WO2024001603A1 - Matériau d'impression tridimensionnel, objet tridimensionnel et procédé d'impression d'objet tridimensionnel - Google Patents

Matériau d'impression tridimensionnel, objet tridimensionnel et procédé d'impression d'objet tridimensionnel Download PDF

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WO2024001603A1
WO2024001603A1 PCT/CN2023/095278 CN2023095278W WO2024001603A1 WO 2024001603 A1 WO2024001603 A1 WO 2024001603A1 CN 2023095278 W CN2023095278 W CN 2023095278W WO 2024001603 A1 WO2024001603 A1 WO 2024001603A1
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printing material
dimensional printing
dimensional
prepolymer
dimensional object
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PCT/CN2023/095278
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English (en)
Chinese (zh)
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吕如松
李晓威
杨前程
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珠海赛纳三维科技有限公司
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Publication of WO2024001603A1 publication Critical patent/WO2024001603A1/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
    • C08F283/006—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
    • 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
    • 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
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Definitions

  • This application relates to the field of three-dimensional printing technology, and in particular to three-dimensional printing materials, three-dimensional objects, and three-dimensional object printing methods.
  • the main process of three-dimensional object printing technology is to obtain a digital model of a three-dimensional object, slice and layer the digital model, and perform data processing and conversion on each slice layer to obtain the printing data of each slice layer.
  • the printing device The printing data is printed layer by layer and superimposed to create a three-dimensional object.
  • Three-dimensional object printing technology mainly includes stereolithography technology (SLA technology for short), digital light processing technology (DLP technology for short), continuous liquid surface manufacturing technology (CLIP technology for short), three-dimensional inkjet printing technology, etc., which are all based on liquid photosensitivity.
  • SLA technology stereolithography technology
  • DLP technology digital light processing technology
  • CLIP technology continuous liquid surface manufacturing technology
  • three-dimensional inkjet printing technology etc., which are all based on liquid photosensitivity.
  • the material undergoes a cross-linking reaction under UV light irradiation and solidifies to form a three-dimensional object.
  • 3D printing materials are crucial to the properties of 3D objects.
  • 3D inkjet printing technology 3D objects printed with existing light-curing 3D inkjet printing materials have poor toughness, are prone to environmental stress cracking, and are weather-resistant.
  • toughening particles are added to light-curing three-dimensional inkjet printing materials to improve the toughness of the three-dimensional object, it is easy to cause the strength of the three-dimensional object to decrease, and the viscosity of the three-dimensional printing material containing toughening particles is higher. If it is used Three-dimensional inkjet printing may cause clogging of the print head. Therefore, it is particularly critical to find a material for three-dimensional inkjet printing that has both hardness and toughness requirements.
  • Embodiments of the present application provide three-dimensional printing materials, three-dimensional objects, and three-dimensional object printing methods. By improving and adjusting the components of the three-dimensional printing materials, the discharge stability of the three-dimensional printing materials can be ensured when using the three-dimensional printing materials.
  • Three-dimensional objects formed from three-dimensional printing materials can have both hardness and toughness, and have strong resistance to environmental stress cracking and temperature resistance.
  • this application provides a three-dimensional printing material.
  • the three-dimensional printing material includes according to mass percentage:
  • the first photocurable component includes a first prepolymer and reactive monomer
  • the second photocurable component includes a second prepolymer
  • the first prepolymer The number average molecular weight is smaller than the number average molecular weight of the second prepolymer, and the surface tension of the first prepolymer is different from the surface tension of the second prepolymer.
  • the first prepolymer and the second prepolymer are independently selected from at least one of polyester acrylate, polyether acrylate, polyurethane acrylate and pure acrylic resin.
  • the reactive monomer is selected from (meth)acrylate monomer, (meth)acrylate derivative, N-acryloylmorpholine, N-vinylpyrrolidone, vinyl ether , vinyl ether derivatives, at least one of acrylamide and acrylamide derivatives.
  • the three-dimensional printing material meets at least one of the following characteristics:
  • the surface tension ⁇ 1 of the first prepolymer is greater than the surface tension ⁇ 2 of the second prepolymer, and satisfies 10mN/m ⁇ ( ⁇ 1- ⁇ 2) ⁇ 15mN/m.
