WO2019210568A1 - 一种可光致固化的组合物 - Google Patents

一种可光致固化的组合物 Download PDF

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WO2019210568A1
WO2019210568A1 PCT/CN2018/093755 CN2018093755W WO2019210568A1 WO 2019210568 A1 WO2019210568 A1 WO 2019210568A1 CN 2018093755 W CN2018093755 W CN 2018093755W WO 2019210568 A1 WO2019210568 A1 WO 2019210568A1
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photocurable composition
composition according
weight
photosensitive resin
ceramic
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PCT/CN2018/093755
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English (en)
French (fr)
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罗小帆
胡梦龙
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苏州聚复高分子材料有限公司
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Publication of WO2019210568A1 publication Critical patent/WO2019210568A1/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
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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Definitions

  • the invention relates to a 3D printing material, in particular to a photocurable ceramic composition which can be used for stereolithography (SLA) or digital light processing (DLP) 3D. print.
  • SLA stereolithography
  • DLP digital light processing
  • the invention also relates to a corresponding ceramic degreasing sintering process.
  • Fine ceramics also known as high-performance ceramics, have high hardness, high melting point, abrasion resistance, corrosion resistance, etc., in the fields of dental products, electronics industry, refractory industry, chemical industry, aerospace industry or food industry. Has been widely used.
  • the preparation process of small quantities of ceramic products mostly involves Subtractive Machining, which involves cutting the material from the starting block of the material to make the preparation more complicated. part.
  • Subtractive Machining which involves cutting the material from the starting block of the material to make the preparation more complicated. part.
  • Ceramic reduction processing can easily cause tool wear, which increases cost and reduces the accuracy of the prepared article.
  • the current common ceramic molding processes such as Gel Casting, Direct Coagulation Casting, Injection Molding, Dry Pressing, etc., need to be based on complex molds. Come on. Complex molds bring high mold processing costs and long mold processing cycles, which determine that these processes can only be used in mass production. Moreover, once the mold is finished, the mold cannot be adjusted. If you need to improve on the basis of the original design, it will take time and money to process the new mold. This situation has become increasingly unable to adapt to the rapid update of high-tech products and the increasingly fierce market competition.
  • the present invention proposes a photocurable ceramic composition which can be used for Stereolithography (SLA) or Digital Light Processing (Digital Light Processing). DLP) 3D printing.
  • SLA Stereolithography
  • DLP Digital Light Processing
  • the present invention designs a corresponding ceramic degreasing sintering process.
  • a photocurable composition comprising: a polymerizable or crosslinked photosensitive resin; ceramic particles; a dispersing agent; and a plasticizer and/or a solvent; wherein the ceramic particles are relative to The photocurable composition is added in an amount of 10% by volume to 80% by volume; the plasticizer is added in an amount of 0.1% by weight to 50% by weight relative to the polymerizable or crosslinked photosensitive resin; the dispersing agent is relative to The ceramic particles are added in an amount of from 0.1% by weight to 20% by weight.
  • the solvent in the photocurable composition, is added in an amount of from 0 to 50% by weight, preferably from 5 to 20% by weight, based on the amount of the polymerizable or crosslinked photosensitive resin.
  • the photosensitive resin is a photosensitive resin which can undergo photocationic curing, a photosensitive resin which can undergo photo-radical curing, or a combination thereof.
  • the photo-cation-curable photosensitive resin comprises:
  • the cationic initiator is added in an amount of from 0.1 to 20% by weight (w/w) based on the total mass of the photosensitive resin.
  • the epoxy polymerizable functional group is an oxirane ring, a propylene oxide ring, an epoxycyclohexane group, or one of the above A derivative of one or more functional groups.
  • the cationic initiator is a photoinitiator that can be excited by ultraviolet light, visible light or infrared light.
  • the cationic initiator is an aryl diazonium salt, a diaryliodonium salt, a triarylsulfonium salt, a triarylselenium salt, an aromatic ferrocene salt. Salt, or a mixture of the above.
  • the cationic initiator is diaryliodonium hexafluoroarsenate, diaryliodonium hexafluoroantimonate, diaryliodonium sulfonate a salt, a diaryliodonium borate, a triarylsulfonium sulfonate, a triarylsulfonium borate, a triarylsulfonium hexafluoroantimonate, or a mixture of the above.
  • the photo-radically curable photosensitive resin comprises: a monomer capable of undergoing radical curing, an oligomer or a high a polymer having at least one free-radically polymerizable functional group, wherein the oligomer has a molecular weight of from 200 to 1,000, a polymer having a molecular weight of from 1,000 to 30,000, and a radical initiator.
  • the radical initiator is added in an amount of from 0.1 to 20% (w/w) based on the total mass of the photosensitive resin.
  • the photo-radically curable photosensitive resin comprises a monomer, an oligomer or a polymer having at least one mercapto group.
  • the content of the monomer, oligomer or polymer having at least one mercapto group in the photocurable composition is from 1 to 20% by weight based on the total weight of the photosensitive resin.
  • the oligomer or polymer having at least one mercapto group has a degree of polymerization of not more than 40 in the photocurable composition.
  • the radical initiator is a photoinitiator which is excited by ultraviolet light, visible light or infrared light.
  • the free radical initiator is benzoin diethyl ether, methyl benzoylformate, hydroxycycloethane benzophenone, phenyl bis (2) , 4,6-trimethylbenzoyl)phosphine oxide, benzothiazole, Irgacure 651, Irgacure 907, Darocur 2959, camphorquinone, alpha-ketoglutaric acid, or a mixture of the above.
  • the ceramic particles are selected from the group consisting of zirconium oxide, aluminum oxide, silicon oxide, hydroxyapatite, silicon carbide, silicon nitride, and aluminum nitride. Or a combination comprising at least one of the above ceramic particles.
  • the ceramic particles in the photocurable composition, have a particle size of from 20 nm to 50 ⁇ m.
  • the surface of the ceramic particles may be coated with a surface modifier.
  • the surface modifying agent described therein is selected from the group consisting of linear or branched carboxylic acids, phosphoric acid, phosphates, silanes, or a mixture of the above.
  • the dispersing agent for uniformly dispersing ceramic particles in a photosensitive resin is selected from the group consisting of an acrylic dispersing agent and a polyvinylpyrrolidone dispersing agent.
  • an acrylic dispersing agent and a polyvinylpyrrolidone dispersing agent.
  • a ceramic article prepared by a method comprising the steps of: subjecting the aforementioned photocurable composition to stereolithography (SLA) or digital light treatment ( Digital light processing (DLP) performs 3D printing; it is heated to 1400 degrees Celsius or more to complete degreasing and sintering.
  • SLA stereolithography
  • DLP Digital light processing
  • the present invention achieves a shortened ceramic component development cycle by providing a photocurable composition suitable for 3D printing and ceramic degreasing sintering, combining ceramic materials with stereolithography (SLA) or digital light processing (DLP) techniques. Reduce design costs and increase design flexibility.
  • SLA stereolithography
  • DLP digital light processing
  • Figure 1 is a schematic diagram of the working principle of the SLA.
  • the invention proposes a new ceramic component manufacturing method, which prints ceramics by means of 3D printing, that is, additive manufacturing or rapid prototyping, in particular, using stereo light curing (SLA) or digital light processing (DLP) technology.
  • SLA stereo light curing
  • DLP digital light processing
  • the embryo is removed, and the photosensitive resin in the green embryo is removed by a degreasing process to form a dense ceramic member by sintering.
  • the method of the invention can greatly shorten the development cycle of the ceramic component, reduce the design cost, and improve the design flexibility. Since materials are stacked in layers during printing, 3D printing does not have the limitations of conventional processes; at the same time, the cost of producing small batches using 3D printing is much lower compared to conventional production processes.
  • the 3D printing process begins with a computer-generated data source that describes the object.
  • This computer generated data source can be based on real objects or virtual objects. For example, a real object can be scanned by a 3D scanner, and the acquired data can be used to generate a data source. Or the data source can be designed to be generated.
  • data sources are typically converted to standard tessellation language files (STLs).
  • STLs standard tessellation language files
  • the 3D printing software will read the file and convert it into hundreds or even millions of slices.
  • the 3D printing software then outputs the machine language (such as Gcode) to the 3D printer.
  • the 3D printer starts to print these slice information layer by layer according to the instruction, and finally generates this object.
  • the print platform 29 is immersed in the resin at a distance from the resin level (this distance is the height at which the lower layer needs to be printed).
  • a laser beam 26 (generally ultraviolet light) is irradiated from the resin bath 21 on the liquid surface of the photosensitive resin. Under the reflection of the galvanometer, the laser draws each layer pattern according to the program.
  • the photosensitive resin is cured as the laser is irradiated.
  • the print platform 29 is controlled by software to move down a distance (this distance is the layer height at which the lower layer needs to be printed).
  • the photosensitive resin flows until it covers the printed layer (if the photosensitive resin has a large viscosity and poor self-flow, a doctor blade is required to help coat the layer). This step is repeated until the entire item is printed. Then, the printing platform moves up out of the resin tank to facilitate the removal of the printed items.
  • Digital light processing as described in US 6,942,830 B2, has a similar principle and structure to that of SLA: the same is the use of ultraviolet light (or visible light) to layer the photosensitive resin liquid in the resin bath. Cured. But the difference is that the SLA uses laser spot scanning, and each layer of the pattern is drawn point by point according to the program under the reflection of the galvanometer; while the DLP uses the surface light source, and the layer pattern is projected once by the dynamic photomask. The photosensitive resin is liquid level, and after the layer is cured, the next layer of the pattern is projected.
  • the dynamic generation can reticle using an LCD screen, a light modulator (light modulator), or digital micromirror device (DMD), such as the Texas Instruments DLP (TM) chip.
  • TM Texas Instruments DLP
  • a photocurable ceramic composition comprising: (a) a photosensitive resin capable of being polymerized or crosslinked; (b) a ceramic is proposed. (c) a dispersing agent; (d) a plasticizer and/or a solvent.
  • the composition and properties of the ceramic photosensitive paste play a decisive role.
  • the viscosity of the ceramic photosensitive paste needs to be small enough and cannot be thixotropy, so that the ceramic photosensitive paste has good fluidity, otherwise it will be difficult to complete the feeding and leveling steps in printing, and will also bring cleaning after printing is completed. trouble.
  • the viscosity of the ceramic photosensitive paste needs to be less than 10,000 mPa ⁇ s at a shear rate of from 1 to 100 s -1 at 25 ° C.
  • the rheological properties of the ceramic photosensitive paste depend on the photosensitive resin; the type, particle size, sphericity, and solid content of the ceramic powder; and the dispersant, plasticizer, and the like selected.
  • the main components of the photosensitive resin include monomers, oligomers or polymers, photoinitiators, and optionally other additives.
  • the photoinitiator absorbs ultraviolet or visible light, it initiates polymerization of the monomer (or oligomer or polymer) to form a long polymer chain.
  • the macroscopic performance is that liquid monomers (or oligomers or polymers) gradually solidify under illumination.
  • the effects of the additive include toning, anti-oxidation, changing the wavelength of absorption of the photoinitiator, accelerating the curing rate, and enhancing the strength after curing.
  • the photosensitive resin used in the present invention includes acrylates and epoxies.
  • the acrylate monomer is used in combination with a free radical photoinitiator. Under illumination, the initiator generates free radicals and initiates free radical polymerization to form long chains of polymers.
  • the advantage of free radical polymerization is that it has a fast reaction speed and a short curing time.
  • the epoxy resin monomer is used in combination with a cationic photoinitiator. Under illumination, such initiators generate cations that initiate ionic polymerization to form long chains of polymers.
  • the epoxy resin has better mechanical properties, solvent resistance and thermal stability after curing than the radically polymerized acrylate resin.
  • the photocurable composition of the present invention comprises not only (a) a polymerizable or crosslinked photosensitive resin comprising a monomer, oligomer or polymer having a functional group capable of undergoing polymerization or crosslinking, and a crosslinking agent Or an initiator, a polymerizable or crosslinked photosensitive resin may undergo radical polymerization or epoxy polymerization; and further comprise (b) ceramic particles; (c) a dispersant; (d) a plasticizer and/or a solvent.
  • the concentration of the agent can adjust the rheological properties of the photocurable composition and the physical properties and degreasing effect after curing.
  • a photosensitive resin having a viscosity of less than 100 mPa ⁇ s (at a shear rate of 1-100 s -1 at 25 ° C).
  • the resulting ceramic photosensitive paste is more severely cured during printing, which may cause deformation warpage.
  • the low functional group monomer, oligomer or polymer has a high long chain content, and after the ceramic photosensitive paste is cured, it is easier to degrease at a high temperature.
  • the cured green part has lower strength and is easily broken.
  • the high functional group monomer, oligomer or polymer has a high long chain content, on the contrary, the cured green part has high strength, but it is more difficult to degrease at high temperature.
  • the radical-curable monomer, oligomer or polymer comprises at least one free-radically polymerizable functional group.
  • the initiator is a free radical initiator.
  • the photosensitive resin undergoes radical polymerization under light conditions.
  • the photosensitive resin may further comprise (iii) at least one fluorenyl group in addition to (i) a monomer capable of radically curing, an oligomer or a high polymer, and (ii) a radical initiator. Monomer, oligomer or polymer.
  • the photosensitive resin undergoes radical decyl olefin polymerization under light conditions.
  • the oxygen inhibition effect of free radical polymerization is the biggest obstacle to SLA/DLP 3D printing. Oxygen quenches the increase in photoinitiator production, which hinders free radical polymerization. In SLA/DLP 3D printing, the curing depth of each layer is only 25-100um, and the oxygen inhibition effect is more obvious. The oxygen inhibition effect causes the surface of the photosensitive resin to not be completely cured or even cured. Therefore, for SLA/DLP 3D printing, the oxygen inhibition effect is a major obstacle. It is possible to avoid the effect of oxygen inhibition on the curing of the material: printing under nitrogen protection; using very high intensity UV light; or increasing the concentration of photoinitiator. However, all three approaches complicate the 3D printing process, limiting the application of this technology and increasing the cost of use.
  • the present invention utilizes a thiol-ene reaction to avoid the inhibition of oxygen inhibition by SLA/DLP 3D printing.
  • Oxygen molecules react with carbon radicals or thiol radicals to form peroxy radicals.
  • the peroxy radical does not quench the polymer chain growth reaction, but will take away the hydrogen atom on the thiol to form another thiol radical, thereby continuing the polymer chain growth reaction. In this way, the oxygen inhibition effect will be avoided.
  • the interaction between the sulfhydryl group and the surface of the ceramic particles can help the ceramic particles to disperse, thereby reducing the viscosity of the ceramic photosensitive paste and avoiding the sedimentation of the ceramic powder.
