WO2022041885A1 - Matériau élastique pour impression 3d et procédé de préparation associé, et procédé et dispositif d'impression - Google Patents

Matériau élastique pour impression 3d et procédé de préparation associé, et procédé et dispositif d'impression Download PDF

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WO2022041885A1
WO2022041885A1 PCT/CN2021/096183 CN2021096183W WO2022041885A1 WO 2022041885 A1 WO2022041885 A1 WO 2022041885A1 CN 2021096183 W CN2021096183 W CN 2021096183W WO 2022041885 A1 WO2022041885 A1 WO 2022041885A1
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printing
elastic material
layer
self
photocurable
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PCT/CN2021/096183
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Chinese (zh)
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杨前程
何兴帮
余嘉
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珠海赛纳三维科技有限公司
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Publication of WO2022041885A1 publication Critical patent/WO2022041885A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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

Definitions

  • the present application relates to a material, in particular to an elastic material for 3D printing and its preparation method, printing method and device, belonging to the technical field of 3D printing.
  • 3D printing technology is called rapid prototyping technology, rapid prototyping technology, additive manufacturing technology, etc. Its basic principle is to slice the 3D model based on slicing software, and the data processor converts the sliced data of the 3D model into layer printing data.
  • the controller controls the printing device to perform layer-by-layer printing according to the layer printing data, and superimpose to form a 3D object.
  • 3D printing technology mainly includes stereo light curing technology (SLA technology for short), digital light processing technology (DLP technology for short), continuous liquid surface manufacturing technology (CLIP technology for short), 3D inkjet printing technology, etc., which are based on
  • SLA technology stereo light curing technology
  • DLP technology digital light processing technology
  • CLIP technology continuous liquid surface manufacturing technology
  • 3D inkjet printing technology etc., which are based on
  • the 3D object is formed by the principle that the liquid photosensitive material undergoes a cross-linking reaction under the irradiation of ultraviolet light and is cured and formed.
  • 3D printing materials are crucial to the properties of 3D objects, especially the development of high-performance elastomer materials for printing elastic 3D objects is still unsatisfactory.
  • the existing light-curing 3D inkjet printing elastomer materials are mainly acrylate systems.
  • the elastic 3D objects printed by such elastomer materials have low strength, poor tear resistance, and sticky surface. question.
  • the present application provides an elastic material for 3D printing.
  • the 3D object obtained by using the elastic material for 3D printing not only has excellent mechanical properties, but also has excellent tensile strength, elongation at break and tear It has excellent crack strength, and also has a good touch, and the surface is refreshing and non-sticky.
  • the present application also provides a method for preparing an elastic material for 3D printing, which can safely and efficiently prepare an elastic material for 3D printing that helps to improve the mechanical properties and tactility of a 3D object.
  • the present application also provides a 3D printing method, which can make the 3D object take into account excellent mechanical properties on the premise of achieving high precision of the 3D object.
  • the present application also provides a 3D object, which not only has excellent mechanical properties, especially tensile strength, elongation at break and tear strength, but also has a good touch, and the surface is refreshing and non-sticky.
  • the present application also provides a 3D printing device for implementing the aforementioned 3D printing method.
  • a first aspect of the present application provides an elastic material for 3D printing
  • the elastic material for 3D printing includes: self-blocking isocyanate, photocurable monofunctional monomer, photocurable crosslinking agent, photoinitiator and auxiliary agent; the The molecular structure of the self-blocking isocyanate contains a uretdione structure and no isocyanate group, and the molecular structure of the photocurable monofunctional monomer contains a vinyl group.
  • the above-mentioned self-blocking isocyanate refers to a dimer that does not contain isocyanate groups obtained by self-blocking the isocyanate group in the isocyanate compound in the form of uretdione.
  • the product after the reaction of monoisocyanate and polyisocyanate is obtained by isocyanate addition with other compounds containing active hydrogen, or it can be obtained by the reaction of polyisocyanate and other compounds containing active hydrogen after isocyanate addition.
  • active hydrogen refers to deprotonated hydrogen atoms attached to N, O, S atoms.
  • the elastic material for 3D printing in this application includes a photo-curing system (mainly including photo-curing monofunctional monomer, photo-curing cross-linking agent, photo-initiator and some auxiliaries) that forms the skeleton of a 3D object and thermal polymerization that improves mechanical properties system (mainly including self-blocking isocyanate), so 3D objects with high precision and excellent mechanical properties (especially tensile strength, elongation at break and tear strength) can be formed after 3D printing.
  • a photo-curing system mainly including photo-curing monofunctional monomer, photo-curing cross-linking agent, photo-initiator and some auxiliaries
  • mechanical properties system mainly including self-blocking isocyanate
  • the photo-curing system in the elastic material for 3D printing is cured under the irradiation of the radiation source to form a polymer network skeleton with certain mechanical strength and precision.
  • the network skeleton is the forming frame of the 3D object and is self-sealing Type isocyanates are dispersed inside the polymer network backbone.
  • the self-blocking isocyanate will undergo a deblocking reaction to release isocyanate compounds, which will thermally polymerize with compounds containing active hydrogen in elastic materials for 3D printing to form elastic polyurethane materials , elastic polyurea material, etc., and then form a dual polymer material structure with the light-curing material, which can effectively improve the tensile strength, elongation at break and tear strength of 3D objects, and make 3D objects feel refreshing without any stickiness.
  • the self-blocking isocyanate Before the deblocking reaction of the self-blocking isocyanate occurs, there will be no reaction between the light-curing system and the thermal polymerization system in this application, especially since the self-blocking isocyanate does not contain isocyanate groups, it will not interact with the light-curing monofunctional monofunctional monomer.
