WO2022033114A1 - Matériau pour moulage tridimensionnel, et objet tridimensionnel et couche en tranches associés - Google Patents

Matériau pour moulage tridimensionnel, et objet tridimensionnel et couche en tranches associés Download PDF

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Publication number
WO2022033114A1
WO2022033114A1 PCT/CN2021/095866 CN2021095866W WO2022033114A1 WO 2022033114 A1 WO2022033114 A1 WO 2022033114A1 CN 2021095866 W CN2021095866 W CN 2021095866W WO 2022033114 A1 WO2022033114 A1 WO 2022033114A1
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active component
group
powder
liquid material
anhydride
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PCT/CN2021/095866
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English (en)
Chinese (zh)
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何兴帮
杨前程
蒋韦
沈为真
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珠海赛纳三维科技有限公司
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Publication of WO2022033114A1 publication Critical patent/WO2022033114A1/fr

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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
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • 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
    • 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
    • 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
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • the present application relates to the technical field of three-dimensional object forming, and in particular, to materials for three-dimensional forming, three-dimensional objects and slice layers thereof.
  • the inkjet printing technology mainly refers to that the print head on the support platform selectively ejects the photosensitive resin material according to the layer patterning data of the three-dimensional object, also known as the printing data, and the radiation source irradiates the ejected photosensitive resin material to form a cured layer. .
  • a binder is selectively sprayed on the polyamide powder layer according to the printing data, and the polyamide powder is bonded together by the binder to form a layer of a three-dimensional object, The layers are repeated and stacked to form a three-dimensional object.
  • a photosensitive resin is selectively sprayed on the polyamide powder layer according to the printing data, and the polyamide powder is encapsulated therein through a photocuring reaction of the photosensitive resin.
  • the polyamide powder in the printed 3D object exists in the form of particles, and the mechanical properties of the 3D object such as tensile strength are not high.
  • the embodiments of the present application provide a three-dimensional molding material, a three-dimensional object, and a slice layer thereof, which can effectively improve the mechanical strength and density of the three-dimensional object.
  • an embodiment of the present application provides a material for three-dimensional molding, the material comprising:
  • powder materials comprising polyamide powder and/or modified polyamide powder
  • a liquid material comprising a first active component that can undergo a polymerization reaction; the first active component dissolves at least part of the polyamide powder and/or the modified polyamide powder, and the powder material does not polymerize itself and does not polymerize with the first active component.
  • the first active component includes an active monomer containing an electrophilic group, and the electrophilic group is selected from a sulfonic acid group, a carboxyl group, and a phenolic hydroxyl group. at least one of them.
  • the reactive monomer containing an electrophilic group is selected from acrylate monomers, methacrylate monomers, vinyl ether monomers, alkenes At least one of propyl ether monomers and polyols.
  • the electrophilic group-containing reactive monomer is a carboxyl-containing reactive monomer; the carboxyl-containing reactive monomer is composed of an acid anhydride and a monohydroxy-containing reactive monomer The monomer is formed through a ring-opening reaction; and/or, the carboxyl-containing active monomer is formed from an acid anhydride and a polyol through a ring-opening reaction.
  • the molar ratio of the acid anhydride to the monohydroxy-containing reactive monomer is 1:(0.8-1.3); and/or,
  • the acid anhydride is selected from at least one of succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; and/or,
  • the monohydroxy-containing active monomer is selected from the group consisting of hydroxy acrylate monomers, monohydroxy methacrylate monomers, monohydroxy vinyl ether monomers, and hydroxy allyl ether monomers. at least one.
  • the molar ratio of the acid anhydride to the dihydric alcohol is 1:1; and/or,
  • the acid anhydride is selected from at least one of succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; and/or,
  • the diol is selected from at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
  • the liquid material further includes a second active component, the second active component can undergo a polymerization reaction, and the second active component does not dissolve the Polyamide powder and/or said modified polyamide powder.
  • the second active component is selected from compounds without electrophilic groups.
  • the second active component is selected from a compound containing a hydroxyl group and/or an epoxy group, and the compound containing a hydroxyl group and/or an epoxy group is A reactive monomer containing a carboxyl group undergoes a chemical reaction; and/or,
  • the hydroxyl group-containing and/or epoxy group-containing compound is selected from at least one of hydroxyacrylate-based monomers, alcohol-based oligomers, epoxy-based oligomers, and epoxy diluents.
  • the first active component and/or the second active component has a swelling group, and the swelling group can participate in a polymerization reaction, and the The swelling group is selected from at least one of spirocyclic ether structure, spirocyclic orthocarbonate structure, spirocyclic orthoester structure, bicyclic orthoester structure and bicyclic lactone structure.
  • the first active component and/or the second active component has a combination of active groups, and the combination of active groups can form the said swelling group; and/or,
  • the active group combination includes any one of a combination of a polyhydric alcohol group and an orthocarbonic acid diester group, and a combination of an epoxy group and a cyclic lactone structure.
  • the mass ratio of the first active component and the second active component in the liquid material is 50%-100%; and/or,
  • the mass ratio of the first active component in the liquid material is 10%-95%; and/or,
  • the mass proportion of the second active component in the liquid material is 5%-90%.
  • the mass ratio of the first active component and the second active component containing swellable groups or capable of forming swellable groups in the liquid material is 0.05 %-50%.
  • the liquid material further includes a first auxiliary agent
  • the first auxiliary agent includes at least one of a free radical initiator, an anionic initiator, a cationic initiator and a catalyst and/or, the mass proportion of the first auxiliary agent in the liquid material is 0%-10%.
  • the liquid material further includes a second auxiliary agent
  • the second auxiliary agent includes a leveling agent, a defoaming agent, a polymerization inhibitor, a surfactant, and an antioxidant.
