CN113388075B - Composition for 3D printing, 3D printing method and device - Google Patents

Composition for 3D printing, 3D printing method and device Download PDF

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CN113388075B
CN113388075B CN202110659489.3A CN202110659489A CN113388075B CN 113388075 B CN113388075 B CN 113388075B CN 202110659489 A CN202110659489 A CN 202110659489A CN 113388075 B CN113388075 B CN 113388075B
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composition
groups
printing
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acrylate
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CN113388075A (en
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吕如松
杨前程
傅佳艺
陈保全
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Zhuhai Sailner 3D Technology Co Ltd
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Zhuhai Sailner 3D Technology Co Ltd
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Priority to PCT/CN2022/097957 priority patent/WO2022258030A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/245—Platforms or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264—Arrangements for irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/295—Heating elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers

Abstract

The invention provides a composition for 3D printing, a 3D printing method and a device. The first aspect of the invention provides a composition for 3D printing, which comprises, by weight, 5-30% of ketoxime blocked diisocyanate, 5-40% of an active hydrogen-containing compound, 5-40% of a first photocuring component, 20-80% of a photocuring monomer, 0-30% of a photocuring oligomer, 0.5-10% of a photoinitiator, 0-1% of a catalyst, 0.05-8% of an auxiliary agent, 0-15% of a filler and 0-5% of a colorant. The composition for 3D printing provided by the invention has adjustable viscosity, is suitable for ink-jet printing and/or three-dimensional photocuring molding technology, and has better thermal stability; and the 3D object printed by the composition provided by the invention has good dimensional stability and mechanical property.

Description

Composition for 3D printing, 3D printing method and device
Technical Field
The invention relates to a composition for 3D printing, a 3D printing method and a device, and relates to the technical field of 3D printing.
Background
The photocuring 3D printing technology mainly comprises a three-dimensional inkjet printing technology (3 DP), a stereolithography technology (SLA), a digital light processing technology (DLP), a continuous liquid level manufacturing technology (CLIP) and the like, wherein liquid photosensitive resin is mainly used as a raw material, and under the condition of light irradiation, the photosensitive resin is subjected to polymerization reaction and is rapidly cured and molded to obtain a 3D object. The photocuring 3D printing technology has the characteristics of high forming precision, high printing efficiency, mature process and the like, and is one of the earliest developed and earliest commercialized 3D printing technologies.
With the continuous development of the photocuring 3D printing equipment and process, raw materials become key factors restricting the development of the photocuring 3D printing technology, for example, in the aspect of physical properties, the photocuring 3D printing technology requires high purity, low viscosity, good stability and low volatility of photosensitive resin; in terms of chemical properties, the photosensitive resin is required to be rapidly polymerized, cured and formed under the condition of illumination, and good mechanical properties and dimensional stability are required after curing. Due to the limitations of the chemical and physical properties of the existing 3D printing material, the application of the photocuring 3D printing technology in the industrial fields such as aerospace, molds, automobiles and the like is hindered.
Disclosure of Invention
The invention provides a composition for 3D printing, a 3D printing method and a device, and a 3D object printed by the composition has good dimensional stability and mechanical property.
The first aspect of the invention provides a composition for 3D printing, which comprises 5-30 wt% of ketoxime blocked diisocyanate, 5-40 wt% of active hydrogen-containing compound, 5-40 wt% of first photocuring component, 20-80 wt% of photocuring monomer, 0-30 wt% of photocuring oligomer, 0.5-10 wt% of photoinitiator, 0-1 wt% of catalyst, 0.05-8 wt% of auxiliary agent, 0-15 wt% of filler and 0-5 wt% of colorant;
the ketoxime blocked diisocyanate has a structure represented by formula 1:
Figure BDA0003113125160000021
wherein R is 1 、R 2 、R 4 And R 5 Independently selected from linear or branched alkyl groups having 1 to 20 carbon atoms; a C3-C20 group having a monocyclic ring, a bridged bicyclic ring, and a bridged tricyclic ring; an aryl group having 6 to 18 carbon atoms; arylalkyl or alkylaryl groups having from 6 to 18 carbon atoms; heteroaryl with 3-20 carbon atoms containing at least one atom of O, N, si, S and P, and heterocyclic group with 3-20 carbon atoms containing at least one atom of O, N, si, S and P;
R 3 selected from the group consisting of linear or branched alkylene groups having 1 to 18 carbon atoms, alicyclic groups having 5 to 18 carbon atoms, arylene groups having 6 to 18 carbon atoms, arylalkylene or alkylarylene groups having 6 to 20 carbon atoms, and naphthalene ring groups having substituted or unsubstituted groups;
the molecular structure of the first light curing component comprises an ethylene group and a heterocyclic group, and the heterocyclic group can generate a thermochemical reaction with a compound containing a ketoxime group after the ketoxime blocking diisocyanate is unblocked;
the photo-curing monomer and the photo-curing oligomer do not have the thermochemical reaction with the ketoxime-group-containing compound after the unblocking of the ketoxime-blocked diisocyanate.
As with the composition, the ketoxime blocked diisocyanate has a deblocking temperature of at least 20 ℃ higher than the printing temperature of the composition.
The deblocking temperature of the ketoxime blocked diisocyanate is T, and T is more than or equal to 100 and less than or equal to 150 ℃.
In the above composition, the heterocyclic group is selected from one or more of epoxy group, butoxycyclo group, tetrahydrofuran group, dioxolane group, dioxane group, trioxane group, propiolactone group, butyrolactone group, azacyclopropane group, azacyclobutane group, cyclobutane group, hexamethylcyclotrisiloxane group and octamethylcyclotetrasiloxane group.
As in the above composition, the first photocurable component is selected from one or more of glycidyl acrylate, hydroxybutyl glycidyl acrylate, 1, 2-epoxy-9-decene, 3, 4-epoxy-1-butene, 1, 2-epoxy-5-hexene, allyl glycidyl ether, glycidyl methacrylate, 1, 2-epoxy-5-hexene, 3- (allyloxy) oxetane, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, allyl 4-oxo-2-oxetanecarboxylate, 2-oxotetrahydrofuran-3-ylmethacrylate, 3- (allyloxy) -5-ethyldihydro-2 (3H) -furanone, 2,4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethylcyclotetrasiloxane.
As the composition, the active hydrogen-containing compound is selected from one or more of polyol, polyamine, polyalcohol amine, liquid unsaturated polyester resin, liquid epoxy resin, liquid phenolic resin, liquid organic silicon resin containing active hydrogen groups and liquid rubber of which the terminal group contains active hydrogen groups.
As for the composition, the molar ratio of the active hydrogen groups in the active hydrogen-containing compound to the isocyanate groups in the ketoxime blocked diisocyanate is (0.9-1.0) to 1.
As in the above composition, the polyol is selected from one or more of ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, cyclohexanedimethanol, 2-ethyl-1, 3-hexanediol, cyclohexanediol, oligomer polyols;
and/or the polyamine is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, cyclohexanediamine, hexamethylenediamine, 1, 8-diaminooctane, 2, 5-diamino-2, 5-dimethylhexane, 1-amino-3, 5-trimethyl-5-aminomethylcyclohexane, oligomer polyamine;
and/or the polyalcohol amine is selected from one or more of 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-butanol.