  • the elastic material for 3D printing comprises, according to the mass fraction: 5-50% of self-blocking isocyanate, 20-80% of photocurable monofunctional monomer, 5-30% of photocurable crosslinking agent, Photoinitiator 0.5-10%, auxiliary agent 0.05-8%, deblocking catalyst 0-4%, photocurable monofunctional resin 0-50%, filler 0-30% and colorant 0-10%.
  • the obtained 3D printed object can be basically made to have excellent mechanical properties, especially excellent tensile strength, elongation at break and tear strength.
  • the self-blocking isocyanate can be deblocked at a certain heating temperature to release the compound with isocyanate group, and the compound with isocyanate group will thermally polymerize with other compounds with active hydrogen to form elastic polyurethane material , elastic polyurea materials, etc.
  • the self-blocking isocyanate of the present application may have an active hydrogen at the end group, for example, the end group may contain a hydroxyl group and/or an amino group.
  • the isocyanate group in the released compound with isocyanate group will undergo thermal polymerization reaction with adjacent active hydrogen to generate corresponding elastic materials such as polyurethane and polyurea, ensuring high efficiency.
  • the thermal polymerization reaction is carried out.
  • the temperature of the deblocking reaction of the self-blocking isocyanate can be used as a control parameter to select a self-blocking isocyanate that is more suitable for the application environment of the elastic material for 3D printing of the present application.
  • the temperature of the self-blocking isocyanate deblocking reaction is not lower than 50°C. The reason is that if the temperature of the self-blocking isocyanate deblocking reaction is too low, once the storage or transportation environment is overheated, the self-blocking isocyanate may be deblocked and thermal polymerization may be triggered, which may affect the system stability of the elastic material for 3D printing. It will cause the impact and easily block the nozzle holes of the print head.
  • the temperature of the self-blocking isocyanate deblocking reaction should not be too high.
  • the temperature of the self-blocking isocyanate deblocking reaction is at least 20°C higher than the printing temperature of the print head, so as to ensure that the elastic material for 3D printing is Stability in the print head.
  • the temperature of the self-blocking isocyanate deblocking reaction does not exceed 200°C. If the temperature of the self-blocking isocyanate deblocking reaction exceeds 200°C, it is necessary to heat the cured object at a temperature higher than 200°C to initiate the self-blocking isocyanate deblocking and thermal polymerization reaction. High temperatures above 200°C will cause aging of 3D printed objects, resulting in reduced mechanical properties.
  • the elastic material for 3D printing of the present application can be selected from at least one self-blocking isocyanate of the structure shown in formula 1.
  • R 1 is selected from alkane group, cycloalkane group or aralkane group, and the alkane group can specifically be a alkane group with 1-12 carbon atoms, and further can be a straight chain alkane group or a branched chain alkane group; Specifically, the alkane group may be a cycloalkane group having 5 to 12 carbon atoms; the aralkane group may be an aralkane group having 6 to 15 carbon atoms.
  • R 2 and R 3 are independently selected from the groups obtained by removing one active hydrogen from an active hydrogen compound, wherein the active hydrogen compound refers to a compound whose two end groups each contain at least one active hydrogen.
  • the active hydrogen compound refers to a compound whose two end groups each contain at least one active hydrogen.
  • ethylene glycol is an active hydrogen compound referred to in this application, and R 2 and R 3 are -OCH 2 CH 2 HO. In the present application, R 2 and R 3 may be the same or different.
  • the above-mentioned active hydrogen compound may be at least one of a small molecular compound and an oligomer with a number average molecular weight of 200-5000.
  • the small molecule compound may be at least one of polyols, polyamines and polyolamines.
  • the polyhydric alcohols include dihydric alcohols, trihydric alcohols, and the like, and dihydric alcohols are preferred in the present application.
  • the polyol may be selected from ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,5-pentanediol, 1 , At least one of 6-hexanediol, 1,9-nonanediol, cyclohexanedimethanol, 2-ethyl-1,3-hexanediol, cyclohexanediol, and the like.
  • the polyamines can be diamines, triamines, etc., and diamines are preferred in the present application. Further, the polyamine is selected from ethylenediamine, propylenediamine, butanediamine, cyclohexanediamine, hexamethylenediamine, 1,8-diaminooctane, 2,5-diamino-2,5 -At least one of dimethylhexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, and the like.
  • the polyolamine may be selected from ethanolamine, aminoethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2,2-dimethylethanol, 2 -Amino-2-ethyl-1-3-propanediol, tris(hydroxymethyl)aminomethane, 1-amino-1-methyl-2-hydroxycyclohexane and 2-amino-2-methyl-1- At least one of butanol and the like.
  • the active hydrogen compound is an oligomer with a number average molecular weight of 200-5000, it is preferably a polyol oligomer.
  • the polyol oligomer is at least selected from polyester polyol, polyether polyol, polyurea polyol, polyurethane polyol, polycaprolactone polyol, polyolefin polyol, polycarbonate polyol, etc. A sort of.
  • the self-blocking isocyanate represented by the above formula 1 can be prepared in the following manner.
  • the preparation method includes adding the diisocyanate dimer shown in formula 2, the compound R 2 H and/or R 3 H, a catalyst and a cosolvent into a reaction vessel, and carrying out a chemical reaction at a certain temperature until the isocyanate content in the reaction vessel is low.
  • the self-blocking isocyanate shown in formula 1 is obtained, wherein the molar ratio of compound R 2 H and/or R 3 H to diisocyanate dimer is 1.95:1-2.05: 1.
  • the reaction temperature should be lower than the deblocking temperature of the uretdione group in the diisocyanate dimer.
  • the compound R 2 H and/or R 3 H, the catalyst and the cosolvent are mixed first, and then the diisocyanate dimer represented by formula 2 is added to the aforementioned mixed system to initiate the reaction.
  • the diisocyanate dimer can be based on hexamethylene-1,6-diisocyanate (referred to as HDI), toluene-2,4-diisocyanate (referred to as TDI), diphenylmethane-4, A dimer of at least one 4'-diisocyanate (MDI for short) in the form of uretdione.