  • at least one of plasticizer and dispersant; and/or, the mass proportion of the second auxiliary agent in the liquid material is 0.1%-30%.
  • the liquid material further includes a colorant, and the colorant accounts for 0%-10% by mass in the liquid material.
  • the average particle size of the powder material is 1 um ⁇ 400 um.
  • the powder material further includes an additive, and the additive includes at least one of a flow aid and a filler.
  • an embodiment of the present application provides a slice layer of a three-dimensional object, where the slice layer of the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned materials.
  • an embodiment of the present application provides a three-dimensional object, wherein the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned materials.
  • the three-dimensional molding materials provided in the embodiments of the present application include powder materials and liquid materials containing a first active component
  • the powder materials include polyamide powder and/or modified polyamide powder
  • the first active component can be polymerized react, and the first active component dissolves at least part of the polyamide powder and/or the modified polyamide powder, the polyamide powder and/or the modified polyamide powder dissolved in the first active component may
  • the polymer formed with the first active component forms a polymer alloy, so that there is good adhesion between the powder materials, between the powder materials and the polymer, and between the printing layers and the layers. connection effect.
  • the formed polymer can be mixed with powder materials to obtain a "sea-island structure" or homogeneous structure with good interface bonding, which can improve the bonding force in and between the slice layers of the three-dimensional object, and improve the mechanical properties of the three-dimensional object. Strength, improve the uniformity of mechanical properties of three-dimensional objects.
  • the first active component in the liquid material of the present application fills the gap between the polyamide powder and/or the modified polyamide powder, and dissolves at least part of the polyamide powder and/or the modified polyamide powder.
  • the amide powder reduces the porosity inside the three-dimensional object and improves the density of the three-dimensional object.
  • the high molecular polymer formed by the polymerization reaction of the first active component and the polyamide powder and/or the modified polyamide powder are mixed at the molecular level to easily obtain a colorless or light-colored transparent three-dimensional object.
  • the first active component in the liquid material of the present application undergoes a polymerization reaction to form a layer of a three-dimensional object, and the three-dimensional object produced has basically no residual small molecular substances, and basically no small molecular substances are precipitated during use, which can achieve safety and environmental protection. requirements.
  • the liquid material of the present application does not contain strong corrosive substances, which improves the safety of preparation of three-dimensional objects.
  • FIG. 1 is a schematic structural diagram of a three-dimensional object additive manufacturing device provided by a specific embodiment of the present application
  • FIG. 2 is a schematic flowchart of a method for additive manufacturing of a three-dimensional object provided by a specific embodiment of the present application
  • 3a-3g are schematic structural diagrams of a three-dimensional object formation process provided by a specific embodiment of the present application.
  • the embodiment of the present application provides a material for three-dimensional molding, including:
  • powder materials comprising polyamide powder and/or modified polyamide powder
  • a liquid material comprising a first active component that can undergo a polymerization reaction; the first active component dissolves at least part of the polyamide powder and/or the modified polyamide powder, and the powder material does not polymerize itself and does not polymerize with the first active component.
  • the first active component in the liquid material undergoes a polymerization reaction to form a high molecular polymer, and the formed high molecular polymer forms a blend with polyamide powder and/or modified polyamide powder, especially when dissolved in The polyamide powder and/or modified polyamide powder in the liquid material are mixed at the molecular level to form a polymer alloy, so that there is a Good connection, showing "sea-island structure" or homogeneous structure, can improve the mechanical strength of three-dimensional objects.
  • the sea-island structure is a two-phase system of blends, in which one phase is a continuous phase and the other is a dispersed phase, and the granular powder material is dispersed in the continuous polymer to form a strong connection , which can improve the mechanical strength of three-dimensional objects.
  • the polyamide powder and the modified polyamide powder may be selected from nylon 6 (PA6), nylon 46 (PA46), nylon 66 (PA66), nylon 11 (PA11), nylon 12 (PA12), nylon 610 (PA610) , nylon 612 (PA612), nylon 1010 (PA1010), nylon 8 (PA8), nylon 9 (PA9) and other nylon materials at least one.
  • the particle shape and particle size of the polyamide powder and modified polyamide powder in this embodiment are not particularly limited.
  • the powder material provided in this embodiment forms the powder material layer
  • the fluidity of the powder material can meet the usage requirements
  • the gap formed between the powder materials can be filled with the applied liquid material
  • the applied liquid material can wet the powder material
  • the surface or at least part of the powder material can be dissolved in the liquid material.
  • the particles of the polyamide powder and/or the modified polyamide powder in this embodiment may be spherical, approximately spherical, dendritic, flake-like, disc-like, needle-like or rod-like according to the difference in the manufacturing process of the powder material. equal shape.
  • the average particle size of the polyamide powder and/or modified polyamide powder is 1 ⁇ m to 400 ⁇ m, for example, it can be 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 30 ⁇ m, 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 250 ⁇ m, 300 ⁇ m, 350 ⁇ m or 400 ⁇ m, polyamide powder And/or the average particle diameter of the modified polyamide powder is preferably 30 ⁇ m to 200 ⁇ m.
  • the particle gap in the polyamide powder and/or the modified polyamide powder is about 5 nm to 100 ⁇ m, for example, it can be 5 nm, 10 nm, 100 nm, 250 nm, 500 nm, 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 25 ⁇ m, 50 ⁇ m, 75 ⁇ m or 100 ⁇ m, here Not limited.
  • the particle gap of the powder material in this embodiment is in the range of 5 nm to 100 ⁇ m.
  • the liquid material When the liquid material is selectively applied to the powder material layer, the liquid material can quickly penetrate into the powder material layer through the gap and retain part of the surface layer, thereby wetting the surface of the polyamide powder and/or the modified polyamide powder in the selected area, and at least partially dissolve the polyamide powder and/or the modified polyamide powder. It should be noted that the dissolution in this example refers to all possible situations except complete insolubility.
