WO2021120809A1 - 一种3d喷墨打印支撑结构用组合物及其制备方法 - Google Patents

一种3d喷墨打印支撑结构用组合物及其制备方法 Download PDF

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Publication number
WO2021120809A1
WO2021120809A1 PCT/CN2020/121051 CN2020121051W WO2021120809A1 WO 2021120809 A1 WO2021120809 A1 WO 2021120809A1 CN 2020121051 W CN2020121051 W CN 2020121051W WO 2021120809 A1 WO2021120809 A1 WO 2021120809A1
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Prior art keywords
composition
inkjet printing
support structure
weight
composition according
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PCT/CN2020/121051
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English (en)
French (fr)
Inventor
余嘉
杨前程
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珠海赛纳三维科技有限公司
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Priority to EP20903179.8A priority Critical patent/EP4047056A4/en
Priority to JP2022529602A priority patent/JP7307276B2/ja
Publication of WO2021120809A1 publication Critical patent/WO2021120809A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present application relates to a printing composition and a preparation method thereof, in particular to a composition for a 3D inkjet printing support structure and a preparation method thereof, and belongs to the technical field of 3D printing.
  • the suspended part under the suspended structure of the object needs to be printed with a support structure so that the target object can be formed; after the target object is formed, the support structure needs to be moved from the target object In addition, it does not affect the surface accuracy of the target object; therefore, the support structure not only needs to have sufficient mechanical strength to support the target object, but also to facilitate removal from the target object.
  • the types of existing support materials can be divided into support materials removed by mechanical force, water-soluble support materials, water-swellable support materials, alkali-soluble support materials, etc. according to the way the support structure is removed; among them, support materials removed by mechanical force
  • the target object may be damaged due to the impact of mechanical force, and the support structure in the small hole structure is difficult to remove; the dissolution and swelling rates of water-soluble support materials and water-swellable support materials in water are slow, especially When the support structure has a large volume, the removal rate of the support structure is slow; in the process of removing the support structure of the alkali-soluble support material, with the extension of time, the alkali-soluble support material quickly reaches saturation, and the removal rate of the support structure slows down, so it is necessary to frequently
  • the alkaline solution is replaced, thus, on the one hand, the removal cost of the supporting structure is increased, and on the other hand, a large amount of alkaline solution is used to cause environmental pollution.
  • the Chinese invention patent CN108136677A discloses a support material composition, comprising an uncurable water-miscible polymer, a first water-miscible curable material and at least a second water-miscible curable material; wherein the second water-miscible
  • the curable material is selected to interfere with multiple intermolecular interactions between multiple polymer chains formed after exposing the first water-miscible material to curing energy.
  • the second curable material is used to interfere with the polymer reaction of the first curable material, thereby reducing the degree of crosslinking of the polymer, so that the support structure formed by photocuring can be easily and easily in an alkaline solution.
  • composition for 3D inkjet printing includes a specific functional reaction promoting material, which is used in conjunction with a photocurable host material to have a significantly improved photocuring reaction conversion rate, and the photocured product has an increased While supporting the strength, it also has a significantly improved dissolution rate in alkaline solutions.
  • the present application provides a method for preparing a composition for 3D inkjet printing, which can effectively prepare the composition for 3D inkjet printing.
  • the present application also provides a 3D inkjet printing device, which can print the composition for 3D inkjet printing by using an inkjet print head.
  • the present application also provides a 3D inkjet printing method, which can use the 3D inkjet printing device to print a support structure using the 3D inkjet printing support structure composition.
  • the present application also provides a supporting structure, which is printed by using the 3D inkjet printing device and the 3D inkjet printing support structure using the composition.
  • the composition for a 3D inkjet printing support structure provided by the present application includes the following components: 18-40 parts by weight of photocurable host material, 2-30 parts by weight of functional reaction promotion Materials, non-curable water-miscible materials, photoinitiators and auxiliary agents.
  • the functional reaction promoting material contains carboxyl groups and active hydrogen in the molecular structure, and the active hydrogen can react with peroxide radicals.
  • the active hydrogen refers to the hydrogen on the carbon atom closest to the functional group. If COOH is a functional group and R 3 and R 4 are selected from hydrogen, the hydrogen is an active hydrogen; if R When 1 is a functional group, the hydrogen on the carbon atom connected to R 1 is also an active hydrogen.
  • the functional reaction promoting material has the structure of the following general formula (I):
  • the R 1 , R 2 , R 3 and R 4 are independently selected from at least one group of hydrogen, hydroxyl, carboxyl, alkoxy, aryloxy, nitrogen-containing heterocycle, oxygen-containing heterocycle and benzene ring, And when R 1 is hydrogen, at least one of R 3 and R 4 is selected from hydrogen; the n and m are independently selected from integers greater than or equal to 1 and n ⁇ 7, m ⁇ 14.
  • the functional reaction promoting material having the structure of general formula (I) can be obtained by conventional methods in the art, for example, synthesized by the method described in CN103524332A, or can be purchased.
  • R 1 , R 2 , R 3 and R 4 is hydrogen.
  • the alkoxy group is a C1-3 lower alkoxy group.
  • Table 1 lists part of the specific structure of the functional reaction promoting material, but the functional reaction promoting material used in the composition of the present application is not limited to Table 1, as long as it satisfies the general formula (I) in the present application
  • the functional reaction promoting materials of the structure are all within the protection scope of this application.
  • the functional reaction promoting material is 5-10 parts by weight.
  • the conversion rate of the photocurable host material to the photocuring reaction is as high as 80-95%.
  • non-curable water-miscible material is 48 to 78 parts by weight
  • the photoinitiator is 1 to 5 parts by weight
  • the auxiliary agent is 0.4 to 5 parts by weight.
  • the photocurable host material is a (meth)acrylate compound and/or (meth)acrylamide compound.
  • the (meth)acrylate compound is a monofunctional (meth)acrylate compound and/or a multifunctional (meth)acrylate compound.
  • the monofunctional (meth)acrylate compound is selected from glycidyl methacrylate (molecular weight 142), 3-(acryloxy)-2-hydroxypropyl methacrylate (molecular weight) 214), 2-(methacryloxy) ethyl 3-hydroxybutyrate (molecular weight 216), hydroxyethyl acrylate (molecular weight 116), 4-hydroxybutyl acrylate (molecular weight 144), polyethylene Alcohol (200) monoacrylate (molecular weight 450), polyethylene glycol (400) monoacrylate (molecular weight 912), methoxy polyethylene glycol (400) monoacrylate (molecular weight 842) and methoxy polyethylene One or more of diol (550) monoacrylate (molecular weight 620).
