端基含有活泼氢基团的液体橡胶中，所述活泼氢基团选自端羟基、端羧基、端胺基、端巯基中的一种或多种，具体地，所述端基含有活泼氢基团的液体橡胶选自端羟基聚丁二烯液体橡胶、端羧基聚丁二烯液体橡胶、端羟基丁腈橡胶、端羧基丁腈橡胶、端胺基聚丁二烯液体橡胶、端胺基丁腈液体橡胶、端巯基聚丁二烯液体橡胶、端巯基丁腈橡胶等含有活泼氢基团的液体橡胶中的一种或多种。
进一步地，液体不饱和聚酯树脂选自邻苯型不饱和聚酯树脂、间苯型不饱和聚酯树脂、对苯型不饱和聚酯树脂、双酚A型不饱和聚酯树脂中的一种或多种；
进一步地，所述液体环氧树脂选自缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、缩水甘油胺类环氧树脂、线型脂肪族类环氧树脂、脂环族类环氧树脂中的一种或多种；
进一步地，所述液体酚醛树脂选自醇溶性酚醛树脂、油溶性酚醛树脂、改性酚醛树脂中的一种或多种；
进一步地，所述含活泼氢基团的液体有机硅树脂中所述活泼氢基团选自羟基、羧基、胺基、巯基中至少一种，具体地，所述含活泼氢基团的液体有机硅树脂选自羟基改性硅油、羧基改性硅油、胺基改性硅油、巯基改性硅油等中的一种或多种。
如上述组合物，所述光固化单体是指分子结构中含有乙烯基类的小分子化合物，用于调整组合物的粘度及性能，具体选自单官能度单体、双官能度单体、多官能度单体中的一种或多种。
如上述组合物，所述单官能度单体选自2-丙烯酸-2-甲氧基酯、乙氧基乙氧基乙基丙烯酸酯、甲氧基聚乙二醇单丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯、丙烯酸-2-苯氧基乙基酯、(2-乙基-2-甲基-1，3-二氧戊基-4-基)丙烯酸酯、烷氧化壬基苯酚丙烯酸酯、乙基化壬基苯酚丙烯酸酯、2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、1-金刚烷基甲基丙烯酸酯、3，3，5-三甲基环己烷丙烯酸酯、3，3，5-三甲基环己烷甲基丙烯酸酯、丙烯酰吗啉、环三羟甲基丙烷缩甲醛丙烯酸酯、3-乙基-3-环氧丙基丙烯酸甲酯、2-苯氧基乙基甲基丙烯酸酯、苯氧乙基丙烯酸酯、邻苯基苯氧乙基丙烯酸酯、N，N’-二甲基丙烯酰胺中的一种或多种；
和/或，所述双官能度单体选自1，6-己二醇二丙烯酸酯(HDDA)、二缩三丙二醇二丙烯酸酯、聚乙二醇(600)二丙烯酸酯、聚乙二醇(1000)二丙烯酸酯、聚乙二醇(200)二甲基丙烯酸酯、聚乙二醇(400)二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三乙二醇二乙烯基醚、丙烯酸聚丁二烯、二氧陆圜二醇二丙烯酸酯、1，9-壬二醇二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、一缩三丙二醇二丙烯酸酯中的一种或多种；
和/或，所述多官能度单体选自二季戊四醇五丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、丙氧化甘油三丙烯酸酯、3(2-羟乙基)异氰尿酸三丙烯酸酯、己内酯改性三(2-丙烯酰氧乙基)异氰尿酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯中的一种或多种。
如上述组合物，所述光固化低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯、环氧丙烯酸酯中的一种或多种。
[根据细则26改正01.07.2022]　
具体地，所述聚氨酯丙烯酸酯可以是美国Bomar公司生产的BR-344、BR-374、BR-970BT、BR-345、BR-541S、BR-774SD、BR-543、BR-970H中的一种或多种；可以是中国台湾长兴公司生产的6113、6115J-80、6101、8000A中的一种或多种；可以是美国沙多玛公司生产的CN9178 NS、CN9010 NS、CN 996 NS、CN985B88、CN975NS中的一种或多种；可以是德国湛新公司生产的Ebecryl 8296、Ebecryl 8296、Ebecryl 8807、Ebecryl 205、Ebecryl 220、Ebecryl 4587、Ebecryl 5129中的一种或多种。