  • the powder material in the present application may also include additives, and the additives include at least one of flow aids and fillers.
  • flow aids are used to improve the fluidity of powder materials, such as silicon dioxide, talc, etc.
  • fillers are used to improve the mechanical strength of three-dimensional objects, such as graphene, carbon nanotubes, glass Fiber, kaolin, etc. are not limited in this embodiment.
  • the liquid material comprises a first reactive component capable of polymerizing, the first reactive component dissolving at least part of the polyamide powder and/or the modified polyamide powder.
  • the first active component completely dissolves the polyamide powder and/or modified polyamide powder in contact with the active component.
  • the first active component may be a substance comprising only one soluble polyamide powder and/or modified polyamide powder, or a substance comprising multiple soluble polyamide powders and/or modified polyamide powders Mixtures, the solubility of various substances to powder materials can be different or the same.
  • the dissolution mentioned in this example refers to all possible situations except complete insolubility.
  • the first active component when 1 g of polyamide powder and/or modified polyamide powder is placed in 100 g of the first active component, at least 1% of the polyamide powder and/or modified polyamide powder dissolves.
  • the first active component completely dissolves the polyamide powder and/or the modified polyamide powder.
  • the dissolution is not limited to normal temperature, and the first active component can also be dissolved in the powder material under the condition of heating and/or stirring; The active ingredient dissolves slowly upon contact with the powder material, and the powder material can be heated to increase the rate of dissolution.
  • the manufacturing safety of the three-dimensional object can be improved.
  • the liquid material containing the first active component fills the gap between the polyamide powder and/or the modified polyamide powder, dissolves the polyamide powder and/or the modified polyamide powder, further reduces the porosity inside the three-dimensional object, and improves the three-dimensional The density of the object.
  • the first active component includes an active monomer containing an electrophilic group
  • the electrophilic group is selected from a sulfonic acid group (-SO 3 H), a carboxyl group (-COOH), a phenolic hydroxyl group ( -C 6 H 4 OH) at least one.
  • the electrophilic group is a carboxyl group (-COOH).
  • the active monomer containing carboxyl group (-COOH) is relatively easy to obtain, and the three-dimensional object made from the active monomer containing carboxyl group (-COOH) is easy to end-cap the carboxyl group in the post-processing process, thereby improving the performance of the three-dimensional object. Stability of 3D objects in aqueous or humid environments.
  • the active monomer containing an electrophilic group is selected from acrylate monomers, methacrylate monomers, vinyl ether monomers, allyl ether monomers, and polyols. at least one.
  • the acrylic monomer containing electrophilic group is selected from acryloyloxyethyl succinic acid monoester, acryloyloxyethyl maleic acid monoester, acryloyloxyethyl phthalic acid monoester, At least one of acryloyloxyethyl hexahydrophthalic acid monoester, acryloyloxyethyl trimellitic anhydride, and the like.
  • the methacrylate monomers containing electrophilic groups are selected from methacryloyloxyethyl succinic acid monoester (MOES), methacryloyloxyethyl maleic acid monoester (MOEM), Methacryloxyethyl phthalate monoester (PAMA), Methacryloxyethyl hexahydrophthalate monoester (HHMA), Methacryloxyethyl trimellitic anhydride (4-META), At least one of hydroxyethyl pyrophthalic anhydride dimethacrylate (PMDM) and the like.
  • MOES methacryloyloxyethyl succinic acid monoester
  • MOEM methacryloyloxyethyl maleic acid monoester
  • PAMA Methacryloxyethyl phthalate monoester
  • HHMA Methacryloxyethyl hexahydrophthalate monoester
  • 4-META Methacryloxyethyl trimellitic anhydr
  • the vinyl ether monomer containing electrophilic group is selected from succinic acid monovinyl ether oxyethyl ester, maleic acid monovinyl ether oxypropyl ester, phthalate monovinyl ether oxyethyl ester at least one of etc.
  • Allyl ether monomers containing electrophilic groups are selected from monoallyl ether oxyethyl succinate, monoallyl ether oxypropyl maleate, monoallyl phthalate At least one of ether oxyethyl ester, etc.;
  • the polyol containing an electrophilic group is at least one selected from the group consisting of monoethylene succinate, monobutylene phthalate, monohexanediol maleate, and the like.
  • the reactive monomer containing a carboxyl group can be selected from 2-methyl-acryloyloxyethylsuccinic acid monoester, methacryloyloxyethyl trimellitic anhydride, and trimellitic anhydride At least one of hydroxyethyl acrylate, methacryloyloxyethyl hexahydrophthalic acid monoester, methacryloyloxyethyl phthalic acid monoester, etc. prepared by the synthetic method.
  • the carboxyl group-containing reactive monomer is generated from an acid anhydride and a monohydroxy-containing reactive monomer through a ring-opening reaction; and/or, the carboxyl group-containing reactive monomer is generated from an acid anhydride and a polyol through a ring-opening reaction.
  • the reactive monomer containing a carboxyl group is generated by an acid anhydride and a reactive monomer containing a monohydroxy group through a ring-opening reaction, and the steps include:
  • the acid anhydride and the active monomer containing monohydroxyl group are added into the reaction vessel in a molar ratio of 1:(0.8-1.3), and 0.05%-0.5% polymerization inhibitor and 0.05%-0.5% antioxidant are selectively added.
  • agent 0% ⁇ 2% catalyst, obtained by reaction below 160°C, preferably, the reaction temperature is 110°C-130°C, the acid value is kept warm to 100mgKOH/g ⁇ 400mgKOH/g, and the material is cooled and discharged to obtain the carboxyl group-containing activity monomer.