  • the multifunctional (meth)acrylate compound is selected from pentaerythritol tetraacrylate (molecular weight 352), pentaerythritol triacrylate (molecular weight 298), polyethylene glycol (200) diacrylate (molecular weight 336) ), one or more of polyethylene glycol (400) diacrylate (molecular weight 508) and polyethylene glycol (600) diacrylate (molecular weight 708).
  • the (meth)acrylamide compound is selected from acryloylmorpholine (molecular weight 141), dimethylacrylamide (molecular weight 99), diethylacrylamide (molecular weight 127), dimethylaminopropyl propylene One or more of amide (molecular weight 156) and hydroxyethyl acrylamide (molecular weight 115).
  • the monofunctional compound with a molecular weight greater than or equal to 300 in the photocurable host material accounts for 15-30 parts by weight, and the photocurable host material
  • the proportion of compounds with a molecular weight greater than 50 and less than 277 is 3-6 parts by weight.
  • the multifunctional (meth)acrylate compound in the photocurable host material accounts for 0-4 parts by weight.
  • the photocurable host material is selected from at least one of (meth)acrylate compounds and (meth)acrylamide compounds with a molecular weight greater than or equal to 300, and at the same time At least one of (meth)acrylate compounds and (meth)acrylamide compounds having a molecular weight of more than 50 and less than 277.
  • the composition has a viscosity of 20-70 cps at 25°C, a surface tension of 26.7-33.5 mN/m, and a viscosity of 8-11 cps at 30-70°C, and a surface tension of 26.7-33.5 mN/m. .
  • the composition is obtained by mixing the components under conditions that avoid the polymerization reaction of the components induced by light.
  • the non-curable water-miscible material is a polyol.
  • the non-curable water-miscible material is penetrated into the network structure formed by the photo-curing reaction, so that the product formed by the photo-curing of the composition is in water or alkaline solution.
  • the dissolution rate in the medium is further increased.
  • the "water-miscible material” itself is liquid, and it is at least partially soluble or dispersible in water, and further, for example, at least 50% of the molecules are soluble in water when it is in contact with (for example, mixed) with water.
  • the polyol may be selected from the group consisting of polyol 3165, polyol 3610, ethylene oxide tetrahydrofuran copolymer (EO/THF copolymer), polypropylene glycol, polypropylene glycol, 1,2-propylene glycol, tripropylene glycol mono One or more of methyl ether, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether (400), polyethylene glycol (400) and polyethylene glycol (200) .
  • polyol 3165 polyol 3610
  • EO/THF copolymer ethylene oxide tetrahydrofuran copolymer
  • polypropylene glycol polypropylene glycol
  • 1,2-propylene glycol 1,2-propylene glycol
  • tripropylene glycol mono One or more of methyl ether, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether (400), poly
  • the photoinitiator is a free radical photoinitiator.
  • the free radical photoinitiator may be selected from benzoin ether, benzoin ⁇ , ⁇ -dimethylbenzyl ketal, ⁇ , ⁇ -diethoxyacetophenone, 2-hydroxy-2-methyl -Phenylacetone-1, 1-hydroxy-cyclohexyl phenyl ketone, 2-isopropylthioxanthone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl acetone-1, 2-Methyl-1-[4-Methylthiophenyl]-2-morpholinyl-1-propanone, [2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanol Ketone-1], benzoyl formate, 2,4,6-trimethylphenylacyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylphenylacyl-diphenyl One or more of phosphine oxide, phenylbis(2,4,6-tritri
  • auxiliary agent is selected from surfactants and/or polymerization inhibitors.
  • the surfactant added to the composition for 3D inkjet printing support structure of the present application has a certain solubility in water or aqueous solution, and its main function is to adjust the surface tension of the composition to enable normal printing and improve the composition’s Fluidity and wetting properties to the substrate.
  • the main function of adding a polymerization inhibitor is to prevent the free radicals in the composition from polymerizing and improve the storage stability of the composition.
  • the polymerization inhibitor is preferably a product that can not only improve the storage stability, but also has no effect on the photocuring reaction of the composition.
  • the surfactant is at least one selected from the group consisting of polyether-modified siloxane and non-silicon polyether.
  • the polyether-modified siloxane may be, for example, various polyether-modified siloxane surfactants on the market, for example, it may be at least one of BYK's trade names BYK345, BYK346, BYK333, etc. It can be at least one of Tego’s product names TEGO wet 270, TEGO Glide 450, etc., and can be AFCONA’s product names AFCONA-3580, AFCONA-3585, AFCONA-3587, AFCONA-3588, etc. At least one.
  • the non-silicon polyether may be various non-silicon polyether surfactants on the market, for example, it may be at least one of BYK's trade name BYK800D, etc., and may be Tego's trade name At least one of TEGO WET 500, TEGO Airex 920, TEGO Airex 921, etc., may be at least one of AFCONA's trade names AFCONA-3500, AFCONA-3590, etc.
  • the polymerization inhibitor may be at least one of the trade names of GENORAD*16, GENORAD*18, GENORAD*20, GENORAD*22, etc., and may be the trade names of BASF under the trade names Tinuvin234, Tinuvin770, At least one of Irganox245, Cytec S100, Cytec 130, etc., can be at least one of Ciba’s trade names Irgastab UV10, Irgastab UV 22D, etc., and can be at least one of Amarico’s MEHQ, etc.
  • One type can be 510 polymerization inhibitor from Shanghai Boer Chemical Reagent Co., Ltd.
  • the present application also provides a method for preparing the composition for 3D inkjet printing support structure, which includes performing the following steps under the condition that each component in the composition is prevented from being induced by light to undergo polymerization reaction:
  • step 1) of the method the order of addition of the components in the process of obtaining the first mixture is not limited.
  • the filtering can be performed in a multiple filtering manner, in particular, a stepwise filtering can be adopted.
  • a microporous filter membrane can be used to filter the second mixture at least twice; wherein the pore size of the microporous filter membrane used in the previous filtration is larger than the pore size of the microporous filter membrane used in the subsequent filtration, and the last time The pore size of the microporous filter membrane used in the filtration is smaller than the pore size of the nozzle orifice of the print head in the 3D inkjet printing device, ensuring that the 3D inkjet printing support structure has good printing fluency and avoiding clogging the nozzle orifice of the print head.
  • the second mixture is processed by two-stage filtration.
  • the first-stage filtration uses glass fiber membranes with a pore size of 0.45-0.6 ⁇ m, and the second-stage filtration uses a polymer with a pore size of 0.2 ⁇ m. Acrylic film.