  • the polymer network obtained by the polymerization of the radical decylene has a lower crosslinking density than the general radical polymerization reaction, which facilitates degreasing.
  • the content of the monomer, oligomer or polymer having at least one mercapto group in the photocurable composition is from 1 to 20% by weight, preferably based on the total weight of the photosensitive resin. It is from 1 to 10% by weight, more preferably from 5 to 10% by weight, which is advantageous for improving the dispersion of the ceramic, the viscosity of the composition and the curing efficiency.
  • monomers, oligomers or polymers having at least one mercapto group include, but are not limited to, tetrakis(3-mercaptopropionic acid) pentaerythritol ester, pentaerythritol tetradecyl acetate, trimethylolpropane tris(3- Mercaptopropionate, 1,2-ethanedithiol, 1,8-octanedithiol, 1,6-hexanedithiol, bis(2-mercaptoethyl)ether, 2,3-dimercapto Diacid.
  • tetrakis(3-mercaptopropionic acid) pentaerythritol ester pentaerythritol tetradecyl acetate
  • trimethylolpropane tris(3- Mercaptopropionate 1,2-ethanedithiol, 1,8-octanedithiol, 1,6-hexanedith
  • the oligomer or polymer having at least one mercapto group has a degree of polymerization of not more than 40, and more preferably, the degree of polymerization is not more than 20.
  • the radically polymerizable functional group has the following structure:
  • X is C or Si; R 1 , R 2 and R 3 are the same or different and are H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group has the following structure:
  • R 1 and R 2 are the same or different and are H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group has the following structure:
  • X is O, S or SO 2 ; and R 1 is H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group has the following structure:
  • X is C or Si; R 1 , R 2 and R 3 are the same or different and are H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group has the following structure:
  • X is C or Si;
  • R 1 , R 2 , R 3 and R 4 are the same or different and are H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group has the following structure:
  • R 1 and R 2 are the same or different and are H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group has the following structure:
  • R 1 is H, halogen, alkyl, haloalkyl, hydroxy, cyano or alkoxy.
  • the radically polymerizable functional group may be an acryloxyalkyl group, an acrylate functional group, an alkenyloxy group, an alkene group, an alkyne group or the like.
  • acryloxyalkyl groups include, but are not limited to, acryloyloxymethyl, methacryloxymethyl, 2-acryloyloxyethyl, 2-methacryloyloxyethyl, 3-acryloyloxypropane Base, 3-methacryloxypropyl or 4-acryloxybutyl.
  • olefinic groups include, but are not limited to, vinyl, allyl, butenyl, pentenyl, hexenyl, and the like.
  • the free radical initiator used can be photoexcited.
  • Optional free radical initiators include, but are not limited to, benzoin diethyl ether, methyl benzoylformate, hydroxycycloethane benzophenone (Irgacure 184 from BASF Corporation), phenyl bis(2,4,6-trimethylbenzene) Formyl)phosphine oxide (XBPO), albendazole, Irgacure 651 (from BASF), Irgacure 907 (from BASF), Darocur 2959 (from BASF), camphorquinone (CQ), alpha-ketoglutarate (KGA), Or a mixture of the above.
  • the radical initiator used may be a single radical initiator or a mixture of a plurality of radical initiators.
  • concentration of the radical initiator is generally 0.1 to 20% (w/w), preferably 1 to 10% (w/w), more preferably 1 to 5% (w/) based on the total mass of the photosensitive resin in the component. w), most preferably from 1 to 3% (w/w).
  • a photosensitive resin which can undergo epoxy polymerization comprises a monomer, oligomer or high polymer having at least one epoxy polymerizable functional group.
  • the initiator is a cationic initiator.
  • the photosensitive resin undergoes epoxy polymerization under light conditions.
  • Epoxy polymerizable functional group means a monovalent oxygen-containing three-membered ring or a four-membered ring-containing ether group.
  • Epoxy polymerizable functional groups include, but are not limited to, 2,3-epoxypropane, 3,4-epoxycyclobutane, 4,5-epoxycyclopentyl, 2-glycidoxyethyl , 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexane)ethyl, 3-(3,4-epoxycyclohexane) Propyl, or a derivative thereof.
  • the cationic initiator used can be photoexcited.
  • Optional cationic initiators include, but are not limited to, iodonium salts, diaryliodonium sulfonates, triarylsulfonium sulfonates, diaryliodonium borate, triarylsulfonium borate.
  • Optional iodonium salt initiators include, but are not limited to, diaryliodonium salts such as bis(alkylbenzene)iodonium hexafluoroantimonate or bis(alkylbenzene)iodohexafluoroarsenate, further, for example, double (Dodecane benzene) iodine hexafluoroantimonate or bis(dodecane benzene) iodine hexafluoroarsenate.
  • diaryliodonium salts such as bis(alkylbenzene)iodonium hexafluoroantimonate or bis(alkylbenzene)iodohexafluoroarsenate, further, for example, double (Dodecane benzene) iodine hexafluoroantimonate or bis(dodecane benzene) iodine hexafluoroarsenate.
  • diaryliodonium sulfonate initiators include, but are not limited to, diaryliodonium perfluoroalkyl sulfonates such as diaryliodonium perfluoroethyl sulfonate, diaryliodonium perfluorooctane sulfonate Acid salt, diaryliodonium perfluorobutyl sulfonate, diaryliodonium perfluoromethyl sulfonate; diaryl iodoaryl sulfonate, such as diaryliodonium p-toluenesulfonate, diaryl Iodododecanebenzenesulfonate, diaryliodonium sulfonate, diaryliodonium 3-nitrobenzenesulfonate.
  • diaryliodonium perfluoroalkyl sulfonates such as diaryliodonium perfluoroethyl sulf
  • Optional triarylsulfonium sulfonate initiators include, but are not limited to, triarylsulfonium perfluoroalkyl sulfonates such as triarylsulfonium perfluoroethylsulfonate, triarylsulfonium perfluorooctanesulfonate, and triaryl Based on perfluorobutyl sulfonate, triarylsulfonium perfluoromethanesulfonate; triarylsulfonyl sulfonate, such as triarylsulfonium p-toluenesulfonate, triarylsulfodedodecanebenzenesulfonate , triaryl benzenesulfonate, triarylsulfonium 3-nitrobenzenesulfonate.
  • triarylsulfonium perfluoroalkyl sulfonates such as triary
  • Optional diaryliodonium borate initiators include, but are not limited to, diaryliodonium perhaloaryl borate.
  • Optional triarylsulfonium borate initiators include, but are not limited to, triarylsulfonium perhaloaryl borate.
  • the cationic initiator used may be a single cationic initiator or a mixture of a plurality of cationic initiators.
  • the concentration of the cationic initiator is generally from 0.1 to 20% (w/w), preferably from 1 to 10% (w/w), more preferably from 1 to 5% (w/w), based on the mass of the photosensitive resin in the component. Most preferably, it is 1 to 3% (w/w).
  • the photosensitive resin used may undergo both radical polymerization and epoxy polymerization.
  • the photosensitive resin to be used may undergo radical polymerization, radical decyl olefin polymerization, and epoxy polymerization.
  • Ceramic refers to a series of inorganic non-metallic solid materials with a crystalline structure.
  • the conventional preparation of ceramics is mainly accomplished by sintering, such as sintering a zirconia ceramic powder into a dense whole at a high temperature of 1500 ° C or higher.
  • Optional ceramic powders include, but are not limited to, zirconia, alumina, silica, hydroxyapatite, silicon carbide, silicon nitride, aluminum nitride.
  • Stabilizers may also be added to the ceramic powder to maintain the crystal form stability of the ceramic.
  • Stabilizers include, but are not limited to, cerium oxide, cerium oxide, calcium oxide, magnesium oxide, cerium oxide, or a mixture of the above.
  • the content of the stabilizer is generally 3-5 wt% based on the mass of the ceramic to be stabilized.
  • high-strength zirconia generally contains 3-5 wt% of cerium oxide to maintain a tetragonal crystal form.
  • Such zirconia ceramics are generally referred to as Y-TZP (yttrium-stabilized tetragonal zirconium dioxide polycrystals).
  • the solid content of the ceramic powder (the ratio of the volume of the ceramic powder to the total volume, expressed in vol%) in the ceramic photosensitive paste of the present invention needs to be as high as possible, so that the ceramic member after sintering can be made dense, high in strength, and small in shrinkage. At the same time, the higher the solid content, the less likely the ceramic photosensitive paste to settle, which ensures the storage stability of the ceramic photosensitive paste.
  • the volume of ceramic particles is from 10% by volume to 80% by volume, preferably from 30% by volume to 70% by volume, more preferably from 40% by volume to 60% by volume, most preferably from 45% by volume to 50% by volume, based on the total volume of the slurry.
  • the diameter of the ceramic powder particles greatly affects the rheological and sintering characteristics of the ceramic photosensitive paste. If the diameter of the ceramic powder particles is too small, the obtained ceramic photosensitive paste does not easily settle after standing, and the sintering temperature of the green sheet is low, but the viscosity of the slurry is too large to obtain a high-solidity ceramic photosensitive paste; If the ceramic powder particle diameter is too large, the obtained ceramic photosensitive paste has a small viscosity, and it is easier to obtain a high solid content ceramic photosensitive paste, but it is not easy to settle after standing, and the greening member has a high sintering temperature.
  • the specific diameter range depends on the choice of ceramic material.
  • the suitable particle diameter of alumina is between 20nm and 50 ⁇ m, preferably between 75nm and 10 ⁇ m.
  • the suitable particle diameter of Y-TZP zirconia is between 20nm and 50 ⁇ m. Between, preferably between 50nm and 35 ⁇ um. Therefore, it is preferred in the present invention that the ceramic particles have a particle size ranging from 20 nm to 50 ⁇ m, more preferably between 50 nm and 35 ⁇ m, and most preferably between 75 nm and 10 ⁇ m.
  • the sphericity refers to the ratio of the surface area of the sphere of the same volume as the object to the surface area of the object.
  • the sphericity of the ball is equal to 1, and the sphericity of other objects is less than one.
  • the ceramic slurry is selected to be ceramic particles, the closer the particle sphericity is to 1, the closer the particles are to the spherical shape, and the lower the viscosity of the ceramic slurry.
  • the sphericity in the present invention is more preferably higher than 0.5, preferably higher than 0.6, more preferably higher than 0.7, further preferably higher than 0.8, still more preferably higher than 0.9.
  • the surface of the ceramic powder particles may be coated with a layer of surface modifier.
  • the surface modifier can be bonded to the surface of the ceramic particle by a chemical bond such as an ionic bond or a covalent bond, thereby improving the wetting effect of the photosensitive resin on the ceramic powder.
  • Optional surface modifiers include, but are not limited to, linear or branched carboxylic acids such as formic acid, acetic acid, propionic acid, octanoic acid, isobutyric acid, pivalic acid, etc.; phosphoric acids, such as methyl phosphate, ethyl phosphate, Propyl phosphate, butyl phosphate, pentyl phosphate, hexyl phosphate, heptyl phosphate, etc.; phosphates such as dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dipentane Phosphate, dihexyl phosphate, diheptyl phosphate, etc.; silane, such as propyltrimethoxysilane, phenyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, trimethyl chloride Si
  • the dispersant is an indispensable component of the ceramic photosensitive paste of the present invention.
  • the molecular chain of the dispersant is wrapped around the surface of the ceramic particles, so that the ceramic particles cannot agglomerate with each other, thereby being better suspended in the photosensitive resin. In this way, the dispersant can help the ceramic particles to be more uniformly dispersed in the photosensitive resin, thereby achieving the purpose of low viscosity and high solid content.
  • Optional dispersing agents include, but are not limited to, polyacrylic dispersing agents (such as RTVanderbilt) ), polyvinylpyrrolidone dispersants (such as RTVanderbilt) 821A and ISP Technologies' PVP K-15), nonylphenol oxyethylate dispersant (such as Union Carbide Corporation) X-100), an amine dispersant (such as HYPERMER KD-2 from ICI Americas), a fatty acid dispersant (such as TEXAPHOR 963 from Henkel), or a mixture of the above.
  • the content of the dispersant is generally from 0.1 to 20% (w/w), preferably from 1 to 10% (w/w), more preferably from 1 to 5% (w/w), based on the mass of the ceramic particles in the component.
  • a dispersing agent, a plasticizer, a surface modifier, a solvent, and the like may be directly added to the mixture of the photosensitive resin and the ceramic powder, and the effect of uniform dispersion is achieved by ball milling for several hours.
  • the dispersing agent, the plasticizer, the surface modifier, the solvent, and the like may be first mixed with the photosensitive resin, and the dispersion effect is achieved by stirring, and then the ceramic powder is added to the dispersing agent, the plasticizer, and the surface.
  • the effect of uniform dispersion is achieved by ball milling for several hours.
  • the dispersing agent and/or the surface modifying agent are first dissolved in the organic solvent, and then the ceramic powder is added to the solution, and the effect of uniform dispersion is achieved by ball milling for several hours; then the solvent is evaporated to dryness, and pulverized and dried to obtain The dried ceramic powder is mixed with the photosensitive resin and ball-milled for several hours to achieve a uniform dispersion effect.
  • a solvent may be added to the ceramic photosensitive paste to further reduce the viscosity.
  • the vaporization temperature of the solvent is lower than the decomposition temperature of the photosensitive resin after curing. Therefore, the solvent will first be detached from the green embryo, leaving holes to facilitate the gasification of the remaining organic matter, thereby improving the degreasing efficiency and avoiding cracking and deformation.
  • the choice of solvent depends on the choice of photosensitive resin. If the photosensitive resin is water-soluble, water can be used as a solvent. If the photosensitive resin is oil-soluble, an organic solvent is used.
  • Solvents include, but are not limited to, water, phthalate derivatives (such as dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate), phosphate derivatives (such as tricresyl phosphate, tributyl phosphate), n-octanol, glycerol, polyethylene glycol, 2-amino-2-methyl-1-propanol, 2-methyl-2,4-pentanediol , tripropylene glycol, tetraethylene glycol, ethyl acetoacetate, triethyl citrate, cyclohexanol, cyclohexanone, diethylene glycol methyl ether, diethylene glycol diethyl ether, dibutyl oxalate, 2, 5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, n-nonanol, isodecyl alcohol
  • the solvent in the green embryo is not removed by heating and gasification during the degreasing process, but is removed by solvent extraction.
  • water-soluble polyethylene glycol is added to the ceramic photosensitive resin.