  • HDI hexamethylene-1,6-diisocyanate
  • TDI toluene-2,4-diisocyanate
  • MDI diphenylmethane-4
  • HDI dimer can be DESMODUR XP-2730 produced by Bayer Corporation, Pittsburgh PA; TDI dimer can be ADOLINK TT produced by Rhein Chemie Rheinau GmBH, DANCURE 999 produced by Danquinsa Gm BH, THANECURE T9 produced by TSE Industries, Inc; MDI dimer can be GRILBOND A2BOND produced by EMS-Griltech.
  • the cosolvent is a monofunctional photocurable monomer that does not contain active hydrogen in its molecular structure, which helps to reduce the viscosity of the system during the preparation of self-blocking isocyanates, improve the reaction rate, and reduce the difficulty of discharging after the synthesis.
  • the co-solvent can be used both as a co-solvent in the synthesis of self-blocking isocyanates and as a formulation component of elastic materials for 3D printing.
  • the co-solvent may be selected from alkyl (meth)acrylates such as isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isooctyl acrylate, isononyl acrylate, lauryl acrylate One or more of acid acrylate, isodecyl acrylate, isodecyl methacrylate, methyl stearyl acrylate, dodecyl methacrylate, isotridecyl methacrylate, etc.
  • alkyl (meth)acrylates such as isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isooctyl acrylate, isononyl acrylate, lauryl acrylate
  • acid acrylate isodecyl acrylate, isodecyl methacrylate, methyl stearyl acrylate, dodecy
  • alkoxylated (meth)acrylates such as 2-acrylic acid-2-methoxyester, ethoxyethoxyethylacrylate, methoxypolyethylene glycol monoacrylate, methoxy One or more of polyethylene glycol methacrylates, etc.
  • alkoxylated (meth)acrylates such as 2-acrylic acid-2-methoxyester, ethoxyethoxyethylacrylate, methoxypolyethylene glycol monoacrylate, methoxy One or more of polyethylene glycol methacrylates, etc.
  • (meth)acrylates with cyclic structures such as tetrahydrofuran acrylate, acrylate-2-phenoxyethyl ester, ( One or more of 2-ethyl-2-methyl-1,3-dioxopentyl-4-yl) acrylate, alkoxylated nonylphenol acrylate, ethylated nonylphenol acrylate, etc.
  • cycloalkyl (meth)acrylates such as isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 3,3,5-trimethylcyclohexane acrylic acid one or more of esters, 3,3,5-trimethylcyclohexane methacrylate, etc.
  • heterocyclic (meth)acrylates such as cyclotrimethylolpropane formal acrylate , one or more of 3-ethyl-3-epoxypropyl methyl acrylate, tetrahydrofuran methacrylate, etc.
  • can be selected from (meth)acrylate with benzene ring structure such as 2-phenoxy One or more of ethyl methacrylate, o-phenylphenoxyethyl acrylate and the like.
  • the catalyst is used to speed up the reaction rate, increase the reaction degree, and reduce the reaction temperature, and exemplarily, can be selected from at least one of dibutyltin dilaurate, stannous octoate, cobalt octoate, lead octoate, zinc naphthenate and the like. Further, the catalyst dosage is 0.01-1% of the total mass in the reaction system.
  • the above-mentioned preparation can be carried out in a glass reactor, a stainless steel reactor, or the like.
  • the photocurable monofunctional monomer of the present application contains a vinyl group, preferably a photocurable monofunctional soft monomer with a vinyl group, and/or a photocurable monofunctional hard monomer with a vinyl group.
  • the vinyl-bearing photocurable monofunctional soft monomer is a monomer containing one vinyl group and capable of forming a homopolymer with a glass transition temperature below 25°C.
  • the vinyl-bearing photocurable monofunctional soft monomer may be selected from the group consisting of alkyl(meth)acrylates, hydroxyalkyl(meth)acrylates, alkoxy(meth)acrylates One or more of esters, (meth)acrylates with cyclic structures, and (meth)acrylates with urethane groups.
  • the alkyl (meth)acrylate may be selected from isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isooctyl acrylate, isononyl acrylate, lauric acid
  • Hydroxyalkyl (meth)acrylate can be selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, etc.;
  • the alkoxylated (meth)acrylates can be selected from 2-acrylate-2-methoxyester, ethoxyethoxyethylacrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol One or more of alcohol methacrylates, etc.;
  • the (meth)acrylate with a cyclic structure can be selected from tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, (2-ethyl-2-methyl-1,3-dioxopentyl- 4-yl) one or more of acrylate, alkoxylated nonylphenol acrylate, ethylated nonylphenol acrylate, etc.;
  • (Meth)acrylates with urethane groups can be selected from urethane acrylates, 2-[[(butylamino)carbonyl]oxo]ethyl acrylate, aliphatic urethane acrylates, etc. one or more of.
  • the vinyl-bearing photocurable monofunctional hard monomer is a monomer containing one vinyl group and capable of forming a homopolymer with a glass transition temperature above 25°C.
  • the photocurable monofunctional hard monomer with a vinyl group may be selected from cycloalkyl (meth)acrylates, heterocyclic (meth)acrylates, (meth)acrylates with a benzene ring structure one or more of acrylate and acryloyl morpholine.
  • the cycloalkyl (meth)acrylate may be selected from isobornyl acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 3,3,5-trimethylcyclohexane acrylic acid One or more of esters, 3,3,5-trimethylcyclohexane methacrylate, etc.;
  • Heterocyclic (meth)acrylate can be selected from one or more of cyclotrimethylolpropane formal acrylate, 3-ethyl-3-epoxypropyl acrylate, tetrahydrofuran methacrylate, etc. ;
  • the (meth)acrylate with a benzene ring structure can be selected from one or more of 2-phenoxyethyl methacrylate, o-phenylphenoxyethyl acrylate and the like.