  • the collected filtrate can also be degassed. By degassing the filtrate, it is further ensured that the composition has very good fluency during use, and the interference of air bubbles in the composition can prevent print disconnection, which in turn affects the molding accuracy of the support structure.
  • the operation mode of the degassing treatment can be reduced pressure degassing, normal pressure degassing or heating degassing, and any two or more degassing methods can also be selected.
  • the time for controlling the degassing treatment does not exceed 5 hours. In the specific implementation process of this application, the degassing time is generally controlled at 0.5 to 3 hours.
  • the 3D inkjet printing device provided by the present application includes an inkjet print head, and the inkjet print head can be used to print the composition for 3D inkjet printing support structure.
  • the present application provides a 3D inkjet printing method.
  • the printing process includes using the 3D inkjet printing device and using the 3D inkjet printing support structure composition to print a support structure.
  • the present application also provides a supporting structure, which is printed by using the 3D inkjet printing device and the composition for the 3D inkjet printing support structure.
  • the support structure includes any structure other than the target object during the printing process of the target object.
  • the composition provided in the present application can also be used to print the target object that meets the requirements.
  • the present application adds a functional reaction promoting material to the composition.
  • the molecular structure of the functional reaction promoting material contains active hydrogen, which acts as a donor of active hydrogen and can free the activity that has been inactivated under the influence of oxygen inhibition.
  • the group regains its activity, and/or, can transform the active free radicals that have been inactivated by the influence of oxygen inhibition to obtain active alkoxy radicals and hydroxyl radicals; sufficient active free radicals under ultraviolet light irradiation
  • Make the photo-curable host material fully undergo the photo-curing reaction to increase the photo-curing conversion rate of the photo-cured host material, so that the photo-cured host with the required supporting structure and mechanical strength can be achieved under the same exposure time and exposure intensity in the 3D inkjet printing process
  • the content of the material is greatly reduced; the content of the photocurable host material in the composition for 3D inkjet printing support structure in the present application is small, and the dissolution rate of the cured composition is greatly increased when the cured composition is placed in an al
  • the functional reaction promoting material in the present application contains a carboxyl group in its molecular structure, and its reaction product itself and its reaction product can react with alkali in an alkaline solution to accelerate the alkali dissolution rate of the photocured support material composition; and the functionality
  • the reaction promoting material contains carboxyl groups in the molecular structure, which is water-soluble or hydrophilic, and can better dissolve in alkaline solutions.
  • composition provided by the present application has a significantly improved conversion rate of the photocuring reaction; and the photocured product has an increased support strength while also having a significantly improved dissolution rate in an alkaline solution.
  • the support structure provided by this application has high support strength.
  • the support structure sample printed according to the standard GB/T 14484-2008 has a support strength of at least 0.1 MPa, which can effectively support the printing of the target object.
  • the support structure provided by this application can quickly dissolve in an alkaline solution and improve the post-processing efficiency of the target object.
  • a support structure sample of 20mm ⁇ 20mm ⁇ 20mm has a dissolution time in an alkaline solution of less than 90min.
  • the composition provided by the present application achieves the support strength of the same cured product (ie, the printed support structure), the content of the photocurable host material in the composition is small, the photocuring reaction rate is increased, and the radiation intensity is reduced Or radiation time, saving energy.
  • the composition provided by this application has a viscosity of 20 to 70 cps at room temperature and 25°C, a surface tension of 26.7 to 33.5 mN/m, and a viscosity of 8 to 11 cps at a working temperature (30-70°C) and a surface tension of 26.7 ⁇ 33.5mN/m.
  • the composition provided in this application can not only perform normal inkjet printing at a high temperature such as 70°C, but also perform normal inkjet printing at a lower working temperature such as 30°C, thereby prolonging the service life of the print head.
  • This embodiment provides a composition for a 3D inkjet printing support structure, which has the following composition in Table 2:
  • the functional reaction promoting materials in Table 2 can be purchased from Tixiai (Shanghai) Chemical Industry Development Co., Ltd. or Sigma-Aldrich (Shanghai) Trading Co., Ltd.
  • the functional reaction promoting material in this example was purchased from TSI (Shanghai) Chemical Industry Development Co., Ltd.
  • composition for 3D inkjet printing support structure is as follows:
  • This embodiment provides a composition for 3D inkjet printing support structure, which has the following composition in Table 3:
  • the functional reaction promotion materials in Table 3 can be purchased from Shanghai Ziyu Material Technology Co., Ltd. or TOKYO CHEMICAL INDUSTRY CO., LTD. (Tokyo Chemical Industry Co., Ltd.).
  • the functional reaction promotion material in this example was purchased from Shanghai Ziyu Material Technology Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that of Example 1, except that the components used are replaced accordingly, and in step (3) of the preparation method, heating and degassing is used to remove The filtrate obtained in step (2) is heated to 40°C for degassing treatment, and the degassing time is 50 minutes.
  • This embodiment provides a composition for 3D inkjet printing support structure, which has the following composition in Table 4:
  • the functional reaction promotion materials in Table 4 can be purchased from Nanjing Chemical Reagent Co., Ltd. or West Asia Chemical Technology (Shandong) Co., Ltd.
  • the functional reaction promotion material in this example was purchased from Nanjing Chemical Reagent Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that of Example 1, except that the components used are replaced accordingly, and in step (3) of the preparation method, the specific time for degassing under reduced pressure is adjusted to 2 hours.
  • This embodiment provides a composition for 3D inkjet printing support structure, which has the following composition in Table 5:
  • the functional reaction promotion materials in Table 5 can be purchased from Shanghai Ziyu Material Technology Co., Ltd. or TOKYO CHEMICAL INDUSTRY CO., LTD. (Tokyo Chemical Industry Co., Ltd.).
  • the functional reaction promotion material in this embodiment was purchased from Shanghai Ziyu Material Technology Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that of Example 1, except that the components used are replaced accordingly, and the step (3) of the preparation method is degassed by standing degassing under normal pressure.
  • the standing time is 3h.
  • This embodiment provides a composition for a 3D inkjet printing support structure, which has the following composition in Table 6:
  • Table 6 Composition of the composition for 3D inkjet printing support structure in Example 5
  • the functional reaction promotion materials in Table 6 can be purchased from Shanghai Ziyu Material Technology Co., Ltd. or TOKYO CHEMICAL INDUSTRY CO., LTD. (Tokyo Chemical Industry Co., Ltd.).
  • the functional reaction promotion material in this embodiment was purchased from Shanghai Ziyu Material Technology Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that in Example 1, except that the components used are replaced accordingly, and step (3) of the preparation method is to use heating and degassing, and step (2) )
  • the obtained filtrate is heated to about 50°C for degassing treatment, and the degassing time is 30 minutes.