  • the molar ratio of the acid anhydride to the monohydroxy-containing reactive monomer can be 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, etc.
  • the acid anhydride and the monohydroxy-containing reactive monomer was 1:1 to ensure complete ring opening of the anhydride.
  • the value of the molar ratio can also be set according to the actual situation, which is not limited here.
  • the acid anhydride is selected from at least one of succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
  • the monohydroxy-containing active monomer is selected from the group consisting of hydroxy acrylate monomers, monohydroxy methacrylate monomers, monohydroxy vinyl ether monomers, and hydroxy allyl ether monomers. at least one.
  • the hydroxyacrylate-based monomer may be hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like.
  • Monohydroxy methacrylate-based monomers may be hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and the like.
  • Monohydroxy vinyl ether-containing monomers may be ethylene glycol monovinyl ether, propylene glycol monovinyl ether, diethylene glycol monovinyl ether, butanediol monovinyl ether, and the like.
  • the hydroxyl group-containing allyl ether monomer may be ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether, butanediol monoallyl ether, and the like.
  • the reactive monomer containing carboxyl group is generated by the ring-opening reaction of acid anhydride and polyol, and the steps include:
  • the acid anhydride and the dihydric alcohol are added to the reaction vessel in a molar ratio of 1:1, and 0.05% to 0.5% of a polymerization inhibitor, 0.05% to 0.5% of an antioxidant, and 0% to 2% of a catalyst are selectively added. It is obtained by reaction below 160°C, preferably, the reaction temperature is 110°C-130°C, the acid value is kept warm to 100mgKOH/g ⁇ 400mgKOH/g, the temperature is lowered and the material is discharged to obtain the active monomer containing carboxyl group.
  • the dihydric alcohol is selected from at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, and hexylene glycol;
  • the acid anhydride is selected from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexanoic anhydride At least one of hydrophthalic anhydride.
  • the mass proportion of the first active component in the liquid material is 10%-95%.
  • it can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 95%.
  • the mass ratio can also be matched according to the actual usage, which is not done here. limited.
  • the mass ratio of the first active component in the liquid material is 30%-90%.
  • the liquid material may also include a second active component that does not dissolve the polyamide powder and/or the modified polyamide powder, that is, the second active component does not dissolve the polyamide powder at all.
  • a second active component that does not dissolve the polyamide powder and/or the modified polyamide powder, that is, the second active component does not dissolve the polyamide powder at all.
  • Amide powder and/or modified polyamide powder can undergo a polymerization reaction by itself, or can participate in a polymerization reaction together with the first reactive component.
  • the second active component does not chemically react with the polyamide powder and/or the modified polyamide powder.
  • the second active component is selected from compounds without electrophilic groups.
  • the second active component is selected from compounds that do not contain electrophilic groups and contain hydroxyl and/or epoxy groups, the compounds that do not contain electrophilic groups and contain hydroxyl and/or epoxy groups.
  • the compound reacts chemically with the carboxyl group-containing reactive monomer. It should be noted that the type of the chemical reaction may be an end-capping reaction or a polymerization reaction.
  • the compound without an electrophilic group and containing a hydroxyl group is selected from at least one of hydroxyacrylate monomers and alcohol oligomers, without an electrophilic group and containing an epoxy group
  • the compound is selected from at least one of epoxy oligomers and epoxy diluents.
  • the hydroxyacrylate-based monomer may be at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like.
  • the alcohol-based oligomer may be at least one of polyester polyol, polyether polyol, polycaprolactone polyol, and the like.
  • the epoxy-based oligomer may be at least one of epoxy resins E-51, E-41, and the like.
  • the epoxy diluent may be at least one of butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether, and the like.
  • the mass ratio of the second active component in the liquid material is 5%-90%.
  • it can be 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%.
  • the mass ratio can also be matched according to the actual usage. This is not limited.
  • the second active component can also fill the gaps between the polyamide powder and/or the modified polyamide powder or the pores inside the powder, so as to further reduce the pores inside the three-dimensional object. rate and improve the density of three-dimensional objects.
  • the second active component can also form properties complementary to the first active component, so that the three-dimensional object has higher properties than when only the first active component is contained.
  • the mass ratio of the first active component and the second active component in the liquid material is 50%-100%; for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%, of course the first active ingredient and the second active ingredient in the liquid material
  • the mass ratio can also be set to other values based on actual needs, which are not limited here.
  • the mass proportion of the active component in the liquid material exceeds 50%, when a high molecular polymer is formed by a polymerization reaction, the high molecular polymer forms a blend with polyamide powder and/or modified polyamide powder, especially with polyamide powder and/or modified polyamide powder.
  • the dissolved polyamide powder and/or modified polyamide powder are mixed at the molecular level to form a polymer alloy, so that there is a Very good connection.
  • the first active component and/or the second active component has a swelling group
  • the swelling group can participate in the polymerization reaction
  • the swelling group is selected from the spirocyclic ether structure, At least one of spirocyclic orthocarbonate structure, spirocyclic orthoester structure, bicyclic orthoester structure and bicyclic lactone structure.
  • the active ingredient containing an intumescent group can be 3,9-diethyl-3,9propenyloxymethyl-1,5,7,11-tetraoxaspiro[5,5]undecane, 3,9-Dihydroxyethyl-3'9'-benzyl-1,5,7,11-tetraoxaspiro[5,5]undecane, etc.
  • the first reactive component and/or the second reactive component has a combination of reactive groups that can form the swelling group during the polymerization reaction.
  • the active group combination includes any one of a combination of a polyhydric alcohol group and an orthocarbonic acid diester group, and a combination of an epoxy group and a cyclic lactone structure.
  • the first active component and/or the second active component has a swelling group or a combination of active groups that can form a swelling group.