  • the photocurable crosslinking agent of the present application helps to increase the crosslinking density of the 3D object, and finally realizes the optimization of the recovery performance and mechanical properties of the 3D object.
  • the photocurable crosslinking agent may be selected from at least one of bifunctional resins and bifunctional monomers.
  • the bifunctional resin is a polymer containing two (meth)acryloyloxy groups in the molecular structure
  • the bifunctional monomer is a monomer containing two (meth)acryloyloxy groups in the molecular structure .
  • the bifunctional resin is selected from bifunctional polyurethane (meth)acrylate, bifunctional polyester (meth)acrylate, bifunctional epoxy (meth)acrylate, polybutadiene (methyl) At least one of acrylates; preferably difunctional urethane (meth)acrylates, polybutadiene (meth)acrylates.
  • the polyurethane structure in the bifunctional polyurethane (meth)acrylate and the polybutadiene structure in the polybutadiene (meth)acrylate are beneficial to enhance the elongation and strength of the 3D object.
  • the bifunctional urethane (meth)acrylate is preferably an aliphatic urethane (meth)acrylate, which has good flexibility and elongation, and currently there are many products on the market, which can be Changxing Materials Industry Co., Ltd.
  • Difunctional polyester (meth)acrylates can be CN7001NS, CN2283NS, etc. of Sartomer Company, Trust7118, Trust7008, Trust7110, Trust7100, etc. of Shenzhen Youyang Technology Co., Ltd., 6343, 6371, 6371, etc. of Changxing Materials Industry Co., Ltd. 6372, etc.;
  • Difunctional epoxy (meth)acrylate can be CN123, CN2003NS, etc. of Sartomer Company, 623A-80, 6215-100, etc. of Changxing Material Industry Co., Ltd.;
  • Polybutadiene (meth)acrylate is an oligomer with a (meth)acrylate group added to polybutadiene, which can be cross-linked by UV light to form both elastomer and polyacrylate properties.
  • Such oligomers are liquid at room temperature, and there are many products on the market, such as Sartomer's CN301, CN302, CN307, CN303, Jamaicaryl 3801, etc., Osaka Organic's BAC15, BAC45, etc., Bomar's BR641, BR643, etc.
  • the bifunctional monomer is preferably triethylene glycol dimethacrylate, polyethylene glycol (300) diacrylate, polyethylene glycol (400) dimethacrylate, polyethylene glycol ( 600) diacrylate, polyethylene glycol (600) dimethacrylate, polypropylene glycol (400) diacrylate, polypropylene glycol (750) diacrylate, 1,12-dodecyl dimethacrylate , (10) Ethoxylated Bisphenol A Dimethacrylate, (20) Ethoxylated Bisphenol A Dimethacrylate, (30) Ethoxylated Bisphenol A Dimethacrylate, (Ethoxylated) 1 , at least one of 6-hexanediol diacrylate and the like.
  • the photoinitiator of the present application is a free radical photoinitiator, specifically, the free radical photoinitiator can be selected from benzoin ether, benzoin ⁇ , ⁇ -dimethylbenzyl ketal, ⁇ , ⁇ -diethoxybenzene Ethyl ketone, 2-hydroxy-2-methyl-1-phenylacetone-1, 1-hydroxy-cyclohexyl benzophenone (referred to as 184), 2-hydroxy-2-methyl-p-hydroxyethyl ether benzene acetone-1, [2-methyl-1-(4-methylmercaptophenyl)-2-morpholinoacetone-1], [2-benzyl-2-dimethylamino-1-(4-morpholinobenzene yl)butanone-1], benzoylformate, 2,4,6-trimethylphenylacyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylphenylacyl- At least one of diphenylphosphine oxide (abbrevi
  • the auxiliary agent of the present application is selected from at least one of a polymerization inhibitor, a leveling agent, a defoaming agent, and a dispersing agent.
  • the function of the polymerization inhibitor in the elastic material is to prevent the free radicals in the elastic material from polymerizing and improve the storage stability of the material.
  • the polymerization inhibitor can be selected from at least one of phenolic, quinone or nitrite polymerization inhibitors, such as hydroquinone, terephthaloquinone, p-hydroxyanisole, 2-tert-butyl terephthalate At least one of phenol, 2,5-di-tert-butylhydroquinone, tris(N-nitroso-N-phenylhydroxylamine) aluminum salt (polymerization inhibitor 510), and the like.
  • the leveling agent is mainly used to improve the fluidity of the elastic material and the wetting performance of the substrate, and at the same time adjust the surface tension of the elastic material so that it can be printed normally.
  • the selection of the leveling agent is not specifically limited in this application.
  • there are many products on the market such as BYK333, BYK377, BYK-UV3530, BYK-UV3575, BYK-UV3535 from BYK, TEGO wet 500, TEGO wet 270, TEGO Glide 450, TEGO RAD 2010 from Digao Company , TEGO RAD 2011, TEGO RAD 2100, TEGO RAD 2200, etc.
  • defoamer The main function of defoamer is to inhibit, reduce and eliminate air bubbles in elastic materials.
  • the selection of the defoaming agent is not specifically limited in this application.
  • there are many products on the market such as BYK1798, BYK055, BYK088, BYK020, BYK025, etc. from BYK, TEGO Airex 920, TEGO Airex 921, TEGO Airex 986, TEGO Foamex 810, TEGO FoamexN, etc.
  • the main function of dispersants is to improve the dispersion stability of particles in elastic materials. As long as the dispersant can meet the above performance requirements, the present application does not specifically limit the selection of the dispersant.
  • there are many products on the market such as BYK102, BYK106, BYK108, BYK110, BYK111, BYK180, Dispers 655, Dispers675, Dispers 710, Dispers 630, Dispers 670, etc.