  • This embodiment provides a composition for 3D inkjet printing support structure, which has the following composition in Table 7:
  • Table 7 Composition of the composition for 3D inkjet printing support structure in Example 6
  • the functional reaction promotion materials in Table 7 can be purchased from Shanghai Ziyu Material Technology Co., Ltd. or TCI Europe.
  • the functional reaction promotion material in this embodiment was purchased from Shanghai Ziyu Material Technology Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that of Example 1, except that the components used are replaced accordingly.
  • This embodiment provides a composition for 3D inkjet printing support structure, which has the following composition in Table 8:
  • Table 8 Composition of the composition for 3D inkjet printing support structure in Example 7
  • the functional reaction promotion materials in Table 8 can be purchased from Shanghai Ziyu Material Technology Co., Ltd. or Simagchem Corporation.
  • the functional reaction promotion material in this embodiment was purchased from Shanghai Ziyu Material Technology Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that of Example 1, except that the components used are replaced accordingly.
  • This embodiment provides a composition for a 3D inkjet printing support structure, which has the following composition in Table 9:
  • Table 9 Composition of the composition for 3D inkjet printing support structure in Example 8.
  • the functional reaction promotion materials in Table 9 can be purchased from Shanghai Ziyu Material Technology Co., Ltd. or TOKYO CHEMICAL INDUSTRY CO., LTD. (Tokyo Chemical Industry Co., Ltd.).
  • the functional reaction promotion material in this embodiment was purchased from Shanghai Ziyu Material Technology Co., Ltd.
  • the preparation method of the composition for 3D inkjet printing support structure in this example is basically the same as that of Example 1, except that the components used are replaced accordingly.
  • This comparative example provides a composition for 3D inkjet printing support structure, which has the following composition in Table 10:
  • Table 10 Composition of the composition for 3D inkjet printing support structure in Comparative Example 1
  • the preparation method of the composition for 3D inkjet printing support structure in Comparative Example 1 is basically the same as that of Example 1, except that the components used are replaced accordingly.
  • This embodiment provides a 3D inkjet printing device, including an inkjet print head, which can use the composition for 3D inkjet printing support structure in any of the foregoing embodiments to print a support structure. Further, it is also possible to print a target object on the supporting structure.
  • This embodiment provides a printing method that can use the 3D inkjet printing device described in Example 9 to print a support structure using the composition for 3D inkjet printing support structure described in any one of Examples 1-8.
  • a DV-I digital viscometer was used to test the viscosity of the composition.
  • a BZY-1 automatic surface tension meter was used to test the surface tension of the composition.
  • composition in this application is applied to Saina J5013D light-curing inkjet printer to print samples of the dimensions required in GB/T 14484-2008 "Determination of Plastic Bearing Strength" (that is, the composition can be cured After the product sample or support structure sample), the support strength is determined by the compression test carried out by the LLOYD tension meter model LR5K PLUS, which is operated under the standard compression combination parameters, and is expressed in MPa relative to the above-mentioned cube.