  • the swellable group also undergoes a chemical reaction, so that the volume of the formed polymer expands, and the volume of the object does not shrink due to the curing process, and the final three-dimensional object has a higher dimensional accuracy.
  • the volume expansion caused by the expansive group can reduce the porosity of the polyamide powder and/or the modified polyamide powder, make the polymer powder densified, and improve the mechanical properties and mechanical strength of the object.
  • the molecular structure of the first active component and/or the second active component may also contain a functional group that does not participate in the polymerization reaction, and the functional group may be a hydrophilic group.
  • the hydrophilic group can improve the water solubility of the first active component and/or the second active component.
  • the hydrophilic group may be a hydroxyl group, a carboxyl group, or the like.
  • the functional group can also be a group containing a flame retardant function, such as a phosphate group, etc., and the functional group can also be a group containing a bactericidal function, such as a quaternary ammonium salt group.
  • the liquid material further includes a first auxiliary agent
  • the first auxiliary agent is used to initiate or catalyze the polymerization reaction of the active component
  • the first auxiliary agent includes a free radical initiator, an anionic initiator, a cationic initiator and at least one of the catalysts.
  • the mass proportion of the first auxiliary agent in the liquid material is 0%-10%, for example, it can be 0%, 1%, 2%, 3% %, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
  • the mass ratio can also be matched according to the actual usage, which is not limited here.
  • the free radical initiator can be a high temperature free radical initiator, such as: tert-butyl benzoyl peroxide, dodecanoyl peroxide, dicumyl peroxide, 2-ethylhexyl peroxide tert-amyl peroxide, tert-butyl 2-ethylhexyl peroxide, tert-butyl peroxide (TBHP), tert-amyl peroxide (TAHP), di-tert-butyl peroxide (DTBP), di-tert-amyl peroxide (DTAP), 3,3-bis(tert-butylperoxy)butyric acid acetic acid, 3,3-bis(tert-amylperoxy)butyric acid ethyl ester, tert-butyl peroxybenzoate (TBPB), 3,3 peroxide One or more of tert-butyl 5-trimethylhexanoate (TBPMH), tert-amyl
  • the free radical initiator can also be a light free radical initiator, such as: benzoin ether, benzoin ⁇ , ⁇ -dimethylbenzyl ketal, ⁇ , ⁇ -diethoxyacetophenone, 2-hydroxy- 2Methyl-phenylacetone-1,1-hydroxy-cyclohexylbenzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone-1, [2-methyl 1-(4 -Methylmercaptophenyl)-2-morpholinoacetone-1], [2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1], benzoylformate , 2,4,6-trimethylphenylacyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylphenylacyl-diphenylphosphine oxide, bis(2,4,6- One or more of trimethyl phenyl acyl) phenyl phosphine oxide, 4-p
  • the anionic initiator can be butyllithium, butyllithium oxide and the like.
  • the cationic initiator can be a mixture of triarylsulfonium hexafluorophosphate, blocked phosphate cationic initiator, 4-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate, 4-isobutylbenzene Base-4'-methylphenyliodonium hexafluorophosphate, ⁇ 6-cumene ferrocene (II) hexafluorophosphate mixture.
  • the catalyst can be stannous isooctanoate, stannous octoate, dibutyltin dilaurate, methyl fluorosulfonic acid, ethyl fluorosulfonic acid, methyl nitrobenzene sulfonic acid, methyl methanesulfonate or tetraphenyl Porphyrin aluminides, etc.
  • the liquid material also includes a second auxiliary agent, and the second auxiliary agent is selected from at least one of a leveling agent, a defoaming agent, a surfactant, a polymerization inhibitor, an antioxidant, a plasticizer, and a dispersing agent.
  • the mass ratio of the second auxiliary agent in the liquid material is 0.1%-30%, for example, it can be 0.1%, 1%, 5%, 10% %, 15%, 20%, 25% or 30%. Of course, the mass ratio can also be matched according to the actual usage, which is not limited here.
  • the mass ratio of the leveling agent in the liquid material is 0.01%-3%; the mass ratio of the defoaming agent in the liquid material is 0.01%-3%; the mass ratio of the surfactant in the liquid material is 0.01%-3%; The ratio is 0%-5%; the mass ratio of the polymerization inhibitor in the liquid material is 0.05%-3%; the mass ratio of the antioxidant in the liquid material is 0.05%-3%; the plasticizer in the liquid material The mass ratio of the dispersant in the liquid material is 0%-25%; the mass ratio of the dispersant in the liquid material is 0%-5%.
  • the function of the leveling agent is to improve the fluidity of the liquid material and the wetting performance of the powder material, and at the same time adjust the surface tension of the liquid material to enable normal printing.
  • the leveling agent used can meet the above performance requirements, there is no restriction on which leveling agent to choose, for example, it can be BYK333, BYK377, BYK1798, BYK-UV3530, BYK-UV3575, BYK-UV3535, etc. , TEGO wet 500, TEGO wet 270, TEGO Glide450, TEGO RAD 2010, TEGO RAD 2011, TEGO RAD 2100, TEGO RAD 2200, etc.
  • the function of the defoamer is to inhibit, reduce and eliminate the bubbles in the liquid material.
  • the defoamer used can achieve the above effect, there is no restriction on which defoamer to choose.
  • it can be BYK055 and BYK088 of BYK. , BYK020, BYK025, etc., TEGO Airex 920, TEGO Airex 921, TEGO Airex 986, TEGO Foamex 810, TEGO Foamex N, etc. from Digao Company, Efka 7081, Efka7082, etc. from Efka Company.
  • the function of the polymerization inhibitor can be to improve the stability of the active component at high temperature, or to prevent the active component from polymerizing in a non-printing state, and to improve the storage stability of the liquid material.