所述聚酯丙烯酸酯可以是德国湛新公司生产的Ebecryl 810、Ebecryl 450、Ebecryl 452、Ebecryl 547、Ebecryl 571、Ebecryl 800、Ebecryl 852、Ebecryl 856等中的一种或多种；韩国美源公司生产的MIRAMER PS420、MIRAMER PS4040、MIRAMER PS4500中的一种或多种；德国巴斯夫公司生产的LR9004、PE9024、PE44F、PE55F中的一种或多种；
环氧丙烯酸酯可以是意大利IGM公司生产的3016、3316、3005中的一种或多种；德国巴斯夫公司生产的LR 8765、LR 8986、LR 9019、LR 8765中的一种或多种；韩国美源公司生产的MIRAMER PE210、MIRAMER PE110H、MIRAMER PE230、MIRAMER EA2235、MIRAMER EA2259中的一种或多种；
如上述组合物，所述光引发剂为自由基光引发剂；
具体地，自由基光引发剂可以选自安息香乙醚、安息香α，α-二甲基苯偶酰缩酮、α，α-二乙氧基苯乙酮、2-羟基-2-甲基-1-苯基-1丙酮(简称1173)、1-羟基-环己基苯甲酮(简称184)、2-羟基-2-甲基-对羟乙基醚基苯基丙酮-1、[2-甲基1-(4-甲巯基苯基)-2-吗啉丙酮-1]、[2-苄基-2-二甲氨基-1-(4-吗啉苯基)丁酮-1]、苯甲酰甲酸酯、2，4，6-三甲基苯基酰基-乙氧基-苯基氧化膦、2，4，6-三甲基苯基酰基-二苯基氧化膦(简称TPO)、双(2，4，6-三甲基苯基酰基)苯基氧化膦(简称819)、4-对甲苯巯基二苯甲酮等中的一种或多种。
如上述组合物，所述催化剂用于催化所述杂环基团与所述封端二异氰酸酯解封后生成的封端剂发生热化学反应，具体选自叔胺类催化剂及其复配催化剂中的一种或多种。
具体地，所述催化剂选自三亚乙基二胺及其复配催化剂、三乙胺及其复配催化剂、N，N-甲基二环环己胺及其复配催化剂、N-甲基吗啉及其复配催化剂、N-乙基吗啉及其复配催化剂、N，N′-二甲基哌嗪及其复配催化剂、N，N′-二乙基哌嗪及其复配催化剂，1，1，3，3-四甲基 哌啶及其复配催化剂中的一种或多种。
如上述组合物，所述助剂选自阻聚剂、流平剂、消泡剂、分散剂中的一种或多种。
具体地，所述阻聚剂的作用主要是阻止自由基发生聚合反应，提高组合物的贮存稳定性，阻聚剂可以选自酚类、醌类或亚硝酸盐类阻聚剂中的一种或多种，例如对苯二酚、对苯二醌、对羟基苯甲醚、2-叔丁基对苯二酚、2，5-二叔丁基对苯二酚、三(N-亚硝基-N-苯基羟胺)铝盐(阻聚剂510)中的一种或多种。
所述流平剂主要用于提高组合物的流动性以及对基材的润湿性能，同时调整组合物的表面张力使其能够正常打印。本申请对流平剂的选择不做具体限定，目前市售的产品较多，可以是毕克公司的BYK333、BYK377、BYK-UV3530、BYK-UV3575、BYK-UV3535等，迪高公司的TEGO wet 500、TEGO wet 270、TEGO Glide 450、TEGO RAD 2010、TEGO RAD 2011、TEGO RAD 2100、TEGO RAD 2200等。
所述消泡剂的主要作用是抑制、降低、消除组合物中的气泡。本申请对消泡剂的选择不做具体限定。目前市售的产品较多，可以是毕克公司的BYK1798、BYK055、BYK088、BYK020、BYK025等，迪高公司的TEGO Airex 920、TEGO Airex 921、TEGO Airex 986、TEGO Foamex 810、TEGO Foamex N等，埃夫卡公司的Efka 7081、Efka7082等。
所述分散剂的主要作用是用于提高组合物中颗粒物的分散稳定性。本申请对分散剂的选择不做具体限定。目前市售的产品较多，可以是BYK102、BYK106、BYK108、BYK110、BYK111、BYK180，迪高Dispers 655、Dispers675、Dispers 710、Dispers 630、Dispers 670等。