  • the composition is applied to the Saina J501 3D light-curing inkjet printer, the nozzle temperature is set at 30-70°C, and the length, width, and height are 20mm ⁇ 20mm ⁇ 20mm cubes.
  • the cube can be It is a product sample or a support structure sample after the composition is cured immersed in 800 mL of a 2% by weight sodium hydroxide aqueous solution, and the time for the cube such as the support structure sample to completely dissolve is recorded.
  • the compositions in Examples 1-8 have a significantly improved photocuring reaction conversion rate, and the photocured product (ie, support structure) has increased At the same time as the support strength, it also has a significantly improved dissolution rate in the alkaline solution.
  • the dissolution time of the printed support structure sample of 20mm ⁇ 20mm ⁇ 20mm in the alkaline solution is less than or equal to 90min.
  • the content of the photocurable host material in the above composition is small, and the photocuring reaction rate is significantly improved.
  • composition provided in the present application can not only perform normal inkjet printing at a high temperature such as 70°C, but also perform normal inkjet printing at a lower working temperature such as 30°C, which can prolong the service life of the print head.

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Abstract

一种3D喷墨打印支撑结构用组合物及其制备方法，所述3D喷墨打印支撑结构用组合物，基于所述组合物的总重，包括以下成分：18～40重量份的光固化主体材料、2～30重量份的功能性反应促进材料、不可固化的水混溶性材料、光引发剂和助剂，所述功能性反应促进材料分子结构中含有羧基及活泼氢，所述活泼氢能与过氧化自由基反应。所述组合物的制备方法也被提供。所述组合物，具有显著提高的光固化反应转化率，并且其光固化产物在具有增加的支撑强度的同时，还具有显著提高的碱性溶液中溶解速率。

Description

一种3D喷墨打印支撑结构用组合物及其制备方法
本申请要求于2019年12月20日提交中国专利局、申请号为201911325181.4、申请名称为“一种3D喷墨打印支撑结构用组合物及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及一种打印用组合物及其制备方法，尤其涉及一种3D喷墨打印支撑结构用组合物及其制备方法，属于3D打印技术领域。
背景技术
3D喷墨打印过程中，例如在打印具有悬空结构的物体时，物体悬空结构下方的悬空部分需要打印支撑结构，以致目标物体能被形成；在目标物体形成之后，支撑结构需要从目标物体上移除且不影响目标物体的表面精度；因此，支撑结构既需要具有足够的机械强度能支撑目标物体，同时还要便于从目标物体上移除。
现有支撑材料的种类根据支撑结构的移除方式可分为：机械力移除的支撑材料、水溶性支撑材料、水溶胀支撑材料和碱溶性支撑材料等；其中，机械力移除的支撑材料在支撑结构移除过程中，由于机械力的撞击作用可能损坏目标物体，且细小孔洞结构中的支撑结构难以去除；水溶性支撑材料和水溶胀支撑材料分别在水中的溶解和溶胀速率慢，尤其在支撑结构体积大时支撑结构的去除速率慢；碱溶性支撑材料在支撑结构去除过程中，随着时间的延长，碱溶性支撑材料很快达到饱和，支撑结构的去除速率减慢，因此需要经常更换碱溶液，从而，一方面提高了支撑结构的去除成本，另一方面使用大量的碱液造成环境污染。
已知中国发明专利CN108136677A公开了一种支撑材料组合物，包括不可固化的水混溶性聚合物、第一水混溶性可固化材料以及至少第二水混溶性可固化材料；其中第二水混溶性可固化材料被选择为用于干扰将第一水混溶性材料暴露于固化能量之后形成的多个聚合物链之间的多个分子间 的相互作用。该已知的现有技术中通过使用第二可固化材料干扰第一可固化材料的聚合物反应，从而降低聚合物的交联度，以致光固化形成的支撑结构在碱性溶液中能容易且有效的除去，减少溶解时间，增加溶解速率，并且不损害支撑材料的机械性能。然而，由于第二水混溶性可固化材料分子结构中含有不饱和双键，在光固化反应过程中该双键也会参与光固化反应，在增加光固化产物的机械强度时，对在碱液中的溶解速率有一定影响。
因此，如何提供一种支撑材料组合物，其光固化产物在具有增加的支撑强度的同时，还具有提高的碱性溶液中溶解速率，成为有待解决的问题。
发明内容
本申请提供的一种3D喷墨打印用组合物，包括特定的功能性反应促进材料，与光固化主体材料搭配使用，具有显著提高的光固化反应转化率，并且其光固化产物在具有增加的支撑强度的同时，还具有显著提高的碱性溶液中溶解速率。
本申请提供的一种制备3D喷墨打印用组合物的方法，能有效的制备所述3D喷墨打印用组合物。
本申请还提供了一种3D喷墨打印装置，能利用喷墨打印头打印所述3D喷墨打印用组合物。
本申请还提供了一种3D喷墨打印方法，能使用所述3D喷墨打印装置，利用所述3D喷墨打印支撑结构用组合物打印支撑结构。
本申请还提供了一种支撑结构，使用所述的3D喷墨打印装置，利用所述的3D喷墨打印支撑结构用组合物打印而成。
本申请提供的一种3D喷墨打印支撑结构用组合物，基于所述组合物的总重，包括以下成分：18～40重量份的光固化主体材料、2～30重量份的功能性反应促进材料，不可固化的水混溶性材料、光引发剂和助剂，所述功能性反应促进材料分子结构中含有羧基及活泼氢，所述活泼氢能与过氧化自由基反应。
在本申请方案中，活泼氢指的是距离功能性基团最近的碳原子上的氢,若COOH是功能性基团，R 3和R 4选自氢时，该氢是活泼氢；若R 1是功能性基团时，与R 1相连的碳原子上的氢也是活泼氢。
在本申请的一个具体实施方式中，所述功能性反应促进材料具有如下通式(Ⅰ)的结构：
Figure PCTCN2020121051-appb-000001