As in the above composition, the oligomer polyol is one or more selected from the group consisting of polyester polyol, poly-epsilon-caprolactone polyol, polycarbonate polyol, polyether polyol, polyoxypropylene polyol and polytetrahydrofuran polyol.
The liquid rubber with the terminal group containing the active hydrogen group is one or more selected from hydroxyl-terminated polybutadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated acrylonitrile-butadiene rubber, carboxyl-terminated acrylonitrile-butadiene rubber, amine-terminated polybutadiene liquid rubber, amine-terminated acrylonitrile-butadiene liquid rubber, mercapto-terminated polybutadiene liquid rubber and mercapto-terminated acrylonitrile-butadiene rubber.
The liquid organic silicon resin containing active hydrogen groups is selected from one or more of hydroxyl modified silicone oil, carboxyl modified silicone oil, amino modified silicone oil and sulfhydryl modified silicone oil.
As in the above composition, the photo-curable monomer is selected from one or more of monofunctional monomers, difunctional monomers and polyfunctional monomers.
As in the above composition, the monofunctional monomer is selected from one or more of 2-methoxy-acrylate, ethoxyethoxyethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol methacrylate, 2-phenoxyethyl acrylate, (2-ethyl-2-methyl-1, 3-dioxolan-4-yl) acrylate, alkoxylated nonylphenol acrylate, ethylated nonylphenol acrylate, ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 3, 5-trimethylcyclohexane acrylate, 3, 5-trimethylcyclohexane methacrylate, acryloylmorpholine, cyclotrimethylolpropane formal acrylate, 3-ethyl-3-epoxypropylmethyl acrylate, 2-phenoxyethyl methacrylate, o-phenylphenoxyethyl acrylate;
and/or the difunctional monomer is selected from one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (1000) diacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol divinyl ether, polybutadiene acrylate, hexamethylenediol diacrylate, 1, 9-nonanediol diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, ethylene glycol dimethacrylate.
And/or, the polyfunctional monomer is selected from one or more of dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated glycerol triacrylate, 3 (2-hydroxyethyl) isocyanuric acid triacrylate, caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 3 (propoxy) glycerol triacrylate.
As in the above composition, the photo-curable oligomer is selected from one or more of urethane acrylate, polyester acrylate and epoxy acrylate.
As in the above composition, the photoinitiator is a free radical photoinitiator.
As the composition, the catalyst is selected from tertiary amine catalysts and compound catalysts thereof.
The catalyst is selected from one or more of triethylene diamine and a compound catalyst thereof, triethylamine and a compound catalyst thereof, N-methyl bicyclic cyclohexylamine and a compound catalyst thereof, N-methyl morpholine and a compound catalyst thereof, N-ethyl morpholine and a compound catalyst thereof, N '-dimethyl piperazine and a compound catalyst thereof, N' -diethyl piperazine and a compound catalyst thereof, and 1, 3-tetramethyl piperidine and a compound catalyst thereof.
The auxiliary agent is one or more selected from polymerization inhibitor, flatting agent, defoaming agent and dispersing agent.
The invention provides a 3D printing method, which comprises the following steps:
acquiring at least one layer of printing data of a 3D object;
ejecting a composition as described in any of the above to form a material layer according to each layer printing data, and providing radiation to the material layer to obtain a printed layer;
and obtaining at least one printing layer which is stacked layer by layer according to the layer printing data to obtain the 3D object.
As in the above method, the method further comprises heating the material layer to cause thermal polymerization of the composition to produce a printed layer.
As in the above method, the method further includes heating at least one printing layer stacked layer by layer to cause thermal polymerization of the composition, thereby obtaining the 3D object.
According to the method, the heating comprises four stages, wherein the heating temperature of the first stage is 80-100 ℃ and the time is 3-10h, the heating temperature of the second stage is increased to 110-130 ℃ and the time is 3-10h, the heating temperature of the third stage is increased to 130-150 ℃ and the time is 3-10h, and the heating temperature of the fourth stage is increased to 150-200 ℃ and the heating time is 3-10h.
In a third aspect, the invention provides an apparatus for carrying out any of the methods described above, the apparatus comprising a shaping chamber, a dispenser, a support platform and a radiation source;
wherein the dispenser, the support platform and the radiation source are arranged in the forming chamber, the dispenser and the radiation source are arranged above the support platform, the dispenser is used for spraying any one of the compositions on the support platform according to layer printing data to form a material layer, and the radiation source is used for irradiating the material layer to obtain a printing layer.
According to the device, the device further comprises a first heating component, wherein the first heating component is arranged in the forming cavity and is used for providing heat energy for the material layer, so that the composition is subjected to thermal polymerization reaction to obtain a printing layer.
According to the device, the device further comprises a second heating component, the second heating component is arranged outside the forming chamber and is used for heating at least one printing layer which is laminated layer by layer, and the composition is subjected to thermal polymerization reaction to obtain the 3D object.
The implementation of the invention has at least the following advantages:
the composition for 3D printing provided by the invention has adjustable viscosity, is suitable for ink-jet printing and/or three-dimensional photocuring molding technology, and has better thermal stability; and the 3D object printed by the composition provided by the invention has good dimensional stability and mechanical property.
Drawings
Fig. 1 is a schematic flow chart of a 3D printing method according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a 3D printing apparatus according to an embodiment of the present invention.
Description of reference numerals:
1-a material container; 2-ink tube; 3-a distributor; 7-3D printing compositions; 8-3D objects; 9-a radiation source; 10-a first heating member; 11-a guide rail; 12-a support platform; 13-a lifting member; 14-a controller; 15-leveling means; 20-forming a cavity.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first aspect of the invention provides a composition for 3D printing, which comprises 5-30 wt% of ketoxime blocked diisocyanate, 5-40 wt% of active hydrogen-containing compound, 5-40 wt% of first photocuring component, 20-80 wt% of photocuring monomer, 0-30 wt% of photocuring oligomer, 0.5-10 wt% of photoinitiator, 0-1 wt% of catalyst, 0.05-8 wt% of auxiliary agent, 0-15 wt% of filler and 0-5 wt% of colorant;
the ketoxime blocked diisocyanate has a structure represented by formula 1:
Figure BDA0003113125160000061
wherein R is 1 、R 2 、R 4 And R 5 Independently selected from linear or branched alkyl groups having 1 to 20 carbon atoms; a C3-C20 group having a monocyclic ring, a bridged bicyclic ring, and a bridged tricyclic ring; an aryl group having 6 to 18 carbon atoms; arylalkyl or alkylaryl groups having from 6 to 18 carbon atoms; heteroaryl with 3-20 carbon atoms containing at least one atom of O, N, si, S and P, and heterocyclic group with 3-20 carbon atoms containing at least one atom of O, N, si, S and P;
R 3 selected from the group consisting of linear or branched alkylene groups having 1 to 18 carbon atoms, alicyclic groups having 5 to 18 carbon atoms, arylene groups having 6 to 18 carbon atoms, arylalkylene or alkylarylene groups having 6 to 20 carbon atoms, and naphthalene ring groups having substituted or unsubstituted groups;
the molecular structure of the first light-curing component comprises an ethylene group and a heterocyclic group, and the heterocyclic group and a compound which can be unsealed by the ketoxime blocked diisocyanate and then contains a ketoxime group undergo a thermochemical reaction;
the photo-curing monomer and the photo-curing oligomer do not have the thermochemical reaction with the ketoxime-group-containing compound after the unblocking of the ketoxime-blocked diisocyanate.