  • the compatibility accelerator is selected from (meth)acryloyloxysilane, cycloaliphatic (meth)acrylate monomers, and propoxylated (meth)acrylate At least one of the monomers.
  • the mass percentage of the first prepolymer in the first photocurable component is 5% to 15%, and the active monomer is in the first photocurable component.
  • the mass percentage of the components is 85% to 95%.
  • the three-dimensional printing material meets at least one of the following characteristics:
  • the surface tension of the first photocurable component is 35mN/m ⁇ 45mN/m;
  • the surface tension of the active monomer is 32 ⁇ 45mN/m;
  • the surface tension of the second photocurable component is 25mN/m ⁇ 30mN/m;
  • the surface tension of the compatible accelerator is 25mN/m ⁇ 32mN/m.
  • the three-dimensional printing material also includes: 0.05% to 8% of auxiliary agents in terms of mass percentage.
  • the auxiliary agents include retarder, leveling agent, dispersant and colorant. At least one.
  • the three-dimensional printing material also includes: retarder 0.01% to 3%, leveling agent 0.01% to 3%, dispersant 0% to 5%, and coloring in terms of mass percentage. Agent 0% ⁇ 5%.
  • the retarder is selected from at least one of antioxidants and polymerization inhibitors.
  • the photoinitiator is selected from at least one of ⁇ -hydroxyketone initiators, acylphosphorus oxide compounds, ⁇ -aminoketones and thioxanthone initiators.
  • the present application provides a three-dimensional object, which is printed and formed by a three-dimensional object additive manufacturing process using the above-mentioned three-dimensional printing material.
  • the three-dimensional object includes a continuous phase and a dispersed phase dispersed around the continuous phase, wherein the continuous phase is formed by the first photocurable component in the three-dimensional printing material through light The dispersed phase is formed after a curing reaction of the second photocurable component in the three-dimensional printing material.
  • the three-dimensional object satisfies at least one of the following characteristics:
  • the glass transition temperature of the continuous phase is 50 to 150°C;
  • the glass transition temperature of the dispersed phase is -40 to -10°C.
  • this application provides a three-dimensional object printing method, which method includes:
  • the above-mentioned three-dimensional printing material is used to form a material layer
  • Energy is provided to solidify at least part of the material layer to form a slice layer, wherein the first photo-curable component in the three-dimensional printing material forms a continuous phase after curing, and the second photo-curable component in the three-dimensional printing material After solidification, a dispersed phase is formed;
  • This application provides a three-dimensional printing material and a three-dimensional object.
  • two photo-curing components with poor compatibility are blended to form a uniform and stable system to ensure the discharge stability of the three-dimensional printing material; photo-curing After the reaction, phase separation occurs due to poor structural compatibility of the two photocurable components.
  • the second photocurable component with a large number average molecular weight can form a dispersed phase
  • the first photocurable component with a small number average molecular weight can form a continuous phase.
  • the dispersed phase toughens the continuous phase without significantly reducing the glass transition temperature of the continuous phase. It has strong environmental stress cracking resistance and temperature resistance, and can take into account both strength and toughness.
  • Figure 1 is a schematic flow chart of a three-dimensional printing method provided by an embodiment of the present application.
  • Figure 2 is a schematic structural diagram of a three-dimensional printing device provided by an embodiment of the present application.
  • 1-Material container 2-Ink supply tube; 3-Inkjet print head; 4-3D printing material; 5-Leveling components; 6-Energy supply device; 7-Guide rail; 8-Support platform; 9-Lifting mechanism; 10-Controller; 11-molding chamber; 12-three-dimensional object.
  • the three-dimensional printing material includes according to mass percentage: 40% to 80% of the first photocurable component, 5% to 50% of the second photocurable component, and 5% of the compatible accelerator. ⁇ 15% and photoinitiator 0.5% ⁇ 10%; wherein, the first photocurable component includes a first prepolymer and an active monomer, and the second photocurable component includes a second prepolymer, so The number average molecular weight of the first prepolymer is smaller than the number average molecular weight of the second prepolymer, and the surface tension of the first prepolymer is different from the surface tension of the second prepolymer.
  • the three-dimensional printing material includes a first photo-curing component and a second photo-curing component with poor structural compatibility.