所述R 1、R 2、R 3和R 4独立选自氢、羟基、羧基、烷氧基、芳氧基、含氮杂环、含氧杂环和苯环中的至少一种基团，且当R 1为氢时，R 3和R 4中至少其一选自氢；所述n，m独立选自大于或等于1的整数且n≤7，m≤14。
在本申请方案中，具有通式(Ⅰ)的结构的功能性反应促进材料可以采用本领域常规方法获得，例如CN103524332A中记载的方法合成得到，或者可以购买得到。
进一步的，R 1、R 2、R 3和R 4中至少一个为氢。
进一步的，通式(Ⅰ)中，n≤2，m≤2。
更进一步的，所述烷氧基为C1-3的低级烷氧基。
具体的，表1列举了所述功能性反应促进材料的部分具体结构，但本申请组合物中使用的功能性反应促进材料不局限于表1，只要满足本申请中通式(I)所述结构的功能性反应促进材料都在本申请的保护范围内。
表1
Figure PCTCN2020121051-appb-000002
Figure PCTCN2020121051-appb-000003
Figure PCTCN2020121051-appb-000004
在本申请的另一个具体实施方式中，所述功能性反应促进材料为5-10重量份。当所述功能性反应促进材料重量在该范围时，所述光固化主体材料发生光固化反应的转化率高达80-95％。
进一步的，所述不可固化的水混溶性材料为48～78重量份，所述光引发剂为1～5重量份，所述助剂为0.4～5重量份。
进一步的，所述光固化主体材料为(甲基)丙烯酸酯类化合物和/或(甲基)丙烯酰胺类化合物。
在本申请的一个具体实施方式中，所述(甲基)丙烯酸酯类化合物为单官能度(甲基)丙烯酸酯类化合物和/或多官能度(甲基)丙烯酸酯类化合物。
更进一步的，所述单官能度(甲基)丙烯酸酯类化合物选自甲基丙烯酸缩水甘油酯(分子量142)，3-(丙烯酰氧基)-2-羟基丙基甲基丙烯酸酯(分子量214)，2-(甲基丙烯酰氧基)乙基3-羟基丁酸酯(分子量216)，丙烯酸羟乙酯(分子量116)，4-羟基丁基丙烯酸酯(分子量144)，聚乙二醇(200)单丙烯酸酯(分子量450)，聚乙二醇(400)单丙烯酸酯(分子量912)，甲氧基聚乙二醇(400)单丙烯酸酯(分子量842)和甲氧基聚乙二醇(550)单丙烯酸酯(分子量620)中的一种或多种。
更进一步的，所述多官能度(甲基)丙烯酸酯类化合物选自季戊四醇四丙烯酸酯(分子量352)，季戊四醇三丙烯酸酯(分子量298)，聚乙二醇(200)二丙烯酸酯(分子量336)，聚乙二醇(400)二丙烯酸酯(分子量508)和聚乙二醇(600)二丙烯酸酯(分子量708)中的一种或多种。
进一步的，所述(甲基)丙烯酰胺类化合物选自丙烯酰吗啉(分子量141)，二甲基丙烯酰胺(分子量99)，二乙基丙烯酰胺(分子量127)，二甲氨基丙基丙烯酰胺(分子量156)和羟乙基丙烯酰胺(分子量115)中 的一种或多种。
在本申请的另一个具体实施方式中，基于所述组合物的总重，所述光固化主体材料中分子量大于或等于300的单官能度化合物占比15～30重量份，以及光固化主体材料中分子量大于50且小于277的化合物的占比3～6重量份。在本申请的方案中，通过控制上述光固化主体材料中不同分子量范围的化合物的比例，使得所述组合物的光固化产物在碱性溶液中的溶解性更好。
进一步的，基于所述组合物的总重，所述光固化主体材料中多官能度(甲基)丙烯酸酯类化合物占0～4重量份。
在本申请的另一个具体实施方式中，所述光固化主体材料选自分子量大于或等于300的(甲基)丙烯酸酯类化合物、(甲基)丙烯酰胺类化合物中的至少一种，同时选自分子量大于50且小于277的(甲基)丙烯酸酯类化合物、(甲基)丙烯酰胺类化合物中的至少一种。
进一步的，所述组合物在25℃下的粘度为20～70cps，表面张力为26.7～33.5mN/m，并且在30-70℃下粘度为8～11cps，表面张力为26.7～33.5mN/m。
在本申请的一个具体实施方式中，所述组合物在避免各成分被光诱发发生聚合反应的条件下混合各成分获得。
在本申请的方案中，所述不可固化的水混溶性材料为多元醇。
在所述组合物的光固化反应过程中，该不可固化的水混溶性材料被渗透到光固化反应形成的网状结构中，使得由该组合物经光固化形成的产物在水或碱性溶液中的溶解速率进一步提高。“水混溶性材料”本身为液态，并且其至少部分可溶于水或分散于水，进一步例如与水接触(例如混合)时至少50％的分子可溶解于水中。
进一步的，所述多元醇可以是选自多元醇3165、多元醇3610、环氧乙烷四氢呋喃共聚物(EO/THF共聚物)、聚丙二醇、聚丙三醇、1,2-丙二醇、三丙二醇单甲醚、二丙二醇单甲醚、三乙二醇二甲醚、聚乙二醇单甲醚(400)、聚乙二醇(400)和聚乙二醇(200)中的一种或多种。
在本申请的实施方式中，所述光引发剂为自由基光引发剂。
进一步的，所述自由基光引发剂可以是选自安息香乙醚、安息香α,α- 二甲基苯偶酰缩酮、α,α-二乙氧基苯乙酮、2-羟基-2-甲基-苯基丙酮-1、1-羟基-环己基苯基甲酮、2-异丙基硫杂蒽酮、2-羟基-2-甲基-对羟乙基醚基苯基丙酮-1、2-甲基-1-[4-甲硫基苯基]-2-吗琳基-1-丙酮、[2-苄基-2-二甲氨基-1-(4-吗啉苯基)丁酮-1]、苯甲酰甲酸酯、2,4,6-三甲基苯基酰基-乙氧基-苯基氧化膦、2,4,6-三甲基苯基酰基-二苯基氧化膦、苯基双(2,4,6-三甲基苯甲酰基)氧化膦和4-对甲苯巯基二苯甲酮中的一种或多种。
进一步的，所述助剂选自表面活性剂和/或阻聚剂。
本申请3D喷墨打印支撑结构用组合物中添加的表面活性剂在水或水性溶液中具有一定的溶解性，其主要作用是调整组合物的表面张力使其能够正常打印，同时提高组合物的流动性以及对基材的润湿性能。添加阻聚剂主要作用是阻止组合物中的自由基发生聚合反应，提高组合物的贮存稳定性，阻聚剂优选既能提高存储稳定性，又对组合物发生光固化反应没有影响的产品。
更进一步的，所述表面活性剂选自聚醚改性硅氧烷和非硅类聚醚中的至少一种。所述聚醚改性硅氧烷例如可以是市面上销售的各种聚醚改性硅氧烷类表面活性剂，例如可以是BYK公司的商品名为BYK345、BYK346、BYK333等中的至少一种，可以是迪高公司的商品名为TEGO wet 270、TEGO Glide 450等中的至少一种，可以是AFCONA公司的商品名为AFCONA-3580、AFCONA-3585、AFCONA-3587、AFCONA-3588等中的至少一种。所述非硅类聚醚可以是市面上销售的各种非硅类聚醚表面活性剂，例如可以是BYK公司的商品名为BYK800D等中的至少一种，可以是迪高公司的商品名为TEGO WET 500、TEGO Airex 920、TEGO Airex 921等中的至少一种，可以是AFCONA公司的商品名为AFCONA-3500、AFCONA-3590等中的至少一种。
更进一步的，所述阻聚剂可以是瑞昂的商品名为GENORAD*16、GENORAD*18、GENORAD*20、GENORAD*22等中的至少一种，可以是巴斯夫的商品名为Tinuvin234、Tinuvin770、Irganox245、氰特S100、氰特130等中的至少一种，可以是汽巴的商品名为Irgastab UV10、Irgastab UV 22D等中的至少一种，可以是美国阿玛瑞科的MEHQ等中的至少一种，可以是上海波尔化学试剂有限公司的510阻聚剂等。
本申请还提供了一种制备所述3D喷墨打印支撑结构用组合物的方法，包括在避免所述组合物中的各成分被光诱发发生聚合反应的条件下进行以下步骤：
1)将除所述光引发剂以外的成分混合均匀，得到第一混合物；随后向所述第一混合物中加入所述光引发剂，得到第二混合物；
2)过滤所述第二混合物，收集滤液即为所述3D喷墨打印支撑结构用组合物。
进一步的，在所述方法的步骤1)中，对于得到第一混合物的过程中对各成分的添加顺序不进行限制。
更进一步的，在所述方法的步骤2)中，过滤可采用多次过滤的方式进行，尤其可以采用逐级过滤的方式。具体的，可采用微孔滤膜对第二混合物进行至少两次过滤；其中，前一次过滤所采用的微孔滤膜的孔径大于后一次过滤所采用的微孔滤膜的孔径，且最后一次过滤所采用的微孔滤膜的孔径小于3D喷墨打印装置中打印喷头喷孔的孔径，确保制得3D喷墨打印的支撑结构具有很好的打印流畅性，避免堵塞打印头喷孔。