  • the elastic material for 3D printing of the present application can also add at least one of a deblocking catalyst, a photocurable monofunctional resin, a filler and a colorant according to further requirements of performance.
  • the deblocking catalyst is used to adjust the deblocking temperature and deblocking rate of the self-blocking isocyanate.
  • the deblocking catalyst is selected from basic catalysts. Specifically, the deblocking catalyst is preferably selected from sodium hydroxide, potassium hydroxide, potassium tributylammonium hydroxide, potassium hydroxide tetrabutylammonium, tri-n-butylphosphine, tetramethylammonium propionate, tetrabutyl benzoate Ammonium.
  • the photocurable monofunctional resin is selected from monofunctional urethane acrylate, monofunctional polyester acrylate, monofunctional polyether acrylate, monofunctional epoxy acrylate, preferably monofunctional urethane acrylate.
  • the filler is selected from silica, carbon black, barium sulfate, aluminum hydroxide, kaolin, talc, and the like.
  • the shrinkage of the molding layer during the curing process can be effectively reduced, the printing accuracy can be improved, and the mechanical properties of the material can also be improved.
  • the elastic material of the present application does not contain a colorant, the elastic material is transparent, and the printed product has high transparency.
  • the colorant can be a pigment or a dye.
  • the preferred pigment is a colorant, and the pigment can be selected from CIPigmentWhite 6, CIPigment Red 3, CIPigment Red 5, CIPigment Red 7, CIPigment Red 9. , CIPigment Red 12, CIPigment Red 13, CIPigment Red 21, CIPigment Red31, CIPigment Red49:1, CIPigment Red 58:1, CIPigment Red 175; CIPigmentYellow 63, CIPigment Yellow 3, CIPigment Yellow 12.
  • CIPigment Yellow 16 CIPigment Yellow 83; one or more of CIPigment Blue 1, CIPigment Blue 10, CIPigment BlueB, Phthalocyanine Blue BX, Phthalocyanine Blue BS, CIPigment Blue61:1, etc.
  • Each component of the elastic material for 3D printing of the present application can exist stably in the dark condition, so the stability is high, so that long-term transportation and storage can be realized, and the phenomenon of blocking the nozzle holes of the print head will not occur.
  • the photo-curing system will complete the photo-curing reaction under the irradiation of radiation to form a molding frame of a 3D object with high precision and certain mechanical properties.
  • the self-blocking isocyanate dispersed inside the molding frame will undergo a deblocking reaction to generate a compound with an isocyanate group, and the isocyanate group will interact with the compound with active hydrogen in the 3D printing elastic material.
  • the 3D object obtained from the elastic material for 3D printing of the present application also has a good touch, and the surface is refreshing and non-sticky.
  • a second aspect of the present application provides a method for preparing an elastic material for 3D printing in the aforementioned first aspect, comprising: adding a photoinitiator and an auxiliary agent into the first system, stirring evenly, and filtering to obtain an elastic material for 3D printing; wherein,
  • the first system includes at least a self-blocking isocyanate, a photocurable monofunctional monomer and a photocurable crosslinking agent.
  • the preparation of the elastic material for 3D printing of the present application needs to be carried out in an environment outside the triggering wavelength range of the photoinitiator, so as to avoid light in the environment to induce polymerization of the components in the elastic material for 3D printing.
  • the first system may also include deblocking catalyst and photocurable monofunctional resin. , at least one of fillers and colorants.
  • N (N ⁇ 2) grade filtration can be used for filtration, wherein the pore size of the filter membrane used in the N-th grade filtration is smaller than the N-th grade of filtration.
  • the pore size of the filter membrane used in the 1st stage filtration, and the pore size of the filter membrane used in the Nth stage filtration is smaller than the pore size of the printing nozzle.
  • two-stage filtration can be adopted.
  • the first-stage filtration uses a glass fiber membrane with a pore size of 0.45 ⁇ m to filter the system after adding the photoinitiator and auxiliary agent, and the collected filtrate adopts a glass fiber membrane with a pore size of 0.22 ⁇ m.
  • the polypropylene membrane (PP membrane for short) is used for the second-stage filtration, and the collected filtrate is the elastic material for 3D printing.
  • the time of degassing treatment is not more than 5h, preferably, the time of degassing is controlled within 1-3h.
  • the operation mode of the degassing treatment is selected from one of reduced pressure degassing, atmospheric pressure degassing and heating degassing.
  • the preparation method of the present application is simple and easy to operate, which is not only conducive to the formation of a stable elastic material for 3D printing, but also to the spraying of the elastic material for 3D printing, so that the use of the elastic material for 3D printing is more convenient, especially suitable for spraying 3D objects. ink printing.
  • FIG. 1 is the flow chart of the 3D printing method of the application, including the following steps:
  • the execution body of the above printing method may be a printing device, and the printing device realizes the above steps S1 to S3 by controlling the distribution of the elastic material for 3D printing and the curing process, and finally produces a 3D object green body.
  • the elastic material for 3D printing needs to be heated.
  • the heating temperature should not be higher than the deblocking temperature of self-blocking isocyanate, and further, it should be at least 20°C lower than the deblocking temperature of self-blocking isocyanate.
  • the heated elastic material for 3D printing is distributed to form an elastic material layer.
  • the distribution is inkjet printing.
  • the layer printing data is the data representing the cross section of the 3D object.
  • the present application does not limit the acquisition method of the layer printing data, and any method for acquiring the layer printing data in the process of 3D object printing in the art can be used, for example, 3D printing Before the object is printed, it is necessary to obtain the model data of the 3D object, and convert the model data to the data format, such as converting it into STL format, PLY format, WRL format and other formats that can be recognized by the slicing software, and use the slicing software to slice and layer the model.