  • the two are blended through a compatible accelerator to form a uniform and stable system to ensure that the three-dimensional printing material
  • the discharge stability of the three-dimensional printing material can effectively prevent the three-dimensional printing material from clogging the print head; after the curing reaction, the first photo-curing component including the first prepolymer with a small number average molecular weight solidifies to form a continuous phase of the three-dimensional object, including a large number average molecular weight
  • the second photocurable component of the second prepolymer solidifies to form the dispersed phase of the three-dimensional object, so that the three-dimensional object can have both the high strength brought by the continuous phase and the high toughness brought by the dispersed phase. In this way, both three-dimensional and The object has high strength and toughness, and has strong resistance to environmental stress cracking and temperature resistance.
  • the continuous phase refers to a substance that disperses other substances in the system.
  • the continuous phase is mainly responsible for the mechanical properties of the system.
  • the continuous phase has high stability and can improve the strength of three-dimensional objects.
  • Dispersed phase refers to substances that exist in the form of fine particles in a dispersed system.
  • the dispersed phase and the continuous phase form a "sea-island structure".
  • the dispersed phase, as an island in the "sea-island structure" can enhance the strength of three-dimensional objects. and resilience.
  • Compatibility accelerator refers to the use of intermolecular bonding forces to promote the combination of two incompatible polymers to obtain a stable blend. Due to the difference in number average molecular weight and surface tension, the first prepolymer and the second prepolymer have poor compatibility. Through the action of the compatibility accelerator, the two can be blended to obtain a uniform and stable system, ensuring The discharge stability of 3D printing materials can effectively prevent 3D printing materials from clogging the print head.
  • 3D inkjet printing technology has higher requirements on the viscosity and smoothness of the 3D printing materials used.
  • the viscosity of the 3D printing material needs to be reduced to suitable
  • the viscosity of normal jetting such as 8cp ⁇ 15cp, especially when the normal operating temperature of the print head is lower than 80°C, requires the viscosity of the 3D printing material to drop to a viscosity suitable for normal jetting in an instant, which requires the 3D printing material to be It has a lower viscosity at room temperature of 25°C, such as less than 50cp.
  • the three-dimensional printing materials provided in some examples of this application have a viscosity of 10cp to 60cp at 25°C and a surface tension of 20mN/m to 35mN/m; and a viscosity of 8cp to 15cp at an operating temperature of 30°C to 70°C. , Surface tension is 20mN/m ⁇ 35mN/m.
  • the printing material has a viscosity and surface tension suitable for print head ejection, which not only facilitates the smooth progress of three-dimensional printing, but also saves energy consumption and effectively extends the service life of the print head.
  • the printed three-dimensional object can basically have excellent mechanical properties and temperature resistance, especially excellent strength, toughness and environmental stress cracking resistance.
  • the first photo-curing component includes a first prepolymer and a reactive monomer. Based on the mass of the first photo-curing component being 100%, the first pre-polymer is in the first photo-curing component. The mass percentage content of the active monomer in the first photocurable component is 5% to 15%, and the mass percentage content of the active monomer in the first photocurable component is 85% to 95%.
  • the first prepolymer is selected from at least one of polyester acrylate, polyether acrylate, polyurethane acrylate and pure acrylic resin.
  • the first prepolymer is preferably polyether acrylate or polyurethane acrylate, such as Bomar's BR-372, Sartomer's CN981NS, N3D-I2939, RAHN's Genomer2235, etc. first pre-gathering
  • the mass percentage content of the material in the first photocurable component can specifically be 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14% or 15%, etc., which is not limited here.
  • the reactive monomer can be used to improve the rheology of the first prepolymer, and under the action of the photoinitiator, the reactive monomer and the first prepolymer undergo a photocuring reaction together, which can increase the curing speed while obtaining higher strength.
  • the first photo-curing component including the first prepolymer and the reactive monomer can ensure the fluidity and curing efficiency of the first photo-curing component.
  • the reactive monomer is selected from (meth)acrylate monomers, (meth)acrylate derivatives, N-acryloylmorpholine (ACMO), N-vinylpyrrolidone, vinyl ethers, ethylene At least one of ether derivatives, acrylamide and acrylamide derivatives.