在本申请具体实施过程中，是采用二级过滤的方式对第二混合物进行处理，其中第一级过滤采用孔径为0.45-0.6μm的玻璃纤维膜，第二级过滤采用孔径为0.2μm的聚丙烯膜。
进一步的，还可以对所收集的滤液进行脱气处理。通过对滤液进行脱气处理，进一步确保所述组合物在使用过程中具有非常好的流畅性，避免因为组合物中的气泡的干扰而引起打印断线、进而影响支撑结构的成型精度。
具体的，脱气处理的操作方式可以是减压脱气、常压脱气或加热脱气，也可以选择其中任意两种或多种脱气方式。一般控制脱气处理的时间不超过5小时，在本申请具体实施过程中，一般将脱气时间控制在0.5～3小时。
本申请提供的一种3D喷墨打印装置，包括喷墨打印头，且所述喷墨打印头能够用于打印所述的3D喷墨打印支撑结构用组合物。
本申请提供的一种3D喷墨打印方法，打印过程包括，使用所述的3D喷墨打印装置，利用所述的3D喷墨打印支撑结构用组合物打印支撑结构。
本申请还提供了一种支撑结构，使用所述的3D喷墨打印装置，利用 所述的3D喷墨打印支撑结构用组合物打印而成。
在本申请方案中，所述支撑结构包括在目标物体打印过程中除目标物体以外的任何结构，当然本申请提供的所述组合物也可以用来打印满足需求的目标物体。
本申请通过在组合物中添加功能性反应促进材料，所述功能性反应促进材料分子结构中含有活泼氢，其作为活泼氢的供体，能使受氧阻聚影响而已经失活的活性自由基重新获得活性，和/或者，能将受氧阻聚影响而已经失活的活性自由基进行转化获得具有活性的烷氧基自由基和羟基自由基；在紫外光照射下充足的活性自由基使光固化主体材料充分发生光固化反应从而提高光固化主体材料的光固化转化率，以致在3D喷墨打印过程中相同曝光时间和曝光强度下达到所需要支撑结构的支撑机械强度的光固化主体材料的含量大大减少；本申请中3D喷墨打印支撑结构用组合物中光固化主体材料的含量少，在将固化后的组合物置于碱性溶液中时，其溶解速率大大提高。本申请中功能性反应促进材料分子结构中含有羧基，其本身及其反应生成物能在碱性溶液中与碱发生反应加速光固化后的支撑材料组合物的碱溶速率；而且所述功能性反应促进材料分子结构中含有羧基，具有水溶性或亲水性，能更好的溶解在碱性溶液中。
本申请方案具有以下优点：
1、本申请提供的组合物，具有显著提高的光固化反应转化率；并且其光固化产物在具有增加的支撑强度的同时，还具有显著提高的碱性溶液中溶解速率。
2、本申请提供的支撑结构支撑强度高，按标准GB/T 14484-2008打印的支撑结构试样，其支撑强度至少为0.1MPa，能有效支撑目标物体的打印。
3、本申请提供的支撑结构能在碱性溶液中快速溶解，提高目标物体的后处理效率，例如20mm×20mm×20mm的支撑结构试样，在碱性溶液中的溶解时间为小于90min。
4、本申请提供的组合物，达到相同固化产物(即打印出的支撑结构)的支撑强度的前提下，所述组合物中的光固化主体材料含量少，提高光固化反应速率，降低辐射强度或辐射时长，节约能源。
5、本申请提供的组合物在室温25℃下的粘度为20～70cps，表面张力 为26.7～33.5mN/m，并且在工作温度(30-70℃)下粘度为8～11cps，表面张力为26.7～33.5mN/m。本申请提供的组合物不仅能在高温下如70℃进行正常的喷墨打印，在较低的工作温度如30℃也能进行正常的喷墨打印，从而可以延长打印头的使用寿命。
具体实施方式
实施例1
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表2的组成：
表2实施例1中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000005
表2中功能性反应促进材料可购买于梯希爱(上海)化成工业发展有限公司或Sigma-Aldrich西格玛奥德里奇(上海)贸易有限公司。在本实施例中的功能性反应促进材料购买于梯希爱(上海)化成工业发展有限公司。
该3D喷墨打印支撑结构用组合物的制备方法如下：
(1)将除光引发剂以外的成分均置于玻璃容器中，采用搅拌器进行搅拌，得到混合均匀的第一混合物；随后向第一混合物中加入光引发剂，继续搅拌至光引发剂完全溶解，得到第二混合物；
(2)用0.6μm的玻璃纤维膜对第二混合物进行一级过滤，再用0.2μm的聚丙烯膜(PP膜)进行二级过滤，得到滤液；
(3)在0.1MPa真空度下，减压抽滤1小时，除去滤液中的气泡，最后得到3D喷墨打印支撑结构用组合物。
实施例2
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表3的组成：
表3实施例2中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000006
表3中功能性反应促进材料可购买于上海梓域材料科技有限公司或TOKYO CHEMICAL INDUSTRY CO.,LTD.(东京化学工业有限责任公司)。在本实施例中的功能性反应促进材料购买于上海梓域材料科技有限 公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换，且在制备方法的步骤(3)中，是采用加热脱气的方式，将步骤(2)所得滤液加热到40℃进行脱气处理，脱气时间50min。
实施例3
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表4的组成：
表4实施例3中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000007
表4中功能性反应促进材料可购买于南京化学试剂股份有限公司或西亚化学科技(山东)有限公司。在本实施例中的功能性反应促进材料购买于南京化学试剂股份有限公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换，且在制备方法的步骤(3)中，减压脱气的具体时间调整为2小时。
实施例4
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表5的组成：
表5实施例4中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000008
表5中功能性反应促进材料可购买于上海梓域材料科技有限公司或TOKYO CHEMICAL INDUSTRY CO.,LTD.(东京化学工业有限责任公司)。在本实施例中的功能性反应促进材料购买于上海梓域材料科技有限公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换，且制备方法的步骤(3)采用常压静置脱气进行脱气处理，静置时间为3h。
实施例5
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表6的组成：
表6实施例5中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000009
Figure PCTCN2020121051-appb-000010
表6中功能性反应促进材料可购买于上海梓域材料科技有限公司或TOKYO CHEMICAL INDUSTRY CO.,LTD.(东京化学工业有限责任公司)。在本实施例中的功能性反应促进材料购买于上海梓域材料科技有限公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换，且制备方法的步骤(3)是采用加热脱气的方式，将步骤(2)所得滤液加热到50℃左右进行脱气处理，脱气时间为30min。
实施例6
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表7的组成：
表7实施例6中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000011
Figure PCTCN2020121051-appb-000012
表7中功能性反应促进材料可购买于上海梓域材料科技有限公司或TCI Europe。在本实施例中的功能性反应促进材料购买于上海梓域材料科技有限公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换。