  • data representing the cross-sectional layer of the object is also called layer print data; the layer print data includes information representing the shape of the object, and/or information representing the color of the object.
  • the elastic material layer is cured, and the elastic material layer is at least partially cured to form a chip layer.
  • Curing in this application refers to irradiating the elastic material layer with a radiation source, so that the photo-curing system (mainly photo-curing monofunctional monomer, photo-curing cross-linking agent, photo-initiator, and some auxiliary agents) in it occurs.
  • the photocuring reaction results in a solidified or semi-solidified state.
  • Specific radiation sources may be UV light, electromagnetic radiation, infrared rays, and the like.
  • the curing system After the curing system is photocured, the curing system encapsulates other components (eg, self-blocking isocyanate) to form a chip layer.
  • other components eg, self-blocking isocyanate
  • the elastic material layer may also be heated to cause the self-blocking isocyanate therein to be deblocked to generate an isocyanate compound and then thermally polymerize.
  • the above steps S1-S2 are repeatedly performed, that is, the elastic material layer is continuously formed on the surface of the previous slicing layer, and the elastic material layer is cured to form a new slicing layer.
  • Multiple slice layers are stacked in sequence to form a 3D object green body.
  • the outline of the 3D object green body is basically the same as the target 3D object.
  • it also includes heating the 3D object green body to obtain the target 3D object.
  • the main purpose of this heat treatment is to trigger the unblocking of the self-blocking isocyanate inside the 3D object green body to undergo thermal polymerization, thereby further improving the mechanical properties of the 3D object, especially the tensile strength, elongation at break and tear strength. further improvement.
  • the tensile strength, elongation at break and tear strength of the 3D object obtained by heating the green 3D object are significantly improved compared to the green 3D object with no thermal polymerization or only a small amount of thermal polymerization.
  • the process of finally heating the 3D object green body can be omitted.
  • the temperature for heating the 3D body green body should not be too high, as long as the self-blocking isocyanate can be deblocked to release the isocyanate group. Excessive temperature will cause 3D objects to be easily aged.
  • the 3D printing method provided in this application combines photocuring and thermal polymerization, makes full use of the advantages of inkjet printing technology, improves the molding accuracy and mechanical properties of 3D objects, and especially optimizes the tensile strength and fracture of 3D objects. Elongation and tear strength performance.
  • a fourth aspect of the present application provides a 3D object, where the 3D object is obtained by printing the elastic material for 3D printing in the first aspect, or by using the 3D printing method in the third aspect.
  • the 3D object of the present application not only has high forming precision, but also has excellent mechanical properties, especially the tensile strength can reach 4-9MPa, the tear strength can reach 8-20MPa, and the elongation at break can reach 100%-500%.
  • FIG. 2 is a schematic structural diagram of the 3D printing device of the present application.
  • the 3D printing device at least includes: a heating part 4, a printing head 3, a supporting platform 12, and a radiation source 9; the printing head 3 is used to distribute the elastic material 7 for 3D printing heated by the first heating part 4 on the supporting platform 12 according to the layer printing data to form an elastic material layer; the radiation source 9 is used to irradiate the elastic material layer to form the slice layer.
  • the first heating member 4 is used to heat the elastic material for 3D printing.
  • the specific process of implementing 3D printing by using the 3D printing device may be as follows: the first heating component 4 heats the elastic material for 3D printing, and the print head 3 distributes the heated elastic material 7 for 3D printing on the support platform 12 according to the layer printing data.
  • the elastic material layer is formed thereon, and the radiation source 9 irradiates the elastic material layer to cure the elastic material layer (at the same time, the radiation source may cause a small amount of self-blocking isocyanate to deblock and initiate thermal polymerization) to form a chip layer.
  • the support platform 12 can be moved down a certain distance in the height direction (ie, the Z direction), so that there is enough space to accommodate a new slice layer.
  • the slice layers are stacked layer by layer in the height direction , forming a 3D object green body 8 .
  • the print head 3 may be a single-channel print head, a multi-channel print head, or a combination of a single-channel print head and a multi-channel print head, and the number of print heads 3 is at least one;
  • the first heating The component 4 is at least one of a metal heating sheet, a heating wire, and a heating spring;
  • the radiation source 9 is a UV LED lamp, a mercury lamp, a metal halide lamp, an electrodeless lamp, a xenon lamp, and the like.
  • the device may further include a storage container 1 for storing the elastic material for 3D printing and capable of transporting the elastic material for 3D printing stored therein to the print head through the ink tube 2, while the first heating
  • the component 4 can heat the reservoir container 1 and/or the ink tube 2 and/or the print head 3 to realize indirect heating of the elastic material for 3D printing, and can also directly heat the storage container 1 and/or the ink tube 2 and/or the elastic material for 3D printing. Or direct heating of the elastic material for 3D printing in print head 3.
  • the device of the present application may further include a second heating part 10 for heating the elastic material layer.
  • the second heating member 10 may be used to heat the elastic material layer, so that the self-blocking isocyanate in the elastic material layer is deblocked and thermal polymerization is induced.
  • the second heating component 10 is selected from at least one of an infrared lamp, a heating plate, a heat preservation plate, a heat dissipation plate, a microwave radiation source, and a temperature controller.
  • the apparatus of the present application may further include a third heating component (not shown), and the third heating component is used for heating the 3D object green body 8 to obtain a 3D object.
  • the 3D object green body 8 may also be heated by the third heating component to promote more self-blocking isocyanates inside the 3D object green body 8 to deblock and thermally polymerize.
  • the heating temperature of the third heating component needs to be higher than the deblocking temperature of the self-blocking isocyanate.
  • the third heating component is selected from at least one of infrared lamps, microwave ovens, heating furnaces, ovens, and high-temperature vacuum drying ovens.