  • the (meth)acrylate monomer can be Sartomer's SR833NS, SR531, Changxing's EM214, etc.
  • the mass percentage content of the reactive monomer in the first photocurable component can specifically be 85%, 86%, 87%, 88%, 89%, 90%, 92%, 94% or 95%, etc., and is not limited here. .
  • the surface tension of the first photocurable component is 35mN/m ⁇ 45mN/m, specifically it can be 35mN/m, 36mN/m, 38mN/m, 40mN/m, 41mN/m, 42mN/m, 43mN/m or 45mN. /m, etc., are not limited here.
  • the surface tension of the active monomer is 32mN/m ⁇ 45mN/m, specifically it can be 32mN/m, 33mN/m, 34mN/m, 35mN/m, 36mN/m, 38mN/m, 40mN/m, 43mN/m or 45mN/m, etc., not limited here.
  • the second photocurable component includes a second prepolymer.
  • the second photocurable component is a second prepolymer.
  • the second prepolymer is selected from at least one of polyester acrylate, polyether acrylate, polyurethane acrylate, and pure acrylic resin.
  • the second prepolymer is preferably polyester acrylate or polyurethane acrylate, such as Sartomer's CN8899NS, CN8891NS, Kyoeisha UFC052, etc.
  • the number average molecular weight M1 of the first prepolymer is less than the number average molecular weight M2 of the second prepolymer, and the surface tension ⁇ 1 of the first prepolymer is greater than that of the second prepolymer.
  • 500 ⁇ the number average molecular weight M1 of the first prepolymer ⁇ 3000, and the value of M1 can specifically be 500, 800, 1000, 1200, 1500, 1800, 2000, 2500, 2800 or 3000, etc., which are not specified here.
  • 3000 ⁇ the number average molecular weight M2 of the second prepolymer ⁇ 15000, the value of M1 can specifically be 3050, 3200, 3500, 4000, 5000, 8000, 9000, 10000 or 15000, etc., which is not limited here.
  • the surface tension ⁇ 1 of the first prepolymer is greater than the surface tension ⁇ 2 of the second prepolymer, and satisfies the value range of 10mN/m ⁇ ( ⁇ 1- ⁇ 2) ⁇ 15mN/m, ( ⁇ 1- ⁇ 2) It is 10mN/m, 11mN/m, 12mN/m, 13mN/m, 14mN/m or 15mN/m, etc., which is not limited here.
  • the surface tension of the first photocurable component is 35mN/m ⁇ 45mN/m, specifically, it can be 35mN/m, 36mN/m, 38mN/m, 40mN/m, 42mN/m or 45mN/m. etc. are not limited here.
  • the surface tension of the second photocurable component is 25mN/m ⁇ 30mN/m, specifically 25mN/m, 26mN/m, 27mN/m, 28mN/m, 29mN/m or 30mN/m. etc. are not limited here.
  • the glass transition temperature (Tg) of the first photocurable component after photocuring reaction is 50°C to 150°C, specifically, it can be 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 100°C, 120°C or 150°C, etc.
  • the glass transition temperature (Tg) of the second photocurable component after the photocuring reaction is -40°C to -10°C, specifically -40°C, -35°C, -30°C, -25°C, -20°C , -15°C or -10°C, etc.
  • the glass transition of the first photo-curable component after the photo-curing reaction will not be significantly reduced after the photo-curing reaction of the second photo-curable component temperature, therefore, the first light-curing component can make the three-dimensional object have a higher thermal deformation temperature, and the second light-curing component can make the three-dimensional object have strong resistance to environmental stress and prevent the three-dimensional object from cracking.
  • the structural compatibility between the two is poor. Furthermore, due to the poor compatibility between the first photocurable component and the second photocurable component, after the photocuring reaction, the first photocurable component with a small number average molecular weight forms a continuous phase of the three-dimensional object, and the second photocurable component with a large number average molecular weight forms a continuous phase of the three-dimensional object.
  • the photocurable component forms the dispersed phase of the three-dimensional object, and the dispersed phase and the continuous phase form a "sea-island structure", in which the continuous phase acts as the sea in the "sea-island structure", the continuous phase ensures strength, and the dispersed phase acts as the "sea-island structure"
  • the islands in the "island structure” are dispersed and toughen the relative continuous phase, ensuring the high strength and toughness of the three-dimensional object.