如上述组合物，所述填料选自二氧化硅、炭黑、硫酸钡、氢氧化铝、高岭土、滑石粉中的一种或多种。
当本申请中组合物中不含有着色剂时，组合物为透明色，打印出的制品具有较高的透明度。当含有着色剂时，着色剂可以是颜料或染料，本申请中优选颜料为着色剂，颜料具体可以选自C.I.PigmentWhite 6、C.I.Pigment Red 3、C.I.Pigment Red 5、C.I.Pigment Red 7、C.I.Pigment Red9、C.I.Pigment Red 12、C.I.Pigment Red 13、C.I.Pigment Red 21、C.I.Pigment Red31、C.I.Pigment Red49：1、C.I.Pigment Red 58：1、C.I.Pigment Red 175；C.I.PigmentYellow 63、C.I.Pigment Yellow 3、C.I.Pigment Yellow 12、C.I.Pigment Yellow 16、C.I.Pigment Yellow 83；C.I.Pigment Blue 1、C.I.Pigment Blue 10、C.I.Pigment BlueB、Phthalocyanine Blue BX、Phthalocyanine Blue BS、C.I.PigmentBlue61：1中的一种或多种。
综上，本申请提供的3D打印用组合物粘度可调，适用于喷墨打印和/或立体光固化成型技术，具有较好的热稳定性；并且使用本申请提供的组合物打印得到的3D物体的尺寸稳定性和力学性能较好。
本申请第二方面提供一种3D打印方法，包括如下步骤：
获取3D物体的至少一个层打印数据；
根据每个层打印数据喷射上述任一所述的组合物以形成材料层，并对所述材料层提供辐射得到打印层；
根据所述层打印数据得到逐层层叠的至少一个打印层，得到所述3D物体。
如上述方法，所述方法还包括，对所述材料层进行加热，使所述组合物发生热聚合反应，得到打印层。
如上述方法，所述方法还包括，对所述逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应，得到所述3D物体。
如上述方法，所述加热包括四个阶段，其中，第一阶段的加热温度为80-100℃，时间为3-10h，第二阶段的加热温度提高至110-130℃，时间为3-10h，第三阶段的加热温度提高至130-150℃，时间为3-10h，第四阶段的加热温度提高至150-200℃，加热3-10h。
本申请第三方面提供一种实施上述任一所述方法的装置，所述装置包括成型腔室、分配器、支撑平台和辐射源；
其中，所述分配器、支撑平台和辐射源设置于所述成型腔室内，所述分配器和所述辐射源设置于所述支撑平台的上方，所述分配器用于根据层打印数据在所述支撑平台上喷射上述任一所述的组合物形成材料层，所述辐射源用于对所述材料层进行辐射以形成打印层。
如上述装置，所述装置还包括第一加热部件，所述第一加热部件设置于所述成型腔室内为所述材料层提供热能，使所述组合物发生热聚合反应得到打印层。
如上述装置，所述装置还包括第二加热部件，所述第二加热部件设置于所述成型腔室外对所述逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应得到所述3D物体。
以下结合具体实施例进行详细阐述，实施例1-10提供的组合物中各组分及重量百分含量见表1，表1中涉及的化合物A、化合物B、化合物C、化合物D、化合物E、化合物F、化合物G的结构如下所示：
Figure PCTCN2022097957-appb-000007
Figure PCTCN2022097957-appb-000008
同时，本申请还提供了对比例1-4用于与实施例1-2进行对比，具体的，对比例1不包括酮肟封端二异氰酸酯，对比例2中不包括第一光固化组分，对比例3中第一光固化组分为正丁基缩水甘油醚，其分子结构中包括环氧基团但不包括乙烯基团，对比例4中包括非封端异氰酸酯，对比例1-4提供的组合物中各组分及重量百分含量见表2。
表1 实施例1-10提供的3D打印用组合物
Figure PCTCN2022097957-appb-000009
Figure PCTCN2022097957-appb-000010