  • the device of the present application may also include a lifting mechanism 13, which is used to change the relative distance between the support platform 12 and the print head 3 in the Z direction, so as to continuously form slice layers and stack them layer by layer to form a 3D object green body 8 .
  • the device of the present application may also include a leveling member 15, which is located between the print head 3 and the radiation source 9, and is used to level the elastic material layer; the leveling member 15 may be a leveling stick, The excess 3D printing elastic material dispensed is taken away by the rotating action of the leveling stick.
  • the apparatus of the present application may further include a controller 14, the controller 14 is used to control the first heating part 4, the second heating part 10, the third heating part, the print head 3, the radiation source 9, the lifting mechanism 13 and the calibration work of at least one of the flat parts 15 .
  • the controller 14 can control the distribution of the heated elastic material 7 by the print head 3 according to the layer printing data, the controller 14 can control the radiation intensity and radiation time of the radiation source 9 to the elastic material layer, and the controller 14 can control The relative distance between the support platform 13 and the print head 3 in the Z direction is the same.
  • the 3D printing device provided in this application is used to implement the aforementioned 3D printing method, and can obtain a 3D object with high molding precision and high mechanical strength.
  • Fig. 1 is the flow chart of the 3D printing method of the application
  • FIG. 2 is a schematic structural diagram of the 3D printing device of the present application.
  • composition of the elastic material for 3D printing in this example is shown in Table 1.
  • the preparation method of the elastic material for 3D printing in this embodiment includes: placing a reaction kettle in a yellow light environment, adding self-blocking isocyanate, photocurable monofunctional monomer, and photocurable crosslinking agent to the reaction kettle according to the formula ratio , heat up to 40-50 °C, stir for 30-40 minutes until the mixture is uniform to obtain the first mixture; then add the photoinitiator and auxiliary according to the formula ratio, stir for more than 60 minutes until the mixture is uniform to obtain the second mixture, cool down to 20- 30°C, adopt the method of two-stage filtration, the first-stage filtration uses glass fiber membrane with a pore size of 0.45 ⁇ m, and the second-stage filtration uses a polypropylene membrane with a pore size of 0.22 ⁇ m. save.
  • R 2 and R 3 are polyether diols (3000 molecular weight) that lose one active hydrogen or 1,4-butanediol that loses one active hydrogen.
  • the deblocking temperature of the self-blocking isocyanate A detected by the following deblocking temperature detection method was about 140°C.
  • the mixture of self-blocking isocyanate and photocurable monomer is placed in a heating furnace (box) filled with inert gas (nitrogen), and gradient heating and heat preservation are carried out (heating rate 5°C/min, every 5°C temperature rise, heat preservation 10min) , and regularly use an infrared spectrometer to detect the isocyanate group.
  • heating furnace box
  • inert gas nitrogen
  • gradient heating and heat preservation are carried out (heating rate 5°C/min, every 5°C temperature rise, heat preservation 10min) , and regularly use an infrared spectrometer to detect the isocyanate group.
  • the isocyanate group is detected, record the heating temperature at this time, which is the deblocking temperature.
  • composition of the elastic material for 3D printing in this example is shown in Table 2.
  • the preparation method of the elastic material for 3D printing in this example is basically the same as that in Example 1, the only difference is that the second-stage filtration is degassed under reduced pressure for 1.5 hours.
  • R 2 and R 3 are polyester diols (2000 molecular weight) that lose one active hydrogen or 1,6-hexanediol that loses one active hydrogen.
  • the deblocking temperature of the self-blocking isocyanate B detected by the method in Example 1 is about 140°C.
  • composition of the elastic material for 3D printing in this example is shown in Table 3.
  • the preparation method of the elastic material for 3D printing in this example is the same as that in Example 1.
  • R 2 and R 3 are polycarbonate diols (2000 molecular weight) that lose one active hydrogen or 1,4-butanediol that loses one active hydrogen.
  • the deblocking temperature of the self-blocking isocyanate C detected by the method in Example 1 is about 140°C.
  • composition of the elastic material for 3D printing in this example is shown in Table 4.
  • the preparation method of the elastic material for 3D printing in this example is the same as that in Example 2.
  • composition of the elastic material for 3D printing in this example is shown in Table 5.
  • the preparation method of the elastic material for 3D printing in this example is the same as that in Example 1.
  • composition of the elastic material for 3D printing in this example is shown in Table 6.
  • Self-blocking isocyanate C 15% deblocking catalyst tri-n-butylphosphine 4% Photocurable Monofunctional Monomer Tetrahydrofuran Acrylate 21.98% Light Curing Monofunctional Resin Monofunctional urethane acrylate 25% Light curing crosslinking agent Bifunctional urethane acrylate 30% photoinitiator 184 4% Auxiliary Inhibitor: Hydroquinone 0.02%
  • the preparation method of the elastic material for 3D printing in this example is the same as that in Example 1.
  • composition of the elastic material for 3D printing in this example is shown in Table 7.
  • the preparation method of the elastic material for 3D printing in this example is the same as that in Example 1.
  • composition of the elastic material for 3D printing in this comparative example is shown in Table 8.
  • the preparation method of the elastic material for 3D printing in this comparative example is the same as that in Example 1.
  • the DV-I digital viscometer was used to test the viscosity of the elastic material for 3D printing at the printing temperature.
  • the Senna light-curing inkjet printer was used to continuously print the elastic material for 3D printing for 4 hours.
  • the ink output of the nozzles before and after printing was tested. There were no more than 10 broken lines before and after printing, that is, the printing fluency was ok, and the test was passed.
  • the elastic materials for 3D printing in the examples of the present application have adjustable viscosity and are suitable for inkjet printing and stereolithography.
  • This embodiment provides a 3D printing method and a 3D printing device.