The invention provides a composition for 3D printing, which comprises 5-30% of ketoxime blocked diisocyanate, 5-40% of compound containing active hydrogen for reacting with diisocyanate after deblocking of the ketoxime blocked diisocyanate, 5-40% of first photocuring component which generates polymerization reaction under the conditions of photoinitiator and light irradiation to form photocuring crosslinking network, 20-80% of photocuring monomer, 0-30% of photocuring oligomer and 0.5-10% of photoinitiator, wherein the total weight of the composition is 100%, andother catalysts, adjuvants, fillers and colorants; wherein the ketoxime-blocked diisocyanate has a structure represented by formula 1, and as can be seen from formula 1, two isocyanate groups are represented by R 3 Linking to give the diisocyanate R 3 Selected from the group consisting of linear or branched alkylene having 1 to 18 carbon atoms, alicyclic group having 5 to 18 carbon atoms, arylene having 6 to 18 carbon atoms, arylalkylene or alkylarylene having 6 to 20 carbon atoms, substituted or unsubstituted naphthalene ring group, and in particular, linear or branched alkylene having 1 to 18 carbon atoms means a group of the formula-C n H 2n Radicals- (1. Ltoreq. N. Ltoreq.18), e.g., -CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、-CH(CH 3 )CH 2 -etc., the alicyclic group having 5 to 18 carbon atoms means a group having 5 to 18 carbon atoms and including at least one carbocyclic ring in the structure, and the arylene group having 6 to 18 carbon atoms means a group having 6 to 18 carbon atoms and including at least one aromatic ring in the structure, for example, -C 6 H 4 -、-C 6 H 3 (CH 3 ) Or the like, an arylalkylene group or an alkylarylene group having 6 to 20 carbon atoms means that the number of carbon atoms is 6 to 20, and the structure includes an arylalkylene group or an alkylarylene group, the arylalkylene group means an alkylene portion to which an aryl group is attached, the alkylarylene group means an arylene portion to which an alkyl group is attached, and the substituted or unsubstituted naphthalene ring group means that the structure includes two or more benzene rings, and the benzene rings may have or may not have a substituent; both ends of the diisocyanate are respectively connected with ketoxime groups containing substituent groups, specifically R 1 、R 2 、 R 4 And R 5 Independently selected from linear or branched alkyl groups having 1 to 20 carbon atoms; a C3-C20 group having a monocyclic ring, a bridged bicyclic ring, and a bridged tricyclic ring; an aryl group having 6 to 18 carbon atoms; arylalkyl or alkylaryl groups having from 6 to 18 carbon atoms; heteroaryl with 3-20 carbon atoms containing at least one atom of O, N, si, S and P, and heterocyclic group with 3-20 carbon atoms containing at least one atom of O, N, si, S and P; the ketoxime blocked diisocyanate has a certain contentWhen the temperature reaches the deblocking temperature, the ketoxime blocked diisocyanate is deblocked to generate a compound containing ketoxime groups and diisocyanate, the diisocyanate and the compound containing active hydrogen are subjected to a thermochemical reaction to generate a macromolecular chain or a crosslinking polymer and form an interpenetrating network of a photocuring crosslinking network and a polymer crosslinking network with the photocuring crosslinking network formed by the first photocuring component, the photocuring monomer, the photocuring oligomer and a photoinitiator, so that the mechanical properties of the 3D object are improved, particularly the tensile strength, the elongation at break, the impact toughness and the tearing resistance, the ketoxime group-containing compound falling off after deblocking is subjected to a thermochemical reaction with heterocyclic groups in the molecular structure of the first photocuring component, and the ketoxime group-containing compound is grafted onto the photocuring crosslinking network, so that no small molecular substances exist in the composition, the dimensional stability of the 3D object is improved, no deformation exists after long-term standing, and the ketoxime group after deblocking is consumed by reaction, so that the deblocking rate of the ketoxime-blocked diisocyanate is further accelerated, and the composition for 3D printing is applicable to inkjet printing and has good thermal stability and/or good stereolithography stability; and the 3D object printed by the composition provided by the invention has good dimensional stability and mechanical property.
Since the ketoxime-blocked diisocyanate can be thermally deblocked at a certain temperature, the thermal deblocking temperature of the ketoxime-blocked diisocyanate is known to have a positive effect on the printing of the 3D object, and specifically, the deblocking temperature of the ketoxime-blocked diisocyanate is at least 20 ℃ higher than the printing temperature of the composition; furthermore, the deblocking temperature of the ketoxime blocked diisocyanate is T, and T is more than or equal to 100 and less than or equal to 150 ℃, so that the ketoxime blocked diisocyanate provided by the invention has good thermal stability.
The ketoxime blocked diisocyanate provided by the invention can be directly purchased or synthesized by self, and the synthesis method is not limited, for example, the method disclosed by the Chinese patent with the publication number of CN110582725A can be adopted, and the following methods disclosed by the invention can also be adopted, specifically:
s1, selecting diisocyanate and a compound containing a ketoxime group, wherein the diisocyanate has a structure shown in a formula 2, and the compound containing the ketoxime group has structures shown in formulas 3 and 4:
Figure BDA0003113125160000081
further, the diisocyanate is selected from one or more of isophorone diisocyanate (abbreviated as IPDI), IPDI trimer, toluene diisocyanate (abbreviated as TDI), hydrogenated TDI, TDI dimer, TDI trimer, diphenylmethane diisocyanate (abbreviated as MDI), polymeric MDI, liquefied MDI hydrogenated MDI, hexamethylene diisocyanate (abbreviated as HDI), HDI trimer, naphthalene diisocyanate (abbreviated as NDI), p-phenylene diisocyanate (abbreviated as PPDI), 1, 4-cyclohexane diisocyanate (abbreviated as CHDI), xylylene diisocyanate (abbreviated as XDI), dimethylbiphenyl diisocyanate (abbreviated as TODI), trimethylhexamethylene diisocyanate (abbreviated as TMDI), and triphenylmethane triisocyanate (abbreviated as TTI).
<xnotran> , ,5- -2- ,2- ,2,2,4,4- -3- ,5- -3- , -2- , (2- ) ,6,7- [ B ] -4 (5H) - , , , , , , , -2- ,2- , ,4- ,3- -3- -2- ,1,3- , , , ,2,2,6,6- -4- , , ,1,2- . </xnotran>
The molar ratio of isocyanate groups in the diisocyanate to ketoxime groups in the ketoxime group-containing compound is 1: (1.0-1.4), it is understood that the compounds represented by formula 3 and formula 4 may be the same or different.
S2, placing the compound containing the ketoxime group in a stirrer for stirring, and meanwhile, slowly dropping diisocyanate to ensure that the temperature of a reaction system is lower than 40 ℃;
s3, after the diisocyanate is slowly dripped, stirring for 30min at room temperature;
and S4, heating to 40-90 ℃, and continuing to react for 4-12h to obtain the ketoxime blocking diisocyanate.