  • the surface tension of the compatibility accelerator is 25 mN/m ⁇ 32 mN/m, which is used to promote the blending of the first photocurable component and the second photocurable component, and the compatibility accelerator and the photoinitiator It can undergo a photocuring reaction together with the second prepolymer, ensuring the uniformity and stability of the three-dimensional printing material system and at the same time, the three-dimensional object can obtain high toughness.
  • the compatibility accelerator is selected from at least one of (meth)acryloyloxysilane, alicyclic (meth)acrylate monomer and propoxylated (meth)acrylate monomer.
  • it can be 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyltriisopropoxysilane, Sartomer's SR420NS, SR506EG and so on.
  • the photoinitiator of this application is a free radical photoinitiator.
  • the free radical photoinitiator may be selected from at least one of ⁇ -hydroxyketone initiators, acylphosphorus oxide compounds, ⁇ -aminoketones and thioxanthone initiators.
  • it can be photoinitiator 1173, photoinitiator 183, photoinitiator TPO, photoinitiator TPO-L, photoinitiator 819, photoinitiator 369, photoinitiator 907, photoinitiator ITX, photoinitiator Agent DETX etc.
  • the three-dimensional printing material also includes: 0.05% to 8% of additives based on mass percentage.
  • the auxiliary agent is selected from at least one of retarder, leveling agent, dispersant and colorant.
  • the three-dimensional printing material also includes: retarder 0.01% to 3%, leveling agent 0.01% to 3%, dispersant 0% to 5%, and colorant 0% to 5% in terms of mass percentage. .
  • the retarder is selected from at least one of antioxidants and polymerization inhibitors.
  • the main function of antioxidants is to delay or inhibit polymer oxidation.
  • they can be antioxidant 1010, antioxidant 168, antioxidant 292, etc.
  • the main function of the polymerization inhibitor is to prevent the free radicals from polymerizing and improve the storage stability of the material.
  • the polymerization inhibitor can be selected from at least one of phenols, quinones or nitrite polymerization inhibitors, such as hydroquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol At least one of the others.
  • the mass percentage of the retarder in the three-dimensional printing material is 0.01% to 3%, for example, it can be 0.01%, 0.05%, 0.08%, 0.1%, 0.3 %, 0.5%, 0.8%, 1.5%, 1.8%, 2%, 2.5% or 3%.
  • its mass percentage can also be proportioned according to actual usage conditions, and is not limited here.
  • Leveling agents are mainly used to improve the fluidity of liquid 3D printing materials and adjust the surface tension of the materials to enable normal printing. As long as the leveling agent can meet the above performance requirements, this application does not place specific restrictions on the selection of leveling agents.
  • the mass percentage of the leveling agent in the three-dimensional printing material is 0.01% to 3%, for example, it can be 0.01%, 0.05%, 0.08%, 0.1%, 0.3 %, 0.5%, 0.8%, 1.5%, 1.8%, 2%, 2.5% or 3%.
  • its mass percentage can also be proportioned according to actual usage conditions, and is not limited here.
  • the main function of dispersants is to improve the dispersion stability of particles in materials. As long as the dispersant can meet the above performance requirements, there is no specific limit on the selection of the dispersant in this application.
  • dispersant There are many products currently on the market, including BYK102, BYK106, BYK108, BYK110, BYK111, BYK180, Digo Dispers 655, Dispers675, Dispers710, Dispers 630, Dispers 670, etc.
  • the mass percentage of the dispersant in the three-dimensional printing material is 0% to 5%, for example, it can be 0%, 1%, 2%, 2.5%, 3% , 3.5%, 4% or 5%. Of course, its mass percentage can also be proportioned according to actual usage conditions, and is not limited here.
  • the material of this application does not contain colorants, the material is transparent, and the printed products have high transparency.
  • the transparency can reach 90%, 80%, 70%, 60%, 50%, etc., which is not limited here.
  • the colorant can be a pigment or a dye.
  • the colorant is preferably a pigment.