Figure PCTCN2022097957-appb-000011
Figure PCTCN2022097957-appb-000012
实施例11
本实施例提供一种3D物体的打印方法，使用上述任一所述的组合物进行3D物体的打印，图1为本申请一实施例提供的3D物体打印方法的流程图，如图1所示，包括如下步骤：
S100、获取3D物体的至少一个层打印数据；
首先，将待打印的3D物体的模型数据进行切片分层和数据处理后得到层打印数据，可以理解的是，层打印数据是表征3D物体横截面的数据，对3D物体进行切片分层和数据处理后即可得到至少一个层打印数据，全部层打印数据逐层叠加即可得到该3D物体的数字模型。本申请对于层打印数据的获取方法不受限制，可以采用本领域中三维物体打印过程中层打印数据的任一种获取方法，例如，3D物体打印之前，需要获取3D物体的模型数据，并对模型数据进行数据格式转换，如转换成STL格式、PLY格式、WRL格式等能被切片软件识别的格式，使用切片软件对模型进行切片分层处理得到切片层数据，以及使用数据处理器对切片层数据进行数据处理，得到层打印数据，该层打印数据包括表示物体形状的信息，和/或表示物体颜色的信息。
S200、根据每个层打印数据喷射上述任一所述的组合物以形成材料层，并对所述材料层进行光辐射得到打印层；
具体地，根据每个层打印数据，喷射上述任一所述的组合物以形成材料层，并对所述材料层进行光辐射使得所述材料层至少部分固化得到打印层，其中，所述固化是指利用辐射源对材料层进行照射，从而使其中的光固化体系发生光固化反应而成为凝固或半凝固状态。
此外，在光固化反应过程中，由于体系的温度升高，材料层组合物中至少部分活性基团封闭型二异氰酸酯与含活泼氢的化合物发生热聚合反应，有助于提高3D物体的力学性能和尺寸稳定性。
S300、根据所述层打印数据得到逐层层叠的至少一个打印层，得到所述3D物体。
按照步骤S200形成一个打印层之后，根据不同的层打印数据重复执行该步骤，即在前一个打印层表面继续形成材料层、对材料层进行辐射形成新的打印层，多个打印层依次叠加，得到最终的3D物体。
在一种实施方式中，为了进一步引发活性基团封闭型二异氰酸酯解封与含活泼氢的化合物发生热聚合反应，从而进一步提升3D物体的力学性能，尤其使拉伸强度和撕裂强度得到进一步的提升，具体地，所述方法还包括，对所述材料层进行加热，使所述组合物发 生热聚合反应，得到打印层。
在另一种实施方式中，也可以在至少一个打印层逐层层叠完成后进行加热，引发内部的活性基团封闭型二异氰酸酯与含有活泼氢的化合物发生热聚合反应，具体地，所述方法还包括，对所述逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应，得到所述3D物体。
需要注意的是，在上述两种实施方式中，加热温度均不宜过高，只要能够引发活性基团封闭型二异氰酸酯发生解封而释放出异氰酸酯基团即可，温度过高会导致3D物体老化。
优选地，在对所述至少一个打印层逐层层叠完成后进行加热，所述加热为梯度加热，包括四个阶段，其中，第一阶段的加热温度为80-100℃，时间为3-10h，第二阶段的加热温度提高至110-130℃，时间为3-10h，第三阶段的加热温度提高至130-150℃，时间为3-10h，第四阶段的加热温度提高至150-200℃，加热3-10h。
本申请中梯度加热的作用在于：使热解封和热聚合缓慢进行，层叠后的打印层在热处理过程中不易变形，模型内部不易产生气孔，提高尺寸稳定性和性能均一性。
综上，本申请提供的3D物体的打印方法，使用上述任一所述的组合物进行打印，有利于提高3D物体的力学性能和尺寸稳定性。
实施例12
本实施例提供一种3D打印装置，用于实施上述3D物体的打印方法，图2为本申请一实施例提供的3D打印装置的结构示意图，如图2所示，该3D打印装置至少包括：成型腔室20、分配器3、支撑平台12和辐射源9，分配器3、支撑平台12和辐射源9设置于成型腔室20内，分配器3和辐射源9位于支撑平台12的上方，分配器3用于根据层打印数据在支撑平台12上喷射组合物7以形成材料层，辐射源9用于对材料层进行辐射以形成打印层。