In the composition, the vinyl group in the first photo-curing component is used for participating in a polymerization reaction to form a photo-curing crosslinking network, and the heterocyclic group is used for reacting with a compound containing a ketoxime group after the ketoxime-blocked diisocyanate is unblocked, specifically, the heterocyclic group is selected from one or more of an epoxy group, a butoxycyclo group, a tetrahydrofuran group, a dioxolane group, a dioxane group, a trioxane group, a propiolactone group, a butyrolactone group, a silatrane group, a azetidine group, a cyclobutane group, a hexamethylcyclotrisiloxane group and an octamethylcyclotetrasiloxane group.
Specifically, the first photocurable component is selected from one or more of glycidyl acrylate, hydroxybutyl glycidyl acrylate, 1, 2-epoxy-9-decene, 3, 4-epoxy-1-butene, 1, 2-epoxy-5-hexene, allyl glycidyl ether, glycidyl methacrylate, 1, 2-epoxy-5-hexene, 3- (allyloxy) oxetane, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, allyl 4-oxo-2-oxetanecarboxylate, 2-oxotetrahydrofuran-3-ylmethacrylate, 3- (allyloxy) -5-ethyldihydro-2 (3H) -furanone, 2,4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethylcyclotetrasiloxane.
The active hydrogen-containing compound is used for reacting with diisocyanate obtained after the unblocking of the ketoxime blocked diisocyanate, and specifically, the active hydrogen-containing compound is selected from one or more of polyol, polyamine, polyalcohol amine, liquid unsaturated polyester resin, liquid epoxy resin, liquid phenolic resin, liquid organosilicon resin containing active hydrogen groups and liquid rubber of which the terminal group contains active hydrogen groups.
Furthermore, the molar ratio of the active hydrogen group in the active hydrogen-containing compound to the isocyanate group in the ketoxime blocked diisocyanate is (0.9-1.0) to 1.
Specifically, the polyhydric alcohol is selected from one or more of ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, cyclohexanedimethanol, 2-ethyl-1, 3-hexanediol, cyclohexanediol, oligomer polyhydric alcohol;
and/or the polyamine is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, cyclohexanediamine, hexamethylenediamine, 1, 8-diaminooctane, 2, 5-diamino-2, 5-dimethylhexane, 1-amino-3, 5-trimethyl-5-aminomethylcyclohexane, oligomer polyamine;
and/or the polyalcohol amine is selected from one or more of 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-butanol.
Specifically, the oligomer polyol refers to an oligomer containing two hydroxyl groups and having a structure shown in formula 5, wherein R is 6 Selected from ether molecule long chain, ester molecule long chain and olefin molecule long chain;
HO-R 6 -OH formula 5
Further, the oligomer polyol is selected from one or more of polyester polyol, poly epsilon-caprolactone polyol, polycarbonate polyol, polyether polyol, poly (acrylic oxide) polyol and polytetrahydrofuran polyol.
Specifically, the oligomer polyamine refers to an oligomer containing two amino groups and having a structure shown in formula 6, wherein R is 7 Selected from ether molecule long chain, ester molecule long chain and olefin molecule long chain;
H 2 N-R 7 -NH 2 and (6).
The oligomer polyamine is selected from one or more of polyether diamine, polyester diamine and aliphatic diamine.
Further, in the liquid rubber with the terminal group containing an active hydrogen group, the active hydrogen group is selected from one or more of a hydroxyl terminal group, a carboxyl terminal group, an amine terminal group and a mercapto terminal group, and specifically, the liquid rubber with the terminal group containing an active hydrogen group is selected from one or more of a hydroxyl terminal polybutadiene liquid rubber, a carboxyl terminal polybutadiene liquid rubber, a hydroxyl terminal nitrile rubber, a carboxyl terminal nitrile rubber, an amine terminal polybutadiene liquid rubber, an amine terminal nitrile liquid rubber, a mercapto terminal polybutadiene liquid rubber, an mercapto terminal nitrile rubber and other liquid rubbers containing an active hydrogen group.
Further, the liquid unsaturated polyester resin is selected from one or more of o-benzene type unsaturated polyester resin, m-benzene type unsaturated polyester resin, p-benzene type unsaturated polyester resin and bisphenol A type unsaturated polyester resin;
further, the liquid epoxy resin is selected from one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin;
further, the liquid phenolic resin is selected from one or more of alcohol-soluble phenolic resin, oil-soluble phenolic resin and modified phenolic resin;
further, the active hydrogen group in the liquid silicone resin containing an active hydrogen group is selected from at least one of hydroxyl, carboxyl, amino and mercapto, specifically, the liquid silicone resin containing an active hydrogen group is selected from one or more of hydroxyl modified silicone oil, carboxyl modified silicone oil, amino modified silicone oil, mercapto modified silicone oil and the like.
The photo-curing monomer is a small molecular compound containing vinyl in the molecular structure, is used for adjusting the viscosity and the performance of the composition, and is specifically selected from one or more of monofunctional monomers, bifunctional monomers and multifunctional monomers.
As in the above composition, the monofunctional monomer is selected from one or more of 2-methoxy-acrylate, ethoxyethoxyethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol methacrylate, 2-phenoxyethyl acrylate, (2-ethyl-2-methyl-1, 3-dioxolan-4-yl) acrylate, alkoxylated nonylphenol acrylate, ethylated nonylphenol acrylate, ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 3, 5-trimethylcyclohexane acrylate, 3, 5-trimethylcyclohexane methacrylate, acryloylmorpholine, cyclotrimethylolpropane formal acrylate, 3-ethyl-3-epoxypropylmethyl acrylate, 2-phenoxyethyl methacrylate, o-phenylphenoxyethyl acrylate;
and/or the difunctional monomer is selected from one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (1000) diacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol divinyl ether, polybutadiene acrylate, hexamethylenediol diacrylate, 1, 9-nonanediol diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, ethylene glycol dimethacrylate;
and/or, the polyfunctional monomer is selected from one or more of dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated glycerol triacrylate, 3 (2-hydroxyethyl) isocyanuric acid triacrylate, caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 3 (propoxy) glycerol triacrylate.
As in the above composition, the photo-curable oligomer is selected from one or more of urethane acrylate, polyester acrylate and epoxy acrylate.
Specifically, the polyurethane acrylate can be one or more of BR-344, BR-374, BR-970BT, BR-345, BR-541S, BR-774SD, BR-543 and BR-970H produced by Bomar company in the United states; can be one or more of 6113, 6115J-80, 6101 and 8000A produced by Changxing company of Taiwan; may be one or more of CN9178 NS, CN9010 NS, CN 996NS, CN985B88 and CN975NS produced by Saedoma, USA; may be one or more of Ebecryl 8296, ebecryl 8807, ebecryl 205, ebecryl 220, ebecryl 4587 and Ebecryl 5129 produced by Zymouth Germany.