  • the pigment can be specifically selected from CIPigment White 6, CIPigment Red 3, CIPigment Red 5, CIPigment Red 7, CIPigment Red9, CIPigment Red 12, CIPigment Red 13, CIPigment Red 21, CIPigment Red31, CIPigment Red49:1, CIPigment Red 58:1, CIPigment Red 175; CIPigment Yellow 63, CIPigment Yellow 3, CIPigment Yellow 12, CIPigment Yellow 16, CIPigment Yellow 83; one or more of CIPigment Blue 1, CIPigment Blue 10, CIPigment Blue B, Phthalocyanine Blue BX, Phthalocyanine Blue BS and CIPigment Blue 61:1.
  • the mass percentage of the colorant in the three-dimensional printing material is 0 to 5%, for example, it can be 0%, 1%, 2%, 2.5%, 3%, 3.5%, 4% or 5%. Of course, its mass percentage can also be proportioned according to actual usage conditions, and is not limited here.
  • Each component of the three-dimensional printing material of the present application can exist stably under light-proof conditions, so it has high stability and can be transported and stored for a long time. Moreover, the viscosity of the three-dimensional printing material is low and will not block the nozzle holes of the print head. Phenomenon.
  • phase separation occurs due to the poor structural compatibility of the two photo-curing components.
  • the second photo-curing component with a large number average molecular weight forms a dispersed phase
  • the first photo-curing component with a small number average molecular weight forms a dispersed phase.
  • the components form a continuous phase, and the dispersed phase acts as a toughener for the continuous phase without significantly reducing the glass transition temperature of the continuous phase, making the printed three-dimensional object both highly resistant to environmental stress and temperature, and not prone to cracking. , and can take into account both strength and toughness.
  • the number average molecular weight of the first prepolymer N3D-I2939 is about 1500, the number average molecular weight of Genomer 2235 is about 500, and the number average molecular weight of BR-372
  • the number average molecular weight is about 3,000; the number average molecular weight of the second prepolymer CN8899NS is about 15,000, the number average molecular weight of UFC052 is about 10,000, and the number average molecular weight of CN8891NS is about 3,000.
  • the number average molecular weight of the first prepolymer MIRAMER PU210 was tested using gel chromatography column method to be less than 3000, and the number average molecular weight of the second prepolymer MIRAMER PU340 was less than 3000.
  • a second aspect of this application provides a three-dimensional printing method using the three-dimensional printing material of the first aspect.
  • Figure 2 is a flow chart of the three-dimensional printing method of this application, which includes the following steps:
  • S2 Provide energy to solidify at least part of the material layer to form a slice layer, wherein the first photo-curable component in the three-dimensional printing material solidifies to form a continuous phase, and the second photo-curable component solidifies to form a dispersed phase;
  • the execution subject of the above-mentioned printing method may be a printing device.
  • the printing device realizes the above-mentioned steps S1 to S3 by controlling the distribution of three-dimensional printing materials and the curing process, and finally manufactures a three-dimensional object.
  • Figure 2 is a schematic structural diagram of a three-dimensional object printing device provided by the present application. As shown in Figure 2, an embodiment of the present application also provides a three-dimensional object forming device for implementing the above three-dimensional object printing method.
  • the device includes:
  • Inkjet print head 3 is used to provide three-dimensional printing material 4 to form a material layer
  • Support platform 8 used to carry the material layer
  • Energy supply device 6 is used to provide energy to solidify at least part of the material layer.
  • the inkjet print head 3 may be a single-channel print head or a multi-channel print head, or a combination of a single-channel print head and a multi-channel print head.
  • the number of inkjet print heads 3 is at least one, and the number of inkjet print heads 3 depends on the amount of three-dimensional printing material used. In other embodiments, the number of inkjet print heads 3 may also be related to the type of three-dimensional printing material used and the amount that needs to be applied. For example, when the liquid phase three-dimensional printing material includes functional materials of different colors, different colors of 3D printing materials are ejected through different inkjet printheads or through different channels of the same inkjet printhead.
  • the volume of a single ink droplet is not enough to meet the needs.
  • multiple inkjet print heads or multiple channel jets can be used for inkjet printing at the same time.
  • the energy provided by the energy supply device 6 may be radiant energy or thermal energy. In this embodiment, the energy provided by the energy supply device 6 is radiant energy.