在一种具体实施方式中，分配器3可以是单通道打印头、多通道打印头中的一种或两种，打印头3的个数至少为1个；
辐射源9为UVLED灯、汞灯、金属卤素灯、无极灯、氙灯等中的一种。
如上述装置，还包括材料容器1和墨管2，材料容器1和墨管2连接，所述墨管2和所述分配器3连接，所述材料容器1用于储存上述任一所述的3D打印用组合物，并且能够将储存在其中的3D打印用组合物通过墨管2输送至分配器3的打印头中。
在喷墨打印过程中，为了使材料组合物能够正常从打印头喷孔中喷出，需要提前对材料组合物进行预热，该预热过程可以发生在材料容器1中、和/或墨管2中、和/或打印头 3中，本申请中不做具体限制。预热的温度需低于活性基团封闭型二异氰酸酯的热解封温度，最好低于20℃，否则材料组合物在喷墨打印之前发生热聚合反应堵塞打印头喷孔。
所述预热部件可以为金属加热片、加热丝、加热弹簧中的至少一种；
如上述装置，还包括第一加热部件10，第一加热部件10位于成型腔室20内为所述材料层提供热能，使所述组合物发生热聚合反应，得到打印层。
在一种实施方式中，第一加热部件10选自红外灯、加热板、保温板、散热板、微波辐射源、控温仪中的一种或多种。
如上述装置，还包括升降部件13，该升降部件13用于改变支撑平台12和分配器3在高度方向(Z方向)的相对距离，以连续形成打印层并逐层叠加形成3D物体8。例如，分配器3喷射3D打印用组合物7至支撑平台12上形成材料层，辐射源9对其进行光辐射使组合物发生光固化反应，第一加热部件10对材料层进行加热使组合物发生热聚合反应，得到打印层后，升降部件13使得支撑平台12在高度方向上(即Z方向)下移一定的距离，从而使具有足够空间容纳新的打印层，当打印层在高度方向上逐层叠加后，形成3D物体8。
如上述装置，还包括校平部件15，校平部件15位于分配器3和辐射源9之间，用于对材料层进行校平；校平部件15可以是校平棍，通过校平棍的旋转作用带走分配的多余的3D打印用材料。
如上述装置，还包括控制器14，控制器14用于控制预热部件、第一加热部件10、分配器3、辐射源9、升降机构13和校平部件15中的至少一个的工作。
比如，控制器14可以根据层打印数据控制分配器3对加热后3D打印用组合物7的分配，控制器14可以控制辐射源9对材料层的辐射强度和辐射时间，控制器14可以控制第一加热部件10对材料的加热温度，控制器14可以控制支撑平台12和分配器3在Z向的相对距离等。
如上述装置，还包括导轨10，分配器3、辐射源9、第一加热部件10和校平部件15按顺序安装在导轨11上，并能在导轨11上移动。
区别于上述装置包括第一加热部件，作为另一种实施方式，装置不包括第一加热部件，而是包括第二加热部件(未图示)，所述第二加热部件设置于成型腔室20外对所述逐层层叠的至少一个打印层(对应图2中的3D物体8)进行加热，使所述3D物体8中组合物发生热聚合反应得到目标3D物体。
在一种实施方式中，第二加热部件选自红外灯、微波炉、加热炉、烘箱、高温真空干燥箱中的一种或多种。
如上述装置，控制器14还可以用于控制第二加热部件对3D物体8进行加热，具体加 热方式如上述实施例11中梯度加热方式所述，在此不再赘述。
使用实施例1-10以及对比例1-4提供的3D打印用组合物进行如下性能测试，测试结果见表3：
1、粘度检测
采用DV-I数显粘度计对上述组合物在打印温度下的粘度进行测试。
2.流畅性测试
采用赛纳光固化喷墨打印机持续打印3D打印用组合物，持续打印4小时，测试打印前后喷头的出墨情况，打印前后断线不超过10根，即打印流畅性ok，通过测试。
3、热稳定性测试
取100g制备好的3D打印材料样品于烧杯中，密封避光，放置于70℃烘箱中，持续保温7天，取出样品，样品无凝胶、无固化，即为通过测试。
采用相同的打印方法打印相同的3D物体，并对3D物体的机械性能进行测试，具体测试方法如下，测试结果见表4：
4、断裂伸长率及拉伸强度测试
将3D打印用材料应用于赛纳光固化喷墨打印机或者SLA 3D打印机上，弹性材料(实施例2、实施例5、对比例2)按照GB/T 528-2009打印所要求尺寸规格的3D物体，按照GB/T 528-2009测试3D物体的断裂伸长率及拉伸强度；硬质材料(其他)按照GB/T 1040.2-2006打印所要求尺寸规格的3D物体，按照GB/T 1040.2-2006测试3D物体的断裂伸长率及拉伸强度。