  • the green embryos are immersed in water for a period of time (for example, about 12 hours), and the polyethylene glycol in the raw embryos is dissolved in water while leaving holes to facilitate the gasification of the remaining organic matter during the degreasing process.
  • ethyl acetoacetate which is soluble in an organic solvent is added to the ceramic photosensitive resin.
  • the embryos are immersed in methylene chloride for a period of time (such as about 12 hours), and the ethyl acetoacetate in the green embryos will be dissolved in methylene chloride while leaving pores to facilitate the gasification of the remaining organic matter during the degreasing process. Get rid of.
  • a plasticizer can be added to the ceramic photosensitive paste.
  • the advantages of adding a plasticizer are as follows: 1.
  • the plasticizer increases the toughness of the green embryo and avoids the occurrence of microcracks due to the internal stress caused by the curing shrinkage of the photosensitive resin (microcracks may expand during degreasing and sintering, thereby greatly reducing the sintering The ceramic strength);
  • the plasticizer will first detach from the raw embryo, leaving holes to facilitate the remaining organic matter gasification and detachment, thereby improving the degreasing efficiency, avoiding cracking deformation and avoiding the embryo's cracking deformation during degreasing;
  • the liquid plasticizer also acts as a solvent to reduce the viscosity of the ceramic photosensitive paste.
  • Optional plasticizers include, but are not limited to, triolein, polyethylene glycol, phthalate derivatives (such as dibutyl phthalate, dihexyl phthalate, orthophthalic acid) Di-n-octyl formate), a phosphate derivative (such as tricresyl phosphate, tributyl phosphate), or a mixture of the above.
  • the content of the plasticizer is generally from 0.1% by weight to 50% by weight, preferably from 1% by weight to 40% by weight, more preferably from 1% by weight to 30% by weight, based on the mass of the photosensitive resin in the component.
  • a colorant may be added to the ceramic photosensitive paste.
  • the colorants herein are mainly transition metal compounds, rather than common organic dyes or pigments, because only transition metal compounds are stably present at the high temperature of degreasing and sintering, so that the sintered ceramics have different colors.
  • Optional transition metal elements include, but are not limited to, iron, ruthenium, osmium, iridium, osmium, tungsten, ruthenium, manganese, or a mixture of the foregoing. These transition metal elements may be selected primarily in the form of a salt, including but not limited to formate, acetate, propionate, butyrate, stearate, palmitate, and the like.
  • the content of the colorant is generally from 0.01 to 1% by weight, and may also be from 0.05 to 0.5% by weight, based on the mass of the ceramic particles in the component.
  • a polymerization inhibitor may be added to the ceramic photosensitive paste to prevent spontaneous polymerization of the ceramic photosensitive paste during storage, thereby prolonging the storage time of the ceramic photosensitive paste.
  • Optional polymerization inhibitors include, but are not limited to, hydroquinone monomethyl ether (MEHQ), 2,6-di-tert-butyl-p-cresol (BHT), phenothiazine, tetramethylpiperidine oxide (TEMPO) ), or a mixture of the above.
  • the content of the polymerization inhibitor is generally 0.001 to 0.5% by weight, and may be 0.01 to 0.05% by weight based on the mass of the photosensitive resin in the component.
  • the photocurable composition of the present invention may further contain various additives which are usually added to this type of resin composition. In one case, multiple additives can be used simultaneously. In another case, these additives may be mixed into the photosensitive resin together with the ceramic particle plasticizer, dispersant, and solvent. Additives that may be selected include, but are not limited to, heat stabilizers, antioxidants, light stabilizers, antistatic agents, pigments, dyes, or combinations of one or more of the foregoing.
  • Suitable heat stabilizers include, for example, organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, etc.; phosphonates such as dimethylphenyl phosphonate A phosphate such as trimethyl phosphate or the like, or a combination comprising at least one of the foregoing heat stabilizers.
  • the heat stabilizer is usually used in an amount of from 0.001 to 0.5 parts by weight based on 100 parts by weight of the photosensitive resin.
  • Suitable antioxidants include, for example, organic phosphites such as tris-(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl)phosphite, di(2,4-di) -tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc.; alkylated monohydric phenol or polyhydric phenol; reaction product of alkylation of polyhydric phenol with diene, for example four [ Methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, etc.; butylated reaction product of p-cresol or dicyclopentadiene; alkylated hydroquinone; Hydroxylated thiodiphenyl ether; benzyl compound; ester of ⁇ -(3,5-di-tert-
  • Suitable light stabilizers include, for example, benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzene And triazole and 2-hydroxy-4-n-octyloxybenzophenone, etc., or a combination comprising at least one of the foregoing light stabilizers.
  • the light stabilizer is usually used in an amount of from 0.1 to 1.0 part by weight based on 100 parts by weight of the photosensitive resin.
  • Suitable antistatic agents include glyceryl monostearate, sodium stearyl sulfonate, sodium dodecyl benzene sulfonate, and the like, or a combination of the foregoing antistatic agents.
  • the antistatic agent is usually used in an amount of from 0.5 to 3.0 parts by weight based on 100 parts by weight of the photosensitive resin.
  • Suitable pigments include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxide, etc.; sulfides such as zinc sulfide, etc.; aluminates; sodium thiosilicates; sulfates, chromium Acid salt, etc.; carbon black; zinc ferrite; ultramarine blue; pigment brown M; pigment red 101; pigment yellow 119; organic pigments such as azo, diazo, quinacridone, anthracene, naphthalene tetracarboxylic acid, flavan Ketone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthraquinone, dioxazine, phthalocyanine, and azo lake; pigment blue 60, pigment red 122, pigment red 149 Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet IV, Pigment Blue 15, Pigment Green 7, Pig
  • Suitable dyes include, for example, organic materials such as coumarin 460 (blue), coumarin 6 (green), nile red, etc.; lanthanide complexes; hydrocarbons and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes (preferably oxazole and oxadiazole dyes); aryl or heteroaryl substituted poly(C2-8) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes and pigments; oxazine dyes; quinolones Carbostyryl) dye; porphyrin dye; acridine dye; anthraquinone dye; aryl methane dye; azo dye; diazo dye; nitro dye; quinone imine dye; tetrazole dye; thiazole dye; anthraquinone dye; Dye; bis-benzoxazolylthiophene (BBOT); and xant
  • the photocurable composition of the present invention can be mixed by grinding at room temperature to uniformly disperse ceramic particles and other additives into the photosensitive resin to prepare a mixed liquid of the composition. According to a preferred embodiment, it can be stirred at a temperature of 200-1000 r/min for 5 to 50 hours at room temperature. The prepared composition can also be more advantageously removed by vacuum removal of minute bubbles in the composition.
  • a method for preparing a photocurable composition comprises: uniformly mixing the components at room temperature, and grinding at a rotation speed of 400 r/min or more for 5, 10, or 20 hours or more; The mixed solution is allowed to stand or stir under vacuum for 5, 8, or more than 10 hours; according to a more preferred embodiment, wherein the respective components are mixed and ground at a rotational speed of 400-1000 r/min for 20-50 hours.
  • the grinding is a ball milling.
  • the resulting mixture is allowed to stand at a vacuum of more than 0.02 MPa for 10-15 hours.
  • a method for preparing a photocurable composition comprises: dissolving a dispersant and/or a surface modifier in a solvent at room temperature, and uniformly mixing with the ceramic particles to be 400 r/min or more. Rotating at a speed of 1, 3, or more than 5 hours; evaporating and drying, crushing to obtain ceramic particles coated with a surface modifier; mixing the obtained ceramic particles with other components such as photosensitive resin, and grinding at a speed of 800 r/min or more 5, 10, or more than 20 hours; and stand or stir for 5, 8, or more than 10 hours under vacuum.
  • the dispersant and/or surface modifier are dissolved in an organic solvent at room temperature, including but not limited to ethanol, methanol, isopropanol, acetone, ethyl acetate, and tetrahydrofuran, and with ceramic particles.
  • an organic solvent including but not limited to ethanol, methanol, isopropanol, acetone, ethyl acetate, and tetrahydrofuran, and with ceramic particles.
  • the mixture was uniformly mixed and ground at a speed of 400-800 r/min for 5-10 hours; evaporatively dried and crushed to obtain ceramic particles having a surface-coated surface modifier.
  • the obtained ceramic particles are mixed with other components such as a photosensitive resin, and then ground at a rotation speed of 800 to 1200 r/min for 20 to 50 hours.
  • the grinding stone ball mill In a further preferred embodiment the grinding stone ball mill.
  • the resulting mixture is allowed to stand for 10-20 hours under a vacuum of more than 0.02 MPa.
  • the viscosity needs to be less than 10000 mPa ⁇ s at a shear rate of 1-100 s -1 , and at the same time, it cannot have thixotropic properties to ensure good fluidity.
  • the type of monomer, oligomer or polymer or the number of functional groups, molecular structure (linear structure or multi-branched structure) and molecular weight, as well as monomers, oligomers or high within the scope of the present invention
  • the concentration of the polymer and the crosslinking agent, the particle size and solid content of the ceramic particles, and the preparation process, etc. can adjust the rheological properties of the photocurable composition and the physical properties and degreasing effect after curing.
  • the prepared composition mixture is subjected to 3D printing by stereolithography (SLA) or digital light processing (DLP) technology to obtain a ceramic green component.
  • SLA stereolithography
  • DLP digital light processing
  • the laser intensity of the photocuring is 0.3-5.0 W, and the laser scanning rate is 200. -4000 mm/s, printing layer thickness is 5-200 ⁇ m.
  • the photocuring in digital light processing (DLP), has an exposure intensity of 0.3 to 5.0 W, an exposure time of 5 to 60 seconds, and a printing layer thickness of 5 to 200 ⁇ m.
  • the ceramic green component is obtained by degreasing the photosensitive resin or the like contained therein to obtain a dense ceramic member of a desired shape by sintering.
  • the degreasing sintering comprises: raising the temperature from room temperature to 400-600 ° C, the heating rate is 0.1-1.5 ° C / min; heating from 400-600 ° C to 1400-1600 ° C, the heating rate is 0.1-1 °C/min; wherein the temperature is maintained at 300-400 ° C for 0.5-2 hours; at 500-600 ° C for 2-5 hours; at 850-950 ° C for 0.5-2 hours; finally natural cooling.
  • the degreasing sintering comprises: raising the temperature from room temperature to 450-550 ° C, the heating rate is 0.1-0.5 ° C / min; heating from 450-550 ° C to 1450-1550 ° C, the heating rate is 0.1-0.5 ° C /min; wherein the temperature is maintained at 300-400 ° C for 0.5-2 hours; at 500-600 ° C for 2-5 hours; at 850-950 ° C for 0.5-2 hours; finally natural cooling.
  • the degreasing process of the ceramic green component is heated from room temperature to 400-600 ° C, and the heating rate is about 1 ° C / min; the sintering process is heated from 400-600 ° C to 1400-1600 ° C, and the temperature is raised. The rate is approximately 1 ° C / min.
  • the degreasing process is from room temperature to 450-550 ° C, the heating rate is about 0.5 ° C / min; the sintering process is from 450-550 ° C to 1450-1550 ° C, the heating rate is about 0.5 ° C /min.
  • the degreasing process is from room temperature to 500-520 ° C, the heating rate is about 0.1 ° C / min; the sintering process is from 500-520 ° C to 1500-1520 ° C, the heating rate is about 0.1 ° C /min.
  • the ceramic green body is heated from room temperature to 150 ° C at 1 ° C / min; from 150 ° C to 350 ° C at 0.5 ° C / min; at 350 ° C for 1 hour; at 0.1 ° C / min from 350
  • the temperature was raised to 550 ° C; the temperature was maintained at 550 ° C for 3 hours; the temperature was raised from 550 ° C to 900 ° C at 0.5 ° C / min; the temperature was maintained at 900 ° C for 1 hour; and the temperature was raised from 900 ° C to 1450 ° C at 1 ° C / min.
  • BYK111 is a dispersant from BYK Chemical Company; “parts” in the table means “parts by weight”, the same below.
  • Preparation of the composition The components were uniformly mixed at room temperature, the ball milling speed was 500 r/min, and the ball milling time was 30 hours. The resulting mixture was allowed to stand under vacuum for 10 hours to remove bubbles to give the desired photocurable composition.
  • One drop of the obtained photocurable composition was dropped on a glass slide, and a laser having a power of 1 W and a wavelength of 355 nm was irradiated at a position of 3 cm above it, and visually observed, the liquidity loss of the liquid droplet was used as an index for judging whether or not it was cured. Record the curing time.
  • compositions of Examples 1, 3 and 4 had a shorter curing time, which was advantageous for the improvement of printing efficiency, and N, N'-methylenebisacrylamide was used.
  • the curing time of the composition of Example 3 was the shortest and most advantageous.
  • BYK111 is a dispersant (fatty acid dispersant) from BYK Chemical Company.
  • Preparation of the composition The components were uniformly mixed at room temperature, and the components were uniformly mixed at room temperature, the rotation speed of the ball mill was 500 r/min, and the ball milling time was 42 hours. The resulting mixture was allowed to stand under vacuum for 10 hours to remove bubbles to give the desired photocurable composition.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . The viscosity of Example 6 is lower than that of Example 5, indicating that the inclusion of an appropriate amount of a monomer or oligomer having a mercapto functional group in the photocurable composition can more effectively assist the dispersion of the ceramic particles in the photosensitive resin, thereby lowering the composition. Viscosity.
  • BYK9076 is a dispersant (polyvinylpyrrolidone dispersant) from BYK Chemical Company.
  • BYK9076 was dissolved in alcohol at a mass ratio of 2:100 at room temperature, and then silica was uniformly mixed, the rotation speed of the ball mill was 500 r/min, and the ball milling time was 5 hours. The resulting mixture was evaporated to dryness and pulverized to give a dried silica powder. The obtained silicon oxide and the photosensitive resin were uniformly mixed, the number of rotations of the ball mill was 800 r/min, and the ball milling time was 35 hours. The resulting mixture was allowed to stand under vacuum for 10 hours to remove bubbles to give the desired photocurable composition.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . It can be seen that the greater the molecular weight of the thiol, the greater the viscosity of the resulting composition.
  • the tetrakis(3-mercaptopropionic acid) pentaerythritol ester has a lower viscosity and is more suitable.
  • Preparation of the composition The components were uniformly mixed at room temperature, the ball milling speed was 800 r/min, and the ball milling time was 24 hours. The resulting mixture was allowed to stand under vacuum for 12 hours to remove air bubbles to give the desired photocurable composition.