  • the energy supply device 6 is an ultraviolet LED lamp, a mercury lamp, a metal halide lamp, or an electrodeless lamp. , xenon lamp, etc.
  • the device may also include a material container 1 and an ink supply tube 2.
  • the material container 1 is used to store three-dimensional printing materials and can transport the three-dimensional printing materials stored therein to the print head through the ink supply tube 2.
  • the three-dimensional object printing device of the present application may also include a lifting mechanism 9, which is connected to the support platform 8 and drives the support platform 8 to rise or fall in the vertical direction to change the height of the support platform 8 and The relative distance between the inkjet print head 3 in the Z direction, thereby continuously forming slices layer by layer and stacking them layer by layer to form the three-dimensional object 12.
  • a lifting mechanism 9 which is connected to the support platform 8 and drives the support platform 8 to rise or fall in the vertical direction to change the height of the support platform 8 and The relative distance between the inkjet print head 3 in the Z direction, thereby continuously forming slices layer by layer and stacking them layer by layer to form the three-dimensional object 12.
  • the three-dimensional object printing device of the present application may also include a leveling component 5 located between the inkjet print head 3 and the energy supply device 6 for leveling the material layer.
  • the leveling component 5 may be a leveling rod, and the distributed excess three-dimensional printing material is taken away by the rotation of the leveling rod.
  • the inkjet print head 3 , the leveling component 5 and the energy supply device 6 are all installed on the carriage (not shown in FIG. 2 ), and the carriage moves back and forth on the guide rail 7 .
  • Material container 1, ink supply tube 2, inkjet print head 3, three-dimensional printing material 4, leveling component 5, energy supply device 6, guide rail 7, support platform 8 and lifting mechanism 9 are all arranged in the molding chamber 11.
  • Chamber 11 may be a sealed chamber.
  • the three-dimensional object printing device of the present application may also include a controller 10 , which is used to control the operation of at least one of the inkjet print head 3 , the energy supply device 6 , the lifting mechanism 9 and the leveling component 5 .
  • the controller 10 can control the inkjet print head 3 to distribute the three-dimensional printing material 4 according to the layer printing data.
  • the controller 10 can control the radiation intensity and radiation time of the material layer by the energy supply device 6.
  • the controller 10 can control The relative distance between the support platform 8 and the inkjet print head 3 in the Z direction, etc.
  • the specific process of using the three-dimensional object forming device to implement three-dimensional printing can be:
  • the 3D printing material can be preheated as needed.
  • the inkjet print head 3 uses the three-dimensional printing material to form a material layer on the support platform 8 according to the layer printing data.
  • the layer printing data is data representing the cross-section of the three-dimensional object.
  • This application is not limited to the acquisition method of the layer printing data. Any acquisition method of the layer printing data in the three-dimensional object printing process in this field can be used, for example, three-dimensional Before printing the object, it is necessary to obtain the model data of the three-dimensional object and convert the model data into a data format, such as STL format, PLY format, WRL format and other formats that can be recognized by the slicing software. Use the slicing software to process the model.
  • Slice layering is processed to obtain data representing the cross-section layer of the object, which is also called 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 energy supply device 6 irradiates the material layer to solidify at least part of the material layer to form a slice layer.
  • the first photo-curable component in the three-dimensional printing material forms a continuous phase after curing
  • the second photo-curable component in the three-dimensional printing material forms a dispersed phase after curing.
  • the controller 10 controls the lifting mechanism 9 to drive the support platform 8 to move down a certain distance (for example, one layer thickness) in the height direction (ie, the Z direction), so that there is enough space to accommodate the new slice layer.
  • Slice layer then after forming a slice layer according to the above S1-S2, repeat the above steps S1-S2, that is, continue to form a material layer on the surface of the previous slice layer, and solidify the material layer to form a new slice layer.
  • a three-dimensional object 12 is formed.
  • This application uses an energy supply device to provide energy to the material layer, so that the three-dimensional printing material undergoes a photocuring reaction and becomes a solidified or semi-solidified state.
  • the specific energy may be UV light.
  • phase separation occurs due to the poor structural compatibility of the two photocurable components.