  • it can be hydroquinone, p-hydroxyanisole, p-benzoquinone, 2-tert-butyl hydroquinone, phenothiazine, etc., and can be Rayon's GENORAD*16, GENORAD*18, GENORAD*20, GENORAD*22, etc., BASF's Tinuvin234, Tinuvin770, Irganox245, Cytec S100, Cytec 130, etc., Ciba's Irgastab UV10, Irgastab UV 22, etc.
  • the function of the surfactant is to adjust the surface tension of the active component suitable for inkjet printing, and to improve the fluidity of the composition and the wetting performance of the powder material.
  • it can be BYK333, BYK325N, BYK345, BYK346, BYK370, BYK800D of BYK company, TEGO 4000, TEGO WET 260, TEGO WET 270, TEGO WET KL245, TEGO Airex 920, TEGO Airex 921 of Digao company.
  • antioxidants are mainly to delay or inhibit the oxidation of polymers, such as 2,6-di-tert-butyl-4-methylphenol, ⁇ -tetra[3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionic acid] pentaerythritol ester, ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl ester, 1,1,3-tris(2-methyl- 4-Hydroxy-5-tert-butylphenyl)butane, 4-[(4,6-dioctylthio-1,3,5-triazin-2-yl)amino]-2,6-di-tert-butyl Ethyl phenol, dilauryl thiodipropionate, tris(nonylphenyl) phosphite, triphenyl phosphite, 2-
  • plasticizers are to improve the toughness of finished three-dimensional objects, such as dioctyl phthalate, butyl benzyl phthalate, diisononyl phthalate, and diisodecyl phthalate.
  • the function of the dispersant is mainly to improve and improve the dispersion stability of the colorant. For example, there is no restriction on which dispersant to choose.
  • the liquid material also includes a colorant, and based on the total mass of the liquid material being 100%, the mass proportion of the colorant in the liquid material is 0-10%, for example, it can be 0%, 1%, 2%, 4%, 6%, 8% or 10%. Of course, the mass ratio can also be matched according to the actual usage, which is not limited here.
  • the liquid material does not contain a colorant
  • the active component dissolves the powder material
  • the high molecular polymer formed by the polymerization reaction of the active component and the powder material are mixed at the molecular level. At this time, it is easy to obtain colorless or light-colored transparent three-dimensional objects.
  • Colored three-dimensional objects can be realized when the liquid material contains colorants.
  • Colorants can be dyes or pigments.
  • Pigment can be selected from CIPigment White 6, CIPigment Red 3, CIPigment Red 5, CIPigment Red 7, CIPigment Red 9, CIPigment Red 12, CIPigment Red 13, CIPigment Red 21, CIPigment Red 31, CIPigment Red 49:1, CIPigment Red 58:1, CIPigment Red 175; CIPigment Yellow 63, CIPigment Yellow 3, CIPigment Yellow 12, CIPigment Yellow 16, CIPigment Yellow 83; CIPigment Blue 1, CIPigment One or more of Blue 10, CI Pigment Blue B, Phthalocyanine Blue BX, Phthalocyanine Blue BS, CI Pigment Blue 61:1, etc.
  • the dyestuff can specifically be selected from CI acid red 37, CI acid red 89 (weak acid red 3B, 2BS), CI acid red 145 (weak acid scarlet GL), CI acid orange 67 (weak acid yellow RXL), CI acid orange 116 ( Acid orange AGT), CI acid orange 156 (weak acid orange 3G), CI acid yellow 42 (weak acid yellow Rs, acid yellow R), CI acid yellow 49 (acid yellow GR200), CI acid blue 277, CI acid blue 344 , CI Acid Blue 350, CI Acid Blue 9 (Brilliant Blue FCF), CI Green 17, CI Acid Green 28, CI Acid Green 41, CI Acid Green 81, CI Acid Violet 17 (Acid Violet 4BNS), CI Acid Violet 54 ( Weak acid brilliant red 10B), CI acid violet 48, CI acid brown 75, CI acid brown 98, CI acid brown 165, CI acid brown 348, CI acid brown 349, CI acid black 26, CI acid black 63,
  • the active components undergo a polymerization reaction to form the slice layer of the three-dimensional object, and no small molecular substances remain in the manufactured three-dimensional object, and no small molecular substances are precipitated during use, thus achieving a safe and environmentally friendly environment. Require.
  • liquid materials prepared according to the carboxyl group-containing active monomers prepared in Examples 1 to 4 have specific examples of components as shown in the following table:
  • the tensile strength test is determined according to GB/T 1040.2-2006 Determination Standard of Plastic Tensile Properties.
  • Density test Using the pycnometer method, with water as the reference, test the density of the sample at 25°C.
  • Test items S1 S2 S3 S4 Ref1 Tensile strength (MPa) 10.73 10.93 9.74 1.51 0.87 Shrinkage(%) -1.71 -1.37 -0.61 -0.63 -0.64 Density (g/cm 3 ) 1.061 1.061 1.058 0.971 0.904
  • the liquid materials provided in Examples 11 to 14 and Comparative Example 1 are combined with the test strips printed by polyamide (nylon 12) powder. According to Table 1, it can be seen that the liquid materials provided in Examples 11 to 14 respectively have carboxyl-containing activities. Monomers (D-11, D-21, D-31, D-41), carboxyl-containing reactive monomers dissolve polyamide (nylon 12) powder, and the liquid material provided in Comparative Example 1 does not contain carboxyl-containing reactive monomers body, only containing the second active component, the tensile strength of the final printed test strips S1-S4 is higher than that of Ref1.
  • the liquid material contains the first active component that can dissolve the polyamide (nylon 12) powder, and the polymer formed by the polymerization reaction of the first active component forms a blend with the dissolved polyamide (nylon 12) powder.