  • the method for testing the dispersion effect and stability of hydroxyapatite in photosensitive resin is as follows: the mixed composition is placed in a transparent measuring cylinder to record the liquid level; if it is still for 1 month, the height of the supernatant is more than the total liquid. The height of the surface is 5%; the smaller the height of the supernatant, the better the dispersion effect and the higher the stability.
  • a dispersant based on the mass of the hydroxyapatite in the component of about 1-5% (w/w) is used, and the dispersion effect and stability are better; and the quality of the hydroxyapatite based on the component is used.
  • the resulting composition has the best dispersion and highest stability.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . It can be seen that in the above examples, a dispersant based on the mass of the hydroxyapatite in the component of about 1-5% (w/w) is used, and the viscosity is low; and the mass based on the hydroxyapatite in the component is used. a dispersant of about 3% (w/w) The resulting composition has the lowest viscosity.
  • Preparation of the composition The surface modifier was dissolved in alcohol at a mass ratio of 2:100 at room temperature, and then mixed with hydroxyapatite, the rotation speed of the ball mill was 500 r/min, and the ball milling time was 5 hours. The resulting mixture was evaporated to dryness and pulverized to give a dried hydroxyapatite powder. The obtained hydroxyapatite was uniformly mixed with a photosensitive resin, the number of rotations of the ball mill was 800 r/min, and the ball milling time was 35 hours. The resulting mixture was allowed to stand under vacuum for 10 hours to remove bubbles to give the desired photocurable composition.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . It can be seen that in the above examples, the compositions obtained in Examples 17-20 using the surface modifier had lower viscosity than the compositions obtained in Example 13 using the surface modifier. The composition obtained in Example 20 using hexyltrimethoxysilane at the same time had the lowest viscosity.
  • Preparation of the composition The surface modifier was dissolved in alcohol at a mass ratio of 2:100 at room temperature, and then mixed with hydroxyapatite, the rotation speed of the ball mill was 500 r/min, and the ball milling time was 5 hours. The resulting mixture was evaporated to dryness and pulverized to give a dried hydroxyapatite powder. The obtained hydroxyapatite was uniformly mixed with a photosensitive resin, the number of rotations of the ball mill was 800 r/min, and the ball milling time was 35 hours. The resulting mixture was allowed to stand under vacuum for 10 hours to remove bubbles to give the desired photocurable composition.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . It can be seen that in the above examples, the compositions obtained in Examples 17-20 using the surface modifier had lower viscosity than the compositions obtained in Example 13 using the surface modifier. The composition obtained in Example 20 using hexyltrimethoxysilane at the same time had the lowest viscosity.
  • hexyltrimethoxysilane having a mass of hydroxyapatite based on the composition of about 1-5% (w/w) is used, and the viscosity is low; and the mass of the hydroxyapatite based on the component is used.
  • the hexyltrimethoxysilane of about 3% (w/w) gives the composition the lowest viscosity.
  • the surface modifier was dissolved in alcohol at a mass ratio of 2:100 at room temperature, and then zirconia was uniformly mixed, the rotation speed of the ball mill was 400 r/min, and the ball milling time was 8 hours.
  • the resulting mixture was evaporated to dryness and pulverized to give dried zirconia powder.
  • the obtained zirconia was uniformly mixed with the photosensitive resin, the number of rotations of the ball mill was 1000 r/min, and the ball milling time was 50 hours.
  • the resulting mixture was allowed to stand under vacuum for 10 hours to remove air bubbles to give the desired photocurable composition.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . It can be seen that in the above examples, as the solid content of zirconia is increased, the viscosity of the resulting composition is increased (as in Example 27).
  • 3D printing experiment using the configured photocurable composition to print ceramic green embryos of size 48mm*4.8mm*1.2mm on the CSL model (SLA technology) of Kunshan Bolimai 3D Printing Technology Co., Ltd. (at room temperature)
  • the laser intensity is 1.8W
  • the laser scanning rate is 750mm/s
  • the printing layer thickness is 25um).
  • the ceramic green body is heated from room temperature to 150 ° C at 1 ° C / min; from 150 ° C to 350 ° C at 0.5 ° C / min; at 350 ° C for 1 hour; from 0.1 ° C / min from 350 ° C to 550 °C; incubated at 550 ° C for 3 hours; from 550 ° C to 900 ° C at 0.5 ° C / min; at 900 ° C for 1 hour; from 1 ° C / min from 900 ° C to 1450 ° C; naturally cooled.
  • a three-point bending test (ISO 6872-2008) was used to determine the three-point bending strength of the zirconia material.
  • the three-point bending strength of the resulting composition after printing and degreasing is stronger.
  • the surface modifier was dissolved in alcohol at a mass ratio of 2:100 at room temperature, and then zirconia was uniformly mixed, the rotation speed of the ball mill was 400 r/min, and the ball milling time was 8 hours.
  • the resulting mixture was evaporated to dryness and pulverized to give dried zirconia powder.
  • the obtained zirconia was uniformly mixed with a photosensitive resin, a plasticizer or a solvent, and the number of rotations of the ball mill was 1000 r/min, and the ball milling time was 50 hours.
  • the resulting mixture was allowed to stand under vacuum for 10 hours to remove air bubbles to give the desired photocurable composition.
  • Viscosity test Viscosity was measured using a vertebral plate viscometer CAP2000 from Brookfield. The test temperature was 25 ° C and the shear rate was 20 s -1 . It can be seen that in the above examples, the viscosity of the resulting composition is reduced to varying degrees after the addition of a plasticizer or solvent.
  • 3D printing experiment using the configured photocurable composition to print ceramic green embryos of size 48mm*4.8mm*1.2mm on the CSL model (SLA technology) of Kunshan Bolimai 3D Printing Technology Co., Ltd. (at room temperature)
  • the laser intensity is 1.8W
  • the laser scanning rate is 750mm/s
  • the printing layer thickness is 25um).
  • the ceramic green body is heated from room temperature to 150 ° C at 1 ° C / min; from 150 ° C to 350 ° C at 0.5 ° C / min; at 350 ° C for 1 hour; from 0.1 ° C / min from 350 ° C to 550 °C; incubated at 550 ° C for 3 hours; from 550 ° C to 900 ° C at 0.5 ° C / min; at 900 ° C for 1 hour; from 1 ° C / min from 900 ° C to 1450 ° C; naturally cooled.
  • a three-point bending test (ISO 6872-2008) was used to determine the three-point bending strength of the zirconia material.