The polyester acrylate can be one or more of Ebecryl 810, ebecryl 450, ebecryl 452, ebecryl 547, ebecryl 571, ebecryl 800, ebecryl 852, ebecryl 856 and the like produced by Zymond Heiny company in Germany; one or more of MIRAMER PS420, MIRAMER PS4040, and MIRAMER PS4500 produced by Korean Source company; one or more of LR9004, PE9024, PE44F and PE55F produced by Pasfu Germany;
the epoxy acrylate may be one or more of 3016, 3316, 3005, manufactured by IGM, italy; one or more of LR 8765, LR 8986, LR 9019 and LR 8765 produced by Pasteur Germany; one or more of MIRAMER PE210, MIRAMER PE110H, MIRAMER PE230, MIRAMER EA2235 and MIRAMER EA2259 from Korean Utility company;
as in the above composition, the photoinitiator is a free radical photoinitiator;
specifically, the radical photoinitiator may be selected from one or more of benzoin ethyl ether, benzoin α, α -dimethyl benzil ketal, α -diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-1 propanone (1173 for short), 1-hydroxy-cyclohexyl benzophenone (184 for short), 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl propanone-1, [ 2-methyl 1- (4-methylmercapto phenyl) -2-morpholinopropanone-1 ], [ 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 ], benzoyl formate, 2,4, 6-trimethylphenyl acyl-ethoxy-phenyl phosphine oxide, 2,4, 6-trimethylphenyl acyl-diphenylphosphine oxide (TPO for short), bis (2, 4, 6-trimethylphenyl acyl) phenyl phosphine oxide (819 for short), 4-p-tolylmercapto benzophenone, and the like.
The catalyst is used for catalyzing the heterocyclic group and the compound containing the ketoxime group after the unblocking of the ketoxime blocked diisocyanate to perform a thermochemical reaction, and is specifically selected from one or more of tertiary amine catalysts and compound catalysts thereof.
Specifically, the catalyst is selected from one or more of triethylene diamine and a compound catalyst thereof, triethylamine and a compound catalyst thereof, N-methyl bicyclic cyclohexylamine and a compound catalyst thereof, N-methyl morpholine and a compound catalyst thereof, N-ethyl morpholine and a compound catalyst thereof, N '-dimethyl piperazine and a compound catalyst thereof, N' -diethyl piperazine and a compound catalyst thereof, and 1, 3-tetramethyl piperidine and a compound catalyst thereof.
The auxiliary agent is one or more selected from polymerization inhibitor, flatting agent, defoaming agent and dispersing agent.
Specifically, the polymerization inhibitor mainly serves to prevent the radical polymerization reaction and improve the storage stability of the composition, and may be one or more selected from phenolic, quinone or nitrite polymerization inhibitors, such as hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt (polymerization inhibitor 510).
The leveling agent is mainly used for improving the fluidity of the composition and the wetting property of a substrate, and simultaneously adjusting the surface tension of the composition to enable normal printing. The selection of the leveling agent is not specifically limited, and the products sold in the market at present are more, such as BYK333, BYK377, BYK-UV3530, BYK-UV3575, BYK-UV3535 and the like of Bick company, TEGO wet 500, TEGO wet270, TEGO Glide 450, TEGO RAD 2010, TEGO RAD 2011, TEGO RAD 2100, TEGO RAD 2200 and the like of Digao company.
The main function of the defoaming agent is to inhibit, reduce and eliminate air bubbles in the composition. The choice of defoaming agent in the present invention is not particularly limited. Currently, many products are commercially available, such as BYK1798, BYK055, BYK088, BYK020, BYK025 and the like of Bick company, TEGO Airex 920, TEGO Airex 921, TEGO Airex 986, TEGO Foamex 810, TEGO Foamex N and the like of Digh company, and Efka 7081, efka7082 and the like of Effa company.
The main function of the dispersant is to improve the dispersion stability of the particulate matter in the composition. The selection of the dispersant in the present invention is not particularly limited. The products sold in the market at present are more, and can be BYK102, BYK106, BYK108, BYK110, BYK111, BYK180, digao Dispers 655, dispers675, dispers 710, dispers 630, dispers 670 and the like.
In the above composition, the filler is selected from one or more of silica, carbon black, barium sulfate, aluminum hydroxide, kaolin and talc.
When the composition of the present invention does not contain a colorant, the composition is transparent, and the printed product has high transparency. When a colorant is contained, the colorant may be a pigment or a dye, and in the present invention, the pigment is preferably a colorant, and the pigment may be specifically selected from the group consisting of c.i. pigment white 6, c.i. pigment Red3, c.i. pigment Red 5, c.i. pigment Red 7, c.i. pigment Red9, c.i. pigment Red 12, c.i. pigment Red 13, c.i. pigment Red 21, c.i. pigment Red31, c.i. pigment Red49: 1. C.I.pigment Red 58: 1, C.I.pigment Red 175; c.i.pigment Yellow 63, c.i.pigment Yellow 3, c.i.pigment Yellow 12, c.i.pigment Yellow 16, c.i.pigment Yellow 83; one or more of C.I.pigment Blue 1, C.I.pigment Blue 10, C.I.pigment Blue B, phthalocyanine Blue BX, phthalocyanine Blue BS and C.I.pigment Blue 61: 1.
In conclusion, the composition for 3D printing provided by the invention has adjustable viscosity, is suitable for ink-jet printing and/or three-dimensional photocuring molding technology, and has better thermal stability; and the 3D object printed by the composition provided by the invention has good dimensional stability and mechanical property.
The invention provides a 3D printing method, which comprises the following steps:
acquiring at least one layer of printing data of a 3D object;
ejecting a composition as described in any of the above to form a material layer according to each layer printing data, and providing radiation to the material layer to obtain a printed layer;
and obtaining at least one printing layer which is stacked layer by layer according to the layer printing data to obtain the 3D object.
As in the above method, the method further comprises heating the material layer to thermally polymerize the composition to form a printed layer.
As in the above method, the method further includes heating at least one printing layer stacked layer by layer to cause thermal polymerization of the composition, thereby obtaining the 3D object.
According to the method, the heating comprises four stages, wherein the heating temperature of the first stage is 80-100 ℃ and the time is 3-10h, the heating temperature of the second stage is increased to 110-130 ℃ and the time is 3-10h, the heating temperature of the third stage is increased to 130-150 ℃ and the time is 3-10h, and the heating temperature of the fourth stage is increased to 150-200 ℃ and the heating time is 3-10h.
In a third aspect, the invention provides an apparatus for carrying out any of the methods described above, the apparatus comprising a shaping chamber, a dispenser, a support platform and a radiation source;
wherein the dispenser, support platform and radiation source are disposed within the forming chamber, the dispenser and radiation source being disposed above the support platform, the dispenser being configured to eject any of the above-described composition-forming material layers on the support platform according to layer print data, and the radiation source being configured to irradiate the material layers to form a printed layer.
According to the device, the device further comprises a first heating component, wherein the first heating component is arranged in the forming cavity and is used for providing heat energy for the material layer, so that the composition is subjected to thermal polymerization reaction to obtain a printing layer.
According to the device, the device further comprises a second heating component, the second heating component is arranged outside the forming chamber and is used for heating at least one printing layer stacked layer by layer, and the composition is subjected to thermal polymerization reaction to obtain the 3D object.