  • the material can be mixed at the molecular level to form a polymer alloy, which can effectively improve the mechanical strength of the final formed object.
  • liquid materials provided in Examples 11 to 14 are combined with the test strips printed with polyamide (nylon 12) powder, wherein the shrinkage of the test strips S2 to S4 is lower than that of the test strip S1.
  • Examples 12 to 14 contain both the first active component and the second active component, while Example 11 only contains the first active component and does not contain the second active component, and cannot form a complementary performance with the first active component.
  • the shrinkage rate of the three-dimensional object printed in Example 11 is higher than that of the three-dimensional objects printed in Examples 12-14. It should be noted that the "-" in the shrinkage rate data indicates that the size is smaller than the actual size.
  • FIG. 1 is a schematic structural diagram of a three-dimensional object additive manufacturing device provided by the application. As shown in FIG. 1 , an embodiment of the present application further provides a three-dimensional object additive manufacturing device.
  • the device includes:
  • the energy supply device 8 is used to provide energy to the powder material layer, so that the first active component in the liquid material undergoes a polymerization reaction, and the powder material itself does not undergo a polymerization reaction and does not interact with the first active component A polymerization reaction occurs separately, and the region where the liquid material is applied in the powder material layer is formed to obtain a sliced layer of a three-dimensional object.
  • the powder supply component 2 includes a powder storage chamber 23 , a lifter 22 and a powder spreader 21 .
  • the powder storage chamber is used to store powder materials 0 .
  • the powder storage chamber 23 has a movable support plate 231 inside.
  • the lifter 22 It is connected with the support plate 231, which can drive the support plate 231 to rise or fall in the Z direction; the powder spreader 21 is used to spread the powder material 0 in the powder storage cavity 23 onto the forming platform 3 to form the powder material layer L0.
  • the pulverizer 21 can be a pulverizing stick or a scraper.
  • the material distributor 6 is an inkjet print head, and the print head can be a single-pass print head or a multi-channel print head.
  • the number of print heads is related to the type of liquid material used and the amount of liquid material to be applied, For example, when the liquid material includes functional materials of different colors, the liquid materials of different colors are ejected through different print heads or different channels of the same print head. For example, when the amount of liquid material that needs to be applied is larger than the volume of a single ink droplet to meet the demand, in order to improve printing efficiency, multiple print heads or multiple channels can be used to eject the same kind of material at the same time.
  • the energy provided by the energy supply device 8 may be radiant energy or thermal energy, and the energy supply device may be selected from at least one of ultraviolet lamps, infrared lamps, microwave emitters, heating wires, heating sheets, and heating plates. It should be noted that the specific choice of which form of energy supply device and the type of active components in the liquid material is related to the type of active components and the type of the first auxiliary, when the active components in the liquid material undergo photopolymerization. During the reaction, the energy supply device 8 provides radiant energy such as ultraviolet radiation at this time, and the photopolymerization reaction of active components is triggered by ultraviolet radiation; when the thermal polymerization reaction of the active components occurs in the liquid material, the energy supply device provides thermal energy at this time. Such as infrared lamps, microwaves, heating wires, heating sheets, and heating plates, which can initiate thermal polymerization of active components through thermal energy.
  • the device for additive manufacturing of three-dimensional objects further includes a lifting mechanism 4, which is connected to the forming platform 3 and drives the forming platform 3 to ascend or descend in a vertical direction.
  • a lifting mechanism 4 which is connected to the forming platform 3 and drives the forming platform 3 to ascend or descend in a vertical direction.
  • the apparatus for additive manufacturing of three-dimensional objects further comprises a preheating part 5 and/or a heating part 10, and the preheating part 5 is used for preheating the powder material layer to promote the first in the liquid material.
  • the active component dissolves the powder material; the heating component 10 is used for heating the powder material layer after the liquid material is applied, so as to promote the first active component in the liquid material to dissolve the powder material.
  • the preheating part 5 and the heating part 10 can be selected from at least one of ultraviolet lamps, infrared lamps, microwave emitters, heating wires, heating sheets, and heating plates, respectively.
  • the preheating part 5 , the material distributor 6 , the heating part 10 and the energy supply device 8 can be installed on the guide rail 11 in sequence and can move on the guide rail 11 .
  • the energy supply device 8 is a device for providing thermal energy
  • the heating component 10 can be eliminated, and the energy supply device 8 is used to heat the powder material layer applied with the liquid material and initiate a polymerization reaction.
  • the three-dimensional object additive manufacturing apparatus may further comprise a temperature monitor (not shown in the figures) for monitoring the temperature of the powder material layer.
  • the three-dimensional object additive manufacturing device further includes a controller 9, which is used to control the powder supply part 2, the material distributor 6, the energy supply device 8, the preheating part 5, the operation of at least one of the heating component 10 and the temperature monitor.
  • the temperature monitor feeds back the monitored temperature to the controller 9, and the controller controls the amount of energy provided by the preheating part 5 and/or the heating part 10 and the energy supply device 8 according to the information fed back by the temperature monitor.
  • FIG. 2 is a schematic flowchart of the method for additive manufacturing of a three-dimensional object provided by the application, as shown in FIG. 2 , and the method for additive manufacturing of a three-dimensional object is further explained in detail below in conjunction with a device for additive manufacturing of a three-dimensional object:
  • Step S01 acquiring a digital model of a three-dimensional object, slicing and layering the digital model of the three-dimensional object, obtaining a plurality of slice layers and layer image data, and generating layer print data according to the layer image data.
  • the original data of the three-dimensional object can be obtained by scanning and three-dimensional modeling can be performed to obtain a digital model of the three-dimensional object, or the digital model of the three-dimensional object can be obtained by designing and constructing a three-dimensional object model, and the digital model can be formatted.