  • the addition of a plasticizer or solvent can lower the viscosity of the resulting composition while improving the three-point bending strength after degreasing and sintering.
  • Preparation of the composition The components were uniformly mixed at room temperature, the ball milling speed was 800 r/min, and the ball milling time was 24 hours. The resulting mixture was allowed to stand under vacuum for 12 hours to remove bubbles to give the desired photocurable composition.
  • 3D printing experiment using the configured photocurable composition to print ceramic green embryos of size 48mm*4.8mm*1.2mm on the CSL model (SLA technology) of Kunshan Bolimai 3D Printing Technology Co., Ltd. (at room temperature)
  • the laser intensity is 1.8W
  • the laser scanning rate is 750mm/s
  • the printing layer thickness is 25um).
  • the ceramic green body is heated from room temperature to 150 ° C at 1 ° C / min; from 150 ° C to 350 ° C at 0.5 ° C / min; at 350 ° C for 1 hour; from 0.1 ° C / min from 350 ° C to 550 °C; incubated at 550 ° C for 3 hours; from 550 ° C to 900 ° C at 0.5 ° C / min; at 900 ° C for 1 hour; from 1 ° C / min from 900 ° C to 1450 ° C; naturally cooled.
  • the photocurable composition of the present invention has excellent fluidity, viscosity, stability, and photocurability, and is therefore suitable for use in stereo light curing (SLA) or digital light processing (DLP).
  • the technical 3D prints the ceramic green embryo and then obtains a dense ceramic product by degreasing and sintering.
  • the invention utilizes the advantages of high-speed forming and high molding precision by using stereo light curing (SLA) or digital light processing (DLP) technology, and stereoscopic curing (SLA) or digital light processing (DLP) technology of materials. Combined with ceramic degreasing and sintering technology, it can shorten the development cycle of ceramic products, reduce design cost and improve design flexibility.

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Abstract

一种可光致固化组合物，其包含光敏树脂、陶瓷颗粒、分散剂以及塑化剂和/或溶剂。这样的组合物可用于立体光固化成型法或数字光处理成型法3D打印。这种打印结合了相应的陶瓷脱脂烧结工艺。烧结后的陶瓷部件具有优异的三点弯曲强度，可以用于多种应用，例如义齿、耐高温喷嘴、耐腐蚀过滤器、化学反应催化剂载体等。

Description

一种可光致固化的组合物 技术领域
发明涉及一种3D打印材料，特别是涉及一种能够光致固化的陶瓷组合物，其能够用于立体光固化成型法(Stereolithography，SLA)或数字光处理成型法(Digital Light Processing，DLP)3D打印。本发明还涉及相应的陶瓷脱脂烧结工艺。
背景技术
精细陶瓷(fine ceramics)，又称高性能陶瓷，具有高硬度、高熔点、耐磨损、耐腐蚀性等优点，在牙科制品、电子工业、耐火工业、化学工业、航天工业或食品工业等领域得到了广泛的应用。
小量制备陶瓷制品的制备工艺，如研磨、钻孔、碾碎、车床切割、火焰切割等，大多涉及减材加工(Subtractive Machining)方法，即将材料从材料的起始块切除，以制备更复杂的部分。但陶瓷材料本身固有的高硬度、高耐磨性等优点，却成了陶瓷减材加工的障碍。陶瓷减材加工很容易造成工具磨损，从而增加了成本并且降低了所制备制品的精确度。目前常见的陶瓷成型工艺，例如凝胶铸模成型(Gel Casting)，直接凝固成型(Direct Coagulation Casting)，注射成型(Injection Molding)，干压成型(Dry Pressing)等，都需要以复杂的模具为基础来进行。而复杂模具带来了高昂的模具加工成本和漫长的模具加工周期，决定了这些工艺只能运用于大量生产。而且一旦模具加工完毕，则无法对模具进行调整。如果需要在原有设计的基础上改进，则又需要耗费时间和金钱去加工新模具。这种状况已越来越不能适应目前高科技产品的快速更新换代和日趋激烈的市场竞争。
因此，本领域需要提供一种更为快速和方便的陶瓷成型方法以及相应的材料。
发明内容
针对现有技术中存在的技术问题，本发明提出了一种能够光致固化的陶瓷组合物，其能够用于立体光固化成型法(Stereolithography，SLA)或数字光处理成型法(Digital Light Processing，DLP)3D打印。同时本发明设计了相应的陶瓷脱脂烧结工艺。
根据本发明的一个方面，一种可光致固化的组合物，包含：可聚合或交联的光敏树脂；陶瓷颗粒；分散剂以及增塑剂和/或溶剂；其中所述陶瓷颗粒相对于可光致固化的组合物的添加量是10体积％至80体积％；所述塑化剂相对于可聚合或交联的光敏树脂的添加量是0.1wt％至50wt％；所述分散剂相对于陶瓷颗粒的添加量是0.1wt％至20wt％。
根据本发明的优选的实施方式，所述可光致固化的组合物中，所述溶剂相对于可聚合或交联的光敏树脂的添加量是0至50wt％，优选是5至20wt％。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述光敏树脂是可发生光致阳离子固化的光敏树脂、可发生光致自由基固化的光敏树脂、或其组合。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述的可发生光致阳离子固化的光敏树脂包含：
可发生阳离子固化的单体、寡聚物或高聚物，其具有至少一个可环氧聚合的官能团，其中寡聚物分子量为200-1000或高聚物分子量为1000-30000；以及阳离子引发剂。
根据本发明的优选实施方式，所述的可光致固化的组合物中，阳离子引发剂的添加量是光敏树脂总重量的0.1至20％(w/w)。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述可环氧聚合的官能团是环氧乙烷环、环氧丙烷环、环氧环己烷基、或上述一种或多种官能团的衍生物。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述阳离子引发剂是一种可被紫外光、可见光或红外光激发的光引发剂。
根据本发明的优选实施方式，所述的可光致固化的组合物中，阳离子引发剂是芳基重氮盐、二芳基碘鎓盐、三芳基锍盐、三芳基硒盐、芳茂铁盐，或者是以上多种的混合物。
根据本发明的优选实施方式，所述的可光致固化的组合物中，阳离子引发剂是二芳基碘六氟砷酸盐、二芳基碘六氟锑酸盐、二芳基碘磺酸盐、二芳基碘硼酸盐、三芳基锍磺酸盐、三芳基锍硼酸盐、三芳基锍六氟锑酸盐，或者是以上多种的混合物。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述的可发生光致自由基固化的光敏树脂包含：可发生自由基固化的单体、寡聚物或是高聚物，其具有至少一个可自由基聚合的官能团，其中寡聚物分子量为200-1000，高聚物分子量为1000-30000；以及自由基引发剂。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述自由基引发剂的添加量是基于光敏树脂总重量的0.1至20％(w/w)。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述可发生光致自由基固化的光敏树脂包含具有至少一个巯基的单体、寡聚物或是高聚物。
根据本发明的优选实施方式，所述的可光致固化的组合物中，具有至少一个巯基的单体、寡聚物或高聚物相对于光敏树脂总重量的含量是1至20wt％。
根据本发明的优选实施方式，所述的可光致固化的组合物中，具有至少一个巯基的寡聚物或高聚物的聚合度不大于40。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述自由基引发剂是一种可被紫外光、可见光或是红外光激发的光引发剂。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述自由基引发剂是安息香二乙醚、苯甲酰甲酸甲酯、羟基环乙烷苯酮、苯基双(2，4，6-三甲基苯甲酰基)氧化膦、巯苯噻唑、Irgacure651、Irgacure907、Darocur2959、樟脑醌、α-酮戊二酸，或者是以上多种的混合物。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述陶瓷颗粒选自氧化锆、氧化铝、氧化硅、羟基磷灰石、碳化硅、氮化硅、氮化铝、或包含上述陶瓷颗粒中的至少一种的组合。
根据本发明的优选实施方式，所述的可光致固化的组合物中，所述陶瓷颗粒的粒度为20nm-50μm。
根据本发明的优选实施方式，所述的可光致固化的组合物中，陶瓷颗粒表面可以包裹一层表面改性剂。其中所述的表面改性剂选自线状或支化的羧酸、磷酸、磷酸酯、硅烷，或者是以上多种的混合物。
根据本发明的优选实施方式，所述的可光致固化的组合物中，用于将陶瓷颗粒均匀分散到光敏树脂中的所述分散剂，选自丙烯酸类分散剂、聚乙烯吡咯烷酮类分散剂、壬基酚氧乙基化物分散剂、胺类分散剂、脂肪酸类分散剂、聚乙二醇类分散剂或聚醚类分散剂中的一种或多种。
根据本发明的另一方面，提供一种陶瓷制品，其由包含如下步骤的方法制备：将前述的可光致固化的组合物通过立体光固化成型法(Stereolithography，SLA)或数字光处理成型(digital light processing，DLP)进行3D打印；加热到1400摄氏度以上，完成脱脂烧结。
本发明通过提供适合3D打印和陶瓷脱脂烧结的光致固化组合物，将陶瓷材料与立体光固化成型(SLA)或数字光处理成型(DLP)技术相结合，从而达到了缩短陶瓷部件开发周期，降低设计成本，提高设计灵活性的目的。
附图说明
下面，将结合附图对本发明的优选实施方式进行进一步详细的说明，其中：
图1是SLA的工作原理示意图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在以下的详细描述中，可以参看作为本申请一部分用来说明本申请的特定实施例的各个说明书附图。在附图中，相似的附图标记在不同图式中描述大体上类似的组件。本申请的各个特定实施例在以下进行了足够详细的描述，使得具备本领域相关知识和技术的普通技术人员可实施本申请的技术方案。应当理解，还可以在本发明范围内，利用其它实施例或者对所列实施例进行改变或改进。
本发明提出了一种新的陶瓷部件制造方法，以3D打印的方式，即增材制造或快速成型方式，特别是利用立体光固化成型(SLA)或数字光处理成型(DLP)技术，打印陶瓷生胚，再利用脱脂工艺除去生胚中的光敏树脂，通过烧结形成致密的陶瓷件。相比于现有的陶瓷成型方式，本发明的方法能够极大缩短陶瓷部件开发周期，降低设计成本，提高设计灵活性。由于材料在打印过程中被层层堆积，3D打印没有传统工艺中的种种限制；同时，与传统生产工艺相比，使用3D打印小批量生产的成本要低得多。
3D打印过程都是从一个描述物体的计算机生成的数据源开始。这一计算机生成的数据源可以是基于真实的物体或者虚拟的物体。比如说，真实的物体可以被3D扫描仪扫描，所取得的数据可以用来产生数据源。或者该数据源可以是被设计生成的。这类数据源一般会被转化为标准曲面细分语言文件(STL)。3D打印软件将会读取该文件，并将其转化为成百上千，甚至上百万的切片。随后3D打印软件输出机器语言(如Gcode)给3D打印机。3D打印机按照指令，开始层层打印这些切片信息，最终生成这一物体。
立体光固化成型(SLA)，如US4,575,330A所述，其工作原理如图1所示：树脂槽21中装满光敏树脂液体。打印平台29浸没在树脂中，与树脂液面保持一段距离(该距离即下层需要打印的层高)。激光26(一般为紫外光)从树脂槽21上方照在光敏树脂的液面上。激光在振镜的反射下，按照程序画出每层图案。随着激光的照射，光敏树脂固化。打印平台29由软件控制向下移动一段距离(该距离即下层需要打印的层高)。光敏树脂流动直到覆盖已打印的这层(如果光敏树脂黏度较大，自流性较差，需要刮刀帮助涂覆这一层)。这个步骤不断重复，直到完成整个物品的打印。而后，打印平台向上移动出树脂槽，方便取下已打印好的物品。
数字光处理成型(digital light processing，DLP)，如US6,942,830B2所述，其原理和结构与SLA有类似之处：同样是使用紫外光(或可见光)将树脂槽中的光敏树脂液体层层固化。但是区别在于：SLA使用激光点扫描，在振镜的反射下，按照程序逐点画出每层图案；而DLP则是使用面光源，透过动态光掩膜版，将该层图案一次投影在光敏树脂液面，待该层固化后，再投影下一层图案。在DLP中，动态光掩膜版的产生可以利用LCD屏，光调制器(light  modulator)，或是数字微镜器件(DMD)比如德州仪器生产的DLP TM芯片。
根据本发明的一些实施方式，为了应用本发明的陶瓷制品制造方法，提出了一种能够光致固化的陶瓷组合物，其包含：(a)能够聚合或交联的光敏树脂；(b)陶瓷颗粒；(c)分散剂；(d)塑化剂和/或溶剂。
本发明所述的3D打印技术中，陶瓷光敏浆料的组分和性质起着决定性作用。陶瓷光敏浆料的黏度需要足够小，同时不能具有触变性，从而陶瓷光敏浆料具有良好的流动性，否则在打印中将难以完成加料和铺平步骤，也会对打印完成后的清理带来麻烦。较好的是，陶瓷光敏浆料的黏度需要在25℃下剪切速率为1-100s -1时小于10000mPa·s。陶瓷光敏浆料的流变性能取决于光敏树脂；陶瓷粉末的种类、颗粒度、球形度、固含量；以及所选用的分散剂、塑化剂等。
在选择光敏树脂的时候，也需要考虑到固化后的光敏树脂能够在脱脂步骤中分解成容易气化的小分子，进而从陶瓷生胚中脱离。碳残留过高的光敏树脂将阻碍陶瓷晶界间的烧结，从而导致烧结后的陶瓷强度下降。所以在选择光敏树脂时，需要避免选择带有芳环或者烷烃环的光敏树脂，比如乙氧化双酚A二甲基丙烯酸酯(Bisphenol A ethoxylate dimethacrylate)由于含有双酚A，脱脂时的碳残留将异常高。
光敏树脂的主要成分包括单体、寡聚物或高聚物、光引发剂、和可选的其他添加剂。当光引发剂吸收紫外或可见光，从而引发单体(或寡聚体或高聚物)聚合形成高分子长链。在宏观上的表现，就是液态的单体(或寡聚体或高聚物)在光照下逐渐固化。而添加剂的作用包括调色、抗氧化、改变光引发剂吸收波长、加快固化速率、增强固化后的强度等用途。