实施例7
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表8的组成：
表8实施例7中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000013
表8中功能性反应促进材料可购买于上海梓域材料科技有限公司或Simagchem Corporation。在本实施例中的功能性反应促进材料购买于上海梓域材料科技有限公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换。
实施例8
本实施例提供一种3D喷墨打印支撑结构用组合物，其具有如下表9的组成：
表9实施例8中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000014
表9中功能性反应促进材料可购买于上海梓域材料科技有限公司或TOKYO CHEMICAL INDUSTRY CO.,LTD.(东京化学工业有限责任公司)。在本实施例中的功能性反应促进材料购买于上海梓域材料科技有限公司。
本实施例中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换。
对比例1
本对比例提供一种3D喷墨打印支撑结构用组合物，其具有如下表10 的组成：
表10对比例1中3D喷墨打印支撑结构用组合物的组成
Figure PCTCN2020121051-appb-000015
对比例1中3D喷墨打印支撑结构用组合物的制备方法与实施例1基本相同，只是所用成分进行相应更换。
实施例9
本实施例提供一种3D喷墨打印装置，包括喷墨打印头，所述喷墨打印头能利用前述任一实施例中的所述3D喷墨打印支撑结构用组合物打印支撑结构。进一步的，还可以在所述支撑结构上打印目标物体。
实施例10
本实施例提供一种打印方法，能使用实施例9所述的3D喷墨打印装置，利用实施例1-8中任一所述3D喷墨打印支撑结构用组合物打印支撑结构。
对上述各实施例以及对比例中的3D喷墨打印支撑结构用组合物进行性能测试，测试方法如下，测试结果参见表11。
1、粘度
采用DV-I数显粘度计测试所述组合物的粘度。
2、表面张力
采用BZY-1全自动表面张力仪测试所述组合物的表面张力。
3、支撑强度
将本申请中的所述组合物应用于赛纳J5013D光固化喷墨打印机上，打印GB/T 14484-2008《塑料承载强度的测定》中所要求尺寸规格的试样(即可以是组合物固化后的产物试样或支撑结构试样)，通过LLOYD张力计型号LR5K PLUS进行的压缩测试来确定其支撑强度，其在标准压缩组合参数下操作，并且相对于上述立方体用MPa表示。
4、溶解速率
将所述组合物应用于赛纳J501 3D光固化喷墨打印机上，设定喷头温度在30-70℃，打印长、宽、高为20mm×20mm×20mm的立方体，打印完成后将立方体(可以是组合物固化后的产物试样或支撑结构试样)浸入800mL 2％重量比的氢氧化钠水溶液中，记录立方体例如支撑结构试样完全溶解的时间。
5、光固化反应转化率
利用红外光谱分析技术，测定所述组合物固化前后的C＝C双键在1648～1589cm -1特征吸收峰面积(固化前A1，固化后A2)，通过公式：C％＝(A1-A2)/A1*100％，测定光固化反应转化率。
表11各实施例及对比例性能参数测试结果
Figure PCTCN2020121051-appb-000016
Figure PCTCN2020121051-appb-000017
可以看出，相比于没有添加功能性反应促进材料的对比例，实施例1-8中的组合物具有显著提高的光固化反应转化率，并且其光固化产物(即支撑结构)在具有增加的支撑强度的同时，还具有显著提高的碱性溶液中溶解速率，打印的20mm×20mm×20mm的支撑结构试样，在碱性溶液中的溶解时间小于等于90min。
在获得相同固化产物(即打印出的支撑结构)的支撑强度的前提下，上述组合物中的光固化主体材料含量少，光固化反应速率显著提高。
本申请提供的组合物不仅能在高温下如70℃进行正常的喷墨打印，在较低的工作温度如30℃也能进行正常的喷墨打印，可以延长打印头的使用寿命。

Claims (18)

  1. 一种3D喷墨打印支撑结构用组合物，其中，基于所述组合物的总重，包括以下成分：18～40重量份的光固化主体材料、2～30重量份的功能性反应促进材料、不可固化的水混溶性材料、光引发剂和助剂，所述功能性反应促进材料分子结构中含有羧基及活泼氢，所述活泼氢能与过氧化自由基反应。
  2. 根据权利要求1所述的组合物，其中，所述功能性反应促进材料具有如下通式(Ⅰ)的结构：
    Figure PCTCN2020121051-appb-100001
    所述R 1、R 2、R 3和R 4独立选自氢、羟基、羧基、烷氧基、芳氧基、含氮杂环、含氧杂环和苯环中的至少一种基团，且当R 1为氢时，R 3和R 4中至少其一选自氢；所述n，m独立选自大于或等于1的整数且n≤7，m≤14。
  3. 根据权利要求2所述的组合物，其中，R 1、R 2、R 3和R 4中至少一个为氢。
  4. 根据权利要求2或3所述的组合物，其中，n≤2，m≤2。
  5. 根据权利要求2-4任一项所述的组合物，其中，所述烷氧基为C1-3的低级烷氧基。
  6. 根据权利要求1-5任一项所述的组合物，其中，所述功能性反应促进材料为5-10重量份。
  7. 根据权利要求1-6任一项所述的组合物，其中，所述不可固化的水混溶性材料为48～78重量份，所述光引发剂为1～5重量份，所述助剂为0.4～5重量份。
  8. 根据权利要求1-7任一项所述的组合物，其中，所述不可固化的水混溶性材料为多元醇。
  9. 根据权利要求1-8任一项所述的组合物，其中，所述光固化主体材料为(甲基)丙烯酸酯类化合物和/或(甲基)丙烯酰胺类化合物。
  10. 根据权利要求9所述的组合物，其中，基于所述组合物的总重，所述光固化主体材料中分子量大于或等于300的单官能度化合物占比15～30重量份，以及光固化主体材料中分子量大于50且小于277的化合物的占比3～6重量份。
  11. 根据权利要求9或10所述的组合物，其中，基于所述组合物的总重，所述光固化主体材料中多官能度(甲基)丙烯酸酯类化合物占0～4重量份。
  12. 根据权利要求1-11任一项所述的组合物，其中，所述组合物在25℃下的粘度为20～70cps，表面张力为26.7～33.5mN/m，并且在30-70℃下粘度为8～11cps，表面张力为26.7～33.5mN/m。
  13. 根据权利要求1-12任一项所述的组合物，其中，所述组合物在避免各成分被光诱发发生聚合反应的条件下混合各成分获得。
  14. 一种制备权利要求1-13任一项所述的3D喷墨打印支撑结构用组合物的方法，包括在避免所述组合物中的各成分被光诱发发生聚合反应的条件下进行以下步骤：
    1)将除所述光引发剂以外的成分混合均匀，得到第一混合物；随后向所述第一混合物中加入所述光引发剂，得到第二混合物；
    2)过滤所述第二混合物，收集滤液即为所述3D喷墨打印支撑结构用组合物。
  15. 一种3D喷墨打印装置，包括喷墨打印头，且所述喷墨打印头能够用于打印权利要求1-13任一项所述的3D喷墨打印支撑结构用组合物。
  16. 一种3D喷墨打印方法，其中，打印过程包括，使用权利要求15所述的3D喷墨打印装置，利用权利要求1-13任一项所述的3D喷墨打印支撑结构用组合物打印支撑结构。
  17. 根据权利要求16所述的打印方法，其中，还包括在所述支撑结构的支撑下打印目标物体。
  18. 一种支撑结构，其中，使用权利要求15所述的3D喷墨打印装置，利用权利要求1-13任一项所述的3D喷墨打印支撑结构用组合物打印而成。
PCT/CN2020/121051 2019-12-20 2020-10-15 一种3d喷墨打印支撑结构用组合物及其制备方法 WO2021120809A1 (zh)

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