  • 3D printing methods include:
  • S102 According to the layer printing data, distribute the heated elastic material for 3D printing to form an elastic material layer;
  • S104 Repeat S102-S103 to form a 3D object green body
  • the 3D printing device used to implement the above printing method includes: a material storage container 1 , an ink tube 2 , a printing head 3 , a first heating part 4 , a third heating part (not shown), and a radiation source 9 , Support platform 12 , lift mechanism 13 , guide rail 11 , controller 14 .
  • the material storage container 1 is used to accommodate the elastic material for 3D printing in the foregoing embodiment or comparative example (hereinafter referred to as the material composition);
  • the ink tube 2 is connected between the material storage container 1 and the print head 3 for providing the material composition to the print head 3;
  • the first heating part 4 is used to heat the material composition of at least one of the material storage container 1, the ink tube 2 and the print head 3, and the heating temperature is lower than that of the self-blocking isocyanate in the material composition.
  • the temperature during sealing is at least 20°C (taking the material composition in Example 1 as an example, the heating temperature of the first heating element 4 is 80°C); in this embodiment, the first heating element 4 is a metal heating sheet, which is fixed in the material storage
  • the bottom and sides of the container 1 are used for indirect heating of the material composition.
  • the controller 14 controls the print head 3 to selectively distribute the heated material composition 7 to the support platform 12 to form an elastic material layer according to the layer printing data.
  • the slice layer printing data is data representing the cross section of the 3D object, including information representing the shape of the object , and/or information representing the color of the object.
  • the controller 14 controls the radiation source 9 to provide radiation to at least partially cure the elastic material layer, and even initiate partial thermal polymerization by increasing the curing temperature, thereby forming the chip layer.
  • the 3D printing device of this embodiment may further include a leveling member 15, which is located between the print head 3 and the radiation source 9 and used to level the elastic material layer; the leveling member 15 may be a leveling stick, The dispensed excess material composition is carried away by the rotating action of the leveling stick.
  • the print head 3 , the leveling member 15 and the radiation source 9 are all mounted on a carriage (not shown in FIG. 2 ), and the carriage moves back and forth on the guide rail 11 .
  • the controller 14 controls the lift mechanism 13 to change the relative distance between the support platform 12 and the print head 3 in the Z direction; in this embodiment, each time a slice layer is formed, the controller 14 controls the lift mechanism 13 to drive the support The platform 12 is moved down a distance of one layer thickness.
  • the controller 14 controls the print head 3 to form an elastic material layer on the previous layer according to the layer printing data and controls the radiation source 9 to provide radiation to at least partially cure the elastic material layer to form a new slice layer; repeat the above steps, layer by layer A 3D object green body 8 is formed.
  • the obtained 3D body green body 8 is placed in the third heating part, and the heating temperature of the third heating part is controlled to be higher than the unsealing temperature of the uretdione in the self-blocking isocyanate (taking the material composition in Example 1 as an example, The heating temperature of the third heating part is controlled to be 150-160° C.), and the 3D body green body 8 is heat-treated in the third heating part for 2-3 hours, so that the self-blocking isocyanate in it is completely opened and the thermal polymer reaction occurs to form polyurethane Elastomer, thereby improving the tensile strength, elongation at break and tear resistance of the target 3D object.
  • this embodiment provides yet another 3D printing method and 3D printing device.
  • 3D printing methods include:
  • S102 According to the layer printing data, distribute the heated elastic material for 3D printing to form an elastic material layer;
  • S104 Repeat S102-S103 to form a 3D object green body.
  • the 3D printing device used to implement the above printing method further includes: a second heating part 10, and the second heating part 10 is used for heating the elastic material layer to induce the formation of the material composition in the 3D printing device.
  • the self-blocking isocyanate is deblocked and thermal polymerization occurs, and the thermal polymerization efficiency is improved.
  • the 3D printed objects formed by using the elastic materials for 3D printing in the examples of the present application have excellent tensile strength, tear strength and elongation at break, and the surface feels good without stickiness.

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Abstract

La présente invention concerne un matériau élastique pour impression 3D et un procédé de préparation associé, et un procédé et un dispositif d'impression. Le matériau élastique pour impression 3D comprend un isocyanate auto-bloqué, un monomère monofonctionnel photodurcissable, un agent de réticulation photodurcissable, un photoamorceur et un agent auxiliaire ; la structure moléculaire de l'isocyanate auto-bloqué comprend une structure d'uretdione et ne comprend pas de groupe isocyanate, et la structure moléculaire du monomère monofonctionnel photodurcissable comprend un groupe vinyle. Un objet 3D obtenu à l'aide du matériau élastique pour impression 3D présente d'excellentes propriétés mécaniques, en particulier présente d'excellentes propriétés de résistance à la traction, d'allongement à la rupture et de résistance à la déchirure, donne une bonne sensation au toucher et possède une surface propre et un toucher non collant.
PCT/CN2021/096183 2020-08-24 2021-05-26 Matériau élastique pour impression 3d et procédé de préparation associé, et procédé et dispositif d'impression WO2022041885A1 (fr)

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CN115141322B (zh) * 2022-06-28 2024-02-27 珠海赛纳三维科技有限公司 三维打印材料及三维物体、三维物体打印方法
CN115627071A (zh) * 2022-10-24 2023-01-20 中国科学院兰州化学物理研究所 一种4d打印光固化氰酸酯油墨及其制备方法以及形状记忆氰酸酯材料
CN115627071B (zh) * 2022-10-24 2023-11-24 中国科学院兰州化学物理研究所 一种4d打印光固化氰酸酯油墨及其制备方法以及形状记忆氰酸酯材料
CN116650852A (zh) * 2023-08-01 2023-08-29 原子高科股份有限公司 一种基于3d打印的放射性核素敷贴器及其制备方法
CN116650852B (zh) * 2023-08-01 2023-12-19 原子高科股份有限公司 一种基于3d打印的放射性核素敷贴器及其制备方法

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