本发明所用的光敏树脂包括丙烯酸酯类和环氧树脂类。丙烯酸酯类的单体 与自由基光引发剂配合使用。在光照下，该类引发剂产生自由基，引发自由基聚合反应形成高分子长链。自由基聚合反应的优势在于其反应速度快，所需的固化时间较短。而环氧树脂类的单体与阳离子光引发剂配合使用。在光照下，该类引发剂产生阳离子，引发离子聚合反应形成高分子长链。与自由基聚合的丙烯酸酯类树脂相比，环氧树脂固化后有更好的机械性能、溶剂抗性和热稳定性。
本发明的可光致固化组合物不仅包含(a)可聚合或交联的光敏树脂，其包含带有可以发生聚合或交联的官能团的单体、寡聚物或高聚物，交联剂或引发剂，可聚合或交联的光敏树脂可以发生自由基聚合或环氧聚合；还包含(b)陶瓷颗粒；(c)分散剂；(d)塑化剂和/或溶剂。
通过调节的分子量，单体、寡聚物或是高聚物的种类或是官能团数目，分子结构(线性结构或多支化结构)，以及单体、寡聚物或是高聚物和交联剂的浓度，可以调节可光致固化组合物的流变性能和固化后的物理性能和脱脂效果。一般来说，分子量越低，官能团数越低，光敏树脂的黏度越低，则混合陶瓷粉末后得到的陶瓷光敏浆料黏度越低。为了使最终的陶瓷光敏浆料有良好的流动性，最好选用黏度低于100mPa·s(在25℃下剪切速率为1-100s -1时)的光敏树脂。但是如果分子量越低，得到的陶瓷光敏浆料在打印时固化收缩越严重，从而可能导致变形翘曲。同时，低官能团数的单体、寡聚物或是高分子长链含量高，则陶瓷光敏浆料固化后，在高温下脱脂更容易。但是固化后的生胚件强度更低，容易断裂。而高官能团数的单体、寡聚物或是高分子长链含量高，则正好相反，固化后的生胚件强度高，但是在高温下脱脂更难。
根据本发明的一种实施方式，(i)可发生自由基固化的单体、寡聚物或是 高聚物包含至少一个可自由基聚合的官能团。在这种情况中，(ii)引发剂是自由基引发剂。该种光敏树脂在光照的条件下发生自由基聚合反应。在另一种情况中，除了(i)可发生自由基固化的单体、寡聚物或是高聚物和(ii)自由基引发剂外，光敏树脂还可以包含(iii)具有至少一个巯基的单体、寡聚物或是高聚物。该种光敏树脂在光照的条件下发生自由基巯基烯聚合反应。
自由基聚合的氧阻聚效应是SLA/DLP 3D打印的最大阻碍。氧气会淬熄光引发剂产生的增加，从而阻碍自由基聚合。而在SLA/DLP 3D打印中，每层固化深度只有25-100um，这时的氧阻聚效应就更加明显。氧阻聚效应会导致光敏树脂表面没有完全固化，甚至于无法固化。所以，对于SLA/DLP 3D打印，氧阻聚效应是一种主要阻碍。可能避免氧阻聚效应影响材料固化的途径有：在氮气保护下打印；使用极高强度的UV光照射；或是提高光引发剂的浓度。但是，这三种途径都使3D打印过程复杂化，限制了这种技术的应用，并增加了使用成本。
本发明利用硫醇-烯反应来避免氧阻聚效应对SLA/DLP 3D打印的阻碍。氧气分子会和碳自由基或是硫醇自由基反应生成过氧自由基。过氧自由基并不会淬熄高分子链增长反应，而会夺去硫醇上的氢原子，从而形成另一个硫醇自由基，从而继续高分子链增长反应。以这种方式，氧阻聚效应将会被避免。
同时，巯基与陶瓷颗粒表面的相互作用可以帮助陶瓷颗粒分散，从而降低陶瓷光敏浆料黏度，避免陶瓷粉末沉降。更进一步地，自由基巯基烯聚合反应所得到的高分子网络的交联密度低于一般的自由基聚合反应，这将给脱脂带来便利。
根据本发明的优选实施方式，所述的可光致固化的组合物中，具有至少一 个巯基的单体、寡聚物或高聚物相对于光敏树脂总重量的含量为1至20wt％，优选的是1至10wt％，更优选是5-10wt％，这对于改善陶瓷的分散、组合物的黏度和固化效率比较有利。
具有至少一个巯基的单体、寡聚物或高聚物的具体例子包括但不限于：四(3-巯基丙酸)季戊四醇酯，季戊四醇四巯基乙酸酯，三羟甲基丙烷三(3-巯基丙酸酯)，1，2-乙二硫醇，1，8-辛二硫醇，1，6-己二硫醇，双(2-巯基乙基)醚，2，3-二巯基丁二酸。
根据本发明的优选实施方式，所述的可光致固化的组合物中，具有至少一个巯基的寡聚物或高聚物的聚合度不大于40，更优选地，聚合度不大于20。
根据本发明的优选实施方式，能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000001
其中，X是C或Si；R 1、R 2、R 3相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的优选实施方式，所述能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000002
其中，R 1、R 2相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的优选实施方式，所述能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000003
其中，X是O、S、SO 2；R 1是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的优选实施方式，所述能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000004
其中，X是C或Si；R 1、R 2、R 3相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的优选实施方式，所述能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000005
其中，X是C或Si；R 1、R 2、R 3、R 4相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的优选实施方式，所述能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000006
其中，R 1、R 2相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的优选实施方式，所述能够自由基聚合的官能团具有以下结构：
Figure PCTCN2018093755-appb-000007
其中，R 1是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
根据本发明的更优选的实施方式，可自由基聚合的官能团可以是丙烯酰氧基烷基、丙烯酸酯官能团、烯氧基、烯烃基、炔烃基等。丙烯酰氧基烷基的例子包括但不限于丙烯酰氧甲基、甲基丙烯酰氧甲基、2-丙烯酰氧乙基、2-甲基丙烯酰氧乙基、3-丙烯酰氧丙基、3-甲基丙烯酰氧丙基或者4-丙烯酰氧丁基。烯烃基的例子包括但不限于乙烯基、烯丙基、丁烯基、戊烯基、己烯基等。
所使用的自由基引发剂可以被光激发。可选用的自由基引发剂包括但不限于安息香二乙醚，苯甲酰甲酸甲酯，羟基环乙烷苯酮(Irgacure184，来自巴斯夫公司)，苯基双(2，4，6-三甲基苯甲酰基)氧化膦(XBPO)，巯苯噻唑，Irgacure651(来自巴斯夫公司)，Irgacure907(来自巴斯夫公司)，Darocur2959(来自巴斯夫公司)，樟脑醌(CQ)，α-酮戊二酸(KGA)，或者是以上多种的混合物。
所使用的自由基引发剂可以是单种自由基引发剂，也可以是多种自由基引发剂的混合物。自由基引发剂的浓度基于组分中光敏树脂的总质量，一般是0.1至20％(w/w)，优选是1至10％(w/w)，更优选是1至5％(w/w)，最优选是1至3％(w/w)。
根据本发明的另一种实施方式，(i)可以发生环氧聚合的光敏树脂包含具有至少一个可环氧聚合的官能团的单体、寡聚物或高聚物。在这种情况中，(ii)引发剂是阳离子引发剂。该种光敏树脂在光照的条件下发生环氧聚合反应。
“可环氧聚合的官能团”是指单价的含氧三元环或四元环的醚类基团。可环氧聚合的官能团包括但不限于2，3-环氧丙烷基、3，4-环氧环丁烷基、4，5- 环氧环戊烷基、2-环氧丙氧基乙基、3-环氧丙氧基丙基、4-环氧丙氧基丁基、2-(3，4-环氧环己烷)乙基、3-(3，4-环氧环己烷)丙基、或其衍生物。
所使用的阳离子引发剂可以被光激发。可选用的阳离子引发剂包括但不限于碘鎓盐、二芳基碘磺酸盐、三芳基锍磺酸盐、二芳基碘硼酸盐、三芳基锍硼酸盐。
可选用的碘鎓盐引发剂包括但不限于二芳基碘盐，比如双(烷基苯)碘六氟锑酸盐或双(烷基苯)碘六氟砷酸盐，进一步地，例如双(十二烷苯)碘六氟锑酸盐或双(十二烷苯)碘六氟砷酸盐。
可选用的二芳基碘磺酸盐引发剂包括但不限于二芳基碘全氟烷基磺酸盐，比如二芳基碘全氟乙基磺酸盐、二芳基碘全氟辛基磺酸盐、二芳基碘全氟丁基磺酸盐、二芳基碘全氟甲基磺酸盐；二芳基碘芳基磺酸盐，比如二芳基碘对甲苯磺酸盐、二芳基碘十二烷苯磺酸盐、二芳基碘苯磺酸盐、二芳基碘3-硝基苯磺酸盐。
可选用的三芳基锍磺酸盐引发剂包括但不限于三芳基锍全氟烷基磺酸盐，比如三芳基锍全氟乙基磺酸盐、三芳基锍全氟辛基磺酸盐、三芳基锍全氟丁基磺酸盐、三芳基锍全氟甲基磺酸盐；三芳基锍芳基磺酸盐，比如三芳基锍对甲苯磺酸盐、三芳基锍十二烷苯磺酸盐、三芳基锍苯磺酸盐、三芳基锍3-硝基苯磺酸盐。
可选用的二芳基碘硼酸盐引发剂包括但不限于二芳基碘全卤芳基硼酸盐。可选用的三芳基锍硼酸盐引发剂包括但不限于三芳基锍全卤芳基硼酸盐。
所使用的阳离子引发剂可以是单种阳离子引发剂，也可以是多种阳离子引发剂的混合物。阳离子引发剂的浓度基于组分中光敏树脂的质量，一般是0.1 至20％(w/w)，优选是1至10％(w/w)，更优选是1至5％(w/w)，最优选是1至3％(w/w)。
在一种情况中，所使用的光敏树脂既可以发生自由基聚合，也可以发生环氧聚合。在另一种情况中，所使用的光敏树脂既可以发生自由基聚合，也可以发生自由基巯基烯聚合，还可以发生环氧聚合。
陶瓷是指一系列有着晶体结构的无机非金属固体材料。陶瓷的传统制备主要通过烧结完成，如在1500℃以上的高温下将氧化锆陶瓷粉末烧结成致密整体。可选用的陶瓷粉末包括但不限于氧化锆、氧化铝、氧化硅、羟基磷灰石、碳化硅、氮化硅、氮化铝。在陶瓷粉末中还可以添加稳定剂以保持陶瓷的晶型稳定。稳定剂包括但不限于氧化铪、氧化钇、氧化钙、氧化镁、氧化铈，或者是以上多种的混合物。稳定剂的含量基于待稳定陶瓷的质量，一般在3-5wt％。比如高强度氧化锆一般含有3-5wt％的氧化钇以保持四方晶系晶型，这种氧化锆陶瓷一般被称为Y-TZP(yttrium-stabilized tetragonal zirconium dioxide polycrystals)。
本发明的陶瓷光敏浆料中陶瓷粉末的固含量(陶瓷粉末的体积占总体积的比例，以vol％表示)需要尽可能高，从而可以保证烧结后的陶瓷件致密、高强度且收缩小。同时，固含量越高，陶瓷光敏浆料越不容易发生沉降，这保证了陶瓷光敏浆料的储存稳定性。为此，陶瓷颗粒的体积占浆料总体积的10体积％至80体积％，优选30体积％至70体积％，更优选40体积％至60体积％，最优选45体积％至50体积％。
陶瓷粉末颗粒直径极大影响着陶瓷光敏浆料的流变性和烧结特性。如果陶瓷粉末颗粒直径过小，则得到的陶瓷光敏浆料静置后不容易沉降，生胚件烧结 温度低，但是浆料黏度过大，无法得到高固含量的陶瓷光敏浆料；另一方面，如果陶瓷粉末颗粒直径过大，则得到的陶瓷光敏浆料黏度小，更容易得到高固含量的陶瓷光敏浆料，但是静置后不容易沉降，同时生胚件烧结温度高。具体直径范围取决于具体的陶瓷材料选择，比如氧化铝的合适颗粒直径是在20nm-50μm之间，最好是在75nm-10μm之间；Y-TZP氧化锆的合适颗粒直径是在20nm-50μm之间，最好是在50nm-35μum之间。因此，本发明中优选陶瓷颗粒的粒度范围为20nm-50μm之间，更优选为50nm-35μm之间，最优选为75nm-10μm之间。
球形度，是指与物体相同体积的球体的表面积和物体的表面积的比。球的球形度等于1，其它物体球形度小于1。在选择陶瓷颗粒配置陶瓷浆料时，颗粒球形度越接近1越好，即颗粒越接近球形，陶瓷浆料的黏度越低。本发明中球形度高于0.5比较有利，优选高于0.6，更优选高于0.7，进一步优选高于0.8，更进一步优选高于0.9。
在一种情况中，陶瓷粉末颗粒的表面可以包裹一层表面改性剂。表面改性剂可以通过化学键(比如离子键或共价键)与陶瓷颗粒表面结合，从而改善光敏树脂对陶瓷粉末的浸润作用。可选用的表面改性剂包括但不限于线状或支化的羧酸，比如甲酸、乙酸、丙酸、辛酸、异丁酸、新戊酸等；磷酸，比如甲基磷酸、乙基磷酸、丙基磷酸、丁基磷酸、戊基磷酸、己基磷酸、庚基磷酸等；磷酸酯，比如二甲基磷酸酯、二乙基磷酸酯、二丙基磷酸酯、二丁基磷酸酯、二戊基磷酸酯、二己基磷酸酯、二庚基磷酸酯等；硅烷，比如丙基三甲氧基硅烷、苯基三甲氧基硅烷、己基三甲氧基硅烷、辛基三甲氧基硅烷、三甲基氯硅烷、三甲基甲氧基硅烷、六甲基二硅氮烷等，或者是以上多种的混合物。表面 改性剂的含量基于组分中陶瓷颗粒的质量，一般是0.1至20％(w/w)，优选是1至10％(w/w)，更优选是1至5％(w/w)。
分散剂是本发明所述的陶瓷光敏浆料中不可或缺的一种组分。分散剂分子链会包裹在陶瓷颗粒的表面，使陶瓷颗粒无法相互团聚，从而更好地悬浮在光敏树脂中。这样，分散剂可以帮助陶瓷颗粒更均匀地分散在光敏树脂中，从而达到低黏度高固含量的目的。可选用的分散剂包括但不限于聚丙烯酸类分散剂(比如R.T.Vanderbilt公司的
Figure PCTCN2018093755-appb-000008
)、聚乙烯吡咯烷酮类分散剂(比如R.T.Vanderbilt公司的
Figure PCTCN2018093755-appb-000009
821A和I.S.P.Technologies的PVP K-15)、壬基酚氧乙基化物分散剂(比如Union Carbide Corporation公司的
Figure PCTCN2018093755-appb-000010
X-100)、胺类分散剂(比如ICI Americas公司的HYPERMER KD-2)、脂肪酸类分散剂(比如Henkel公司的TEXAPHOR 963)，或者是以上多种的混合物。分散剂的含量基于组分中陶瓷颗粒的质量，一般是0.1至20％(w/w)，优选是1至10％(w/w)，更优选是1至5％(w/w)。
在制备陶瓷光敏树脂的过程中，分散剂、塑化剂、表面改性剂、溶剂等可以直接加入光敏树脂和陶瓷粉末的混合物中，通过球磨数小时达到均匀分散的效果。在另一种情况下，分散剂、塑化剂、表面改性剂、溶剂等可以先与光敏树脂混合，通过搅拌的方式达到分散效果，随后再将陶瓷粉末加入分散剂、塑化剂、表面改性剂、溶剂等与光敏树脂的混合物中，通过球磨数小时达到均匀分散的效果。在另一种情况下，分散剂和/或表面改性剂先溶于有机溶剂，再将陶瓷粉末加入该溶液中，通过球磨数小时达到均匀分散的效果；随后将溶剂蒸干，粉碎干燥得到干燥的陶瓷粉末，再与光敏树脂混合，通过球磨数小时达到均匀分散的效果。
在一种情况中，陶瓷光敏浆料中可添加溶剂，从而进一步降低黏度。在脱脂过程中，溶剂的气化温度低于固化后的光敏树脂的分解温度。所以溶剂会先从生胚中脱离，留下孔洞，方便余下的有机质气化脱离，从而提高脱脂效率，避免开裂变形。溶剂的选择取决于光敏树脂的选择。如果光敏树脂是水溶性的，水可以作为溶剂。如果光敏树脂是油溶性的，则选用有机溶剂。需要选择沸点较高的有机溶剂，避免溶剂挥发，导致陶瓷光敏浆料在储存或打印时黏度变化。在另一种情况中，陶瓷光敏浆料中可添加多种具有不同沸点的溶剂，从而在脱脂过程中，溶剂将会分段气化脱离，从而避免在某一时间段溶剂大量气化导致开裂变形。
可选用的溶剂包括但不限于水，邻苯二甲酸酯衍生物(比如邻苯二甲酸二丁酯、邻苯二甲酸二己酯、邻苯二甲酸二正辛酯)、磷酸酯衍生物(比如磷酸三甲苯酯、磷酸三丁酯)、正辛醇、甘油、聚乙二醇、2-氨基-2-甲基-1-丙醇、2-甲基-2，4-戊二醇、三丙二醇、四缩乙二醇、乙酰乙酸乙酯、柠檬酸三乙酯、环己醇、环己酮、二乙二醇甲醚、二乙二醇二乙醚、草酸二丁酯、2，5-二甲氧基四氢呋喃、2，5-二乙氧基四氢呋喃、正壬醇、异壬醇，或者是以上多种的混合物。溶剂的含量基于组分中光敏树脂的质量，一般是0至50wt％，较好是5至20wt％。
在一种情况中，生胚中的溶剂不是在脱脂过程中加热气化除去的，而是通过溶剂萃取除去的。比如在陶瓷光敏树脂中加入可溶于水的聚乙二醇。打印完成后，将生胚浸入水中一段时间(如约12小时)，生胚中的聚乙二醇将溶于水，同时留下孔洞，方便余下的有机质在脱脂过程中气化脱离。同样的，如果在陶瓷光敏树脂中加入可溶于有机溶剂的乙酰乙酸乙酯。打印完成后，将生胚浸入 二氯甲烷中一段时间(如约12小时)，生胚中的乙酰乙酸乙酯将溶于二氯甲烷，同时留下孔洞，方便余下的有机质在脱脂过程中气化脱离。