The following detailed description is provided in conjunction with specific examples, wherein the components and weight percentages of the compositions provided in examples 1-6 are shown in table 1, and the structural formulas of compound a, compound B, and compound C referred to in table 1 are as follows:
Figure BDA0003113125160000151
meanwhile, the invention also provides comparative examples 1-4 for comparison with examples 1-2, specifically, comparative example 1 does not include ketoxime blocked diisocyanate, comparative example 2 does not include the first light-curing component, comparative example 3 includes n-butyl glycidyl ether, the molecular structure of which includes epoxy groups but does not include vinyl groups, comparative example 4 includes non-blocked isocyanate, and the compositions provided by comparative examples 1-4 have the components and weight percentage shown in table 2.
Table 1 compositions for 3D printing provided in examples 1-6
Figure BDA0003113125160000171
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Figure BDA0003113125160000181
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Figure BDA0003113125160000191
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Figure BDA0003113125160000201
Example 7
This embodiment provides a printing method for a 3D object, which uses any one of the above-mentioned compositions to print the 3D object, and fig. 1 is a flowchart of the printing method for the 3D object according to an embodiment of the present invention, as shown in fig. 1, including the following steps:
s100, acquiring at least one layer of printing data of the 3D object;
firstly, slicing, layering and data processing are carried out on model data of a 3D object to be printed to obtain layer printing data, wherein the layer printing data are data representing the cross section of the 3D object, at least one layer of printing data can be obtained after slicing, layering and data processing are carried out on the 3D object, and the layer printing data are overlapped layer by layer to obtain a digital model of the 3D object. The method for acquiring layer print data in the present invention is not limited, and any method for acquiring layer print data in the three-dimensional object printing process in the art may be adopted, for example, before the 3D object is printed, model data of the 3D object needs to be acquired, and data format conversion is performed on the model data, for example, conversion is performed into a format which can be recognized by slicing software, such as STL format, PLY format, WRL format, etc., slicing and layering processing is performed on the model using the slicing software to obtain slicing layer data, and data processing is performed on the slicing layer data using a data processor to obtain layer print data, where the layer print data includes information representing the shape of the object and/or information representing the color of the object.
S200, spraying any one of the compositions according to printing data of each layer to form a material layer, and carrying out light radiation on the material layer to obtain a printing layer;
specifically, according to each layer printing data, ejecting the composition to form a material layer, and irradiating the material layer with light to at least partially cure the material layer to obtain a printed layer, wherein the curing means irradiating the material layer with a radiation source to make the photocuring system therein undergo a photocuring reaction to become a solidified or semi-solidified state.
In addition, during the photocuring reaction, due to the increase of the temperature of the system, at least part of the active group-blocked diisocyanate in the material layer composition is subjected to thermal polymerization reaction with the active hydrogen-containing compound, which contributes to the improvement of the mechanical properties and the dimensional stability of the 3D object.
S300, obtaining at least one printing layer which is stacked layer by layer according to the layer printing data, and obtaining the 3D object.
After a printing layer is formed according to the step S200, the step is repeatedly executed according to different layer printing data, that is, a material layer is continuously formed on the surface of the previous printing layer, the material layer is irradiated to form a new printing layer, and the plurality of printing layers are sequentially overlapped to obtain the final 3D object.
In one embodiment, in order to further initiate the thermal polymerization reaction of the reactive group blocked diisocyanate with the active hydrogen-containing compound to further improve the mechanical properties of the 3D object, particularly the tensile strength and tear strength, the method further comprises heating the material layer to thermally polymerize the composition to obtain the printed layer.
In another embodiment, after the at least one printing layer is laminated layer by layer, heating may be performed to initiate thermal polymerization reaction between the internal active group-blocked diisocyanate and the compound containing active hydrogen, and specifically, the method further includes heating at least one printing layer laminated layer by layer to cause thermal polymerization reaction of the composition, so as to obtain the 3D object.
It should be noted that in both embodiments, the heating temperature is not too high, as long as the reactive group-blocked diisocyanate is capable of being deblocked to release isocyanate groups, and too high a temperature may cause the 3D object to age.
Preferably, after the at least one printing layer is laminated layer by layer, heating is performed, wherein the heating is gradient heating and comprises four stages, wherein the heating temperature of the first stage is 80-100 ℃ and the time is 3-10h, the heating temperature of the second stage is increased to 110-130 ℃ and the time is 3-10h, the heating temperature of the third stage is increased to 130-150 ℃ and the time is 3-10h, and the heating temperature of the fourth stage is increased to 150-200 ℃ and the heating time is 3-10h.
The effect of gradient heating in the invention is that: thermal sealing and thermal polymerization are slowly carried out, the stacked printing layers are not easy to deform in the thermal treatment process, air holes are not easy to generate in the model, and the dimensional stability and the performance uniformity are improved.
In conclusion, the printing method of the 3D object provided by the invention is beneficial to improving the mechanical property and the dimensional stability of the 3D object by using any one of the compositions for printing.
Example 8
The present embodiment provides a 3D printing apparatus, configured to implement the printing method for the 3D object, and fig. 2 is a schematic structural diagram of the 3D printing apparatus according to an embodiment of the present invention, as shown in fig. 2, the 3D printing apparatus at least includes: a forming chamber 20, a dispenser 3, a support platform 12, and a radiation source 9, the dispenser 3, the support platform 12, and the radiation source 9 being disposed within the forming chamber 20, the dispenser 3 and the radiation source 9 being positioned above the support platform 12, the dispenser 3 being configured to eject a composition 7 on the support platform 12 to form a layer of material in accordance with layer printing data, the radiation source 9 being configured to irradiate the layer of material to form a printed layer.
In one embodiment, the distributor 3 may be one or both of a single pass printhead, a multi-pass printhead, and the number of printheads 3 is at least 1;
the radiation source 9 is one of a UV LED lamp, a mercury lamp, a metal halogen lamp, an electrodeless lamp, a xenon lamp, and the like.
The device further comprises a material container 1 and an ink tube 2, wherein the material container 1 is connected with the ink tube 2, the ink tube 2 is connected with the dispenser 3, the material container 1 is used for storing any one of the 3D printing compositions, and the 3D printing composition stored in the material container can be conveyed to a printing head of the dispenser 3 through the ink tube 2.
In the ink jet printing process, in order to enable the material composition to be ejected from the nozzle of the print head normally, the material composition needs to be preheated in advance, and the preheating process can occur in the material container 1, and/or in the ink tube 2, and/or in the print head 3, and the invention is not limited in particular. The preheating temperature is lower than the thermal blocking temperature of the active group blocked diisocyanate, preferably lower than 20 ℃, otherwise the material composition undergoes thermal polymerization to block the nozzle of the printing head before ink jet printing.
The preheating part can be at least one of a metal heating sheet, a heating wire and a heating spring;
as the device, the device also comprises a first heating part 10, and the first heating part 10 is positioned in the forming chamber 20 to provide heat energy for the material layer, so that the composition is subjected to thermal polymerization reaction to obtain a printing layer.
In one embodiment, the first heating element 10 is selected from one or more of an infrared lamp, a heating plate, a heat-insulating plate, a heat-dissipating plate, a microwave radiation source, and a temperature controller.