5、冲击强度测试
将3D打印用材料应用于赛纳光固化喷墨打印机或者SLA 3D打印机上，打印GB/T1043.1-2008所要求尺寸规格的3D物体，按照GB/T1043.1-2008测试冲击强度。
6、撕裂性测试
将3D打印用材料应用于赛纳光固化喷墨打印机或者SLA 3D打印机上，打印GB/T 529-2008所要求尺寸规格的3D物体，按照GB/T 529-2008测试撕裂强度。
7、尺寸稳定性测试
将3D打印用组合物应用于赛纳光固化喷墨打印机或者SLA 3D打印机上，打印长、宽、高分别为10mm、10mm、10mm的方块；打印完成后，进行热处理，第一阶段的加热温度为90℃，时间为2h，第二阶段的加热温度为110℃，时间为3h，第三阶段的加热温度为140℃，时间为4h；自然冷却至25℃，测量热处理后方块的长、宽、高，所测长、 宽、高均为10±0.1mm时，即尺寸稳定性好，通过测试，否则为不通过测试。
表3 实施例1-10以及对比例1-4提供的组合物的性能测试结果
Figure PCTCN2022097957-appb-000013
表4 使用实施例1-10以及对比例1-4提供的组合物得到的3D物体的性能测试结果
Figure PCTCN2022097957-appb-000014
根据表3-表4提供的测试结果可知，本申请提供的3D打印用组合物的粘度可调，适用于喷墨打印和/或立体光固化成型技术；并且，本申请提供的3D打印用组合物可以是弹性材料或者硬质材料，使用该组合物打印得到的3D物体具有较好的力学性能和尺寸稳定 性。
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。

Claims (25)

  1. 一种3D打印用组合物，其中，所述组合物按照重量百分含量包括封端二异氰酸酯5-30％、含活泼氢的化合物5-40％、第一光固化组分5-40％、光固化单体20-80％、光固化低聚物0-30％、光引发剂0.5-10％、催化剂0-1％、助剂0.05-8％、填料0-15％和着色剂0-5％；
    所述封端二异氰酸酯具有式1所示的结构：
    Figure PCTCN2022097957-appb-100001
    其中，R 9，R 10独立选自以下结构中的一种：
    Figure PCTCN2022097957-appb-100002
    其中，R 1、R 2、R 4和R 5独立地选自具有1-20个碳原子的直链或支链烷基；具有单环、桥连的双环以及桥连的三环的C3-C20基团；具有6-18个碳原子的芳基；具有6-18个碳原子的芳基烷基或烷基芳基；含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂芳基，含O、N、Si、S、P中至少一种原子的具有3-20个碳原子的杂环基；
    R 8选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环己基、烯丙基、(甲基)丙烯酰氧基乙基中的一种；
    R 3选自具有1-18个碳原子的直链或支链亚烷基、具有5-18个碳原子的亚脂环基、具有6-18个碳原子的亚芳基、具有6-20个碳原子的芳基亚烷基或烷基亚芳香基、具有取代或非取代基团的萘环基；
    所述第一光固化组分的分子结构中包括乙烯基团和杂环基团，且所述杂环基团能与所述封端二异氰酸酯解封后形成的封端剂发生热化学反应；
    所述光固化单体和所述光固化低聚物均不与所述封端剂发生所述热化学反应。
  2. 根据权利要求1所述的组合物，其中，所述封端二异氰酸酯的解封温度高于所述组合物打印温度至少20℃。
  3. 根据权利要求2所述的组合物，其中，所述封端二异氰酸酯的解封温度为T，且100≤T≤150℃。
  4. 根据权利要求1-3任一项所述的组合物，其中，所述杂环基团选自环氧基团、丁氧环基团、四氢呋喃基团、二氧五环基团、二氧六环基团、三氧六环基团、丙内酯基团、丁内酯基团、杂氮环丙烷基团、杂氮环丁烷基团、环硫丁烷基团、六甲基环三硅氧烷基团、八甲基环四硅氧烷基团、2，5-二氧戊环-1-酮基团中的一种或多种。