  • the second photocurable component with a large number average molecular weight forms the dispersed phase of the three-dimensional object, and the first photocurable component with a small number average molecular weight forms a dispersed phase.
  • the continuous phase of a three-dimensional object can form a three-dimensional object with a phase separation structure.
  • the dispersed phase acts as a toughener for the continuous phase and does not significantly reduce the glass transition temperature of the continuous phase. It has strong resistance to environmental stress cracking. and temperature resistance, and three-dimensional objects can have both high strength and high toughness.
  • This application uses the three-dimensional printing materials provided in Examples 1-4 and Comparative Examples 1-4, and prints three-dimensional objects through the three-dimensional printing device and three-dimensional printing method, and conducts the following performance tests on the three-dimensional objects. The specific results are shown in the table 3, 4.
  • the viscosity of 3D printing materials was tested using a DV-I digital viscometer.
  • a platinum plate surface tensiometer was used to test the surface tension of each component of the three-dimensional printing material.
  • Senna J501 3D light-curing inkjet printer uses the Senna J501 3D light-curing inkjet printer to continuously print 3D printing materials for 4 hours. Test the ink output of the nozzle before and after printing. There are no more than 10 broken lines before and after printing, which means the printing fluency is ok and the test is passed.
  • the measured performance test results of the three-dimensional printing materials provided in Examples 1 to 4 and Comparative Examples 1-4 are shown in Table 3.
  • the measured performance test results of the three-dimensional printing materials provided in Examples 1 to 4 and Comparative Examples 1-4 are made of The performance test results of the three-dimensional object are shown in Table 4.
  • the three-dimensional printing materials provided in this application are suitable for inkjet printing; and, the three-dimensional objects (Examples 1-4) printed using the three-dimensional printing materials have high mechanical properties.
  • three-dimensional objects have excellent tensile strength, bending strength, impact strength, and Shore hardness, and have a high thermal deformation temperature, that is, three-dimensional objects have high temperature resistance.
  • Example 3 due to the higher content of the second prepolymer, the tensile strength and flexural strength are slightly weaker, but the impact strength is the highest. This is because the dispersed phase formed by the second photocurable component increases, and more dispersed phases can The toughness of three-dimensional objects is further improved, that is, the impact resistance is increased.
  • the first photocurable component and the second photocurable component are compatible, making it difficult to generate a continuous phase and a dispersed phase, and the resulting three-dimensional object has poor toughness (impact strength).
  • Comparative Example 3 no compatible accelerator is used, so the first photocurable component and the second photocurable component cannot form a uniform system, and the inkjet printing fluency is extremely poor, so it is not suitable for inkjet printing.
  • Comparative Example 4 uses a second prepolymer with a smaller number average molecular weight, which makes it difficult to generate a continuous phase and a dispersed phase, and the three-dimensional object formed has poor mechanical properties (tensile strength, bending strength, impact strength).

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Abstract

La présente invention concerne un matériau d'impression tridimensionnel, un objet tridimensionnel et un procédé d'impression de l'objet tridimensionnel. Le matériau d'impression tridimensionnel comprend, en pourcentage en poids, 40 % à 80 % d'un premier constituant photodurcissable, 5 % à 50 % d'un second constituant photodurcissable, 5 % à 15 % d'un accélérateur de compatibilité et 0,5 % à 10 % d'un photo-initiateur, le premier constituant photodurcissable comprenant un premier prépolymère et un monomère actif, le second constituant photodurcissable comprenant un second prépolymère, le poids moléculaire moyen en nombre du premier prépolymère étant inférieur à celui du second prépolymère, et la tension de surface du premier prépolymère étant différente de celle du second prépolymère. Selon le matériau d'impression tridimensionnel et l'objet tridimensionnel fournis par la présente invention, la stabilité d'évacuation du matériau d'impression tridimensionnel peut être assurée et l'objet tridimensionnel formé à l'aide du matériau d'impression tridimensionnel peut répondre à la fois à la dureté et à la ténacité et présente une résistance à la fissuration sous contrainte environnementale et une résistance à la température relativement fortes.
PCT/CN2023/095278 2022-06-28 2023-05-19 Matériau d'impression tridimensionnel, objet tridimensionnel et procédé d'impression d'objet tridimensionnel WO2024001603A1 (fr)

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