As with the apparatus described above, further includes an elevating member 13, the elevating member 13 being configured to vary the relative distance between the support platform 12 and the dispenser 3 in the height direction (Z direction) to continuously form printed layers and to superpose the printed layers one upon another to form the 3D object 8. For example, the dispenser 3 sprays the 3D printing composition 7 onto the support platform 12 to form a material layer, the radiation source 9 radiates light to make the composition undergo a photocuring reaction, the first heating component 10 heats the material layer to make the composition undergo a thermal polymerization reaction to obtain a printed layer, and the lifting component 13 moves the support platform 12 downward in the height direction (i.e., Z direction) by a certain distance to make enough space to accommodate a new printed layer, and when the printed layers are stacked layer by layer in the height direction, the 3D object 8 is formed.
As in the device described above, it also comprises leveling means 15, the leveling means 15 being located between the distributor 3 and the radiation source 9 for leveling the layer of material; the leveling member 15 may be a leveling roller that takes away dispensed excess 3D printing material by the rotating action of the leveling roller.
The above apparatus further comprises a controller 14, wherein the controller 14 is used for controlling the operation of at least one of the preheating part, the first heating part 10, the distributor 3, the radiation source 9, the lifting mechanism 13 and the leveling part 15.
For example, the controller 14 may control the dispensing of the heated 3D printing composition 7 by the dispenser 3 according to layer printing data, the controller 14 may control the radiation intensity and radiation time of the radiation source 9 to the material layer, the controller 14 may control the heating temperature of the first heating member 10 to the material, the controller 14 may control the relative distance between the support platform 12 and the dispenser 3 in the Z-direction, and the like.
The above apparatus further comprises a guide rail 10, and the dispenser 3, the radiation source 9, the first heating member 10 and the leveling member 15 are sequentially mounted on the guide rail 11 and can move on the guide rail 11.
As another embodiment, the apparatus does not include the first heating component, but includes a second heating component (not shown) disposed outside the forming chamber 20 to heat at least one printing layer (corresponding to the 3D object 8 in fig. 2) stacked layer by layer, so that the composition in the 3D object 8 undergoes a thermal polymerization reaction to obtain the target 3D object.
In one embodiment, the second heating member is selected from one or more of an infrared lamp, a microwave oven, a heating oven, an oven, and a high temperature vacuum drying oven.
As with the above device, the controller 14 may also be configured to control the second heating component to heat the 3D object 8, and the specific heating manner is as described in the gradient heating manner in embodiment 7, which is not described herein again.
The following performance tests were performed using the compositions for 3D printing provided in examples 1-6 and comparative examples 1-4, and the test results are shown in table 3:
1. viscosity detection
The viscosity of the above composition at the printing temperature was measured using a DV-I digimatic viscometer.
2. Fluency test
Continuously printing the 3D printing composition by using a Saina photocuring ink-jet printer for 4 hours, testing the ink discharge condition of the spray heads before and after printing, and testing the printing smoothness ok after no more than 10 broken lines before and after printing.
3. Thermal stability test
And (3) placing 100g of the prepared 3D printing material sample in a beaker, sealing and protecting from light, placing the beaker in a70 ℃ oven, keeping the temperature for 7 days continuously, and taking out the sample, wherein the sample is free from gel and solidification, and the test is passed.
The same 3D object is printed by the same printing method, and the mechanical property of the 3D object is tested, wherein the specific test method is as follows, and the test result is shown in table 4:
4. elongation at break and tensile Strength test
Applying the 3D printing material to a Saina photocuring ink-jet printer or an SLA 3D printer, printing a 3D object with required size specification according to GB/T528-2009 to obtain an elastic material (example 2, example 5 and comparative example 2), and testing the elongation at break and tensile strength of the 3D object according to GB/T528-2009; hard materials (others) 3D objects of the required dimensional specifications were printed according to GB/T1040.2-2006 and the 3D objects were tested for elongation at break and tensile strength according to GB/T1040.2-2006.
5. Impact strength test
The 3D printing material is applied to a Saina photocuring ink-jet printer or an SLA 3D printer, a 3D object with the required size and specification of GB/T1043.1-2008 is printed, and the impact strength is tested according to GB/T1043.1-2008.
6. Tear test
The 3D printing material is applied to a Saina photocuring ink-jet printer or an SLA 3D printer, a 3D object with the required size specification of GB/T529-2008 is printed, and the tear strength is tested according to GB/T529-2008.
7. Dimensional stability test
Applying the 3D printing composition to a Saina photocuring ink-jet printer or an SLA 3D printer, and printing squares with the length, width and height of 10mm, 10mm and 10mm respectively; after printing is finished, carrying out heat treatment, wherein the heating temperature of the first stage is 90 ℃ and the time is 2 hours, the heating temperature of the second stage is 110 ℃ and the time is 3 hours, and the heating temperature of the third stage is 140 ℃ and the time is 4 hours; and naturally cooling to 25 ℃, measuring the length, width and height of the square block after heat treatment, wherein when the measured length, width and height are all 10 +/-0.1 mm, the dimensional stability is good, and the test is passed, otherwise, the test is not passed.
Table 3 results of performance testing of the compositions provided in examples 1-6 and comparative examples 1-4
Figure BDA0003113125160000251
Table 4 results of performance testing of 3D objects obtained using the compositions provided in examples 1-6 and comparative examples 1-4
Figure BDA0003113125160000261
According to the test results provided in tables 3-4, the viscosity of the composition for 3D printing provided by the present invention is adjustable, and the composition is suitable for inkjet printing and/or stereolithography; in addition, the composition for 3D printing provided by the invention can be an elastic material or a hard material, and a 3D object printed by using the composition has better mechanical property and dimensional stability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (22)

1. The composition for 3D printing is characterized by comprising 5-30 wt% of ketoxime blocked diisocyanate, 5-40 wt% of active hydrogen-containing compound, 5-40 wt% of first photocuring component, 20-80 wt% of photocuring monomer, 0-30 wt% of photocuring oligomer, 0.5-10 wt% of photoinitiator, 0-1 wt% of catalyst, 0.05-8 wt% of auxiliary agent, 0-15 wt% of filler and 0-5 wt% of colorant;
the ketoxime blocked diisocyanate has a structure represented by formula 1:
Figure FDA0003985139720000011
wherein R is 1 、R 2 、R 4 And R 5 Independently selected from linear or branched alkyl groups having 1 to 20 carbon atoms; a C3-C20 group having a monocyclic ring, a bridged bicyclic ring, and a bridged tricyclic ring; an aryl group having 6 to 18 carbon atoms; arylalkyl or alkylaryl groups having from 6 to 18 carbon atoms; heteroaryl with 3-20 carbon atoms containing at least one atom of O, N, si, S and P, and heterocyclic group with 3-20 carbon atoms containing at least one atom of O, N, si, S and P;
R 3 selected from the group consisting of linear or branched alkylene groups having 1 to 18 carbon atoms, alicyclic groups having 5 to 18 carbon atoms, arylene groups having 6 to 18 carbon atoms, arylalkylene or alkylarylene groups having 6 to 20 carbon atoms, and naphthalene ring groups having substituted or unsubstituted groups;
the molecular structure of the first light-curing component comprises an ethylene group and a heterocyclic group, and the heterocyclic group can perform thermochemical reaction with a compound containing a ketoxime group after deblocking the ketoxime blocked diisocyanate;
the photo-curing monomer and the photo-curing oligomer do not perform the thermochemical reaction with the ketoxime group-containing compound after the ketoxime-blocked diisocyanate is unblocked;
the ketoxime blocked diisocyanate has a deblocking temperature greater than the printing temperature of the composition.