  5. 根据权利要求4所述的组合物，其中，所述第一光固化组分选自丙烯酸缩水甘油酯、丙烯酸羟丁基缩水甘油醚、丙烯酰氧基碳酸甘油酯、1，2-环氧-9-癸烯、3，4-环氧-1-丁烯、1，2-环氧-5-己烯、烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、1，2-环氧基-5-己烯、3-(烯丙氧基)氧杂环丁烷、丙烯酸四氢糠基酯、甲基丙烯酸四氢糠基酯、烯丙基4-氧代-2-氧杂环丁烷羧酸酯、2-氧代四氢呋喃-3-基甲基丙烯酸酯、3-(烯丙氧基)-5-乙基二氢-2(3H)-呋喃酮、2，4，6-三乙烯基-2，4，6-三甲基环三硅氧烷、1，3，5，7-四乙烯基-1，3，5，7-四甲基环四硅氧烷中的一种或多种。
  6. 根据权利要求1-5任一项所述的组合物，其中，所述含活泼氢的化合物选自多元醇、多元胺、多元醇胺、液体不饱和聚酯树脂、液体环氧树脂、液体酚醛树脂、含活泼氢基团的液体有机硅树脂、端基含有活泼氢基团的液体橡胶中的一种或多种。
  7. 根据权利要求6所述的组合物，其中，所述含活泼氢的化合物中活泼氢基团与所述酮肟封端二异氰酸酯中异氰酸根的摩尔比为(0.9-1.0)∶1。
  8. 根据权利要求6或7所述的组合物，其中，所述多元醇选自乙二醇、丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇、新戊二醇、1，5-戊二醇、1，6-己二醇、1，9-壬二醇、环己烷二甲醇、2-乙基-1，3-己二醇、3-羟乙基氧乙基-1-羟乙基苯二醚、氢化双酚A、环己二醇、低聚物多元醇中的一种或多种；
    和/或，所述多元胺选自乙二胺、丙二胺、丁二胺、环己二胺、六亚甲基二胺、1，8-二氨基辛烷、2，5-二氨基-2，5-二甲基己烷、1-氨基-3，3，5-三甲基-5-氨甲基环己烷、低聚物多元胺中的一种或多种；
    和/或，所述多元醇胺选自乙醇胺、氨基乙基乙醇胺、2-氨基-1-丙醇、2-氨基-2-甲基-1-丙醇、2-氨基-2，2-二甲基乙醇、2-氨基-2-乙基-1-3-丙二醇、三(羟甲基)氨基甲烷、1-氨基-1-甲基-2-羟基环己烷和2-氨基-2-甲基-1-丁醇中的一种或多种。
  9. 根据权利要求8所述的组合物，其中，所述低聚物多元醇选自聚酯多元醇、聚ε-己内酯多元醇、聚碳酸酯多元醇、聚醚多元醇、聚氧化丙烯酸多元醇、聚四氢呋喃多元醇中的一种或多种。
  10. 根据权利要求6所述的组合物，其中，所述端基含有活泼氢基团的液体橡胶选自端羟基聚丁二烯液体橡胶、端羧基聚丁二烯液体橡胶、端羟基丁腈橡胶、端羧基丁腈橡胶、端胺基聚丁二烯液体橡胶、端胺基丁腈液体橡胶、端巯基聚丁二烯液体橡胶、端巯基丁腈橡胶中的一种或多种。
  11. 根据权利要求6所述的组合物，其中，所述含活泼氢基团的液体有机硅树脂选自羟基改性硅油、羧基改性硅油、胺基改性硅油、巯基改性硅油中的一种或多种。
  12. 根据权利要求1-11任一项所述的组合物，其中，所述光固化单体选自单官能度 单体、双官能度单体、多官能度单体中的一种或多种。
  13. 根据权利要求12所述的组合物，其中，所述单官能度单体选自2-丙烯酸-2-甲氧基酯、乙氧基乙氧基乙基丙烯酸酯、甲氧基聚乙二醇单丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯、丙烯酸-2-苯氧基乙基酯、(2-乙基-2-甲基-1，3-二氧戊基-4-基)丙烯酸酯、烷氧化壬基苯酚丙烯酸酯、乙基化壬基苯酚丙烯酸酯、2-[[(丁基氨基)羰基]氧代]丙烯酸乙酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、1-金刚烷基甲基丙烯酸酯、3，3，5-三甲基环己烷丙烯酸酯、3，3，5-三甲基环己烷甲基丙烯酸酯、丙烯酰吗啉、环三羟甲基丙烷缩甲醛丙烯酸酯、3-乙基-3-环氧丙基丙烯酸甲酯、2-苯氧基乙基甲基丙烯酸酯、苯氧乙基丙烯酸酯、邻苯基苯氧乙基丙烯酸酯、N，N’-二甲基丙烯酰胺中的一种或多种；