在一种情况中，陶瓷光敏浆料中可添加塑化剂。加入塑化剂的优点有：1、塑化剂增加生胚的韧性，避免由于光敏树脂固化收缩带来的内应力导致产生微裂纹(微裂纹可能在脱脂烧结时扩展，从而极大地降低烧结后的陶瓷强度)；2、塑化剂会先从生胚中脱离，留下孔洞，方便余下的有机质气化脱离，从而提高脱脂效率，避免开裂变形从而避免生胚在脱脂时开裂变形；3、液体塑化剂也起到溶剂的作用，可以降低陶瓷光敏浆料的黏度。可选用的塑化剂包括但不限于甘油三油酸酯、聚乙二醇、邻苯二甲酸酯衍生物(比如邻苯二甲酸二丁酯、邻苯二甲酸二己酯、邻苯二甲酸二正辛酯)、磷酸酯衍生物(比如磷酸三甲苯酯、磷酸三丁酯)，或者是以上多种的混合物。塑化剂的含量基于组分中光敏树脂的质量，一般是0.1wt％至50wt％，优选1wt％至40wt％，更优选1wt％至30wt％。
在一种情况中，陶瓷光敏浆料中可添加着色剂。此处的着色剂主要是过渡金属化合物，而不是常见的有机染料或颜料，因为只有过渡金属化合物在脱脂烧结的高温下稳定存在，从而使烧结后的陶瓷带有不同的颜色。可选用的过渡金属元素包括但不限于铁、铈、镨、铽、镧、钨、锇、锰，或者是以上多种的混合物。可选用的这些过渡金属元素主要以盐的形式存在，包括但不限于甲酸盐、醋酸盐、丙酸盐、丁酸盐、硬脂酸盐、棕榈酸盐等。着色剂的含量基于组分中陶瓷颗粒的质量，一般是0.01至1wt％，也可以是0.05至0.5wt％。
在一种情况中，陶瓷光敏浆料中可添加阻聚剂，避免陶瓷光敏浆料在存储中发生自发的聚合反应，从而延长陶瓷光敏浆料的储存时间。可选用的阻聚剂 包括但不限于对苯二酚单甲基醚(MEHQ)、2，6-二叔丁基對甲酚(BHT)、吩噻嗪、四甲基哌啶氧化物(TEMPO)，或者是以上多种的混合物。阻聚剂的含量基于组分中光敏树脂的质量，一般是0.001至0.5wt％，也可以是0.01至0.05wt％。
除了所述光敏树脂、陶瓷颗粒、分散剂、塑化剂和溶剂，本发明的可光致固化组合物还可包含通常添加到这种类型的树脂组合物中的各种添加剂。在一种情况中，可同时使用多种添加剂。在另一种情况中，可将这些添加剂与陶瓷颗粒塑化剂、分散剂和溶剂一同混合入光敏树脂中。可以选择的添加剂包括但不限于热稳定剂，抗氧化剂，光稳定剂，防静电剂，颜料，染料，或者一种或者多种前述添加剂的组合。
合适的热稳定剂包括，例如，有机亚磷酸酯例如亚磷酸三苯酯，三-(2，6-二甲基苯基)亚磷酸酯等；膦酸酯例如膦酸二甲基苯酯等，磷酸酯例如磷酸三甲酯等，或者包括至少一种前述热稳定剂的组合。热稳定剂通常的用量为0.001至0.5重量份，基于100重量份的光敏树脂。
合适的抗氧化剂包括，例如，有机亚磷酸酯例如三-(壬基苯基)亚磷酸酯，三(2，4-二-叔丁基苯基)亚磷酸酯，二(2，4-二-叔丁基苯基)季戊四醇二亚磷酸酯，二硬脂基季戊四醇二亚磷酸酯等；烷基化的一元酚或者多元酚；多元酚与二烯的烷基化的反应产物，例如四[亚甲基(3，5-二叔丁基-4-羟基氢化肉桂酸酯)]甲烷等；对-甲酚或者二环戊二烯的丁基化的反应产物；烷基化的氢醌；羟基化的硫基二苯基醚；苄基化合物；β-(3，5-二叔丁基-4-羟基苯基-丙酸与一元醇或者多元醇的酯；β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或者多元醇的酯；硫基烷基或者硫基芳基化合物的酯例如二硬脂基硫基丙酸 酯，二月桂基硫基丙酸酯，二-十三烷基硫基二丙酸酯，十八烷基-3-(3，5-二叔丁基-4-羟基苯基)丙酸酯，季戊四基-四[3-(3，5-二叔丁基-4-羟基苯基)丙酸酯等；β-(3，5-二叔丁基-4-羟基苯基)-丙酸的酰胺等，或者包括至少一种前述抗氧化剂的组合。抗氧化剂通常的用量为0.001至0.5重量份，基于100重量份的光敏树脂。
合适的光稳定剂包括，例如，苯并三唑例如2-(2-羟基-5-甲基苯基)苯并三唑，2-(2-羟基-5-叔辛基苯基)-苯并三唑和2-羟基-4-正辛氧基二苯甲酮等，或者包括至少一种前述光稳定剂的组合。光稳定剂通常的用量为0.1至1.0重量份，基于100重量份的光敏树脂。
合适的防静电剂包括，甘油单硬脂酸酯，硬脂基磺酸钠，十二烷基苯磺酸钠等，或者前述防静电剂的组合。防静电剂通常的用量为0.5至3.0重量份，基于100重量份的光敏树脂。
合适的颜料包括例如无机颜料例如金属氧化物和混合的金属氧化物如氧化锌、二氧化钛、氧化铁等；硫化物，如硫化锌等；铝酸盐；钠硫代硅酸盐；硫酸盐、铬酸盐等；炭黑；铁酸锌；群青蓝；颜料棕M；颜料红101；颜料黄119；有机颜料，如偶氮、重氮、喹吖啶酮、茈、萘四羧酸、黄烷士酮、异吲哚啉酮、四氯异吲哚啉酮、蒽醌、蒽嵌蒽二醌、二噁嗪、酞菁、和偶氮色淀；颜料蓝60、颜料红122、颜料红149、颜料红177、颜料红179、颜料红202、颜料紫四、颜料蓝15、颜料绿7、颜料黄147和颜料黄150，或包含至少一种前述颜料的组合。必要时通过添加颜料，可调节光敏浆料在3D打印中对紫外光的吸收。颜料通常的用量为0.01至10重量份，基于100重量份的光敏树脂。
合适的染料包括例如有机材料，例如香豆素460(蓝)、香豆素6(绿)，尼罗 红等；镧系络合物；烃和取代的烃染料；多环芳烃染料；闪烁染料(优选噁唑和噁二唑染料)；芳基或杂芳基取代的聚(C2-8)烯烃染料；羰花青染料；阴丹酮染料；酞菁染料和颜料；噁嗪染料；喹诺酮(carbostyryl)染料；卟啉染料；吖啶染料；蒽醌染料；芳基甲烷染料；偶氮染料；重氮染料；硝基染料；醌亚胺染料；四唑染料；噻唑染料；茈染料；茈酮染料；二-苯并噁唑基噻吩(BBOT)；和咕吨染料；噻吨染料；荧光团，如抗斯托克司频移染料，其吸收近红外波长并发射可见波长等；发光染料，如5-氨基-9-二乙基亚氨基苯并(a)吩嗪阳离子过氣酸盐(5-amino-9-diethyliminobenzo(a)phenoxazoniumperchlorate)；尼罗红；罗丹明700；噁嗪750；罗丹明800；IR125；IR144；IR140；IR132；IR26；IR5；二苯基己三烯；二苯基丁二烯；四苯基丁二烯；萘；蒽；9，10-二苯基蒽；芘；屈(chrysene)；红荧烯(Rubrene)；晕苯(coronene)；菲等，或者包括至少一种前述染料的组合。必要时通过添加染料，可调节光敏浆料在3D打印中对紫外光的吸收。染料通常的用量为0.1至5重量份，基于100重量份的光敏树脂。
本发明的光致固化组合物可以在室温下通过研磨来混合，从而使陶瓷颗粒及其他添加剂均匀分散到光敏树脂中来制备组合物的混合液。根据优选的实施方式，可以在室温下，以200-1000r/min的转速搅拌5到50小时。制备的组合物还可以以真空除去组合物中的微小气泡，更为有利。
根据本发明的一些优选实施方式，可光致固化的组合物的制备方法，包括：室温下将各个组分混合均匀，以400r/min以上的转速研磨5、10、或20小时以上；将所得混合液在真空下静置或搅拌5、8、或10小时以上；根据更优选的实施方式，其中各个组分混合后以400-1000r/min的转速研磨20-50小时。根据进一步优选的实施方式所述研磨为球磨。
根据进一步优选的实施方式中，将所得混合液在大于0.02MPa的真空度下静置10-15小时。
根据本发明的一些优选实施方式，可光致固化组合物的制备方法，包括：室温下将分散剂和/或表面改性剂溶解于溶剂，并与陶瓷颗粒混合均匀，以400r/min以上的转速研磨1、3、或5小时以上；蒸发干燥，进行破碎得到表面包裹了表面改性剂的陶瓷颗粒；将所得陶瓷颗粒与光敏树脂等其他组分混合均匀，以800r/min以上的转速研磨5、10、或20小时以上；以及真空下静置或搅拌5、8、或10小时以上。
根据一些优选的实施方式，在室温下将分散剂和/或表面改性剂溶解于有机溶剂，包括但不限于乙醇、甲醇、异丙醇、丙酮、乙酸乙酯、和四氢呋喃，并与陶瓷颗粒混合均匀，以400-800r/min的转速研磨5-10小时；蒸发干燥，进行破碎得到表面包裹了表面改性剂的陶瓷颗粒。
根据更优选的实施方式，所得陶瓷颗粒与光敏树脂等其他组分混合后，再以800-1200r/min的转速研磨20-50小时。在进一步优选的实施方式中所述研磨石球磨。
根据进一步优选的实施方式中，所得到的混合液在真空大于0.02MPa的真空度下静置10-20小时。
对于所制备的组合物混合液，其黏度需要在剪切速率1-100s -1时小于10000mPa·s，同时不能具有触变性，以保证其具有良好的流动性。在本发明的范围内通过调节单体、寡聚物或是高聚物的种类或是官能团数目，分子结构(线性结构或多支化结构)和分子量，以及单体、寡聚物或是高聚物和交联剂的浓度，陶瓷颗粒的粒度及固含量以及制备过程等，可以调节可光致固化组合物的流变 性能和固化后的物理性能和脱脂效果。
根据本发明的实施方式，制备的组合物混合液通过立体光固化成型(SLA)或数字光处理成型(DLP)技术进行3D打印，得到陶瓷生胚部件。
根据本发明的一些优选实施方式，立体光固化成型法(Stereolithography，SLA)和数字光处理成型(digital light processing，DLP)中，光固化成型的激光强度为0.3-5.0W，激光扫描速率为200-4000mm/s，打印层厚为5-200μm。
根据本发明的一些优选实施方式，数字光处理成型(digital light processing，DLP)中，光固化成型的曝光强度为0.3-5.0W，曝光时间为5-60秒，打印层厚为5-200μm。
根据本发明的实施方式，陶瓷生胚部件通过脱脂除去所含的光敏树脂等、通过烧结得到所需形状的致密陶瓷件。
根据本发明的一些优选实施方式，脱脂烧结包括：由室温升温至400-600℃，升温速率为0.1-1.5℃/min；由400-600℃升温至1400-1600℃，升温速率为0.1-1℃/min；其中在300-400℃时保温0.5-2小时；500-600℃时保温2-5小时；850-950℃时保温0.5-2小时；最后自然冷却。
根据本发明的优选实施方式，脱脂烧结包括：由室温升温至450-550℃，升温速率为0.1-0.5℃/min；由450-550℃升温至1450-1550℃，升温速率为0.1-0.5℃/min；其中在300-400℃时保温0.5-2小时；500-600℃时保温2-5小时；850-950℃时保温0.5-2小时；最后自然冷却。
根据本发明的优选实施方式，陶瓷生胚部件的脱脂工艺为由室温升温至400-600℃，升温速率约为1℃/min；烧结工艺为由400-600℃升温至1400-1600℃，升温速率约为1℃/min。在更优选的实施方式中，脱脂工艺为由 室温升温至450-550℃，升温速率约为0.5℃/min；烧结工艺为由450-550℃升温至1450-1550℃，升温速率约为0.5℃/min。在进一步优选的实施方式中，脱脂工艺为由室温升温至500-520℃，升温速率约为0.1℃/min；烧结工艺为由500-520℃升温至1500-1520℃，升温速率约为0.1℃/min。在一些优选的实施方式中，陶瓷生胚以1℃/min从室温升温至150℃；以0.5℃/min从150℃升温至350℃；在350℃保温1小时；以0.1℃/min从350℃升温至550℃；在550℃保温3小时；以0.5℃/min从550℃升温至900℃；在900℃保温1小时；以1℃/min从900℃升温至1450℃。
实施例
1.不同的可自由基聚合单体对固化速度的影响参见表1中实施例
表1
Figure PCTCN2018093755-appb-000011
注：BYK111是来自毕克化学公司的分散剂；表中“份”指“重量份”，下同。
组合物的制备：室温下将各个组分混合均匀，球磨的转速为500r/min，球磨时间为30小时。将所得混合液在真空下静置10小时除去气泡，得到所需的 可光致固化组合物。取一滴所得的可光致固化组合物滴于载玻片上，使用功率为1W，波长为355nm的激光器在其上方3cm处照射，肉眼观察，以液滴丧失流动性为判断其是否固化的指标，记录固化时间。在上述实施例1、2、3和4中，实施例1、3和4组合物的固化时间较短，有利于打印效率的提高，而使用了N，N′-亚甲基双丙烯酰胺的实施例3组合物的固化时间最短，最有利。
2.自由基巯基烯聚合反应对氧阻聚效应及黏度的影响参见表2中实施例
表2
Figure PCTCN2018093755-appb-000012
注：BYK111是来自毕克化学公司的分散剂(脂肪酸类分散剂)。
组合物的制备：室温下将各个组分混合均匀，室温下将各个组分混合均匀，球磨的转速为500r/min，球磨时间为42小时。将所得混合液在真空下静置10小时除去气泡，得到所需的可光致固化组合物。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。实施例6的黏度低于实施例5，说明在光致固化组合物中包含适量的具有巯基官能团的单体或寡聚物可以更为有效帮助陶瓷颗粒分散在光敏树脂中，从而降低组合物的黏度。
3D打印实验：使用所配置的可光致固化组合物在SprintRay公司的MoonRay机型(DLP技术)上打印尺寸为50mm*50mm*10mm的测试模型(室温下，曝光强度50％，每层曝光时间30秒)。在上述实施例5中，打印件表面依然有未能完全固化的光敏树脂，触感粘手。而实施例6中，打印件表面完全固化，触感光滑。在光致固化组合物中包含适量的具有巯基官能团的单体或寡聚物可以更为有效地改善组合物的固化性质。
3.硫醇单体、寡聚物和高聚物对组合物黏度的影响参见表3中实施例
表3
Figure PCTCN2018093755-appb-000013
注1：其中4arm-PEGn-SH的化学结构式如下图。当n＝10-20时，为寡聚物；当n＞20时，为高聚物。
Figure PCTCN2018093755-appb-000014
注2：BYK9076是来自毕克化学公司的分散剂(聚乙烯吡咯烷酮类分散 剂)。
组合物的制备：室温下将BYK9076以质量比2∶100溶解于酒精中，再加入氧化硅混合均匀，球磨的转速为500r/min，球磨时间为5小时。将所得混合液蒸干，并粉碎干燥得到干燥的氧化硅粉末。将所得的氧化硅与光敏树脂混合均匀，球磨的转速为800r/min，球磨时间为35小时。将所得混合液在真空下静置10小时除去气泡，得到所需的可光致固化组合物。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。可以看出，硫醇的分子量越大，得到的组合物的黏度越大。在上述实施例7、8和9中，使用四(3-巯基丙酸)季戊四醇酯和4arm-PEGn-SH(n＝10)的实施例7和8的黏度适合用于SLA或DLP 3D打印，而四(3-巯基丙酸)季戊四醇酯所带来的黏度更低，更为合适。实施例10，通过降低了高聚物4arm-PEGn-SH(n＝40)的含量，从而把组合物的黏度降低至10000mPa·s以下，也可达到满足要求的黏度。
4.基于环氧树脂的组合物中分散剂含量对分散效果和黏度的影响参见表4
表4
Figure PCTCN2018093755-appb-000015
Figure PCTCN2018093755-appb-000016
注：
Figure PCTCN2018093755-appb-000017
是来自R.T.Vanderbilt公司的分散剂(胺类分散剂)。
组合物的制备：室温下将各个组分混合均匀，球磨的转速为800r/min，球磨时间为24小时。将所得混合液在真空下静止12小时除去气泡，得到所需的可光致固化组合物。
羟基磷灰石在光敏树脂中的分散效果及稳定性的测试方法为：将混合好的组合物至于透明量筒中，记录液面高度；静止1个月，看上层清液的高度是否超过总液面高度的5％；上层清液的高度越小，说明分散效果越好，稳定性越高。在上述实施例中，使用基于组分中羟基磷灰石质量为约1-5％(w/w)的分散剂，分散效果和稳定性较好；而使用基于组分中羟基磷灰石质量为3％(w/w)左右的分散剂
Figure PCTCN2018093755-appb-000018
所得到的组合物的分散效果最好，稳定性最高。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。可以看出，在上述实施例中，使用基于组分中羟基磷灰石质量为约1-5％(w/w)的分散剂，黏度较低；而使用基于组分中羟基磷灰石质量为3％(w/w)左右的分散剂
Figure PCTCN2018093755-appb-000019
所得到的组合物的黏度最低。
5.加入不同表面改性剂对黏度的影响参见表5中实施例
表5
Figure PCTCN2018093755-appb-000020
注：
Figure PCTCN2018093755-appb-000021
是来自R.T.Vanderbilt公司的分散剂。