  • Conversion such as converting into STL format, PLY format, WRL format and other formats that can be recognized by slicing software, and then use slicing software to slice and layer the model to obtain slice layer image data, and process the layer image data to obtain a representation of the object.
  • layer print data includes information representing the shape of the object, and/or information representing the color of the object.
  • a powder material layer is formed by using a powder material.
  • the powder supply part 2 may be used to provide powder material 0 to the forming platform 3 to form a powder material layer L0 .
  • Step S11 preheating the powder material layer.
  • the preheating component 5 preheats the powder material layer L0 to increase the temperature of the powder material, which is helpful for the powder material layer L0 in step S20.
  • the rate of dissolution of the powder material by the first active ingredient is facilitated when the liquid material is applied thereon.
  • the preheating temperature is related to the properties of the powder material used, preferably the preheating temperature is below the melting point or melting temperature of the powder material.
  • the powder material can be prevented from sticking, which is conducive to the penetration of the liquid material into the gaps between the powder material particles, thereby improving the first active group. Dissolution rate of powder material.
  • Step S20 applying a liquid material on the powder material layer according to the layer printing data.
  • the material dispenser 6 can apply the liquid material 7 on the powder material layer L0 according to the layer printing data to form a layer patterned area 31; the liquid material 7 penetrates into the gap of the powder material and covers The surface layer of the powder material, thereby wetting the surface of the powder material.
  • the liquid material 7 comprises a first reactive component capable of polymerizing, which dissolves at least part of the powder material. As shown in FIG. 3d, the powder material in the layer patterned region 31 is dissolved by the first active component, so that the powder material and the active component are mixed at a molecular level.
  • Step S21 heating the powder material layer after applying the liquid material to promote the first active component in the liquid material to dissolve the powder material.
  • the heating member 10 heats the powder material layer L0 on the powder material layer L0 applied with the liquid material 7, which further promotes the first active component to dissolve the powder material, so that the powder material can be completely dissolved in a short time, and the powder
  • the material and the first active component are mixed at the molecular level and mixed evenly, so that the polymer and the powder material formed by the polymerization reaction of the first active component also reach the molecular level mixing, thereby forming a polymer alloy and improving the three-dimensional object formed. mechanical strength.
  • Step S30 supplying energy to the powder material layer to cause a polymerization reaction of the active components in the liquid material, and forming the region where the liquid material is applied in the powder material layer to obtain a slice layer of a three-dimensional object.
  • the energy supply device 8 provides energy to the powder material layer L0 to polymerize the active components to form a high molecular polymer to form the slice layer Lw of the three-dimensional object.
  • the energy provided by the energy supply device 8 can further promote the first active component to dissolve the powder material, the active component undergoes a polymerization reaction to form a high molecular polymer, and the formed high molecular polymer is formed with the powder material.
  • the blend especially the molecular-level mixing with the dissolved powder material, forms a polymer alloy, which makes the powder materials, between the powder materials and the polymer of the active component, and between the printing layers and the layers have good adhesion. connection effect.
  • the formed high molecular polymer can be mixed with the powder material to obtain a "sea-island structure" or a homogeneous structure with good interface bonding, which improves the mechanical strength of the three-dimensional object.
  • the material distributor 6 applies the liquid material 7 on the powder material layer L0 according to the layer printing data, and the spray amount of the liquid material can be adjusted to realize three-dimensional objects with different properties in different regions.
  • step S30 the method further includes: step S40, confirming whether the current slice layer is the last layer.
  • the forming platform 3 is driven by the lifting mechanism 4 to descend by at least one layer thickness, and the powder supply part 2 provides a new The powder material layer L0 is on top of the previously formed layer, the liquid material dispenser 6 applies the liquid material 7 according to the layer printing data to form a new layer patterned area 31 on the powder material layer L0, the energy supply device 8 supplies energy to the layer pattern to form a new slice layer of the three-dimensional object; this process is repeated to form the three-dimensional object W.
  • Step S50 when it is confirmed that the current slice layer is the last layer, heat treatment is performed on the formed three-dimensional object to improve the mechanical strength of the three-dimensional object.
  • the whole three-dimensional object W is heated by using the preheating part 5 and/or the heating part 10, or the whole three-dimensional object W is taken out and placed in a heating furnace for heating (Fig. Not shown), on the one hand, the powder dissolving effect is better, the porosity between powder materials is reduced, and the molded object is more dense, and on the other hand, the active component is further polymerized, thereby improving the tensile strength of the three-dimensional object W.
  • the embodiment of the present application further provides a slice layer of a three-dimensional object, where the slice layer of the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned three-dimensional molding material.
  • An embodiment of the present application further provides a three-dimensional object, wherein the three-dimensional object is formed by printing the three-dimensional object additive manufacturing process using the above-mentioned material for three-dimensional forming.

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Abstract

La présente invention concerne un matériau pour moulage tridimensionnel, et un objet tridimensionnel et une couche en tranches associés. Le matériau comprend : un matériau en poudre, comprenant une poudre de polyamide et/ou une poudre de polyamide modifiée; et un matériau liquide, comprenant un premier composant actif, le premier composant actif étant apte à la polymérisation, le premier composant actif dissolvant au moins une partie de la poudre de polyamide et/ou de la poudre de polyamide modifiée, et le matériau en poudre lui-même ne se polymérisant pas et ne polymérisant pas avec le premier composant actif. Le matériau pour moulage tridimensionnel et l'objet tridimensionnel et la couche en tranches associés dans des modes de réalisation de la présente invention peuvent améliorer efficacement la résistance mécanique et la densité d'un objet tridimensionnel.
PCT/CN2021/095866 2020-08-11 2021-05-25 Matériau pour moulage tridimensionnel, et objet tridimensionnel et couche en tranches associés WO2022033114A1 (fr)

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