    和/或，所述双官能度单体选自1，6-己二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、聚乙二醇(600)二丙烯酸酯、聚乙二醇(1000)二丙烯酸酯、聚乙二醇(200)二甲基丙烯酸酯、聚乙二醇(400)二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三乙二醇二乙烯基醚、丙烯酸聚丁二烯、二氧陆圜二醇二丙烯酸酯、1，9-壬二醇二丙烯酸酯、乙氧化双酚A二甲基丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、一缩三丙二醇二丙烯酸酯中的一种或多种；
    和/或，所述多官能度单体选自二季戊四醇五丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、丙氧化甘油三丙烯酸酯、3(2-羟乙基)异氰尿酸三丙烯酸酯、己内酯改性三(2-丙烯酰氧乙基)异氰脲酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、3(丙氧基)丙三醇三丙烯酸酯中的一种或多种。
  14. 根据权利要求1-13任一项所述的组合物，其中，所述光固化低聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯、环氧丙烯酸酯中的一种或多种。
  15. 根据权利要求1-14任一项所述的组合物，其中，所述光引发剂为自由基光引发剂。
  16. 根据权利要求1-15任一项所述的组合物，其中，所述催化剂选自叔胺类催化剂及其复配催化剂中的一种或多种。
  17. 根据权利要求16所述的组合物，其中，所述催化剂选自三亚乙基二胺及其复配催化剂、三乙胺及其复配催化剂、N，N-甲基二环环己胺及其复配催化剂、N-甲基吗啉及其复配催化剂、N-乙基吗啉及其复配催化剂、N，N′-二甲基哌嗪及其复配催化剂、N，N′-二乙基哌嗪及其复配催化剂，1，1，3，3-四甲基哌啶及其复配催化剂中的一种或多种。
  18. 根据权利要求1-17任一项所述的组合物，其中，所述助剂选自阻聚剂、流平剂、消泡剂、分散剂中的一种或多种。
  19. 一种3D打印方法，其中，包括如下步骤：
    获取3D物体的至少一个层打印数据；
    根据每个层打印数据喷射权利要求1-18任一项所述的组合物以形成材料层，并对所述材料层提供辐射得到打印层；
    根据所述层打印数据得到逐层层叠的至少一个打印层，得到所述3D物体。
  20. 根据权利要求19所述的方法，其中，所述方法还包括，对所述材料层进行加热，使所述组合物发生热聚合反应，得到打印层。
  21. 根据权利要求19所述的方法，其中，所述方法还包括，对所述逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应，得到所述3D物体。
  22. 根据权利要求21所述的方法，其中，所述加热包括四个阶段，其中，第一阶段的加热温度为80-100℃，时间为3-10h，第二阶段的加热温度提高至110-130℃，时间为3-10h，第三阶段的加热温度提高至130-150℃，时间为3-10h，第四阶段的加热温度提高至150-200℃，加热3-10h。
  23. 一种实施权利要求19-22任一项所述方法的装置，其中，所述装置包括成型腔室、分配器、支撑平台和辐射源；
    其中，所述分配器、支撑平台和辐射源设置于所述成型腔室内，所述分配器和所述辐射源设置于所述支撑平台的上方，所述分配器用于根据层打印数据在所述支撑平台上喷射权利要求1-18任一项所述的组合物形成材料层，所述辐射源用于对所述材料层进行辐射以得到打印层。
  24. 根据权利要求23所述的装置，其中，所述装置还包括第一加热部件，所述第一加热部件设置于所述成型腔室内为所述材料层提供热能，使所述组合物发生热聚合反应得到打印层。
  25. 根据权利要求23所述的装置，其中，所述装置还包括第二加热部件，所述第二加热部件设置于所述成型腔室外对逐层层叠的至少一个打印层进行加热，使所述组合物发生热聚合反应得到所述3D物体。
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