2. The composition of claim 1, wherein the ketoxime-blocked diisocyanate has a deblocking temperature at least 20 ℃ greater than a printing temperature of the composition.
3. The composition of claim 2, wherein the ketoxime-blocked diisocyanate has a deblocking temperature T of 100 ℃ T.ltoreq.150 ℃.
4. A composition according to any of claims 1 to 3, characterised in that the heterocyclic group is selected from one or more of epoxy groups, butoxycyclo groups, tetrahydrofurane groups, dioxolane groups, dioxanone groups, trioxane groups, propiolactone groups, butyrolactone groups, azacyclopropane groups, azacyclobutane groups, cyclobutane groups, hexamethylcyclotrisiloxane groups, octamethylcyclotetrasiloxane groups.
5. The composition of claim 4, wherein the first photocurable component is selected from one or more of glycidyl acrylate, hydroxybutyl glycidyl acrylate, 1, 2-epoxy-9-decene, 3, 4-epoxy-1-butene, 1, 2-epoxy-5-hexene, allyl glycidyl ether, glycidyl methacrylate, 1, 2-epoxy-5-hexene, 3- (allyloxy) oxetane, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, allyl 4-oxo-2-oxetanecarboxylate, 2-oxo-tetrahydrofuran-3-yl methacrylate, 3- (allyloxy) -5-ethyldihydro-2 (3H) -furanone, 2,4, 6-trivinyl-2, 4, 6-trimethylcyclotrisiloxane, 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethylcyclotetrasiloxane.
6. The composition according to any one of claims 1 to 3, wherein the active hydrogen-containing compound is selected from one or more of polyols, polyamines, polyalcohol amines, liquid unsaturated polyester resins, liquid epoxy resins, liquid phenolic resins, liquid silicone resins containing active hydrogen groups, and liquid rubbers containing active hydrogen groups at the end groups.
7. The composition of claim 6, wherein the molar ratio of active hydrogen groups in the active hydrogen-containing compound to isocyanate groups in the ketoxime blocked diisocyanate is (0.9-1.0): 1.
8. the composition of claim 6, wherein the polyol is selected from one or more of ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, cyclohexanedimethanol, 2-ethyl-1, 3-hexanediol, cyclohexanediol, oligomeric polyols;
and/or the polyamine is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, cyclohexanediamine, hexamethylenediamine, 1, 8-diaminooctane, 2, 5-diamino-2, 5-dimethylhexane, 1-amino-3, 5-trimethyl-5-aminomethylcyclohexane, oligomer polyamine;
and/or the polyalcohol amine is selected from one or more of 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-butanol.
9. The composition of claim 8, wherein the oligomer polyol is selected from one or more of polyester polyols, polyepsilon caprolactone polyols, polycarbonate polyols, polyether polyols, polyoxy acrylic polyols, polytetrahydrofuran polyols.
10. The composition of claim 6, wherein the liquid rubber with the terminal group containing an active hydrogen group is one or more selected from hydroxyl-terminated polybutadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated nitrile rubber, carboxyl-terminated nitrile rubber, amine-terminated polybutadiene liquid rubber, amine-terminated nitrile liquid rubber, mercapto-terminated polybutadiene liquid rubber and mercapto-terminated nitrile rubber.
11. The composition according to claim 6, wherein the liquid silicone resin containing active hydrogen groups is one or more selected from the group consisting of hydroxyl-modified silicone oil, carboxyl-modified silicone oil, amino-modified silicone oil and mercapto-modified silicone oil.
12. A composition according to any of claims 1 to 3, wherein the photocurable monomer is selected from one or more of monofunctional monomers, difunctional monomers and multifunctional monomers.
13. The composition of claim 12, wherein the monofunctional monomer is selected from one or more of 2-methoxy acrylate, ethoxyethoxyethyl acrylate, methoxypolyethylene glycol monoacrylate, methoxypolyethylene glycol methacrylate, 2-phenoxyethyl acrylate, 2-ethyl-2-methyl-1, 3-dioxopentyl-4-yl) acrylate, alkoxylated nonylphenol acrylate, ethoxylated nonylphenol acrylate, ethyl 2- [ [ (butylamino) carbonyl ] oxo ] acrylate, isobornyl methacrylate, 1-adamantyl methacrylate, 3, 5-trimethylcyclohexane acrylate, 3, 5-trimethylcyclohexane methacrylate, acryloylmorpholine, cyclotrimethylolpropane formal acrylate, 3-ethyl-3-epoxypropylmethyl acrylate, 2-phenoxyethyl methacrylate, o-phenylphenoxyethyl acrylate;
and/or the difunctional monomer is selected from one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (600) diacrylate, polyethylene glycol (1000) diacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol divinyl ether, polybutadiene acrylate, dioxan diol diacrylate, 1, 9-nonanediol diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, ethylene glycol dimethacrylate;
and/or, the polyfunctional monomer is selected from one or more of dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated glycerol triacrylate, 3 (2-hydroxyethyl) isocyanuric acid triacrylate, caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 3 (propoxy) glycerol triacrylate.
14. The composition of any of claims 1-3, wherein the light-curable oligomer is selected from one or more of urethane acrylates, polyester acrylates, and epoxy acrylates.
15. A composition according to any one of claims 1 to 3, wherein the photoinitiator is a free radical photoinitiator.
16. The composition of any one of claims 1-3, wherein the catalyst is selected from one or more of tertiary amine catalysts and built catalysts thereof.
17. The composition of claim 16, wherein the catalyst is selected from one or more of triethylene diamine and its complex catalyst, triethylamine and its complex catalyst, N-methyl dicyclohexylamine and its complex catalyst, N-methyl morpholine and its complex catalyst, N-ethyl morpholine and its complex catalyst, N '-dimethyl piperazine and its complex catalyst, N' -diethyl piperazine and its complex catalyst, and 1, 3-tetramethyl piperidine and its complex catalyst.
18. The composition according to any one of claims 1 to 3, wherein the auxiliary agent is selected from one or more of a polymerization inhibitor, a leveling agent, a defoaming agent and a dispersing agent.
19. A3D printing method is characterized by comprising the following steps:
acquiring at least one layer of printing data of the 3D object;
jetting the composition of any one of claims 1-18 according to each layer printing data to form a material layer and providing radiation to the material layer to obtain a printed layer;
and obtaining at least one printing layer which is stacked layer by layer according to the layer printing data to obtain the 3D object.
20. The method of claim 19, further comprising heating the layer of material to thermally polymerize the composition to provide a printed layer.
21. The method of claim 19, further comprising heating the at least one printed layer stacked one above the other to cause thermal polymerization of the composition to produce the 3D object.
22. The method of claim 21, wherein the heating comprises four stages, wherein the first stage is heated at a temperature of 80-100 ℃ for 3-10 hours, the second stage is heated at a temperature of 110-130 ℃ for 3-10 hours, the third stage is heated at a temperature of 130-150 ℃ for 3-10 hours, and the fourth stage is heated at a temperature of 150-200 ℃ for 3-10 hours.
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