组合物的制备：室温下将表面改性剂以质量比2∶100溶解于酒精中，再加入羟基磷灰石混合均匀，球磨的转速为500r/min，球磨时间为5小时。将所得混合液蒸干，并粉碎干燥得到干燥的羟基磷灰石粉末。将所得的羟基磷灰石与光敏树脂混合均匀，球磨的转速为800r/min，球磨时间为35小时。将所得混合液在真空下静置10小时除去气泡，得到所需的可光致固化组合物。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。可以看出，上述实施例中，使用表面改性剂的实施例17-20所得到组合物的黏度比使用表面改性剂的实施例13所得到组合物的黏度更低。同时使用己基三甲氧基硅烷的实施例20所得到组合物 的黏度最低。
6.加入不同表面改性剂量对黏度的影响参见表6中实施例
表6
Figure PCTCN2018093755-appb-000022
注：
Figure PCTCN2018093755-appb-000023
是来自R.T.Vanderbilt公司的分散剂。
组合物的制备：室温下将表面改性剂以质量比2∶100溶解于酒精中，再加入羟基磷灰石混合均匀，球磨的转速为500r/min，球磨时间为5小时。将所得混合液蒸干，并粉碎干燥得到干燥的羟基磷灰石粉末。将所得的羟基磷灰石与光敏树脂混合均匀，球磨的转速为800r/min，球磨时间为35小时。将所得混合液在真空下静置10小时除去气泡，得到所需的可光致固化组合物。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。可以看出，上述实施例中，使用表面改性剂的实施例17-20所得到组合物的黏度比使用表面改性剂的实施例13所得 到组合物的黏度更低。同时使用己基三甲氧基硅烷的实施例20所得到组合物的黏度最低。在上述实施例中，使用基于组分中羟基磷灰石质量为约1-5％(w/w)的己基三甲氧基硅烷，黏度较低；而使用基于组分中羟基磷灰石质量为3％(w/w)左右的己基三甲氧基硅烷，所得到的组合物的黏度最低。
7.不同固含量对黏度以及烧结后三点弯曲强度的影响参见表7中实施例
表7
Figure PCTCN2018093755-appb-000024
组合物的制备：室温下将表面改性剂以质量比2∶100溶解于酒精中，再加入氧化锆混合均匀，球磨的转速为400r/min，球磨时间为8小时。将所得混合液蒸干，并粉碎干燥得到干燥的氧化锆粉末。将所得的氧化锆与光敏树脂混合均匀，球磨的转速为1000r/min，球磨时间为50小时。将所得混合液在真空下静止10小时除去气泡，得到所需的可光致固化组合物。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。可以看出，上述实施例中，随着氧化锆 固含量的提高，所得到的组合物的黏度增加(如实施例27)。
3D打印实验：使用所配置的可光致固化组合物在昆山博力迈三维打印科技有限公司的CSL机型(SLA技术)上打印尺寸为48mm*4.8mm*1.2mm的陶瓷生胚(室温下，激光强度1.8W，激光扫描速率750mm/s，打印层厚25um)。
脱脂烧结工艺：陶瓷生胚以1℃/min从室温升温至150℃；以0.5℃/min从150℃升温至350℃；在350℃保温1小时；以0.1℃/min从350℃升温至550℃；在550℃保温3小时；以0.5℃/min从550℃升温至900℃；在900℃保温1小时；以1℃/min从900℃升温至1450℃；自然冷却。
三点弯曲测试(ISO 6872-2008)用于测定该氧化锆材料的三点弯曲强度。在上述实施例中，随着氧化锆固含量的提高，所得到的组合物打印并脱脂烧结后的三点弯曲强度越强。
8.添加溶剂、塑化剂对黏度以及烧结后三点弯曲强度的影响参见表8中实施例
表8
Figure PCTCN2018093755-appb-000025
Figure PCTCN2018093755-appb-000026
组合物的制备：室温下将表面改性剂以质量比2∶100溶解于酒精中，再加入氧化锆混合均匀，球磨的转速为400r/min，球磨时间为8小时。将所得混合液蒸干，并粉碎干燥得到干燥的氧化锆粉末。将所得的氧化锆与光敏树脂、塑化剂或溶剂混合均匀，球磨的转速为1000r/min，球磨时间为50小时。将所得混合液在真空下静止10小时除去气泡，得到所需的可光致固化组合物。
黏度测试：使用Brookfield公司出品的椎板粘度仪CAP2000测试黏度。测试温度为25℃，剪切速率为20s -1。可以看出，上述实施例中，添加塑化剂或溶剂后，所得到的组合物的黏度有不同程度的降低。
3D打印实验：使用所配置的可光致固化组合物在昆山博力迈三维打印科技有限公司的CSL机型(SLA技术)上打印尺寸为48mm*4.8mm*1.2mm的陶瓷生胚(室温下，激光强度1.8W，激光扫描速率750mm/s，打印层厚25um)。
脱脂烧结工艺：陶瓷生胚以1℃/min从室温升温至150℃；以0.5℃/min从150℃升温至350℃；在350℃保温1小时；以0.1℃/min从350℃升温至550℃；在550℃保温3小时；以0.5℃/min从550℃升温至900℃；在900℃保温1小时；以1℃/min从900℃升温至1450℃；自然冷却。
三点弯曲测试(ISO 6872-2008)用于测定该氧化锆材料的三点弯曲强度。在上述实施例中，加入塑化剂或溶剂可以降低所得到组合物的黏度，同时可以提高脱脂烧结后的三点弯曲强度。
9.含有其他添加剂的实施例参见表9
表9
Figure PCTCN2018093755-appb-000027
注1：
Figure PCTCN2018093755-appb-000028
是来自R.T.Vanderbilt公司的分散剂。
组合物的制备：室温下将各个组分混合均匀，球磨的转速为800r/min，球磨时间为24小时。将所得混合液在真空下静置12小时除去气泡，得到所需的可光致固化组合物。
3D打印实验：使用所配置的可光致固化组合物在昆山博力迈三维打印科技有限公司的CSL机型(SLA技术)上打印尺寸为48mm*4.8mm*1.2mm的陶瓷生胚(室温下，激光强度1.8W，激光扫描速率750mm/s，打印层厚25um)。
脱脂烧结工艺：陶瓷生胚以1℃/min从室温升温至150℃；以0.5℃/min从150℃升温至350℃；在350℃保温1小时；以0.1℃/min从350℃升温至550℃；在550℃保温3小时；以0.5℃/min从550℃升温至900℃；在900℃保温1小 时；以1℃/min从900℃升温至1450℃；自然冷却。
在上述实施例中，加入阻聚剂、着色剂、热稳定剂和抗氧化剂对脱脂烧结后的三点弯曲强度影响不大。阻聚剂、着色剂、热稳定剂和抗氧化剂的添加量很少就可以起到足够好的阻聚、着色或抗氧化的作用。
通过以上实施例结果可见，本发明的光固化组合物具有优异的流动性、黏度、稳定性以及光固化成型性，从而适合用于通过立体光固化成型(SLA)或数字光处理成型(DLP)技术3D打印出陶瓷生胚，再通过脱脂烧结得到致密的陶瓷制品。本发明由于利用了立体光固化成型(SLA)或数字光处理成型(DLP)技术的成型速度快、成型精度高等优势，将材料的立体光固化成型(SLA)或数字光处理成型(DLP)技术与陶瓷脱脂烧结技术相结合，从而达到缩短陶瓷制品开发周期，降低设计成本，提高设计灵活性的目的。
上述实施例仅供说明本发明之用，而并非是对本发明的限制，有关技术领域的普通技术人员，在不脱离本发明范围的情况下，还可以做出各种变化和变型，因此，所有等同的技术方案也应属于本发明公开的范畴。

Claims (34)

  1. 一种可光致固化的组合物，包含：可聚合或交联的光敏树脂；陶瓷颗粒；分散剂；塑化剂和/或溶剂；其中所述陶瓷颗粒相对于可光致固化的组合物的添加量是10体积％至80体积％；所述塑化剂相对于可聚合或交联的光敏树脂的添加量是0.1wt％至50wt％；所述分散剂相对于陶瓷颗粒的添加量是0.1wt％至20wt％。
  2. 根据权利要求1所述的可光致固化的组合物，其中所述陶瓷颗粒相对于可光致固化的组合物的添加量是30体积％至70体积％，优选40体积％至60体积％，更优选45体积％至50体积％。
  3. 根据权利要求1或2所述的可光致固化的组合物，其中所述塑化剂相对于可聚合或交联的光敏树脂的添加量是1wt％至40wt％，优选1wt％至30wt％。
  4. 根据权利要求1-3任一所述的可光致固化的组合物，其中所述分散剂相对于陶瓷颗粒的添加量是0.1wt％至10wt％，优选1wt％至5wt％。
  5. 根据权利要求1-4任一所述的可光致固化的组合物，其中所述溶剂相对于可聚合或交联的光敏树脂的添加量是0至50wt％，优选是5至20wt％。
  6. 根据权利要求1-4任一所述的可光致固化的组合物，其中所述光敏树脂是可发生光致阳离子固化的光敏树脂、可发生光致自由基固化的光敏树脂、或其组合。
  7. 根据权利要求6所述的可光致固化的组合物，其中所述的可发生光致阳离子固化的光敏树脂包含：可发生阳离子固化的单体、寡聚物或高聚物，其具有至少一个可环氧聚合的官能团，其中寡聚物分子量为200-1000或高聚物 分子量为1000-30000；以及阳离子引发剂。
  8. 根据权利要求7所述的可光致固化的组合物，其中阳离子引发剂的添加量是光敏树脂总重量的0.1至20wt％，优选1至10wt％，更优选1至5wt％。
  9. 根据权利要求7或8所述的可光致固化的组合物，其中所述可环氧聚合的官能团是环氧乙烷环、环氧丙烷环、环氧环己烷基、或上述一种或多种官能团的衍生物。
  10. 根据权利要求7-9中任一所述的可光致固化的组合物，其中所述阳离子引发剂是一种可被紫外光、可见光或红外光激发的光引发剂。
  11. 根据权利要求10所述的可光致固化的组合物，其中阳离子引发剂是芳基重氮盐、二芳基碘鎓盐、三芳基锍盐、三芳基硒盐、芳茂铁盐，或者是以上多种的混合物。
  12. 根据权利要求10所述的可光致固化的组合物，其中阳离子引发剂是二芳基碘六氟砷酸盐、二芳基碘六氟锑酸盐、二芳基碘磺酸盐、二芳基碘硼酸盐、三芳基锍磺酸盐、三芳基锍硼酸盐、三芳基锍六氟锑酸盐，或者是以上多种的混合物。
  13. 根据权利要求6所述的可光致固化的组合物，其中所述的可发生光致自由基固化的光敏树脂包含：
    可发生自由基固化的单体、寡聚物或是高聚物，其具有至少一个可自由基聚合的官能团，其中寡聚物分子量为200-1000，高聚物分子量为1000-30000；以及自由基引发剂。
  14. 根据权利要求13所述的可光致固化的组合物，所述自由基引发剂的添加量是基于光敏树脂总重量的0.1至20wt％，优选1至10wt％，更优选1至5 wt％。
  15. 根据权利要求13或14所述的可光致固化的组合物，其中所述可发生光致自由基固化的光敏树脂包含具有至少一个巯基的单体、寡聚物或是高聚物。
  16. 根据权利要求15所述的可光致固化的组合物，其中具有至少一个巯基的单体、寡聚物或是高聚物相对于光敏树脂总重量的含量是1至20wt％，优选是1-10wt％，更优选是5-10wt％。
  17. 根据权利要求15或16所述的可光致固化的组合物，其中具有至少一个巯基的寡聚物或高聚物的聚合度不大于40。
  18. 根据权利要求13-17中任一所述的可光致固化的组合物，其中可自由基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100001
    其中，X是C或Si；R 1、R 2、R 3相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  19. 根据权利要求13-17中任一所述的可光致固化的组合物，其中所述可自由基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100002
    其中，R 1、R 2相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  20. 根据权利要求13-17中任一所述的可光致固化的组合物，所述可自由 基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100003
    其中，X是O、S、SO 2；R 1是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  21. 根据权利要求13-17中任一所述的可光致固化的组合物，其中所述可自由基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100004
    其中，X是C或Si；R 1、R 2、R 3相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  22. 根据权利要求13-17中任一所述的可光致固化的组合物，其中所述可自由基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100005
    其中，X是C或Si；R 1、R 2、R 3、R 4相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  23. 根据权利要求13-17中任一所述的可光致固化的组合物，其中所述可自由基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100006
    其中，R 1、R 2相同或不同，而且是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  24. 根据权利要求13-17中任一所述的可光致固化的组合物，其中所述可自由基聚合的官能团具有以下结构：
    Figure PCTCN2018093755-appb-100007
    其中，R 1是H、卤素、烷基、卤烷基、羟基、氰基、烷氧基。
  25. 根据权利要求13-24中任一所述的可光致固化的组合物，其中所述自由基引发剂是一种可被紫外光、可见光或是红外光激发的光引发剂。
  26. 根据权利要求25所述的可光致固化的组合物，其中所述自由基引发剂是安息香二乙醚、苯甲酰甲酸甲酯、羟基环乙烷苯酮、苯基双(2，4，6-三甲基苯甲酰基、)氧化膦、巯苯噻唑、Irgacure651、Irgacure907、Darocur2959、樟脑醌、α-酮戊二酸，或者是以上多种的混合物。
  27. 根据权利要求1-26中任一所述的可光致固化的组合物，其中所述陶瓷颗粒的粒度为20nm-50μm，优选为50nm-35μm，更优选为75nm-10μm。
  28. 根据权利要求1-27中任一所述的可光致固化的组合物，其中所述陶瓷颗粒选自氧化锆、氧化铝、氧化硅、羟基磷灰石、碳化硅、氮化硅、氮化铝、或包含上述陶瓷颗粒中的至少一种的组合。
  29. 根据权利要求1-28中任一所述的可光致固化的组合物，还包含表面改性剂，其中所述的表面改性剂选自线状或支化的羧酸、磷酸、磷酸酯、硅烷，或者是以上多种的混合物。
  30. 根据权利要求1-29中任一所述的可光致固化的组合物，其中所述分散剂选自丙烯酸类分散剂、聚乙烯吡咯烷酮类分散剂、壬基酚氧乙基化物分散剂、胺类分散剂、脂肪酸类分散剂、聚乙二醇类分散剂或聚醚类分散剂中的一种或 多种。
  31. 根据权利要求1-30中任一所述的可光致固化的组合物，其中所述塑化剂选自甘油三油酸酯、聚乙二醇、邻苯二甲酸酯衍生物、磷酸酯衍生物，或者是以上多种的混合物。
  32. 根据权利要求1-31中任一所述的可光致固化的组合物，其中所述溶剂选自水，邻苯二甲酸酯(比如邻苯二甲酸二丁酯、邻苯二甲酸二己酯、邻苯二甲酸二正辛酯)、磷酸酯(比如磷酸三甲苯酯、磷酸三丁酯)、正辛醇、甘油、聚乙二醇、2-氨基-2-甲基-1-丙醇、2-甲基-2，4-戊二醇、三丙二醇、四缩乙二醇、乙酰乙酸乙酯、柠檬酸三乙酯、环己醇、环己酮、二乙二醇甲醚、二乙二醇二乙醚、草酸二丁酯、2，5-二甲氧基四氢呋喃、2，5-二乙氧基四氢呋喃、正壬醇、异壬醇，或者是以上多种的混合物。
  33. 根据权利要求1-32中任一所述的可光致固化的组合物，其还包含选自以下添加剂中的一种或多种：陶瓷着色剂、阻聚剂、热稳定剂、抗氧化剂、光稳定剂、防静电剂、颜料和染料。
  34. 一种陶瓷制品，其由权利要求1-33任一所述的可光致固化的组合物通过立体光固化成型法(Stereolithography，SLA)或数字光处理成型(digital light processing，DLP)法光固化成型为生坯后，加热脱脂烧结得到。
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